UC DAVIS: CHEM 4B

GENERAL CHEMISTRY
FOR MAJORS II

Delmar Larsen
University of California, Davis
 UC Davis: Chem 4H
General Chemistry for Majors II

Delmar Larsen
University of California, Davis
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TABLE OF CONTENTS

Unit I: Chemical Thermodynamics

I: Fundamentals of Thermochemistry (Heat and Enthalpy)
1.1: Systems, States and Processes
1.2: Heat as a Mechanism to Transfer Energy
1.3: Work as a Mechanism to Transfer Energy
1.4: The First Law of Thermodynamics
1.5: Heat Capacity and Calorimetry
1.6: Molecules as Energy Carriers and Converters
1.7: Heats of Reactions - ΔU and ΔH
1.8: Indirect Determination of ΔH - Hess's Law
1.9: Standard Enthalpies of Formation
1.10: Fuels as Sources of Energy
1.E: Fundamentals of Thermochemistry (Exercises)
II: Principles of Thermodynamics (Entropy and Gibbs Energy)
2.1: The Nature of Spontaneous Processes
2.2: Entropy and Spontaneity - A Molecular Statistical Interpretation
2.3: Entropy and Heat - Experimental Basis of the Second Law of Thermodynamics
2.4: Entropy Changes and Spontaneity
2.5: Entropy Changes in Reversible Processes
2.6: Quantum States, Microstates, and Energy Spreading
2.7: The Third Law of Thermodynamics
2.8: Gibbs Energy
2.E: Principles of Thermodynamics (Exercises)

Unit II: Physical Equilibria

III: Solids, Liquids, and Phase Transitions
3.1: Bulk Properties of Gases, Liquids, and Solids - Molecular Interpretation
3.2: Intermolecular Forces - Origins in Molecular Structure
3.3: Intermolecular Forces in Liquids
3.4: Phase Equilibrium
3.5: Phase Transitions
3.6: Phase Diagrams
3.7: Clausius-Clapeyron Equation
3.8: The Solid State
3.9: Bonding in Metals
3.E: Solids, Liquids, and Phase Transitions (Exercises)
IV: Solutions
4.0: Types of Solutions - Some Terminology
4.1: Composition of Solutions
4.2: Nature of Dissolved Species
4.3: Phase Equilibrium in Solutions - Nonvolatile Solutes
4.4: Phase Equilibrium in Solutions - Volatile Solutes
4.5: Separating Volatile Solutions - Distillation
4.6: Colloidal Suspensions
4.E: Solutions (Exercises)

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Unit III: Chemical Equilibria
V: Chemical Equilibrium
5.1: The Nature of Chemical Equilibrium
5.2: The Empirical Law of Mass Action
5.3: Thermodynamic Description of the Equilibrium State
5.4: The Law of Mass Action for Related and Simultaneous Equilibria
5.5: Gas-Phase and Heterogeneous Reaction Equilibria
5.6: The Direction of Change in Chemical Reactions: Empirical Description
5.7: The Direction of Change in Chemical Reactions - Thermodynamic Explanation
5.8: Distribution between Immiscible Phases - Extraction and Separation Processes
5.E: Chemical Equilibrium (Exercises)
VI: Acid–Base Equilibria
6.1: Classifications of Acids and Bases
6.2: The Brønsted-Lowry Scheme
6.3: Acid and Base Strength
6.4: Equilibria Involving Weak Acids and Bases
6.5: Buffer Solutions
6.6: Acid-Base Titration Curves
6.7: Polyprotic Acids
6.8: A Deeper Look - Exact Treatment of Acid-Base Equilibria
6.9: Organic Acids and Bases - Structure and Reactivity
6.10: Lewis Bases as Nucleophilic Reactants in Organic Reactions
VII: Solubility and Precipitation Equilibria
7.1: The Nature of Solubility Equilibria
7.2: Ionic Equilibria between Solids and Solutions
7.3: Precipitation and the Solubility Product
7.4: The Effects of pH on Solubility
7.5: Complex Ions and Solubility
7.6: A Deeper Look - Selective Precipitation of Ions

Index

Glossary

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 SECTION OVERVIEW

Unit I: Chemical Thermodynamics

Thermochemistry is the study of the energy and heat associated with chemical reactions and/or physical transformations. A
reaction may release or absorb energy, and a phase change may do the same, such as in melting and boiling. Thermochemistry
focuses on these energy changes, particularly on the system's energy exchange with its surroundings. Thermochemistry is useful in
predicting reactant and product quantities throughout the course of a given reaction.
Chemical thermodynamics studies the nature of the role of entropy in the process of chemical reactions and provided the bulk of
expansion and knowledge of the field. Other formulations of thermodynamics emerged in the following decades. The combination
of enthalpy and entropy can be used to predict whether a reaction is spontaneous or non-spontaneous (i.e., favorable or unfavorable
to occur). Statistical thermodynamics, or statistical mechanics, concerns itself with statistical predictions of the collective motion of
particles from their microscopic behavior.

I: Fundamentals of Thermochemistry (Heat and Enthalpy)

1.1: Systems, States and Processes
1.2: Heat as a Mechanism to Transfer Energy
1.3: Work as a Mechanism to Transfer Energy
1.4: The First Law of Thermodynamics
1.5: Heat Capacity and Calorimetry
1.6: Molecules as Energy Carriers and Converters
1.7: Heats of Reactions - ΔU and ΔH
1.8: Indirect Determination of ΔH - Hess's Law
1.9: Standard Enthalpies of Formation
1.10: Fuels as Sources of Energy
1.E: Fundamentals of Thermochemistry (Exercises)

II: Principles of Thermodynamics (Entropy and Gibbs Energy)

2.1: The Nature of Spontaneous Processes
2.2: Entropy and Spontaneity - A Molecular Statistical Interpretation
2.3: Entropy and Heat - Experimental Basis of the Second Law of Thermodynamics
2.4: Entropy Changes and Spontaneity
2.5: Entropy Changes in Reversible Processes
2.6: Quantum States, Microstates, and Energy Spreading
2.7: The Third Law of Thermodynamics
2.8: Gibbs Energy
2.E: Principles of Thermodynamics (Exercises)

Thumbnail: Dancing Flames of burning charcoal in the dark. (CC SA-BY 3.0; Oscar).

Unit I: Chemical Thermodynamics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
 CHAPTER OVERVIEW

I: Fundamentals of Thermochemistry (Heat and Enthalpy)

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

This chapter introduces you to thermochemistry, a branch of chemistry that describes the energy changes that occur during
chemical reactions. In some situations, the energy produced by chemical reactions is actually of greater interest to chemists than the
material products of the reaction. For example, the controlled combustion of organic molecules, primarily sugars and fats, within
our cells provides the energy for physical activity, thought, and other complex chemical transformations that occur in our bodies.
Similarly, our energy-intensive society extracts energy from the combustion of fossil fuels, such as coal, petroleum, and natural gas,
to manufacture clothing and furniture, heat your home in winter and cool it in summer, and power the car or bus that gets you to
class and to the movies.
1.1: Systems, States and Processes
1.2: Heat as a Mechanism to Transfer Energy
1.3: Work as a Mechanism to Transfer Energy
1.4: The First Law of Thermodynamics
1.5: Heat Capacity and Calorimetry
1.6: Molecules as Energy Carriers and Converters
1.7: Heats of Reactions - ΔU and ΔH
1.8: Indirect Determination of ΔH - Hess's Law
1.9: Standard Enthalpies of Formation
1.10: Fuels as Sources of Energy
1.E: Fundamentals of Thermochemistry (Exercises)

Thumbnail: Dancing Flames of burning charcoal in the dark. (CC SA-BY 3.0; Oscar),

I.1: Outside Links

Barrow, Gordon M. "Thermodynamics should be built on energy-not on heat and work." J. Chem. Educ. 1988: 65, 122.
Brouwer, Henry. "Small-scale thermochemistry experiment (ML)." J. Chem. Educ. 1991:68, A178.
King, Edward L. "Thermodynamics of the thermal decomposition of water by closed chemical cycles." J. Chem. Educ. 1981,
58, 975.
Peckham, G. D., McNaught, Ian J. 'Heat and work are not "forms of energy".' J. Chem. Educ. 1993: 70, 103.

I: Fundamentals of Thermochemistry (Heat and Enthalpy) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.

1
1.1: Systems, States and Processes
 Learning Objectives
To understand the concept of energy and its various forms.
To know the relationship between energy, work, and heat.

Because energy takes many forms, only some of which can be seen or felt, it is defined by its effect on matter. For example,
microwave ovens produce energy to cook food, but we cannot see that energy. In contrast, we can see the energy produced by a
light bulb when we switch on a lamp. In this section, we describe the forms of energy and discuss the relationship between energy,
heat, and work.

1.1.1: Forms of Energy

The forms of energy include thermal energy, radiant energy, electrical energy, nuclear energy, and chemical energy (Figure 1.1.1).
Thermal energy results from atomic and molecular motion; the faster the motion, the greater the thermal energy. The temperature of
an object is a measure of its thermal energy content. Radiant energy is the energy carried by light, microwaves, and radio waves.
Objects left in bright sunshine or exposed to microwaves become warm because much of the radiant energy they absorb is
converted to thermal energy. Electrical energy results from the flow of electrically charged particles. When the ground and a cloud
develop a separation of charge, for example, the resulting flow of electrons from one to the other produces lightning, a natural form
of electrical energy. Nuclear energy is stored in the nucleus of an atom, and chemical energy is stored within a chemical compound
because of a particular arrangement of atoms.

Figure 1.1.1 : Forms of Energy. (a) Thermal energy results from atomic and molecular motion; molten steel at 2,000°C has high
thermal energy. (b) Radiant energy (e.g., from the sun) is the energy in light, microwaves, and radio waves. (c) Lightning is an
example of electrical energy, which is due to the flow of electrically charged particles. (d) Nuclear energy is released when
particles in the nucleus of the atom are rearranged. (e) Chemical energy results from the particular arrangement of atoms in a
chemical compound; the heat and light produced in this reaction are due to energy released during the breaking and reforming of
chemical bonds. (CC BY-SA-NC; anonymous)
Electrical energy, nuclear energy, and chemical energy are different forms of potential energy (PE), which is energy stored in an
object because of the relative positions or orientations of its components. A brick lying on the windowsill of a 10th-floor office has
a great deal of potential energy, but until its position changes by falling, the energy is contained. In contrast, kinetic energy (KE) is
energy due to the motion of an object. When the brick falls, its potential energy is transformed to kinetic energy, which is then
transferred to the object on the ground that it strikes. The electrostatic attraction between oppositely charged particles is a form of
potential energy, which is converted to kinetic energy when the charged particles move toward each other.

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Energy can be converted from one form to another (Figure 1.1.2) or, as we saw with the brick, transferred from one object to
another. For example, when you climb a ladder to a high diving board, your body uses chemical energy produced by the
combustion of organic molecules. As you climb, the chemical energy is converted to mechanical work to overcome the force of
gravity. When you stand on the end of the diving board, your potential energy is greater than it was before you climbed the ladder:
the greater the distance from the water, the greater the potential energy. When you then dive into the water, your potential energy is
converted to kinetic energy as you fall, and when you hit the surface, some of that energy is transferred to the water, causing it to
splash into the air. Chemical energy can also be converted to radiant energy; one common example is the light emitted by fireflies,
which is produced from a chemical reaction.

Figure 1.1.2 : Interconversion of Forms of Energy. When a swimmer steps off the platform to dive into the water, potential energy
is converted to kinetic energy. As the swimmer climbs back up to the top of the diving platform, chemical energy is converted to
mechanical work. (CC BY-SA-NC; anonymous)
Although energy can be converted from one form to another, the total amount of energy in the universe remains constant. This is
known as the law of conservation of energy: Energy cannot be created or destroyed.

1.1.2: Kinetic and Potential Energy

The kinetic energy of an object is related to its mass m and velocity v :
1 2
KE = mv (1.1.1)
2

For example, the kinetic energy of a 1360 kg (approximately 3000 lb) automobile traveling at a velocity of 26.8 m/s (approximately
60 mi/h) is
1
2
KE = (1360 kg)(26.8 ms) (1.1.2)
2

5 2
= 4.88 × 10 g ⋅ m

Because all forms of energy can be interconverted, energy in any form can be expressed using the same units as kinetic energy. The
SI unit of energy, the joule (J), is named after the British physicist James Joule (1818–1889), an early worker in the field of energy,
is defined as 1 kilogram·meter2/second2 (kg·m2/s2). Because a joule is such a small quantity of energy, chemists usually express
energy in kilojoules (1 kJ = 103 J). For example, the kinetic energy of the 1360 kg car traveling at 26.8 m/s is 4.88 × 105 J or 4.88 ×
102 kJ. It is important to remember that the units of energy are the same regardless of the form of energy, whether thermal, radiant,
chemical, or any other form. Because heat and work result in changes in energy, their units must also be the same.

To demonstrate, let’s calculate the potential energy of the same 1360 kg automobile if it were parked on the top level of a parking
garage 36.6 m (120 ft) high. Its potential energy is equivalent to the amount of work required to raise the vehicle from street level

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to the top level of the parking garage, which is
w = F d. (1.1.3)

The force (F ) exerted by gravity on any object is equal to its mass (m, in this case, 1360 kg) times the acceleration (a ) due to
gravity (g, 9.81 m/s2 at Earth’s surface). The distance (d ) is the height (h) above street level (in this case, 36.6 m). Thus the
potential energy of the car is as follows:
PE = F d = m a d = m gh (1.1.4)

9.81 m
= (1360 Kg) ( ) (36.6 m)
2
s

2
Kg ⋅ m
5
= 4.88 × 10
2
s

5
= 4.88 × 10 J = 488 kJ

The units of potential energy are the same as the units of kinetic energy. Notice that in this case the potential energy of the
stationary automobile at the top of a 36.6 m high parking garage is the same as its kinetic energy at 60 mi/h.

If the vehicle fell from the roof of the parking garage, its potential energy would be converted to kinetic energy, and it is reasonable
to infer that the vehicle would be traveling at 60 mi/h just before it hit the ground, neglecting air resistance. After the car hit the
ground, its potential and kinetic energy would both be zero.

Potential energy is usually defined relative to an arbitrary standard position (in this case, the street was assigned an elevation of
zero). As a result, we usually calculate only differences in potential energy: in this case, the difference between the potential energy
of the car on the top level of the parking garage and the potential energy of the same car on the street at the base of the garage.

1.1.3: Units of Energy

The units of energy are the same for all forms of energy. Energy can also be expressed in the non-SI units of calories (cal), where 1
cal was originally defined as the amount of energy needed to raise the temperature of exactly 1 g of water from 14.5 °C to 15.5
°C.We specify the exact temperatures because the amount of energy needed to raise the temperature of 1 g of water 1 °C varies

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slightly with elevation. To three significant figures, however, this amount is 1.00 cal over the temperature range 0 °C–100 °C. The
name is derived from the Latin calor, meaning “heat.” Although energy may be expressed as either calories or joules, calories were
defined in terms of heat, whereas joules were defined in terms of motion. Because calories and joules are both units of energy,
however, the calorie is now defined in terms of the joule:
1 cal ≡ 4.184 J (exactly) (1.1.5)

1 J = 0.2390 cal (1.1.6)

In this text, we will use the SI units—joules (J) and kilojoules (kJ)—exclusively, except when we deal with nutritional information.

 Example 1.1.1: Kinetic Energy of Baseballs

a. If the mass of a baseball is 149 g, what is the kinetic energy of a fastball clocked at 100 mi/h?
b. A batter hits a pop fly, and the baseball (with a mass of 149 g) reaches an altitude of 250 ft. If we assume that the ball was 3
ft above home plate when hit by the batter, what is the increase in its potential energy?

Given
mass and velocity or height

Asked for
kinetic and potential energy

Strategy
Use Equation 1.1.1 to calculate the kinetic energy and Equation 1.1.4 to calculate the potential energy, as appropriate.

Solution
a. The kinetic energy of an object is given by 1

2
mv
2
In this case, we know both the mass and the velocity, but we must
convert the velocity to SI units:

100 mi 1 h 1 min 1.61 km 1000 m

v =( ) ( ) ( )( ) ( )
60 min 60 s 1 mi
1 h 1 km

= 44.7 m/s

The kinetic energy of the baseball is therefore (via Equation 1.1.1)

2
1 1 kg 44.7 m
KE = 149 g ( )( )
2 1000 g s

2
2
kg ⋅ m
= 1.49 × 10
2
s

2
= 1.49 × 10 J

b. The increase in potential energy is the same as the amount of work required to raise the ball to its new altitude, which is
(250 − 3) = 247 feet above its initial position. Thus

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 1 kg 9.81 m ⎛ 0.3048 m ⎞
P E = 149 g ( )( ) (247 ft )
2
1000 g s ⎝ 1 ft ⎠

2
kg ⋅ m
2
= 1.10 × 10
2
s

2
= 1.10 × 10 J

 Exercise 1.1.1
a. In a bowling alley, the distance from the foul line to the head pin is 59 f t and 10 in. (18.26 m). If a 16 lb (7.3 kg)
13

16

bowling ball takes 2.0 s to reach the head pin, what is its kinetic energy at impact? (Assume its speed is constant.)
b. What is the potential energy of a 16 lb bowling ball held 3.0 ft above your foot?

Answer a
3.10 × 102 J
Answer b
65 J

1.1.4: Systems and Surroundings

To study the flow of energy during a chemical reaction, we need to distinguish between a system, the small, well-defined part of the
universe in which we are interested (such as a chemical reaction), and its surroundings, the rest of the universe, including the
container in which the reaction is carried out (Figure 1.1.3). In the discussion that follows, the mixture of chemical substances that
undergoes a reaction is always the system, and the flow of heat can be from the system to the surroundings or vice versa.

Figure 1.1.3 : A System and Its Surroundings. The system is that part of the universe we are interested in studying, such as a
chemical reaction inside a flask. The surroundings are the rest of the universe, including the container in which the reaction is
carried out. (CC BY-SA-NC; anonymous)
Three kinds of systems are important in chemistry. An open system can exchange both matter and energy with its surroundings. A
pot of boiling water is an open system because a burner supplies energy in the form of heat, and matter in the form of water vapor
is lost as the water boils. A closed system can exchange energy but not matter with its surroundings. The sealed pouch of a ready-
made dinner that is dropped into a pot of boiling water is a closed system because thermal energy is transferred to the system from
the boiling water but no matter is exchanged (unless the pouch leaks, in which case it is no longer a closed system). An isolated
system exchanges neither energy nor matter with the surroundings. Energy is always exchanged between a system and its
surroundings, although this process may take place very slowly. A truly isolated system does not actually exist. An insulated
thermos containing hot coffee approximates an isolated system, but eventually the coffee cools as heat is transferred to the
surroundings. In all cases, the amount of heat lost by a system is equal to the amount of heat gained by its surroundings and vice
versa. That is, the total energy of a system plus its surroundings is constant, which must be true if energy is conserved.
The state of a system is a complete description of a system at a given time, including its temperature and pressure, the amount of
matter it contains, its chemical composition, and the physical state of the matter. A state function is a property of a system whose
magnitude depends on only the present state of the system, not its previous history. Temperature, pressure, volume, and potential
energy are all state functions. The temperature of an oven, for example, is independent of however many steps it may have taken
for it to reach that temperature. Similarly, the pressure in a tire is independent of how often air is pumped into the tire for it to reach
that pressure, as is the final volume of air in the tire. Heat and work, on the other hand, are not state functions because they are path

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dependent. For example, a car sitting on the top level of a parking garage has the same potential energy whether it was lifted by a
crane, set there by a helicopter, driven up, or pushed up by a group of students (Figure 1.1.4). The amount of work expended to get
it there, however, can differ greatly depending on the path chosen. If the students decided to carry the car to the top of the ramp,
they would perform a great deal more work than if they simply pushed the car up the ramp (unless, of course, they neglected to
release the parking brake, in which case the work expended would increase substantially!). The potential energy of the car is the
same, however, no matter which path they choose.

Figure 1.1.4 : Elevation as an Example of a State Function. The change in elevation between state 1 (at the bottom of the parking
garage) and state 2 (at the top level of the parking garage) is the same for both paths A and B; it does not depend on which path is
taken from the bottom to the top. In contrast, the distance traveled and the work needed to reach the top do depend on which path is
taken. Elevation is a state function, but distance and work are not state functions. (CC BY-SA-NC; anonymous)

1.1.5: Summary
Thermochemistry is a branch of chemistry that qualitatively and quantitatively describes the energy changes that occur during
chemical reactions. Energy is the capacity to do work. Mechanical work is the amount of energy required to move an object a
given distance when opposed by a force. Thermal energy is due to the random motions of atoms, molecules, or ions in a
substance. The temperature of an object is a measure of the amount of thermal energy it contains. Heat (q) is the transfer of
thermal energy from a hotter object to a cooler one. Energy can take many forms; most are different varieties of potential energy
(PE), energy caused by the relative position or orientation of an object. Kinetic energy (KE) is the energy an object possesses due
to its motion. Energy can be converted from one form to another, but the law of conservation of energy states that energy can be
neither created nor destroyed. The most common units of energy are the joule (J), defined as 1 (kg·m2)/s2, and the calorie, defined
as the amount of energy needed to raise the temperature of 1 g of water by 1°C (1 cal = 4.184 J).

1.1: Systems, States and Processes is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

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1.2: Heat as a Mechanism to Transfer Energy
 Learning Objectives
To calculate changes in internal energy
Distinguish the related properties of heat, thermal energy, and temperature
Define and distinguish specific heat and heat capacity, and describe the physical implications of both
Perform calculations involving heat, specific heat, and temperature change

Thermal energy is kinetic energy associated with the random motion of atoms and molecules. Temperature is a quantitative
measure of “hot” or “cold.” When the atoms and molecules in an object are moving or vibrating quickly, they have a higher
average kinetic energy (KE), and we say that the object is “hot.” When the atoms and molecules are moving slowly, they have
lower KE, and we say that the object is “cold” (Figure 1.2.1). Assuming that no chemical reaction or phase change (such as
melting or vaporizing) occurs, increasing the amount of thermal energy in a sample of matter will cause its temperature to increase.
And, assuming that no chemical reaction or phase change (such as condensation or freezing) occurs, decreasing the amount of
thermal energy in a sample of matter will cause its temperature to decrease.

Figure 1.2.1 : (a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.
Heat (q) is the transfer of thermal energy between two bodies at different temperatures. Heat flow (a redundant term, but one
commonly used) increases the thermal energy of one body and decreases the thermal energy of the other. Suppose we initially have
a high temperature (and high thermal energy) substance (H) and a low temperature (and low thermal energy) substance (L). The
atoms and molecules in H have a higher average KE than those in L. If we place substance H in contact with substance L, the
thermal energy will flow spontaneously from substance H to substance L. The temperature of substance H will decrease, as will the
average KE of its molecules; the temperature of substance L will increase, along with the average KE of its molecules. Heat flow
will continue until the two substances are at the same temperature (Figure 1.2.2).

Figure 1.2.2 : (a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies.
(b) When they are put into contact with each other, collisions between the molecules result in the transfer of kinetic (thermal)
energy from the hotter to the cooler matter. (c) The two objects reach “thermal equilibrium” when both substances are at the same
temperature, and their molecules have the same average kinetic energy.
Matter undergoing chemical reactions and physical changes can release or absorb heat. A change that releases heat is called an
exothermic process. For example, the combustion reaction that occurs when using an oxyacetylene torch is an exothermic process
—this process also releases energy in the form of light as evidenced by the torch’s flame (Figure 1.2.3a). A reaction or change that
absorbs heat is an endothermic process. A cold pack used to treat muscle strains provides an example of an endothermic process.
When the substances in the cold pack (water and a salt like ammonium nitrate) are brought together, the resulting process absorbs
heat, leading to the sensation of cold.

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 Figure 1.2.3 : (a) An oxyacetylene torch produces heat by the combustion of acetylene in oxygen. The energy released by this
exothermic reaction heats and then melts the metal being cut. The sparks are tiny bits of the molten metal flying away. (b) A cold
pack uses an endothermic process to create the sensation of cold. (credit a: modification of work by “Skatebiker”/Wikimedia
commons).

 Heat does not "Flow" nor does Heat "Transfer"

The definition of heat is the transfer of thermal energy between two bodies at different temperatures, since temperature is a
measure of the average kinetic energy of a sample, this means that heat is the flow of kinetic energy from one spot to another.
Therefore, heat is the process of the energy flow and a specific system; a system does not "contain" heat, therefore heat cannot
be "transferred" nor does not "flow."
The concept of heat flow originates from the incorrect theory in the 19th century called caloric theory that postulated that heat
was connect to a mythical fluid that flows from hotter systems to colder systems. Unfortunately, the vernacular usage of terms
involving heat flowing is ingrained in the English language and it is difficulty to avoid them in scientific discussions of
thermodynamics. Nevertheless, it is important to emphasize that the important concept that heat does not flow.

1.2.1: Direction of Heat "Flow": Endothermic vs. Exothermic Processes

The reaction of powdered aluminum with iron(III) oxide, known as the thermite reaction, generates an enormous amount of heat—
enough, in fact, to melt steel. The balanced chemical equation for the reaction is as follows:
2 Al(s) + Fe O (s) → 2 Fe(s) + Al O (s) (1.2.1)
2 3 2 3

We can also write this chemical equation as

2 Al(s) + Fe O (s) → 2 Fe(s) + Al O (s) + heat (1.2.2)
2 3 2 3

to indicate that heat is one of the products. Chemical equations in which heat is shown as either a reactant or a product are called
thermochemical equations. In this reaction, the system consists of aluminum, iron, and oxygen atoms; everything else, including
the container, makes up the surroundings. During the reaction, so much heat is produced that the iron liquefies. Eventually, the
system cools; the iron solidifies as heat is transferred to the surroundings. A process in which heat (q) is transferred from a system
to its surroundings is described as exothermic. By convention, q < 0 for an exothermic reaction.

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 Thermite Reactions - Compilation

When you hold an ice cube in your hand, heat from the surroundings (including your hand) is transferred to the system (the ice),
causing the ice to melt and your hand to become cold. We can describe this process by the following thermochemical equation:

heat + H O(s) → H O(l) (1.2.3)

2 2

When heat is transferred to a system from its surroundings, the process is endothermic. By convention, q > 0 for an endothermic
reaction. It is poor form to have a heat term in the chemical reaction like in Equations 1.2.2 and 1.2.3 since heat is it not a true
species in the reaction. However, this is a convenient approach to represent exothermic and endothermic behavior and is commonly
used by chemists.

By convention, q < 0 for an exothermic reaction and q > 0 for an endothermic reaction.

 Exercise 1.2.1

Decide whether the following are endothermic or exothermic processes

a. water evaporates off a shower door
b. an acid tablet being added to a pool and the surrounding water heats up
c. NH Cl is dissolved in water and the solution cools
4

d. the burning of a log in a campfire

Hint
During an endothermic process heat is absorbed from surroundings, causing them to cool, so in every case where there is
cooling there is most likely an endothermic process taking place. For exothermic reactions energy is being released to the
surroundings and so the surroundings feel like they have been heated by the process.
Answer a
endothermic
Answer b
exothermic
Answer c
endothermic
Answer d
exothermic

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  Application: Heat can do more than increase temperature
Most substances expand as their temperature increases and contract as their temperature decreases. This property can be used
to measure temperature changes, as shown in Figure 1.2.4. The operation of many thermometers depends on the expansion and
contraction of substances in response to temperature changes.

Figure 1.2.4 : (a) In an alcohol or mercury thermometer, the liquid (dyed red for visibility) expands when heated and contracts
when cooled, much more so than the glass tube that contains the liquid. (b) In a bimetallic thermometer, two different metals (such
as brass and steel) form a two-layered strip. When heated or cooled, one of the metals (brass) expands or contracts more than the
other metal (steel), causing the strip to coil or uncoil. Both types of thermometers have a calibrated scale that indicates the
temperature. (credit a: modification of work by “dwstucke”/Flickr). (c) The demonstration allows one to view the effects of heating
and cooling a coiled bimetallic strip.A bimetallic coil from a thermometer reacts to the heat from a lighter, by uncoiling and then
coiling back up when the lighter is removed. Animation used with permission from Hustvedt (via Wikipedia)

1.2.2: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

This page titled 1.2: Heat as a Mechanism to Transfer Energy is shared under a CC BY license and was authored, remixed, and/or curated by
OpenStax.

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1.3: Work as a Mechanism to Transfer Energy
 Learning Objectives
To define work
To identify mechanical and pressure-volume work

One definition of energy is the capacity to do work. There are many kinds of work, including mechanical work, electrical work,
and work against a gravitational or a magnetic field. Here we will consider only mechanical work and focus on the work done
during changes in the pressure or the volume of a gas.

1.3.1: Mechanical Work

The easiest form of work to visualize is mechanical work (Figure 1.3.1), which is the energy required to move an object a distance
d when opposed by a force F , such as gravity (Figure 1.3.1):

w =F d (1.3.1)

with w is work, F is opposing force, and d is distance.

Figure 1.3.1 : One form of energy is mechanical work, the energy required to move an object of mass m through distance d when
opposed by a force F , i.e., as gravity. (CC BY-SA-NC; anonymous)
Because the force (F ) that opposes the action is equal to the mass (m) of the object times its acceleration (a ), Equation 1.3.1 can
be rewritten to:

w =mad (1.3.2)

with w is work, m is mass, a is acceleration, and d is distance.

Recall from that weight is a force caused by the gravitational attraction between two masses, such as you and Earth. Hence for
works against gravity (on Earth), a can be set to g = 9.8 m/s . Consider the mechanical work required for you to travel from the
2

first floor of a building to the second. Whether you take an elevator or an escalator, trudge upstairs, or leap up the stairs two at a
time, energy is expended to overcome the opposing force of gravity. The amount of work done (w) and thus the energy required
depends on three things:
1. the height of the second floor (the distance d );
2. your mass, which must be raised that distance against the downward acceleration due to gravity; and
3. your path.

1.3.2: Pressure-Volume (PV) Work

To describe this pressure–volume work (PV work), we will use such imaginary oddities as frictionless pistons, which involve no
component of resistance, and ideal gases, which have no attractive or repulsive interactions. Imagine, for example, an ideal gas,
confined by a frictionless piston, with internal pressure P and initial volume V (Figure 1.3.2). If P = P , the system is at
int i ext int

equilibrium; the piston does not move, and no work is done. If the external pressure on the piston (P ) is less than P , however,
ext int

then the ideal gas inside the piston will expand, forcing the piston to perform work on its surroundings; that is, the final volume (
V ) will be greater than V . If P
f i ext >P int , then the gas will be compressed, and the surroundings will perform work on the system.

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 Figure 1.3.2 : PV Work demonstrated with a frictionless piston. (a) if the external pressure is less than P , the ideal gas inside the
int

piston will expand, forcing the piston to perform work on its surroundings. The final volume (V ) will be greater than V . (b)
f i

Alternatively, if the external pressure is greater than P , the gas will be compressed, and the surroundings will perform work on
int

the system.
If the piston has cross-sectional area A , the external pressure exerted by the piston is, by definition, the force per unit area:
F
Pext = (1.3.3)
A

The volume of any three-dimensional object with parallel sides (such as a cylinder) is the cross-sectional area times the height (
V = Ah ). Rearranging Equation 1.3.3 to give

F = Pext A (1.3.4)

and defining the distance the piston moves (d ) as Δh , we can calculate the magnitude of the work performed by the piston by
substituting into Equation 1.3.1:

w = F d = Pext AΔh (1.3.5)

The change in the volume of the cylinder (ΔV ) as the piston moves a distance d is ΔV = AΔh , as shown in Figure 1.3.3.

Figure : Work Performed with a change in volume. The change in the volume (ΔV ) of the cylinder housing a piston is
1.3.3

ΔV = AΔh as the piston moves. The work performed by the surroundings on the system as the piston moves inward is given by
Equation 1.3.6 .
The PV work performed is thus

1.3.2 https://chem.libretexts.org/@go/page/42252
 w = Pext ΔV (1.3.6)

The units of work obtained using this definition are correct for energy: pressure is force per unit area (newton/m2) and volume has
units of cubic meters, so
F newton
3
w =( ) (ΔV ) = ×m = newton ⋅ m = joule (1.3.7)
2
A m
ext

If we use atmospheres for P and liters for V, we obtain units of L·atm for work. These units correspond to units of energy, as shown
in the different values of the ideal gas constant R:
0.08206 L ⋅ atm 8.314 J
R = = (1.3.8)
mol ⋅ K mol ⋅ K

Thus 0.08206 L·atm = 8.314 J and 1 L·atm = 101.3 J.

Whether work is defined as having a positive sign or a negative sign is a matter of convention. Heat flow is defined from a system
to its surroundings as negative; using that same sign convention, we define work done by a system on its surroundings as having a
negative sign because it results in a transfer of energy from a system to its surroundings. This is an arbitrary convention and one
that is not universally used. Some engineering disciplines are more interested in the work done on the surroundings than in the
work done by the system and therefore use the opposite convention. Because ΔV > 0 for an expansion, Equation 1.3.6 must be
written with a negative sign to describe PV work done by the system as negative:
w = −Pext ΔV (1.3.9)

The work done by a gas expanding against an external pressure is therefore negative, corresponding to work done by a system on
its surroundings. Conversely, when a gas is compressed by an external pressure, ΔV < 0 and the work is positive because work is
being done on a system by its surroundings.

 A Matter of Convention

For the thermochemistry

Heat is positive when energy is transferred from the surroundings to the system
Work is positive when energy is transferred from the surroundings to the system

 Example 1.3.2: Internal Combustion Engine

A small high-performance internal combustion engine has six cylinders with a total nominal displacement (volume) of 2.40 L
and a 10:1 compression ratio (meaning that the volume of each cylinder decreases by a factor of 10 when the piston
compresses the air–gas mixture inside the cylinder prior to ignition). How much work in joules is done when a gas in one
cylinder of the engine expands at constant temperature against an opposing pressure of 40.0 atm during the engine cycle?
Assume that the gas is ideal, the piston is frictionless, and no energy is lost as heat.
Given: final volume, compression ratio, and external pressure
Asked for: work done
Strategy
Calculate the final volume of gas in a single cylinder. Then compute the initial volume of gas in a single cylinder from the
compression ratio. Use Equation 1.3.9 to calculate the work done in liter-atmospheres. Convert from liter-atmospheres to
joules.
Solution
A To calculate the work done, we need to know the initial and final volumes. The final volume is the volume of one of the six
cylinders with the piston all the way down: Vf = 2.40 L/6 = 0.400 L. With a 10:1 compression ratio, the volume of the same
cylinder with the piston all the way up is Vi = 0.400 L/10 = 0.0400 L. Work is done by the system on its surroundings, so work
is negative.

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 w = −Pext ΔV

= −(40.0 atm)(0.400 L − 0.0400 L)

= −14.4 L ⋅ atm

Converting from liter-atmospheres to joules,

w = −(14.4 L ⋅ atm)[101.3 J/(L ⋅ atm)]

3
= −1.46 × 10 J

In the following exercise, you will see that the concept of work is not confined to engines and pistons. It is found in other
applications as well.

 Exercise 1.3.2: Work required to Breath

Breathing requires work, even if you are unaware of it. The lung volume of a 70 kg man at rest changed from 2200 mL to 2700
mL when he inhaled, while his lungs maintained a pressure of approximately 1.0 atm.
a. How much work in liter-atmospheres and joules was required to take a single breath?
b. During exercise, his lung volume changed from 2200 mL to 5200 mL on each in-breath.
c. How much additional work in joules did he require to take a breath while exercising?

Answer
−0.500 L·atm, or −50.7 J; −304 J; if he takes a breath every three seconds, this corresponds to 1.4 Calories per minute (1.4
kcal).

 Example 1.3.1: Expansion (PV) work

a. How much work is done by a gas that expands from 2 liters to 5 liters against an external pressure of 750 mmHg?
b. How much work is done by 0.54 moles of a gas that has an initial volume of 8 liters and expands under the following
conditions: 30 oC and 1.3 atm?
c. How much work is done by a gas (P=1.7 atm, V=1.56 L) that expands against an external pressure of 1.8 atm?

Solution a
w = −P ΔV

ΔV = Vf inal − VInitial = 5 L − 2 L = 3L

Convert 750 mmHg to atm:

750mmH g ∗ 1/760(atm/mmH g) = 0.9868atm.

W = −pΔV = −(.9868 atm)(3 L) = −2.96 L atm.

Solution b
First we must find the final volume using the ideal gas law:

pV = nRT

or
nRT
V =
P

(0.54 moles)(0.082057(L atm)/(mol K))(303 K)

= = 10.33 L
1.3 atm

1.3.4 https://chem.libretexts.org/@go/page/42252
 ΔV = Vf inal − Vinitial

= 10.3 L − 8 L = 2.3 L

Then from Equation 1.3.6

w = −pΔV = −(1.3 atm)(2.3 L) = −3 L ⋅ atm.

Solution c
w = −pΔV = −(1.8 atm) ΔV .

Given p , V , and p , find V : p

1 1 2 2 1 V1 = p2 V2 (at constant T and n )
V1 P1
V2 = = (1.56L ∗ 1.7atm)/1.8atm = 1.47L
P2

Now,

ΔV = V2 − V1 = 1.47 L − 1.56 L = −0.09

w = −(1.8atm) ∗ (−0.09L) = 0.162Latm.

1.3.3: Work in Chemical Transformations

Suppose, for example, that the system under study is a mass of steam heated by the combustion of several hundred pounds of coal
and enclosed within a cylinder housing a piston attached to the crankshaft of a large steam engine. The gas is not ideal, and the
cylinder is not frictionless. Nonetheless, as steam enters the engine chamber and the expanding gas pushes against the piston, the
piston moves, so useful work is performed. In fact, PV work launched the Industrial Revolution of the 19th century and powers the
internal combustion engine on which most of us still rely for transportation.

Figure 1.3.4 : Work Is Not a State Function. In pathway A, the volume of a gas is initially increased while its pressure stays
constant (step 1). Its pressure is then decreased while the volume remains constant (step 2). Pathway B reverses these steps.
Although (V , P ) and (V , P ) are identical in both cases, the amount of work done (shaded area) depends on the pathway taken.
1 1 2 2

(Cc BY-NC-SA; Anonymous by request)

In contrast to internal energy, work is not a state function. We can see this by examining Figure 1.3.4, in which two different, two-
step pathways take a gaseous system from an initial state to a final state with corresponding changes in temperature. In pathway A,
the volume of a gas is initially increased while its pressure stays constant (step 1); then its pressure is decreased while the volume
remains constant (step 2). In pathway B, the order of the steps is reversed. The temperatures, pressures, and volumes of the initial
and final states are identical in both cases, but the amount of work done, indicated by the shaded areas in the figure, is substantially
different. As we can see, the amount of work done depends on the pathway taken from (V , P ) to (V , P ), which means that
1 1 2 2

work is not a state function.

Internal energy is a state function, whereas work is not.

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1.3.4: Work and Chemical Reactions
Consider, for example, a reaction that produces a gas, such as dissolving a piece of copper in concentrated nitric acid. The chemical
equation for this reaction is as follows:
Cu(s) + 4 HNO (aq) ⟶ Cu(NO ) (aq) + 2 H O(l) + 2 NO (g) (1.3.10)
3 3 2 2 2

If the reaction is carried out in a closed system that is maintained at constant pressure by a movable piston, the piston will rise as
nitrogen dioxide gas is formed (Figure 1.3.5). The system is performing work by lifting the piston against the downward force
exerted by the atmosphere (i.e., atmospheric pressure). We find the amount of PV work done by multiplying the external pressure P
by the change in volume caused by movement of the piston (ΔV ). At a constant external pressure (here, atmospheric pressure)
w = −P ΔV (1.3.11)

The negative sign associated with P V work done indicates that the system loses energy. If the volume increases at constant
pressure (ΔV > 0), the work done by the system is negative, indicating that a system has lost energy by performing work on its
surroundings. Conversely, if the volume decreases (ΔV < 0), the work done by the system is positive, which means that the
surroundings have performed work on the system, thereby increasing its energy.

Figure 1.3.5 : An Example of Work Performed by a Reaction Carried Out at Constant Pressure. (a) Initially, the system (a copper
penny and concentrated nitric acid) is at atmospheric pressure. (b) When the penny is added to the nitric acid, the volume of NO 2

gas that is formed causes the piston to move upward to maintain the system at atmospheric pressure. In doing so, the system is
performing work on its surroundings.

1.3.5: Enthalpy
The symbol U represents the internal energy of a system, which is the sum of the kinetic energy and potential energy of all its
components. It is the change in internal energy that produces heat plus work. To measure the energy changes that occur in chemical
reactions, chemists usually use a related thermodynamic quantity called enthalpy (H) (from the Greek enthalpein, meaning “to
warm”). The enthalpy of a system is defined as the sum of its internal energy U plus the product of its pressure P and volume V :
H = U +PV (1.3.12)

Because internal energy, pressure, and volume are all state functions, enthalpy is also a state function.
If a chemical change occurs at constant pressure (i.e., for a fixed P , ΔP =0 ), the change in enthalpy (ΔH ) is
ΔH = Δ(U + P V ) (1.3.13)

= ΔU + Δ(P V ) (1.3.14)

= ΔU + P ΔV (1.3.15)

Substituting q + w for ΔU (Equation 1.3.15) and −w for P ΔV (Equation 1.3.11), we obtain

ΔH = ΔU + P ΔV

= qp + w − w

= qp (1.3.16)

The subscript p is used here to emphasize that this equation is true only for a process that occurs at constant pressure. From
Equation 1.3.16 we see that at constant pressure the change in enthalpy, ΔH of the system, defined as H −H , is equal
f inal initial

1.3.6 https://chem.libretexts.org/@go/page/42252
to the heat gained or lost.
ΔH = Hf inal − Hinitial = qp (1.3.17)

Just as with ΔU , because enthalpy is a state function, the magnitude of ΔH depends on only the initial and final states of the
system, not on the path taken. Most important, the enthalpy change is the same even if the process does not occur at constant
pressure.

To find ΔH for a reaction, measure q under constant pressure.

p

1.3.6: Summary
All forms of energy can be interconverted. Three things can change the energy of an object: the transfer of heat, work performed on
or by an object, or some combination of heat and work.

1.3.7: Outside Links

Gasparro, Frances P. "Remembering the sign conventions for q and w in deltaU = q - w." J. Chem. Educ. 1976: 53, 389.
Koubek, E. "PV work demonstration (TD)." J. Chem. Educ. 1980: 57, 374. '

1.3: Work as a Mechanism to Transfer Energy is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

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1.4: The First Law of Thermodynamics
 Learning Objectives
To calculate changes in internal energy
Distinguish the related properties of heat, thermal energy, and temperature
Define and distinguish specific heat and heat capacity, and describe the physical implications of both
Perform calculations involving heat, specific heat, and temperature change

The relationship between the energy change of a system and that of its surroundings is given by the first law of thermodynamics,
which states that the energy of the universe is constant. We can express this law mathematically as follows:
ΔUuniv = ΔUsys + ΔUsurr = 0 (1.4.1)

or
ΔUsys = −ΔUsurr (1.4.2)

where the subscripts univ, sys, and surr refer to the universe, the system, and the surroundings, respectively. Thus the change in
energy of a system is identical in magnitude but opposite in sign to the change in energy of its surroundings.

The tendency of all systems, chemical or otherwise, is to move toward the state with the
lowest possible energy.
An important factor that determines the outcome of a chemical reaction is the tendency of all systems, chemical or otherwise, to
move toward the lowest possible overall energy state. As a brick dropped from a rooftop falls, its potential energy is converted to
kinetic energy; when it reaches ground level, it has achieved a state of lower potential energy. Anyone nearby will notice that
energy is transferred to the surroundings as the noise of the impact reverberates and the dust rises when the brick hits the ground.
Similarly, if a spark ignites a mixture of isooctane and oxygen in an internal combustion engine, carbon dioxide and water form
spontaneously, while potential energy (in the form of the relative positions of atoms in the molecules) is released to the
surroundings as heat and work. The internal energy content of the CO /H O product mixture is less than that of the isooctane O
2 2 2

reactant mixture. The two cases differ, however, in the form in which the energy is released to the surroundings. In the case of the
falling brick, the energy is transferred as work done on whatever happens to be in the path of the brick; in the case of burning
isooctane, the energy can be released as solely heat (if the reaction is carried out in an open container) or as a mixture of heat and
work (if the reaction is carried out in the cylinder of an internal combustion engine). Because heat and work are the only two ways
in which energy can be transferred between a system and its surroundings, any change in the internal energy of the system is the
sum of the heat transferred (q) and the work done (w):
ΔUsys = q + w (1.4.3)

First Law of Thermodynamics

Although q and w are not state functions on their own, their sum (ΔU ) is independent of the path taken and is therefore a state
sys

function. A major task for the designers of any machine that converts energy to work is to maximize the amount of work obtained
and minimize the amount of energy released to the environment as heat. An example is the combustion of coal to produce
electricity. Although the maximum amount of energy available from the process is fixed by the energy content of the reactants and
the products, the fraction of that energy that can be used to perform useful work is not fixed. Because we focus almost exclusively
on the changes in the energy of a system, we will not use “sys” as a subscript unless we need to distinguish explicitly between a
system and its surroundings.

Although q and w are not state functions, their sum (ΔU sys ) is independent of the path
taken and therefore is a difference of a state function.

1.4.1 https://chem.libretexts.org/@go/page/42253
  Example 1.4.1

A sample of an ideal gas in the cylinder of an engine is compressed from 400 mL to 50.0 mL during the compression stroke
against a constant pressure of 8.00 atm. At the same time, 140 J of energy is transferred from the gas to the surroundings as
heat. What is the total change in the internal energy (ΔU ) of the gas in joules?
Given: initial volume, final volume, external pressure, and quantity of energy transferred as heat
Asked for: total change in internal energy
Strategy:
A. Determine the sign of q to use in Equation 1.4.3.
B. From Equation 1.4.3 calculate w from the values given. Substitute this value into Equation 1.4.3 to calculate ΔU .

Solution
A From Equation 1.4.3, we know that ΔU = q + w (First Law of Thermodynamics). We are given the magnitude of q (140 J)
and need only determine its sign. Because energy is transferred from the system (the gas) to the surroundings, q is negative by
convention.
B Because the gas is being compressed, we know that work is being done on the system, so w must be positive. From Equation
1.4.3,

w = −Pext ΔV

101.3 J
= −8.00 atm(0.0500 L − 0.400 L) ( )
L ⋅ atm

= 284 J

Thus

ΔU = q + w

= −140 J + 284 J

= 144 J

In this case, although work is done on the gas, increasing its internal energy, heat flows from the system to the surroundings,
decreasing its internal energy by 144 J. The work done and the heat transferred can have opposite signs.

 Exercise 1.4.1
A sample of an ideal gas is allowed to expand from an initial volume of 0.200 L to a final volume of 3.50 L against a constant
external pressure of 0.995 atm. At the same time, 117 J of heat is transferred from the surroundings to the gas. What is the total
change in the internal energy (ΔU ) of the gas in joules?

Answer
−216 J

By convention, both heat flow and work have a negative sign when energy is transferred from a system to its surroundings and vice
versa.

1.4.1: Summary
The first law of thermodynamics states that the energy of the universe is constant. The change in the internal energy of a system is
the sum of the heat transferred and the work done. The heat flow is equal to the change in the internal energy of the system plus the
P V work done. When the volume of a system is constant, changes in its internal energy can be calculated by substituting the ideal

gas law into the equation for ΔU .

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1.5: Heat Capacity and Calorimetry
 Learning Objectives
Explain the technique of calorimetry
Calculate and interpret heat and related properties using typical calorimetry data
To use calorimetric data to calculate enthalpy changes.

1.5.1: Heat Capacity

We now introduce two concepts useful in describing heat flow and temperature change. The heat capacity (C ) of a body of matter
is the quantity of heat (q) it absorbs or releases when it experiences a temperature change (ΔT ) of 1 degree Celsius (or
equivalently, 1 kelvin)
q
C = (1.5.1)
ΔT

Heat capacity is determined by both the type and amount of substance that absorbs or releases heat. It is therefore an extensive
property—its value is proportional to the amount of the substance.
For example, consider the heat capacities of two cast iron frying pans. The heat capacity of the large pan is five times greater than
that of the small pan because, although both are made of the same material, the mass of the large pan is five times greater than the
mass of the small pan. More mass means more atoms are present in the larger pan, so it takes more energy to make all of those
atoms vibrate faster. The heat capacity of the small cast iron frying pan is found by observing that it takes 18,140 J of energy to
raise the temperature of the pan by 50.0 °C
18, 140 J
Csmall pan = = 363 J/°C
50.0 °C

The larger cast iron frying pan, while made of the same substance, requires 90,700 J of energy to raise its temperature by 50.0 °C.
The larger pan has a (proportionally) larger heat capacity because the larger amount of material requires a (proportionally) larger
amount of energy to yield the same temperature change:
90, 700 J
Clarge pan = = 1814 J/°C
50.0 °C

The specific heat capacity (c ) of a substance, commonly called its specific heat, is the quantity of heat required to raise the
temperature of 1 gram of a substance by 1 degree Celsius (or 1 kelvin):
q
c = (1.5.2)
mΔT

Specific heat capacity depends only on the kind of substance absorbing or releasing heat. It is an intensive property—the type, but
not the amount, of the substance is all that matters. For example, the small cast iron frying pan has a mass of 808 g. The specific
heat of iron (the material used to make the pan) is therefore:
18, 140 J
ciron = = 0.449 J/g °C
(808 g)(50.0 °C )

The large frying pan has a mass of 4040 g. Using the data for this pan, we can also calculate the specific heat of iron:
90, 700J
ciron = = 0.449 J/g °C
(4, 040 g)(50.0 °C )

Although the large pan is more massive than the small pan, since both are made of the same material, they both yield the same
value for specific heat (for the material of construction, iron). Note that specific heat is measured in units of energy per temperature
per mass and is an intensive property, being derived from a ratio of two extensive properties (heat and mass). The molar heat
capacity, also an intensive property, is the heat capacity per mole of a particular substance and has units of J/mol °C (Figure 1.5.1).

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 Figure 1.5.1 : Due to its larger mass, a large frying pan has a larger heat capacity than a small frying pan. Because they are made of
the same material, both frying pans have the same specific heat. (CC BY; Mark Blaser via OpenStax).
The heat capacity of an object depends on both its mass and its composition. For example, doubling the mass of an object doubles
its heat capacity. Consequently, the amount of substance must be indicated when the heat capacity of the substance is reported. The
molar heat capacity (Cp) is the amount of energy needed to increase the temperature of 1 mol of a substance by 1°C; the units of Cp
are thus J/(mol•°C).The subscript p indicates that the value was measured at constant pressure. The specific heat (c ) is the amount
s

of energy needed to increase the temperature of 1 g of a substance by 1°C; its units are thus J/(g•°C).
We can relate the quantity of a substance, the amount of heat transferred, its heat capacity, and the temperature change either via
moles (Equation 1.5.3) or mass (Equation 1.5.4):

q = ncp ΔT (1.5.3)

where
nis the number of moles of substance and
cpis the molar heat capacity (i.e., heat capacity per mole of substance), and
ΔT = T −T
f inal is the temperature change.
initial

q = m cs ΔT (1.5.4)

where
m is the mass of substance in grams,
is the specific heat (i.e., heat capacity per gram of substance), and
cs

ΔT = T −T
f inal is the temperature change.
initial

Both Equations 1.5.3 and 1.5.4 are under constant pressure (which matters) and both show that we know the amount of a substance
and its specific heat (for mass) or molar heat capcity (for moles), we can determine the amount of heat, q, entering or leaving the
substance by measuring the temperature change before and after the heat is gained or lost.
The specific heats of some common substances are given in Table 1.5.1. Note that the specific heat values of most solids are less
than 1 J/(g•°C), whereas those of most liquids are about 2 J/(g•°C). Water in its solid and liquid states is an exception. The heat
capacity of ice is twice as high as that of most solids; the heat capacity of liquid water, 4.184 J/(g•°C), is one of the highest known.
The specific heat of a substance varies somewhat with temperature. However, this variation is usually small enough that we will
treat specific heat as constant over the range of temperatures that will be considered in this chapter. Specific heats of some common
substances are listed in Table 1.5.1.
Table 1.5.1 : Specific Heats of Common Substances at 25 °C and 1 bar
Substance Symbol (state) Specific Heat (J/g °C)

helium He(g) 5.193

water H2O(l) 4.184

ethanol C2H6O(l) 2.376

ice H2O(s) 2.093 (at −10 °C)

water vapor H2O(g) 1.864

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 Substance Symbol (state) Specific Heat (J/g °C)

nitrogen N2(g) 1.040

air mixture 1.007

oxygen O2(g) 0.918

aluminum Al(s) 0.897

carbon dioxide CO2(g) 0.853

argon Ar(g) 0.522

iron Fe(s) 0.449

copper Cu(s) 0.385

lead Pb(s) 0.130

gold Au(s) 0.129

silicon Si(s) 0.712

quartz SiO (s)

2
0.730

The value of C is intrinsically a positive number, but ΔT and q can be either positive or negative, and they both must have the
same sign. If ΔT and q are positive, then heat flows from the surroundings into an object. If ΔT and q are negative, then heat
flows from an object into its surroundings.
If a substance gains thermal energy, its temperature increases, its final temperature is higher than its initial temperature, then
ΔT > 0 and q is positive. If a substance loses thermal energy, its temperature decreases, the final temperature is lower than the

initial temperature, so ΔT < 0 and q is negative.

 Example 1.5.1: Measuring Heat

A flask containing 8.0 × 10 2

g of water is heated, and the temperature of the water increases from 21 °C to 85 °C. How much
heat did the water absorb?
Solution
To answer this question, consider these factors:
the specific heat of the substance being heated (in this case, water)
the amount of substance being heated (in this case, 800 g)
the magnitude of the temperature change (in this case, from 21 °C to 85 °C).
The specific heat of water is 4.184 J/g °C (Table 1.5.1), so to heat 1 g of water by 1 °C requires 4.184 J. We note that since
4.184 J is required to heat 1 g of water by 1 °C, we will need 800 times as much to heat 800 g of water by 1 °C. Finally, we
observe that since 4.184 J are required to heat 1 g of water by 1 °C, we will need 64 times as much to heat it by 64 °C (that is,
from 21 °C to 85 °C).
This can be summarized using Equation 1.5.4:
q = m cs ΔT

= m cs (Tfinal − Tinitial)

= (4.184 J/ g °C) × (800 g ) × (85 − 21)°C

= (4.184 J/ g ° C ) × (800 g ) × (64)° C

= 210, 000 J(= 210 kJ)

Because the temperature increased, the water absorbed heat and q is positive.

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  Exercise 1.5.1

How much heat, in joules, must be added to a 5.00 × 10 2

g iron skillet to increase its temperature from 25 °C to 250 °C? The
specific heat of iron is 0.451 J/g °C.
Answer
4
5.07 × 10 J

Note that the relationship between heat, specific heat, mass, and temperature change can be used to determine any of these
quantities (not just heat) if the other three are known or can be deduced.

 Example 1.5.2: Determining Other Quantities

A piece of unknown metal weighs 348 g. When the metal piece absorbs 6.64 kJ of heat, its temperature increases from 22.4 °C
to 43.6 °C. Determine the specific heat of this metal (which might provide a clue to its identity).
Solution
Since mass, heat, and temperature change are known for this metal, we can determine its specific heat using Equation 1.5.4:

q = m cs ΔT = m cs (Tf inal − Tinitial )

Substituting the known values:

6, 640 J = (348 g)cs (43.6 − 22.4) °C

Solving:
6, 640 J
c = = 0.900 J/g °C
(348 g)(21.2°C )

Comparing this value with the values in Table 1.5.1, this value matches the specific heat of aluminum, which suggests that the
unknown metal may be aluminum.

 Exercise 1.5.2
A piece of unknown metal weighs 217 g. When the metal piece absorbs 1.43 kJ of heat, its temperature increases from 24.5 °C
to 39.1 °C. Determine the specific heat of this metal, and predict its identity.

Answer
c = 0.45 J/g °C ; the metal is likely to be iron from checking Table 1.5.1.

 Example 1.5.3: Solar Heating

A home solar energy storage unit uses 400 L of water for storing thermal energy. On a sunny day, the initial temperature of the
water is 22.0°C. During the course of the day, the temperature of the water rises to 38.0°C as it circulates through the water
wall. How much energy has been stored in the water? (The density of water at 22.0°C is 0.998 g/mL.)

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 Passive solar system. During the day (a), sunlight is absorbed by water circulating in the water wall. At night (b), heat stored
in the water wall continues to warm the air inside the house.
Given: volume and density of water and initial and final temperatures
Asked for: amount of energy stored
Strategy:
A. Use the density of water at 22.0°C to obtain the mass of water (m) that corresponds to 400 L of water. Then compute ΔT
for the water.
B. Determine the amount of heat absorbed by substituting values for m, c , and ΔT into Equation 1.5.1.
s

Solution:
A The mass of water is

1000 mL 0.998 g 5
mass of H2 O = 400 L ( )( ) = 3.99 × 10 g H2 O
1 L 1 mL

The temperature change (ΔT) is 38.0°C − 22.0°C = +16.0°C.

B From Table 1.5.1, the specific heat of water is 4.184 J/(g•°C). From Equation 1.5.4, the heat absorbed by the water is thus

⎛ 4.184 J ⎞
5 o 7 4
q = m cs ΔT = (3.99 × 10 g ) (16.0 C ) = 2.67 × 10 J = 2.67 × 10 kJ
⎝ g ⋅
o
C ⎠

Both q and ΔT are positive, consistent with the fact that the water has absorbed energy.

 Exercise 1.5.3: Solar Heating

Some solar energy devices used in homes circulate air over a bed of rocks that absorb thermal energy from the sun. If a house
uses a solar heating system that contains 2500 kg of sandstone rocks, what amount of energy is stored if the temperature of the
rocks increases from 20.0°C to 34.5°C during the day? Assume that the specific heat of sandstone is the same as that of quartz
(SiO2) in Table 1.5.1.

Answer
4
2.7 × 10 kJ

Even though the mass of sandstone is more than six times the mass of the water in Example 1.5.1 , the amount of thermal
energy stored is the same to two significant figures.

1.5.2: Heat "Flow" to Thermal Equilibrium

When two objects at different temperatures are placed in contact, heat flows from the warmer object to the cooler one until the
temperature of both objects is the same. The law of conservation of energy says that the total energy cannot change during this

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process:
qcold + qhot = 0 (1.5.5)

The equation implies that the amount of heat that flows from a warmer object is the same as the amount of heat that flows into a
cooler object. Because the direction of heat flow is opposite for the two objects, the sign of the heat flow values must be opposite:
qcold = −qhot (1.5.6)

Thus heat is conserved in any such process, consistent with the law of conservation of energy.

The amount of heat lost by a warmer object equals the amount of heat gained by a cooler
object.
Substituting for q from Equation 1.5.4 gives

[m cs ΔT ] + [m cs ΔT ] =0
cold hot

which can be rearranged to give

[m cs ΔT ] = −[m cs ΔT ] (1.5.7)
cold hot

When two objects initially at different temperatures are placed in contact, we can use Equation 1.5.7 to calculate the final
temperature if we know the chemical composition and mass of the objects.

 Example 1.5.4: Thermal Equilibration of Copper and Water

If a 30.0 g piece of copper pipe at 80.0°C is placed in 100.0 g of water at 27.0°C, what is the final temperature? Assume that no
heat is transferred to the surroundings.
Given: mass and initial temperature of two objects
Asked for: final temperature
Strategy: Using Equation 1.5.7 and writing ΔT = T −T for both the copper and the water, substitute the
f inal initial

appropriate values of m, c , and T

s into the equation and solve for T
initial . f inal

Solution
We can adapt Equation 1.5.7to solve this problem, remembering that ΔT = Tf inal − Tinitial :

[m cs (Tf inal − Tinitial )] + [m cs (Tf inal − Tinitial )] =0

Cu H2 O

Substituting the data provided in the problem and Table 1.5.1 gives
(30 g) (0.385 J/(g°C ))(Tf inal − 80°C ) + (100 g)(4.184 J/(g°C ))(Tf inal − 27.0°C ) = 0

o o
Tf inal (11.6 J / C ) − 924 J + Tf inal (418.4 J / C ) − 11, 300 J =0

o
Tf inal (430 J/ (g ⋅ C )) = 12, 224 J

o
Tf inal = 28.4 C

 Exercise 1.5.4A: Thermal Equilibration of Gold and Water

If a 14.0 g chunk of gold at 20.0°C is dropped into 25.0 g of water at 80.0°C, what is the final temperature if no heat is
transferred to the surroundings?

Answer
80.0°C

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  Exercise 1.5.4B: Thermal Equilibration of Aluminum and Water
A 28.0 g chunk of aluminum is dropped into 100.0 g of water with an initial temperature of 20.0°C. If the final temperature of
the water is 24.0°C, what was the initial temperature of the aluminum? (Assume that no heat is transferred to the
surroundings.)

Answer
90.6°C

1.5.3: Measuring Heat "Flow"

One technique we can use to measure the amount of heat involved in a chemical or physical process is known as calorimetry.
Calorimetry is used to measure amounts of heat transferred to or from a substance. To do so, the heat is exchanged with a calibrated
object (calorimeter). The change in temperature of the measuring part of the calorimeter is converted into the amount of heat (since
the previous calibration was used to establish its heat capacity). The measurement of heat transfer using this approach requires the
definition of a system (the substance or substances undergoing the chemical or physical change) and its surroundings (the other
components of the measurement apparatus that serve to either provide heat to the system or absorb heat from the system).
Knowledge of the heat capacity of the surroundings, and careful measurements of the masses of the system and surroundings and
their temperatures before and after the process allows one to calculate the heat transferred as described in this section.
A calorimeter is a device used to measure the amount of heat involved in a chemical or physical process.

Figure 1.5.2 : In a calorimetric determination, either (a) an exothermic process occurs and heat, q, is negative, indicating that
thermal energy is transferred from the system to its surroundings, or (b) an endothermic process occurs and heat, q, is positive,
indicating that thermal energy is transferred from the surroundings to the system.
The thermal energy change accompanying a chemical reaction is responsible for the change in temperature that takes place in a
calorimeter. If the reaction releases heat (qrxn < 0), then heat is absorbed by the calorimeter (qcalorimeter > 0) and its temperature
increases. Conversely, if the reaction absorbs heat (qrxn > 0), then heat is transferred from the calorimeter to the system (qcalorimeter
< 0) and the temperature of the calorimeter decreases. In both cases, the amount of heat absorbed or released by the calorimeter is
equal in magnitude and opposite in sign to the amount of heat produced or consumed by the reaction. The heat capacity of the
calorimeter or of the reaction mixture may be used to calculate the amount of heat released or absorbed by the chemical reaction.
The amount of heat released or absorbed per gram or mole of reactant can then be calculated from the mass of the reactants.

The amount of heat absorbed or released by the calorimeter is equal in magnitude and opposite in sign to the amount of heat
produced or consumed by the reaction.

1.5.3.1: Constant-Pressure Calorimetry

Because ΔH is defined as the heat flow at constant pressure, measurements made using a constant-pressure calorimeter (a device
used to measure enthalpy changes in chemical processes at constant pressure) give ΔH values directly. This device is particularly
well suited to studying reactions carried out in solution at a constant atmospheric pressure. A “student” version, called a coffee-cup

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calorimeter (Figure 1.5.3), is often encountered in general chemistry laboratories. Commercial calorimeters operate on the same
principle, but they can be used with smaller volumes of solution, have better thermal insulation, and can detect a change in
temperature as small as several millionths of a degree (10−6 °C).

Figure 1.5.3 : A Coffee-Cup Calorimeter. This simplified version of a constant-pressure calorimeter consists of two Styrofoam cups
nested and sealed with an insulated stopper to thermally isolate the system (the solution being studied) from the surroundings (the
air and the laboratory bench). Two holes in the stopper allow the use of a thermometer to measure the temperature and a stirrer to
mix the reactants.
Before we practice calorimetry problems involving chemical reactions, consider a simpler example that illustrates the core idea
behind calorimetry. Suppose we initially have a high-temperature substance, such as a hot piece of metal (M), and a low-
temperature substance, such as cool water (W). If we place the metal in the water, heat will flow from M to W. The temperature of
M will decrease, and the temperature of W will increase, until the two substances have the same temperature—that is, when they
reach thermal equilibrium. If this occurs in a calorimeter, ideally all of this heat transfer occurs between the two substances, with
no heat gained or lost by either the calorimeter or the calorimeter’s surroundings. Under these ideal circumstances, the net heat
change is zero:
q substance M +q substance W =0 (1.5.8)

This relationship can be rearranged to show that the heat gained by substance M is equal to the heat lost by substance W:
q substance M = −q substance W (1.5.9)

The magnitude of the heat (change) is therefore the same for both substances, and the negative sign merely shows that q substance M

and qsubstance W are opposite in direction of heat flow (gain or loss) but does not indicate the arithmetic sign of either q value (that
is determined by whether the matter in question gains or loses heat, per definition). In the specific situation described, q substance M

is a negative value and qsubstance W is positive, since heat is transferred from M to W.

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 Figure 1.5.4 : In a simple calorimetry process, (a) heat, q, is transferred from the hot metal, M , to the cool water, W , until (b) both
are at the same temperature.

 Example 1.5.5: Heat between Substances at Different Temperatures

A 360-g piece of rebar (a steel rod used for reinforcing concrete) is dropped into 425 mL of water at 24.0 °C. The final
temperature of the water was measured as 42.7 °C. Calculate the initial temperature of the piece of rebar. Assume the specific
heat of steel is approximately the same as that for iron (Table T4), and that all heat transfer occurs between the rebar and the
water (there is no heat exchange with the surroundings).
Solution
The temperature of the water increases from 24.0 °C to 42.7 °C, so the water absorbs heat. That heat came from the piece of
rebar, which initially was at a higher temperature. Assuming that all heat transfer was between the rebar and the water, with no
heat “lost” to the surroundings, then heat given off by rebar = −heat taken in by water, or:
qrebar = −qwater

Since we know how heat is related to other measurable quantities, we have:

(c × m × ΔT )rebar = −(c × m × ΔT )water

Letting f = final and i = initial, in expanded form, this becomes:

crebar × mrebar × (Tf ,rebar − Ti,rebar) = −cwater × mwater × (Tf ,water − Ti,water)

The density of water is 1.0 g/mL, so 425 mL of water = 425 g. Noting that the final temperature of both the rebar and water is 42.7
°C, substituting known values yields:

(0.449 J/g °C)(360g)(42.7°C − Ti,rebar) = −(4.184 J/g °C)(425 g)(42.7°C − 24.0°C)

(4.184 J/g °C)(425 g)(42.7°C − 24.0°C)

Ti,rebar = + 42.7°C
(0.449 J/g °C)(360 g)

Solving this gives T i,rebar = 248 °C, so the initial temperature of the rebar was 248 °C.

 Exercise 1.5.5A

A 248-g piece of copper is dropped into 390 mL of water at 22.6 °C. The final temperature of the water was measured as 39.9
°C. Calculate the initial temperature of the piece of copper. Assume that all heat transfer occurs between the copper and the
water.

Answer
The initial temperature of the copper was 335.6 °C.

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  Exercise 1.5.5B
A 248-g piece of copper initially at 314 °C is dropped into 390 mL of water initially at 22.6 °C. Assuming that all heat transfer
occurs between the copper and the water, calculate the final temperature.

Answer
The final temperature (reached by both copper and water) is 38.8 °C.

This method can also be used to determine other quantities, such as the specific heat of an unknown metal.

 Example 1.5.6: Identifying a Metal by Measuring Specific Heat

A 59.7 g piece of metal that had been submerged in boiling water was quickly transferred into 60.0 mL of water initially at
22.0 °C. The final temperature is 28.5 °C. Use these data to determine the specific heat of the metal. Use this result to identify
the metal.

Solution
Assuming perfect heat transfer, heat given off by metal = −heat taken in by water, or:
qmetal = −qwater

In expanded form, this is:

cmetal × mmetal × (Tf ,metal − Ti,metal) = −cwater × mwater × (Tf ,water − Ti,water)

Noting that since the metal was submerged in boiling water, its initial temperature was 100.0 °C; and that for water, 60.0 mL = 60.0
g; we have:

(cmetal )(59.7 g)(28.5°C − 100.0°C) = −(4.18 J/g °C)(60.0 g)(28.5°C − 22.0°C)

Solving this:
−(4.184 J/g °C)(60.0 g)(6.5°C)
cmetal = = 0.38 J/g °C
(59.7 g)(−71.5°C)

Comparing this with values in Table T4, our experimental specific heat is closest to the value for copper (0.39 J/g °C), so we
identify the metal as copper.

 Exercise 1.5.6

A 92.9-g piece of a silver/gray metal is heated to 178.0 °C, and then quickly transferred into 75.0 mL of water initially at 24.0
°C. After 5 minutes, both the metal and the water have reached the same temperature: 29.7 °C. Determine the specific heat and
the identity of the metal. (Note: You should find that the specific heat is close to that of two different metals. Explain how you
can confidently determine the identity of the metal).

Answer
cmetal = 0.13 J/g °C

This specific heat is close to that of either gold or lead. It would be difficult to determine which metal this was based solely
on the numerical values. However, the observation that the metal is silver/gray in addition to the value for the specific heat
indicates that the metal is lead.

When we use calorimetry to determine the heat involved in a chemical reaction, the same principles we have been discussing apply.
The amount of heat absorbed by the calorimeter is often small enough that we can neglect it (though not for highly accurate
measurements, as discussed later), and the calorimeter minimizes energy exchange with the surroundings. Because energy is

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neither created nor destroyed during a chemical reaction, there is no overall energy change during the reaction. The heat produced
or consumed in the reaction (the “system”), qreaction, plus the heat absorbed or lost by the solution (the “surroundings”), qsolution,
must add up to zero:

qreaction + qsolution = 0 (1.5.10)

This means that the amount of heat produced or consumed in the reaction equals the amount of heat absorbed or lost by the
solution:
qreaction = −qsolution (1.5.11)

This concept lies at the heart of all calorimetry problems and calculations. Because the heat released or absorbed at constant
pressure is equal to ΔH, the relationship between heat and ΔHrxn is
ΔHrxn = qrxn = −qcalorimater = −m cs ΔT (1.5.12)

The use of a constant-pressure calorimeter is illustrated in Example 1.5.7.

 Example 1.5.7: Heat of Solution

When 5.03 g of solid potassium hydroxide are dissolved in 100.0 mL of distilled water in a coffee-cup calorimeter, the
temperature of the liquid increases from 23.0°C to 34.7°C. The density of water in this temperature range averages 0.9969
g/cm3. What is ΔH soln(in kilojoules per mole)? Assume that the calorimeter absorbs a negligible amount of heat and, because
of the large volume of water, the specific heat of the solution is the same as the specific heat of pure water.
Given: mass of substance, volume of solvent, and initial and final temperatures
Asked for: ΔHsoln
Strategy:
A. Calculate the mass of the solution from its volume and density and calculate the temperature change of the solution.
B. Find the heat flow that accompanies the dissolution reaction by substituting the appropriate values into Equation 1.5.1.
C. Use the molar mass of KOH to calculate ΔHsoln.
Solution:
A To calculate ΔHsoln, we must first determine the amount of heat released in the calorimetry experiment. The mass of the
solution is

(100.0 mL H O) (0.9969 g/ mL ) + 5.03 g KOH = 104.72 g

2

The temperature change is (34.7°C − 23.0°C) = +11.7°C.

B Because the solution is not very concentrated (approximately 0.9 M), we assume that the specific heat of the solution is the
same as that of water. The heat flow that accompanies dissolution is thus

qcalorimater = m cs ΔT

⎛ 4.184 J ⎞
o
= (104.72 g ) (11.7 C )
⎝ o ⎠
g ⋅ C

= 5130 J

= 5.13 kJ

The temperature of the solution increased because heat was absorbed by the solution (q > 0). Where did this heat come from? It
was released by KOH dissolving in water. From Equation 1.5.1, we see that

ΔHrxn = −qcalorimeter = −5.13 kJ

This experiment tells us that dissolving 5.03 g of KOH in water is accompanied by the release of 5.13 kJ of energy. Because
the temperature of the solution increased, the dissolution of KOH in water must be exothermic.
C The last step is to use the molar mass of KOH to calculate ΔH soln - the heat associated when dissolving 1 mol of KOH :

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 56.11 g
5.13 kJ
ΔHsoln = ( )( )
5.03 g 1 mol

= −57.2 kJ/mol

 Exercise 1.5.7: Heat of Dissolving

A coffee-cup calorimeter contains 50.0 mL of distilled water at 22.7°C. Solid ammonium bromide (3.14 g) is added and the
solution is stirred, giving a final temperature of 20.3°C. Using the same assumptions as in Example 1.5.7, find ΔH for soln

NH4Br (in kilojoules per mole).

Answer
16.6 kJ/mol

1.5.3.2: Constant-Volume Calorimetry

Constant-pressure calorimeters are not very well suited for studying reactions in which one or more of the reactants is a gas, such
as a combustion reaction. The enthalpy changes that accompany combustion reactions are therefore measured using a constant-
volume calorimeter, such as the bomb calorimeter (A device used to measure energy changes in chemical processes. shown
schematically in Figure 1.5.4). The reactant is placed in a steel cup inside a steel vessel with a fixed volume (the “bomb”). The
bomb is then sealed, filled with excess oxygen gas, and placed inside an insulated container that holds a known amount of water.
Because combustion reactions are exothermic, the temperature of the bath and the calorimeter increases during combustion. If the
heat capacity of the bomb and the mass of water are known, the heat released can be calculated.

Figure 1.5.4 : A Bomb Calorimeter. After the temperature of the water in the insulated container has reached a constant value, the
combustion reaction is initiated by passing an electric current through a wire embedded in the sample. Because this calorimeter
operates at constant volume, the heat released is not precisely the same as the enthalpy change for the reaction. (CC BY-SA-NC;
anonymous)
Because the volume of the system (the inside of the bomb) is fixed, the combustion reaction occurs under conditions in which the
volume, but not the pressure, is constant. The heat released by a reaction carried out at constant volume is identical to the change in
internal energy (ΔU ) rather than the enthalpy change (ΔH); ΔU is related to ΔH by an expression that depends on the change in
the number of moles of gas during the reaction. The difference between the heat flow measured at constant volume and the
enthalpy change is usually quite small, however (on the order of a few percent). Assuming that ΔU < ΔH , the relationship
between the measured temperature change and ΔHcomb is given in Equation 1.5.13, where Cbomb is the total heat capacity of the
steel bomb and the water surrounding it
ΔHcomb < qcomb = qcalorimater = Cbomb ΔT (1.5.13)

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To measure the heat capacity of the calorimeter, we first burn a carefully weighed mass of a standard compound whose enthalpy of
combustion is accurately known. Benzoic acid (C6H5CO2H) is often used for this purpose because it is a crystalline solid that can
be obtained in high purity. The combustion of benzoic acid in a bomb calorimeter releases 26.38 kJ of heat per gram (i.e., its
ΔHcomb = −26.38 kJ/g). This value and the measured increase in temperature of the calorimeter can be used to determine Cbomb.
The use of a bomb calorimeter to measure the ΔHcomb of a substance is illustrated in Example 1.5.8.

Physical Chemistry iBook - Bomb Calori…

Calori…

Video 1.5.1 : Video of view how a bomb calorimeter is prepared for action.

 Example 1.5.8: Combustion of Glucose

The combustion of 0.579 g of benzoic acid in a bomb calorimeter caused a 2.08°C increase in the temperature of the
calorimeter. The chamber was then emptied and recharged with 1.732 g of glucose and excess oxygen. Ignition of the glucose
resulted in a temperature increase of 3.64°C. What is the ΔHcomb of glucose?

Given: mass and ΔT for combustion of standard and sample

Asked for: ΔHcomb of glucose
Strategy:
A. Calculate the value of qrxn for benzoic acid by multiplying the mass of benzoic acid by its ΔHcomb. Then use Equation 1.5.1
to determine the heat capacity of the calorimeter (Cbomb) from qcomb and ΔT.
B. Calculate the amount of heat released during the combustion of glucose by multiplying the heat capacity of the bomb by the
temperature change. Determine the ΔHcomb of glucose by multiplying the amount of heat released per gram by the molar
mass of glucose.
Solution:
The first step is to use Equation 1.5.1 and the information obtained from the combustion of benzoic acid to calculate Cbomb.
We are given ΔT, and we can calculate qcomb from the mass of benzoic acid:

qcomb = (0.579 g ) (−26.38 kJ/ g ) = −15.3 kJ

From Equation 1.5.1,

1.5.13 https://chem.libretexts.org/@go/page/42251
 qcomb −15.3 kJ o
−Cbomb = = = −7.34 kJ / C
o
ΔT 2.08 C

B According to the strategy, we can now use the heat capacity of the bomb to calculate the amount of heat released during the
combustion of glucose:
o o
qcomb = −Cbomb ΔT = (−7.34 kJ / C ) (3.64 C ) = −26.7 kJ

Because the combustion of 1.732 g of glucose released 26.7 kJ of energy, the ΔHcomb of glucose is
180.16 g
−26.7 kJ 3
ΔHcomb = ( )( ) = −2780 kJ/mol = 2.78 × 10 kJ/mol
1.732 g mol

This result is in good agreement (< 1% error) with the value of ΔH comb = −2803 kJ/mol that calculated using enthalpies of
formation.

 Exercise 1.5.8: Combustion of Benzoic Acid

When 2.123 g of benzoic acid is ignited in a bomb calorimeter, a temperature increase of 4.75°C is observed. When 1.932 g of
methylhydrazine (CH3NHNH2) is ignited in the same calorimeter, the temperature increase is 4.64°C. Calculate the ΔHcomb of
methylhydrazine, the fuel used in the maneuvering jets of the US space shuttle.

Answer
−1.30 × 103 kJ/mol

1.5.4: Summary
Calorimetry measures enthalpy changes during chemical processes, where the magnitude of the temperature change depends on the
amount of heat released or absorbed and on the heat capacity of the system. Calorimetry is the set of techniques used to measure
enthalpy changes during chemical processes. It uses devices called calorimeters, which measure the change in temperature when a
chemical reaction is carried out. The magnitude of the temperature change depends on the amount of heat released or absorbed and
on the heat capacity of the system. The heat capacity (C) of an object is the amount of energy needed to raise its temperature by
1°C; its units are joules per degree Celsius. The specific heat (c ) of a substance is the amount of energy needed to raise the
s

temperature of 1 g of the substance by 1°C, and the molar heat capacity (c ) is the amount of energy needed to raise the
p

temperature of 1 mol of a substance by 1°C. Liquid water has one of the highest specific heats known. Heat flow measurements can
be made with either a constant-pressure calorimeter, which gives ΔH values directly, or a bomb calorimeter, which operates at
constant volume and is particularly useful for measuring enthalpies of combustion.
Thermal energy itself cannot be measured easily, but the temperature change caused by the flow of thermal energy between objects
or substances can be measured. Calorimetry describes a set of techniques employed to measure enthalpy changes in chemical
processes using devices called calorimeters. To have any meaning, the quantity that is actually measured in a calorimetric
experiment, the change in the temperature of the device, must be related to the heat evolved or consumed in a chemical reaction.
We begin this section by explaining how the flow of thermal energy affects the temperature of an object.

1.5.5: Contributors and Attributions

Anonymous
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed

1.5.14 https://chem.libretexts.org/@go/page/42251
 under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

1.5: Heat Capacity and Calorimetry is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1.5.15 https://chem.libretexts.org/@go/page/42251
1.6: Molecules as Energy Carriers and Converters
 Learning Objectives

Make sure you thoroughly understand the following essential concepts:

Describe the sources of potential energy and kinetic energy contained in a molecule.
Describe the nature of "thermal" energy, and how it relates to other forms of kinetic energy and to temperature.
Explain why the simplest molecules (monatomic and diatomic) have smaller heat capacities than polyatomic molecules.
Similarly, explain why the dependence of heat capacity on the temperature is different for monatomic and polyatomic
molecules.

All molecules at temperatures above absolute zero possess thermal energy— the randomized kinetic energy associated with the
various motions the molecules as a whole, and also the atoms within them, can undergo. Polyatomic molecules also possess
potential energy in the form of chemical bonds. Molecules are thus both vehicles for storing and transporting energy, and the
means of converting it from one form to another when the formation, breaking, or rearrangement of the chemical bonds within
them is accompanied by the uptake or release of heat.

1.6.1: Internal Energy: Potential + Kinetic

Chemical substances are made of atoms, or more generally, of positively charged nuclei surrounded by negatively charged
electrons. A molecule such as dihydrogen, H2, is held together by electrostatic attractions mediated by the electrons shared between
the two nuclei. The total potential energy of the molecule is the sum of the repulsions between like charges and the attractions
between electrons and nuclei:

P Etotal = P Eelectron−electron + P Enucleus−nucleus + P Enucleus−electron (1.6.1)

In other words, the potential energy of a molecule depends on the time-averaged relative locations of its constituent nuclei and
electrons. This dependence is expressed by the familiar potential energy curve which serves as an important description of the
chemical bond between two atoms.
Translation refers to movement of an object as a complete unit. Translational motions of molecules in solids or liquids are
restricted to very short distances comparable to the dimensions of the molecules themselves, whereas in gases the molecules
typically travel hundreds of molecular diameters between collisions. In gaseous hydrogen, for example, the molecules will be
moving freely from one location to another; this is called translational motion, and the molecules therefore possess
translational kinetic energy
2
mv
K Etrans = (1.6.2)
2

in which v stands for the average velocity of the molecules; you may recall from your study of gases that v , and therefore
KE , depends on the temperature.
trans

In addition to translation, molecules composed of two or more atoms can possess other kinds of motion.
Because a chemical bond acts as a kind of spring, the two atoms in H2 will have a natural vibrational frequency. In more
complicated molecules, many different modes of vibration become possible, and these all contribute a vibrational term KE vib

to the total kinetic energy.

Finally, a molecule can undergo rotational motions which give rise to a third term KE . rot

Thus the total kinetic energy of a molecule is the sum

K Etotal = K Etrans + K Evib + K Erot (1.6.3)

The total energy of the molecule (i.e, its internal energy U ) is just the sum of total kinetic and potential energies:
U = K Etotal + P Etotal (1.6.4)

Although Equation 1.6.4 is simple and straightforward, it cannot take us very far in understanding and predicting the behavior of
even one molecule, let alone a large number of them. The reason, of course, is the chaotic and unpredictable nature of molecular

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motion. Fortunately, the behavior of a large collection of molecules, like that of a large population of people, can be described by
statistical methods.

1.6.2: How Molecules "Store" Thermal Energy

As noted previously, the heat capacity of a substance is a measure of how sensitively its temperature is affected by a change in heat
content; the greater the heat capacity, the less effect a given flow of heat q will have on the temperature.

Thermal energy is randomized kinetic energy and temperature is a measure of it.

For monatomic gases, temperature is a measure of the average kinetic energy due to translational motions of molecules. If
vibrational or rotational motions are also active (e.g., diatomic gases), these motions will also accept thermal energy and reduce the
amount that goes into translational motions. Because the temperature depends only on the latter, the effect of the other kinds of
motions will be to reduce the dependence of the internal energy on the temperature, thus raising the heat capacity of a substance.
Table 1.6.1 : Molar heat capacities (kJ mol–1 K–1) of some gaseous substances at constant pressure.
monatomic diatomic triatomic

He 20.5 CO 29.3 H O
2
33.5

Ne 20.5 N
2
29.5 D O
2
34.3

Ar 20.5 F
2
31.4 CO
2
37.2

Kr 20.5 Cl
2
33.9 CS
2
45.6

Whereas monatomic molecules can only possess translational thermal energy, two additional kinds of motions become possible in
polyatomic molecules. A linear molecule has an axis that defines two perpendicular directions in which rotations can occur; each
represents an additional degree of freedom, so the two together contribute a total of ½ R to the heat capacity.
1 1 1 3
Ctrans = R + R + R = R (1.6.5)
2 2 2 2
   
x dimension y dimension z dimension translation in 3D

Vibrational and rotational motions are not possible for monatomic species such as the noble gas elements, so these substances have
the lowest heat capacities. Moreover, as you can see in the leftmost column of Table 1.6.1, their heat capacities are all the same.
This reflects the fact that translational motions are the same for all particles; all such motions can be resolved into three directions
in space, each contributing one degree of freedom to the molecule and ½R to its heat capacity (Equation 1.6.5) where R is the gas
constant, 8.314 J K .–1

Think of a "degree of freedom" as a motion that contributes to the total kinetic

energy of a molecule.
For a non-linear molecule, rotations are possible along all three directions of space, so these molecules have a rotational heat
capacity of 3/2R.
1 1 1 3
Crot = R + R + R = R (1.6.6)
 2 2 2 2
  
nonlinear molecules
x rotation y rotation z rotation

Linear molecules can only rotate in two dimensions so rotational motions in linear molecules contribute less than rotational
motions in nonlinear molecules to the heat capacity.
1 1
Crot = R + R =R (1.6.7)
 2 2
 
linear molecules
x rotation y rotation

Finally, the individual atoms within a molecule can move relative to each other, producing a vibrational motion. A nonlinear
molecule consisting of N atoms can vibrate in 3N – 6 different ways or modes, while a linear molecule has 3N − 5 modes. Each
vibrational mode contributes R (rather than ½ R) to the total heat capacity (these results come from advanced mechanics and will
not be proven here).

1.6.2 https://chem.libretexts.org/@go/page/96609
 vib degrees of freedom


Cvib = (3N − 5) R (1.6.8)


linear molecules

and
vib degrees of freedom


Cvib = (3N − 6) R (1.6.9)


nonlinear molecules

The total heat capacity of a mole of gas molecules is then

Cp = Ctrans + Crot + Cvib (1.6.10)

which differs based on the geometry and number of atoms in the molecule considered (Equations 1.6.6 - 1.6.9) as shown in Table
1.6.2.

Table 1.6.2 : Contribution of molecular motions to heat capacity

translation Rotation vibration
type of motion →

monatomic 3/2R 0 0

diatomic 3/2R R R (N = 2 in Equation 1.6.8)

3/2R (nonlinear) or R (3N – 6)R (nonlinear) or

polyatomic 3/2R
(linear) (3N – 5)R (linear)

separation between adjacent levels, (kJ mol–

1) 6.0 × 10–17 J (O2) 373 J (HCl) 26,000 J (HCl)

Now we are in a position to understand why more complicated molecules have higher heat capacities. The total kinetic energy of a
molecule is the sum of those due to the various kinds of motions:
K Etotal = K Etrans + K Erot + K Evib (1.6.11)

When a monatomic gas absorbs heat, all of the energy ends up in translational motion, and thus goes to increase its temperature. In
a polyatomic gas, by contrast, the absorbed energy is partitioned among the other kinds of motions; since only the translational
motions contribute to the temperature, the temperature rise is smaller, and thus the heat capacity is larger. There is one very
significant complication, however: classical mechanics predicts that the energy is always partitioned equally between all degrees of
freedom. Experiments, however, show that this is observed only at quite high temperatures. The reason is that these motions are all
quantized. This means that only certain increments of energy are possible for each mode of motion, and unless a certain minimum
amount of energy is available, a given mode will not be active at all and will contribute nothing to the heat capacity.

1.6.3: Translational Energy Levels are Effectively Continuous

The shading in Figure 1.6.1 indicates the average thermal energy available at 300 K. Only those levels within this range will have
significant occupancy as indicated by the thickness of the lines in the two rightmost columns. At 300 K, only the lowest vibrational
states and the first few rotational states will be active. Most of the thermal energy will be confined to the translational levels whose
minute spacing (10–17 J) causes them to appear as a continuum although technically quantized (by the particle in a box quantum
model).

Figure 1.6.1 : Different energy levels associated with translation, rotation, and vibration compared to an arbitrary thermal energy
(tan lelvel).

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Heat capacity of dihydrogen as a function of temperature. Figure 1.6.2 is typical of those for other polyatomic molecules, and
shows the practical consequences of the spacings of the various forms of thermal energy. Thus translational motions are available at
virtually all temperatures, but contributions to heat capacity by rotational or vibrational motions can only develop at temperatures
sufficiently large to excite these motions.

Figure 1.6.2 : The molar heat capacity of hydrogen as a function of temperature (on a logarithmic scale). The three “steps” or
“plateaus” show different numbers of degrees of freedom that the typical energies of molecules must achieve to activate.
Translational kinetic energy corresponds to three degrees of freedom, rotational to another two, and vibrational to yet another two.
(CC BY; OpenStax).
It turns out that translational energy levels are spaced so closely that these motions are active almost down to absolute zero, so all
gases possess a heat capacity of at least 3/2 R at all temperatures. Rotational motions do not get started until intermediate
temperatures, typically 300-500K, so within this range heat capacities begin to increase with temperature. Finally, at very high
temperatures, vibrations begin to make a significant contribution to the heat capacity
The strong intermolecular forces of liquids and many solids allow heat to be channeled into vibrational motions involving more
than a single molecule, further increasing heat capacities. One of the well known “anomalous” properties of liquid water is its high
heat capacity (75 J mol–1 K–1) due to intermolecular hydrogen bonding, which is directly responsible for the moderating influence
of large bodies of water on coastal climates.

 Heat capacities of metals

Metallic solids are a rather special case. In metals, the atoms oscillate about their equilibrium positions in a rather uniform way
which is essentially the same for all metals, so they should all have about the same heat capacity. We can model the atoms of a
solid as attached to neighboring atoms by springs (Figure 1.6.3).

Figure 1.6.3 : In a simple model of a solid element, each atom is attached to others by six springs, two for each possible
motion: x, y, and z. Each of the three motions corresponds to two degrees of freedom, one for kinetic energy and one for
potential energy. (CC BY-SA OpenStax).
Analogously to the discussion of vibration in the previous module, each atom has six degrees of freedom: one kinetic and one
potential for each of the x-, y-, and z-directions. Accordingly, the molar specific heat of a metal should be 3R. This result,

1.6.4 https://chem.libretexts.org/@go/page/96609
 known as the Law of Dulong and Petit, works fairly well experimentally at room temperature. In the 19th century these
workers discovered that the molar heat capacities of all the metallic elements they studied were around to 25 J mol–1 K–1,
which is close to what classical physics predicts for crystalline metals. This observation played an important role in
characterizing new elements, for it provided a means of estimating their molar masses by a simple heat capacity measurement.

1.6.4: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook

This page titled 1.6: Molecules as Energy Carriers and Converters is shared under a CC BY license and was authored, remixed, and/or curated by
Stephen Lower via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon
request.
14.3: Molecules as Energy Carriers and Converters by Stephen Lower is licensed CC BY 3.0. Original source:
http://www.chem1.com/acad/webtext/virtualtextbook.html.

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1.7: Heats of Reactions - ΔU and ΔH
Learning Objectives
To understand how enthalpy pertains to chemical reactions

When we study energy changes in chemical reactions, the most important quantity is usually the enthalpy of reaction (ΔH ), the rxn

change in enthalpy that occurs during a reaction (such as the dissolution of a piece of copper in nitric acid). If heat flows from a
system to its surroundings, the enthalpy of the system decreases, so ΔH is negative. Conversely, if heat flows from the
rxn

surroundings to a system, the enthalpy of the system increases, so ΔH is positive. Thus ΔH

rxn < 0 for an exothermic reaction,
rxn

and ΔH rxn > 0 for an endothermic reaction. In chemical reactions, bond breaking requires an input of energy and is therefore an

endothermic process, whereas bond making releases energy, which is an exothermic process. The sign conventions for heat flow
and enthalpy changes are summarized in the following table:

Reaction Type q ΔHrxn

< 0 (heat flows from a system to its

exothermic <0
surroundings)
> 0 (heat flows from the surroundings to a
endothermic >0
system)

If ΔH rxn is negative, then the enthalpy of the products is less than the enthalpy of the reactants; that is, an exothermic reaction is
energetically downhill (Figure 1.7.1a). Conversely, if ΔH is positive, then the enthalpy of the products is greater than the
rxn

enthalpy of the reactants; thus, an endothermic reaction is energetically uphill (Figure 1.7.1b).

Bond breaking ALWAYS requires an input of energy; bond making ALWAYS releases
energy.

Figure 1.7.1 : The Enthalpy of Reaction. Energy changes in chemical reactions are usually measured as changes in enthalpy. (a) If
heat flows from a system to its surroundings, the enthalpy of the system decreases, ΔH rxn is negative, and the reaction is
exothermic; it is energetically downhill. (b) Conversely, if heat flows from the surroundings to a system, the enthalpy of the system
increases, ΔH rxn is positive, and the reaction is endothermic; it is energetically uphill.
Two important characteristics of enthalpy and changes in enthalpy are summarized in the following discussion.
Reversing a reaction or a process changes the sign of ΔH. Ice absorbs heat when it melts (electrostatic interactions are
broken), so liquid water must release heat when it freezes (electrostatic interactions are formed):
heat + H O(s) ⟶ H O(l) ΔH > 0 (1.7.1)
2 2

H O(l) ⟶ H O(s) + heat ΔH < 0 (1.7.2)

2 2

In both cases, the magnitude of the enthalpy change is the same; only the sign is different.
Enthalpy is an extensive property (like mass). The magnitude of ΔH for a reaction is proportional to the amounts of the
substances that react. For example, a large fire produces more heat than a single match, even though the chemical reaction—the
combustion of wood—is the same in both cases. For this reason, the enthalpy change for a reaction is usually given in kilojoules
per mole of a particular reactant or product. Consider Equation 1.7.3, which describes the reaction of aluminum with iron(III)

1.7.1 https://chem.libretexts.org/@go/page/42254
 oxide (Fe2O3) at constant pressure. According to the reaction stoichiometry, 2 mol of Fe, 1 mol of Al2O3, and 851.5 kJ of heat
are produced for every 2 mol of Al and 1 mol of Fe2O3 consumed:
2 Al(s) + Fe O (s) ⟶ 2 Fe(s) + Al O (s) + 851.5 kJ (1.7.3)
2 3 2 3

Thus ΔH = −851.5 kJ/mol of Fe O . We can also describe ΔH for the reaction as −425.8 kJ/mol of Al: because 2 mol of
2 3

Al are consumed in the balanced chemical equation, we divide −851.5 kJ by 2. When a value for ΔH , in kilojoules rather than
kilojoules per mole, is written after the reaction, as in Equation 1.7.3, it is the value of ΔH corresponding to the reaction of the
molar quantities of reactants as given in the balanced chemical equation:
2 Al(s) + Fe O (s) ⟶ 2 Fe(s) + Al O (s) ΔHrxn = −851.5 kJ (1.7.4)
2 3 2 3

If 4 mol of Al and 2 mol of Fe2O3 react, the change in enthalpy is 2 × (−851.5 kJ) = −1703 kJ. We can summarize the
relationship between the amount of each substance and the enthalpy change for this reaction as follows:
851.5 kJ 425.8 kJ 1703 kJ
− =− =− (1.7.5)
2 mol Al 1 mol Al 4 mol Al

The relationship between the magnitude of the enthalpy change and the mass of reactants is illustrated in Example 1.7.1.

Example

Certain parts of the world, such as southern California and Saudi Arabia, are short of fresh water for drinking. One possible
solution to the problem is to tow icebergs from Antarctica and then melt them as needed. If ΔH is 6.01 kJ/mol for the reaction
H O(s) → H O(l) at 0°C and constant pressure, how much energy would be required to melt a moderately large iceberg with
2 2

a mass of 1.00 million metric tons (1.00 × 106 metric tons)? (A metric ton is 1000 kg.)
Given: energy per mole of ice and mass of iceberg
Asked for: energy required to melt iceberg
Strategy:
A. Calculate the number of moles of ice contained in 1 million metric tons (1.00 × 106 metric tons) of ice.
B. Calculate the energy needed to melt the ice by multiplying the number of moles of ice in the iceberg by the amount of
energy required to melt 1 mol of ice.
Solution:
A Because enthalpy is an extensive property, the amount of energy required to melt ice depends on the amount of ice present.
We are given ΔH for the process—that is, the amount of energy needed to melt 1 mol (or 18.015 g) of ice—so we need to
calculate the number of moles of ice in the iceberg and multiply that number by ΔH (+6.01 kJ/mol):

⎛ 1000 kg ⎞ ⎛ 1000 g ⎞⎛ ⎞
6
1 mol H2 O
moles H2 O = 1.00 × 10 metric tons H2 O
⎝1 metric ton ⎠ ⎝ 1 kg ⎠ ⎝ 18.015 g H2 O ⎠

10
= 5.55 × 10 molH2 O

B The energy needed to melt the iceberg is thus

6.01 kJ
10 11
( ) (5.55 × 10 mol H2 O ) = 3.34 × 10 kJ
mol H2 O

Because so much energy is needed to melt the iceberg, this plan would require a relatively inexpensive source of energy to be
practical. To give you some idea of the scale of such an operation, the amounts of different energy sources equivalent to the
amount of energy needed to melt the iceberg are shown in the table below.
Possible sources of the approximately 3.34 × 1011 kJ needed to melt a 1.00 × 106 metric ton iceberg
Combustion of 3.8 × 103 ft3 of natural gas
Combustion of 68,000 barrels of oil
Combustion of 15,000 tons of coal

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 1.1 × 108 kilowatt-hours of electricity

Exercise

If 17.3 g of powdered aluminum are allowed to react with excess Fe 2

O
3
, how much heat is produced?

Answer
273 kJ

1.7.1: Types of Enthalpies of Reactions

One way to report the heat absorbed or released would be to compile a massive set of reference tables that list the enthalpy changes
for all possible chemical reactions, which would require an incredible amount of effort. Fortunately, Hess’s law allows us to
calculate the enthalpy change for virtually any conceivable chemical reaction using a relatively small set of tabulated data, such as
the following:
Enthalpy of combustion (ΔH ) is the change in enthalpy that occurs during a combustion reaction. Enthalpy changes have
comb

been measured for the combustion of virtually any substance that will burn in oxygen; these values are usually reported as the
enthalpy of combustion per mole of substance.
Enthalpy of fusion (ΔH ) is the enthalpy change that accompanies the melting (fusion) of 1 mol of a substance. The
f us

enthalpy change that accompanies the melting, or fusion, of 1 mol of a substance; these values have been measured for almost
all the elements and for most simple compounds.
Enthalpy of vaporization (ΔH ) is the enthalpy change that accompanies the vaporization of 1 mol of a substance. The
vap

enthalpy change that accompanies the vaporization of 1 mol of a substance; these values have also been measured for nearly all
the elements and for most volatile compounds.
Enthalpy of solution (ΔH ) is the change in enthalpy that occurs when a specified amount of solute dissolves in a given
soln

quantity of solvent.
Table 1.7.1 : Enthalpies of Vaporization and Fusion for Selected Substances at Their Boiling Points and Melting Points
Substance ΔHvap (kJ/mol) ΔHfus (kJ/mol)

argon (Ar) 6.3 1.3

methane (CH4) 9.2 0.84

ethanol (CH3CH2OH) 39.3 7.6

benzene (C6H6) 31.0 10.9

water (H2O) 40.7 6.0

mercury (Hg) 59.0 2.29

iron (Fe) 340 14

The sign convention is the same for all enthalpy changes: negative if heat is released by
the system and positive if heat is absorbed by the system.

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 Enthalpy of Reaction

Enthalpy of Reaction: https://youtu.be/z2KUaIEF9qI

1.7.2: Summary
Enthalpy is a state function used to measure the heat transferred from a system to its surroundings or vice versa at constant
pressure. Only the change in enthalpy (ΔH ) can be measured. A negative ΔH means that heat flows from a system to its
surroundings; a positive ΔH means that heat flows into a system from its surroundings. For a chemical reaction, the enthalpy of
reaction (ΔH ) is the difference in enthalpy between products and reactants; the units of ΔHrxn are kilojoules per mole.
rxn

Reversing a chemical reaction reverses the sign of ΔH . rxn

The magnitude of ΔHrxn also depends on the physical state of the reactants and the products because processes such as melting
solids or vaporizing liquids are also accompanied by enthalpy changes: the enthalpy of fusion (ΔH ) and the enthalpy of
f us

vaporization (ΔH ), respectively. The overall enthalpy change for a series of reactions is the sum of the enthalpy changes for
vap

the individual reactions, which is Hess’s law. The enthalpy of combustion (ΔH ) is the enthalpy change that occurs when a
comb

substance is burned in excess oxygen.

1.7.3: Contributors and Attributions

Modified by Joshua Halpern (Howard University)

1.7: Heats of Reactions - ΔU and ΔH is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
7.6: Heats of Reactions - ΔU and ΔH is licensed CC BY-NC-SA 4.0.

1.7.4 https://chem.libretexts.org/@go/page/42254
1.8: Indirect Determination of ΔH - Hess's Law
 Learning Objectives
To use Hess’s law and thermochemical cycles to calculate enthalpy changes of chemical reactions.

Because enthalpy is a state function, the enthalpy change for a reaction depends on only two things:
1. the masses of the reacting substances and
2. the physical states of the reactants and products.
It does not depend on the path by which reactants are converted to products. If you climbed a mountain, for example, the altitude change would not
depend on whether you climbed the entire way without stopping or you stopped many times to take a break. If you stopped often, the overall change in
altitude would be the sum of the changes in altitude for each short stretch climbed. Similarly, when we add two or more balanced chemical equations to
obtain a net chemical equation, ΔH for the net reaction is the sum of the ΔH values for the individual reactions. This principle is called Hess’s law,
after the Swiss-born Russian chemist Germain Hess (1802–1850), a pioneer in the study of thermochemistry. Hess’s law allows us to calculate ΔH
values for reactions that are difficult to carry out directly by adding together the known ΔH values for individual steps that give the overall reaction,
even though the overall reaction may not actually occur via those steps.
We can illustrate Hess’s law using the thermite reaction. The overall reaction shown in Equation 1.8.1 can be viewed as occurring in three distinct steps
with known ΔH values. As shown in Figure 1.8.1:
1. The first reaction produces 1 mol of solid aluminum oxide (Al O ) and 2 mol of liquid iron at its melting point of 1758°C (Equation 1.8.1a); the
2 3

enthalpy change for this reaction is −732.5 kJ/mol of Fe O . 2 3

2. The second reaction is the conversion of 2 mol of liquid iron at 1758°C to 2 mol of solid iron at 1758°C (Equation 1.8.1b); the enthalpy change for
this reaction is −13.8 kJ/mol of Fe (−27.6 kJ per 2 mol Fe).
3. In the third reaction, 2 mol of solid iron at 1758°C is converted to 2 mol of solid iron at 25°C (Equation 1.8.1c); the enthalpy change for this
reaction is −45.5 kJ/mol of Fe (−91.0 kJ per 2 mol Fe).
As you can see in Figure 1.8.1, the overall reaction is given by the longest arrow (shown on the left), which is the sum of the three shorter arrows
(shown on the right). Adding Equations 1.8.1a-1.8.1c} gives the overall reaction, shown Equation 1.8.1d:
o o o o
2Al (s, 25 C ) + F e2 O3 (s, 25 C ) → 2F e (l, 1758 C ) + Al2 O3 (s, 1758 C ) ΔH = −732.5 kJ (reaction a)

o o
2F e (l, 1758 C ) → 2F e (s, 1758 C ) ΔH = − 27.6 kJ (reaction b)
(1.8.1)
o o o o
2F e (s, 1758 C ) + 2Al (s, 1758 C ) → 2F e (s, 25 C ) + 2Al (s, 25 C ) ΔH = − 91.0 kJ (reaction c)

o o o o
2Al (s, 25 C ) + F e2 O3 (s, 25 C ) → 2Al (s, 25 C ) + 2F e2 O3 (s, 25 C ) ΔH = −852.2 kJ (total reaction d)

By Hess’s law, the enthalpy change for part (d) is the sum of the enthalpy changes for parts (a), (b), and (c). In essence, Hess’s law enables us to
calculate the enthalpy change for the sum of a series of reactions without having to draw a diagram like that in Figure 1.8.1.

Figure 1.8.1 : Energy Changes Accompanying the Thermite Reaction. Because enthalpy is a state function, the overall enthalpy change for the reaction
of 2 mol of Al(s) with 1 mol of Fe2O3(s) is −851.1 kJ, whether the reaction occurs in a single step (ΔH4, shown on the left) or in three hypothetical steps
(shown on the right) that involve the successive formation of solid Al2O3 and liquid iron (ΔH1), solid iron at 1758°C (ΔH2), and solid iron at 25°C
(ΔH3). Thus ΔH4 = ΔH1 + ΔH2 + ΔH3, as stated by Hess’s law.
Comparing parts (a) and (d) in Equation 1.8.1 also illustrates an important point: The magnitude of ΔH for a reaction depends on the physical states of
the reactants and the products (gas, liquid, solid, or solution). When the product is liquid iron at its melting point (part (a) in Equation 1.8.1), only 732.5
kJ of heat are released to the surroundings compared with 852 kJ when the product is solid iron at 25°C (part (d) in Equation 1.8.1). The difference, 120
kJ, is the amount of energy that is released when 2 mol of liquid iron solidifies and cools to 25°C. It is important to specify the physical state of all
reactants and products when writing a thermochemical equation.
When using Hess’s law to calculate the value of ΔH for a reaction, follow this procedure:

1.8.1 https://chem.libretexts.org/@go/page/42255
1. Identify the equation whose ΔH value is unknown and write individual reactions with known ΔH values that, when added together, will give the
desired equation. We illustrate how to use this procedure in Example 1.8.1.
2. Arrange the chemical equations so that the reaction of interest is the sum of the individual reactions.
3. If a reaction must be reversed, change the sign of ΔH for that reaction. Additionally, if a reaction must be multiplied by a factor to obtain the
correct number of moles of a substance, multiply its ΔH value by that same factor.
4. Add together the individual reactions and their corresponding ΔH values to obtain the reaction of interest and the unknown ΔH.

 Example 1.8.1

When carbon is burned with limited amounts of oxygen gas (O ), carbon monoxide (CO) is the main product:
2

2 C(s) + O (g) ⟶ 2 CO(g) ΔH = −221.0 kJ (reaction 1)

2

When carbon is burned in excess O2, carbon dioxide (CO2) is produced:

C(s) + O (g) → CO (g) ΔH = −393.5 kJ (reaction 2)
2 2

Use this information to calculate the enthalpy change per mole of CO for the reaction of CO with O to give CO . 2 2

Given: two balanced chemical equations and their ΔH values

Asked for: enthalpy change for a third reaction
Strategy:
A. After balancing the chemical equation for the overall reaction, write two equations whose ΔH values are known and that, when added together,
give the equation for the overall reaction. (Reverse the direction of one or more of the equations as necessary, making sure to also reverse the
sign of ΔH .)
B. Multiply the equations by appropriate factors to ensure that they give the desired overall chemical equation when added together. To obtain the
enthalpy change per mole of CO, write the resulting equations as a sum, along with the enthalpy change for each.
Solution:
A We begin by writing the balanced chemical equation for the reaction of interest:
1
CO(g) + O (g) ⟶ CO (g) ΔHrxn =? (reaction 3)
2 2 2

There are at least two ways to solve this problem using Hess’s law and the data provided. The simplest is to write two equations that can be added
together to give the desired equation and for which the enthalpy changes are known. Observing that CO, a reactant in reaction 2 and a product in
Equation reaction 1, we can reverse reaction 1 to give

2C O (g) → 2C (s) + O2 (g) ΔH = +221.0 kJ

Because we have reversed the direction of the reaction, the sign of ΔH is changed. We can use reaction 2, as written because its product, CO2, is
the product we want in reaction 3,:
C(s) + O (g) ⟶ CO (s) ΔH = −393.5 kJ (1.8.2)
2 2

B Adding these two equations together does not give the desired reaction, however, because the numbers of C(s) on the left and right sides do not
cancel. According to our strategy, we can multiply the second equation by 2 to obtain 2 mol of C(s) as the reactant:
2 C(s) + 2 O (g) ⟶ 2 CO (s) ΔH = −787.0 kJ (1.8.3)
2 2

Writing the resulting equations as a sum, along with the enthalpy change for each, gives

2C O (g) → 2C (s) + O2 (g) ΔH = −ΔH1 = +221.0 kJ

(1.8.4)
2C (s) + 2 O2 (g) → 2C O2 (g) ΔH = −Δ2H2 = −787.0 kJ

2C O (g) + O2 (g) → 2C O2 (g) ΔH = −566.0 kJ

Note that the overall chemical equation and the enthalpy change for the reaction are both for the reaction of 2 mol of CO with O , and the problem 2

asks for the amount per mole of CO. Consequently, we must divide both sides of the final equation and the magnitude of ΔH by 2:
1
C O (g) + O2 (g) → C O2 (g) ΔH = −283.0 kJ
2

An alternative and equally valid way to solve this problem is to write the two given equations as occurring in steps. Note that we have multiplied
the equations by the appropriate factors to allow us to cancel terms:

(A) 2C (s) + O2 (g) → 2CO (g) ΔHA = ΔH1 = +221.0 kJ

(B) 2CO (g) + O2 (g) → 2C O2 (g) ΔHB = ?

(1.8.5)

(C) 2C (s) + 2 O2 (g) → 2C O2 (g) ΔH = 2ΔH2 = 2 × (−393.5 kJ ) = −787.0 kJ

1.8.2 https://chem.libretexts.org/@go/page/42255
 The sum of reactions A and B is reaction C, which corresponds to the combustion of 2 mol of carbon to give CO2. From Hess’s law, ΔHA + ΔHB =
ΔHC, and we are given ΔH for reactions A and C. Substituting the appropriate values gives
−221.0 kJ + ΔHB = −787.0 kJ

ΔHB = −566.0

This is again the enthalpy change for the conversion of 2 mol of CO to CO2. The enthalpy change for the conversion of 1 mol of CO to CO2 is
therefore −566.0 ÷ 2 = −283.0 kJ/mol of CO, which is the same result we obtained earlier. As you can see, there may be more than one correct way
to solve a problem.

 Exercise 1.8.1
The reaction of acetylene (C2H2) with hydrogen (H2) can produce either ethylene (C2H4) or ethane (C2H6):

C2 H2 (g) + H2 (g) → C2 H4 (g) ΔH = −175.7 kJ/mol C2 H2

C2 H2 (g) + 2 H2 (g) → C2 H6 (g) ΔH = −312.0 kJ/mol C2 H2

What is ΔH for the reaction of C2H4 with H2 to form C2H6?

Answer
−136.3 kJ/mol of C2H4

1.8.1: Summary
Hess's law is that the overall enthalpy change for a series of reactions is the sum of the enthalpy changes for the individual reactions. For a chemical
reaction, the enthalpy of reaction (ΔH ) is the difference in enthalpy between products and reactants; the units of ΔHrxn are kilojoules per mole.
rxn

Reversing a chemical reaction reverses the sign of ΔH . rxn

1.8.2: Contributors and Attributions

Modified by Joshua Halpern (Howard University)

1.8: Indirect Determination of ΔH - Hess's Law is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1.8.3 https://chem.libretexts.org/@go/page/42255
1.9: Standard Enthalpies of Formation
 Learning Objectives
To understand Enthalpies of Formation and be able to use them to calculate Enthalpies of Reaction

One way to report the heat absorbed or released by chemical reactions would be to compile a massive set of reference tables that list the
enthalpy changes for all possible chemical reactions, which would require an incredible amount of effort. Fortunately, Hess’s law allows
us to calculate the enthalpy change for virtually any conceivable chemical reaction using a relatively small set of tabulated data, starting
from the elemental forms of each atom at 25 oC and 1 atm pressure.
Enthalpy of formation (ΔH ) is the enthalpy change for the formation of 1 mol of a compound from its component elements, such as
f

the formation of carbon dioxide from carbon and oxygen. The formation of any chemical can be as a reaction from the corresponding
elements:

elements → compound

which in terms of the the Enthalpy of formation becomes

ΔHrxn = ΔHf (1.9.1)

For example, consider the combustion of carbon:

C(s) + O (g) ⟶ CO (g)

2 2

then

ΔHrxn = ΔHf [C O2 (g)]

The sign convention for ΔHf is the same as for any enthalpy change: ΔHf < 0 if heat is released when elements combine to form a
compound and ΔH > 0 if heat is absorbed.
f

The sign convention is the same for all enthalpy changes: negative if heat is released by the system and positive if heat is absorbed
by the system.

1.9.1: Standard Enthalpies of Formation

The magnitude of ΔH for a reaction depends on the physical states of the reactants and the products (gas, liquid, solid, or solution), the
pressure of any gases present, and the temperature at which the reaction is carried out. To avoid confusion caused by differences in
reaction conditions and ensure uniformity of data, the scientific community has selected a specific set of conditions under which enthalpy
changes are measured. These standard conditions serve as a reference point for measuring differences in enthalpy, much as sea level is
the reference point for measuring the height of a mountain or for reporting the altitude of an airplane.
The standard conditions for which most thermochemical data are tabulated are a pressure of 1 atmosphere (atm) for all gases and a
concentration of 1 M for all species in solution (1 mol/L). In addition, each pure substance must be in its standard state, which is usually
its most stable form at a pressure of 1 atm at a specified temperature. We assume a temperature of 25°C (298 K) for all enthalpy changes
given in this text, unless otherwise indicated. Enthalpies of formation measured under these conditions are called standard enthalpies of
formation (ΔH ) The enthalpy change for the formation of 1 mol of a compound from its component elements when the component
o
f

elements are each in their standard states. The standard enthalpy of formation of any element in its most stable form is zero by definition.

The standard enthalpy of formation of any element in its standard state is zero by definition.
For example, although oxygen can exist as ozone (O3), atomic oxygen (O), and molecular oxygen (O2), O2 is the most stable form at 1
atm pressure and 25°C. Similarly, hydrogen is H2(g), not atomic hydrogen (H). Graphite and diamond are both forms of elemental
carbon, but because graphite is more stable at 1 atm pressure and 25°C, the standard state of carbon is graphite (Figure 1.9.1). Therefore,
O (g), H (g), and graphite have ΔH values of zero.
o
2 2 f

1.9.1 https://chem.libretexts.org/@go/page/42256
 Figure 1.9.1 : Elemental Carbon. Although graphite and diamond are both forms of elemental carbon, graphite is slightly more stable at 1
atm pressure and 25°C than diamond is. Given enough time, diamond will revert to graphite under these conditions. Hence graphite is the
standard state of carbon.
The standard enthalpy of formation of glucose from the elements at 25°C is the enthalpy change for the following reaction:
o
6C (s, graphite) + 6 H2 (g) + 3 O2 (g) → C6 H12 O6 (s) ΔH = −1273.3 kJ (1.9.2)
f

It is not possible to measure the value of ΔH o for glucose, −1273.3 kJ/mol, by simply mixing appropriate amounts of graphite, O ,
o
f 2

and H and measuring the heat evolved as glucose is formed since the reaction shown in Equation 1.9.2 does not occur at a measurable
2

rate under any known conditions. Glucose is not unique; most compounds cannot be prepared by the chemical equations that define their
standard enthalpies of formation. Instead, values of ΔH o are obtained using Hess’s law and standard enthalpy changes that have been
o
f

measured for other reactions, such as combustion reactions. Values of ΔH for an extensive list of compounds are given in Table T1.
o
f

Note that ΔH values are always reported in kilojoules per mole of the substance of interest. Also notice in Table T1 that the standard
o
f

enthalpy of formation of O2(g) is zero because it is the most stable form of oxygen in its standard state.

 Example 1.9.1: Enthalpy of Formation

For the formation of each compound, write a balanced chemical equation corresponding to the standard enthalpy of formation of
each compound.
a. HCl(g)
b. MgCO (s) 3

c. CH (CH )3 2 14
CO H(s)
2
(palmitic acid)

Given:
compound formula and phase.
Asked for:
balanced chemical equation for its formation from elements in standard states
Strategy:
Use Table T1 to identify the standard state for each element. Write a chemical equation that describes the formation of the
compound from the elements in their standard states and then balance it so that 1 mol of product is made.
Solution:
To calculate the standard enthalpy of formation of a compound, we must start with the elements in their standard states. The
standard state of an element can be identified in Table T1: by a ΔH value of 0 kJ/mol. o
f

Hydrogen chloride contains one atom of hydrogen and one atom of chlorine. Because the standard states of elemental hydrogen
and elemental chlorine are H (g) and Cl (g), respectively, the unbalanced chemical equation is
2 2

H (g) + Cl (g) → HCl(g)

2 2

Fractional coefficients are required in this case because ΔHof values are reported for 1 mol of the product, HCl. Multiplying both
H (g) and Cl (g) by 1/2 balances the equation:
2 2

1 1
H (g) + Cl (g) → HCl(g)
2 2 2 2

1.9.2 https://chem.libretexts.org/@go/page/42256
 The standard states of the elements in this compound are Mg(s) , C(s, graphite), and O 2
(g) . The unbalanced chemical equation
is thus

Mg(s) + C(s, graphite) + O (g) → MgCO (s)

2 3

This equation can be balanced by inspection to give

3
Mg(s) + C(s, graphite) + O (g) → MgCO (s)
2 2 3

Palmitic acid, the major fat in meat and dairy products, contains hydrogen, carbon, and oxygen, so the unbalanced chemical
equation for its formation from the elements in their standard states is as follows:

C(s, graphite) + H (g) + O (g) → CH (CH ) CO H(s)

2 2 3 2 14 2

There are 16 carbon atoms and 32 hydrogen atoms in 1 mol of palmitic acid, so the balanced chemical equation is

16 C(s, graphite) + 16 H (g) + O (g) ⟶ CH (CH ) CO H(s)

2 2 3 2 14 2

 Exercise 1.9.1
For the formation of each compound, write a balanced chemical equation corresponding to the standard enthalpy of formation of
each compound.
a. NaCl(s)
b. H SO (l)
2 4

c. CH CO H(l) (acetic acid)

3 2

Answer a
1
Na(s) + Cl (g) → NaCl(s)
2 2

Answer b
1
H (g) + S (s) + 2 O (g) → H SO (l)
2 8 8 2 2 4

Answer c
2 C(s) + O (g) + 2 H (g) ⟶ CH CO H(l)
2 2 3 2

De nition of Heat of Formation Reactions

Definition of Heat of Formation Reactions: https://youtu.be/A20k0CK4doI

1.9.2: Standard Enthalpies of Reaction

Tabulated values of standard enthalpies of formation can be used to calculate enthalpy changes for any reaction involving substances
whose ΔH values are known. The standard enthalpy of reaction ΔH
o
f
is the enthalpy change that occurs when a reaction is carried
o
rxn

out with all reactants and products in their standard states. Consider the general reaction

1.9.3 https://chem.libretexts.org/@go/page/42256
 aA + bB → cC + dD (1.9.3)

where A , B , C , and D are chemical substances and a , b , c , and d are their stoichiometric coefficients. The magnitude of ΔH is the ο

sum of the standard enthalpies of formation of the products, each multiplied by its appropriate coefficient, minus the sum of the standard
enthalpies of formation of the reactants, also multiplied by their coefficients:
o o o o o
ΔHrxn = [cΔH (C ) + dΔH (D)] − [aΔH (A) + bΔH (B)] (1.9.4)
f f f f

 
products reactants

More generally, we can write

o o o
ΔHrxn = ∑ mΔH (products) − ∑ nΔH (reactants) (1.9.5)
f f

where the symbol ∑ means “sum of” and m and n are the stoichiometric coefficients of each of the products and the reactants,
respectively. “Products minus reactants” summations such as Equation 1.9.5 arise from the fact that enthalpy is a state function. Because
many other thermochemical quantities are also state functions, “products minus reactants” summations are very common in chemistry;
we will encounter many others in subsequent chapters.

"Products minus reactants" summations are typical of state functions.

To demonstrate the use of tabulated ΔHο values, we will use them to calculate ΔHrxn for the combustion of glucose, the reaction that
provides energy for your brain:
C H O (s) + 6 O (g) → 6 CO (g) + 6 H O(l) (1.9.6)
6 12 6 2 2 2

Using Equation 1.9.5, we write

o o o o o
ΔH = {6ΔH [C O2 (g)] + 6ΔH [ H2 O (g)]} − {ΔH [ C6 H12 O6 (s)] + 6ΔH [ O2 (g)]} (1.9.7)
f f f f f

From Table T1, the relevant ΔHοf values are ΔHοf [CO2(g)] = -393.5 kJ/mol, ΔHοf [H2O(l)] = -285.8 kJ/mol, and ΔHοf [C6H12O6(s)] =
-1273.3 kJ/mol. Because O2(g) is a pure element in its standard state, ΔHοf [O2(g)] = 0 kJ/mol. Inserting these values into Equation 1.9.7
and changing the subscript to indicate that this is a combustion reaction, we obtain
o
ΔH = [6 (−393.5 kJ/mol) + 6 (−285.8 kJ/mol)] − [−1273.3 + 6 (0 kJ mol)] (1.9.8)
comb

= −2802.5 kJ/mol (1.9.9)

As illustrated in Figure 1.9.2, we can use Equation 1.9.8 to calculate ΔH for glucose because enthalpy is a state function. The figure
f
ο

shows two pathways from reactants (middle left) to products (bottom). The more direct pathway is the downward green arrow labeled
ΔH
ο
comb
. The alternative hypothetical pathway consists of four separate reactions that convert the reactants to the elements in their
standard states (upward purple arrow at left) and then convert the elements into the desired products (downward purple arrows at right).
The reactions that convert the reactants to the elements are the reverse of the equations that define the ΔH values of the reactants. ο
f

Consequently, the enthalpy changes are

o o
ΔH = ΔH [glucose (s)]
1 f

⎛ 1273.3 kJ ⎞
= −1 mol glucose
⎝1 mol glucose ⎠

= +1273.3 kJ

o o
ΔH = 6ΔH [ O2 (g)]
2 f

0 kJ
=6 mol O2 ( )
1 mol O2

= 0 kJ (1.9.10)

Recall that when we reverse a reaction, we must also reverse the sign of the accompanying
enthalpy change (Equation 1.9.4 since the products are now reactants and vice versa.
The overall enthalpy change for conversion of the reactants (1 mol of glucose and 6 mol of O2) to the elements is therefore +1273.3 kJ.

1.9.4 https://chem.libretexts.org/@go/page/42256
 Figure 1.9.1 : A Thermochemical Cycle for the Combustion of Glucose. Two hypothetical pathways are shown from the reactants to the
products. The green arrow labeled ΔHοcomb indicates the combustion reaction. Alternatively, we could first convert the reactants to the
elements via the reverse of the equations that define their standard enthalpies of formation (the upward arrow, labeled ΔHο1 and ΔHο2 ).
Then we could convert the elements to the products via the equations used to define their standard enthalpies of formation (the downward
arrows, labeled ΔHο3 and ΔHο4 ). Because enthalpy is a state function, ΔHοcomb is equal to the sum of the enthalpy changes ΔHο1 + ΔHο2
+ ΔHο3 + ΔHο4.
The reactions that convert the elements to final products (downward purple arrows in Figure 1.9.2) are identical to those used to define
the ΔHοf values of the products. Consequently, the enthalpy changes (from Table T1) are

393.5 kJ
o o
ΔH = ΔH [C O2 (g)] = 6 mol C O2 ( ) = −2361.0 kJ
3 f
1 mol C O2
(1.9.11)

−285.8 kJ
o o
ΔH = 6ΔH [ H2 O (l)] = 6 mol H2 O ( ) = −1714.8 kJ
4 f
1 mol H2 O

The overall enthalpy change for the conversion of the elements to products (6 mol of carbon dioxide and 6 mol of liquid water) is
therefore −4075.8 kJ. Because enthalpy is a state function, the difference in enthalpy between an initial state and a final state can be
computed using any pathway that connects the two. Thus the enthalpy change for the combustion of glucose to carbon dioxide and water
is the sum of the enthalpy changes for the conversion of glucose and oxygen to the elements (+1273.3 kJ) and for the conversion of the
elements to carbon dioxide and water (−4075.8 kJ):
o
ΔH = +1273.3 kJ + (−4075.8 kJ) = −2802.5 kJ (1.9.12)
comb

This is the same result we obtained using the “products minus reactants” rule (Equation 1.9.5) and ΔHοf values. The two results must be
the same because Equation 1.9.12 is just a more compact way of describing the thermochemical cycle shown in Figure 1.9.1.

 Example 1.9.2: Heat of Combustion

Long-chain fatty acids such as palmitic acid (CH (CH ) CO H) are one of the two major sources of energy in our diet (ΔH
3 2 14 2
o
f

=−891.5 kJ/mol). Use the data in Table T1 to calculate ΔHοcomb for the combustion of palmitic acid. Based on the energy released in
combustion per gram, which is the better fuel — glucose or palmitic acid?
Given: compound and ΔH valuesο
f

Asked for: ΔH ο
comb
per mole and per gram
Strategy:
A. After writing the balanced chemical equation for the reaction, use Equation 1.9.5 and the values from Table T1 to calculate
ΔH
ο
comb
the energy released by the combustion of 1 mol of palmitic acid.
B. Divide this value by the molar mass of palmitic acid to find the energy released from the combustion of 1 g of palmitic acid.
Compare this value with the value calculated in Equation 1.9.8 for the combustion of glucose to determine which is the better
fuel.
Solution:
A To determine the energy released by the combustion of palmitic acid, we need to calculate its ΔH
f
ο
. As always, the first
requirement is a balanced chemical equation:

1.9.5 https://chem.libretexts.org/@go/page/42256
 C16 H32 O2(s) + 23 O2(g) → 16C O2(g) + 16 H2 O(l)

Using Equation 1.9.5 (“products minus reactants”) with ΔHοf values from Table T1 (and omitting the physical states of the reactants
and products to save space) gives
o o o
ΔH = ∑ mΔH (products) − ∑ nΔH (reactants)
comb f f

= [16 (−393.5 kJ/mol C O2 ) + 16 (−285.8 kJ/mol H2 O )]

− [−891.5 kJ/mol C16 H32 O2 + 23 (0 kJ/mol O2 )]

= −9977.3 kJ/mol

This is the energy released by the combustion of 1 mol of palmitic acid.

B The energy released by the combustion of 1 g of palmitic acid is

9977.3 kJ 1 mol
o
ΔH per gram = ( )( ) = −38.910 kJ/g
comb
1 mol 256.42 g

As calculated in Equation 1.9.8, \(ΔH^o_f\) of glucose is −2802.5 kJ/mol. The energy released by the combustion of 1 g of glucose
is therefore

−2802.5 kJ 1 mol
o
ΔH per gram = ( )( ) = −15.556 kJ/g
comb
1 mol 180.16 g

The combustion of fats such as palmitic acid releases more than twice as much energy per gram as the combustion of sugars such as
glucose. This is one reason many people try to minimize the fat content in their diets to lose weight.

 Exercise 1.9.2: Water–gas shift reaction

Use Table T1 to calculate ΔH o

rxn for the water–gas shift reaction, which is used industrially on an enormous scale to obtain H2(g):

CO(g) + H O(g) ⟶ CO (g) + H (g)

2 2 2

Answer
−41.2 kJ/mol

We can also measure the enthalpy change for another reaction, such as a combustion reaction, and then use it to calculate a compound’s
ΔH
ο
f
which we cannot obtain otherwise. This procedure is illustrated in Example 1.9.3.

 Example 1.9.3: Tetraethyllead

Beginning in 1923, tetraethyllead [(C H ) Pb] was used as an antiknock additive in gasoline in the United States. Its use was
2 5 4

completely phased out in 1986 because of the health risks associated with chronic lead exposure. Tetraethyllead is a highly
poisonous, colorless liquid that burns in air to give an orange flame with a green halo. The combustion products are CO (g), 2

H O(l), and red PbO(s) . What is the standard enthalpy of formation of tetraethyllead, given that ΔH is −19.29 kJ/g for the
ο
2 f

combustion of tetraethyllead and ΔH of red PbO(s) is −219.0 kJ/mol?

ο
f

Given: reactant, products, and ΔH ο

comb
values

1.9.6 https://chem.libretexts.org/@go/page/42256
Asked for: ΔH of the reactants
f
ο

Strategy:
A. Write the balanced chemical equation for the combustion of tetraethyl lead. Then insert the appropriate quantities into Equation
ο
1.9.5 to get the equation for ΔH f of tetraethyl lead.

B. Convert ΔH per gram given in the problem to ΔH

ο
comb
per mole by multiplying ΔH per gram by the molar mass of
ο
comb
ο
comb

tetraethyllead.
C. Use Table T1 to obtain values of ΔH for the other reactants and products. Insert these values into the equation for ΔH of
ο
f
ο
f

tetraethyl lead and solve the equation.

Solution:
A The balanced chemical equation for the combustion reaction is as follows:

2 (C H ) Pb(l) + 27 O (g) → 2 PbO(s) + 16 CO (g) + 20 H O(l)

2 5 4 2 2 2

Using Equation 1.9.5 gives

o o o o o o
ΔH = [2ΔH (P bO) + 16ΔH (C O2 ) + 20ΔH (H2 O)] − [2ΔH ((C2 H5 ) P b) + 27ΔH (O2 )]
comb f f f f 4 f

Solving for ΔH f
o
[ (C H ) Pb]
2 5 4
gives
o
27 ΔH
o o o o o comb
ΔH ((C2 H5 ) P b) = ΔH (P bO) + 8ΔH (C O2 ) + 10ΔH (H2 O) − ΔH (O2 ) −
f 4 f f f f
2 2

The values of all terms other than ΔH o

f
[ (C H ) Pb]
2 5 4
are given in Table T1.

B The magnitude of ΔH is given in the problem in kilojoules per gram of tetraethyl lead. We must therefore multiply this value
o
comb

by the molar mass of tetraethyl lead (323.44 g/mol) to get ΔH for 1 mol of tetraethyl lead: o
comb

323.44 g
−19.29 kJ
o
ΔH =( )( )
comb
g mol

= −6329 kJ/mol

Because the balanced chemical equation contains 2 mol of tetraethyllead, ΔH o

rxn is

⎛ ⎞
−6329 kJ
o
ΔHrxn = 2 mol (C2 H 5)4 P b ⎜ ⎟
⎝1 mol (C2 H 5) P b ⎠
4

= −12, 480 kJ

C Inserting the appropriate values into the equation for ΔH f

o
[ (C H ) Pb]
2 5 4
gives
o
ΔH [ (C2 H4 ) P b] = [1 mol P bO × 219.0 kJ/mol] + [8 mol C O2 × (−393.5 kJ/mol)] + [10 mol H2 O × (−285.8 kJ/mol)]
f 4

+ [−27/2 mol O2 ) × 0 kJ/mol O2 ] [12, 480.2 kJ/mol (C2 H5 ) P b]

4

= −219.0 kJ − 3148 kJ − 2858kJ − 0kJ + 6240 kJ = 15kJ/mol

 Exercise 1.9.3

Ammonium sulfate, (NH ) SO , is used as a fire retardant and wood preservative; it is prepared industrially by the highly
4 2 4

exothermic reaction of gaseous ammonia with sulfuric acid:

2 NH (g) + H SO (aq) → (NH ) SO (s)

3 2 4 4 2 4

The value of o
is -179.4 kJ/mole H
ΔHrxn
2
SO
4
. Use the data in Table T1 to calculate the standard enthalpy of formation of
ammonium sulfate (in kilojoules per mole).

Answer
−1181 kJ/mol

1.9.7 https://chem.libretexts.org/@go/page/42256
 Calculating H° using Hf°

Calculating DH° using DHf°: https://youtu.be/Y3aJJno9W2c

1.9.3: Summary
The standard state for measuring and reporting enthalpies of formation or reaction is 25 oC and 1 atm.
The elemental form of each atom is that with the lowest enthalpy in the standard state.
The standard state heat of formation for the elemental form of each atom is zero.
The enthalpy of formation (ΔH ) is the enthalpy change that accompanies the formation of a compound from its elements. Standard
f

enthalpies of formation (ΔH ) are determined under standard conditions: a pressure of 1 atm for gases and a concentration of 1 M for
f
o

species in solution, with all pure substances present in their standard states (their most stable forms at 1 atm pressure and the
temperature of the measurement). The standard heat of formation of any element in its most stable form is defined to be zero. The
standard enthalpy of reaction (ΔH ) can be calculated from the sum of the standard enthalpies of formation of the products (each
o
rxn

multiplied by its stoichiometric coefficient) minus the sum of the standard enthalpies of formation of the reactants (each multiplied by its
stoichiometric coefficient)—the “products minus reactants” rule. The enthalpy of solution (ΔH ) is the heat released or absorbed
soln

when a specified amount of a solute dissolves in a certain quantity of solvent at constant pressure.

1.9.4: Contributors and Attributions

Modified by Joshua Halpern (Howard University)

1.9: Standard Enthalpies of Formation is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
7.8: Standard Enthalpies of Formation is licensed CC BY-NC-SA 4.0.

1.9.8 https://chem.libretexts.org/@go/page/42256
1.10: Fuels as Sources of Energy
 Learning Objectives
To use thermochemical concepts to solve environmental issues.

Our contemporary society requires the constant expenditure of huge amounts of energy to heat our homes, provide telephone and
cable service, transport us from one location to another, provide light when it is dark outside, and run the machinery that
manufactures material goods. The United States alone consumes almost 106 kJ per person per day, which is about 100 times the
normal required energy content of the human diet. This figure is about 30% of the world’s total energy usage, although only about
5% of the total population of the world lives in the United States. In contrast, the average energy consumption elsewhere in the
world is about 105 kJ per person per day, although actual values vary widely depending on a country’s level of industrialization. In
this section, we describe various sources of energy and their impact on the environment.

1.10.1: Fuels
According to the law of conservation of energy, energy can never actually be “consumed”; it can only be changed from one form to
another. What is consumed on a huge scale, however, are resources that can be readily converted to a form of energy that is useful
for doing work. Energy that is not used to perform work is either stored as potential energy for future use or transferred to the
surroundings as heat.
A major reason for the huge consumption of energy by our society is the low efficiency of most machines in transforming stored
energy into work. Efficiency can be defined as the ratio of useful work accomplished to energy expended. Automobiles, for
example, are only about 20% efficient in converting the energy stored in gasoline to mechanical work; the rest of the energy is
released as heat, either emitted in the exhaust or produced by friction in bearings and tires. The production of electricity by coal- or
oil-powered steam turbines (Figure 1.10.1) is can be more than 50% efficient.

Figure 1.10.1 : Electricity from Coal. A coal-powered electric power plant uses the combustion of coal to produce steam, which
drives a turbine to produce electricity.
In general, it is more efficient to use primary sources of energy directly (such as natural gas or oil) than to transform them to a
secondary source such as electricity prior to their use. For example, if a furnace is well maintained, heating a house with natural gas
is about 70% efficient. In contrast, burning the natural gas in a remote power plant, converting it to electricity, transmitting it long
distances through wires, and heating the house by electric baseboard heaters have an overall efficiency of less than 35%.
The total expenditure of energy in the world each year is about 3 × 1017 kJ. 80% of this energy is provided by the combustion of
fossil fuels: oil, coal, and natural gas (the sources of the energy consumed in the United States in 2019 are shown in Figure 1.10.2).
Natural gas and petroleum are the preferred fuels because many of the products derived from them are gases or liquids that are
readily transported, stored, and burned. Natural gas and petroleum are derived from the remains of marine creatures that died
hundreds of millions of years ago and were buried beneath layers of sediment. As the sediment turned to rock, the tremendous heat
and pressure inside Earth transformed the organic components of the buried sea creatures to petroleum and natural gas.

1.10.1 https://chem.libretexts.org/@go/page/42257
 Figure 1.10.2 : Energy Consumption in the United States by Source, 2014. More than 75% of the total energy expended is provided
by the combustion of fossil fuels, such as oil, coal, and natural gas. (Public Domain; U.S. Energy Information Administration)

1.10.2: Coal
Coal is a complex solid material derived primarily from plants that died and were buried hundreds of millions of years ago and
were subsequently subjected to high temperatures and pressures. Because plants contain large amounts of cellulose, derived from
linked glucose units, the structure of coal is more complex than that of petroleum (Figure 1.10.3). In particular, coal contains a
large number of oxygen atoms that link parts of the structure together, in addition to the basic framework of carbon–carbon bonds.
It is impossible to draw a single structure for coal; however, because of the prevalence of rings of carbon atoms (due to the original
high cellulose content), coal is more similar to an aromatic hydrocarbon than an aliphatic one.

Figure 1.10.3 : The Structures of Cellulose and Coal. (a) Cellulose consists of long chains of cyclic glucose molecules linked by
hydrogen bonds. (b) When cellulose is subjected to high pressures and temperatures for long periods of time, water is eliminated,
and bonds are formed between the rings, eventually producing coal. This drawing shows some of the common structural features of
coal; note the presence of many different kinds of ring structures.
Table 1.10.1 : Properties of Different Types of Coal
Hydrogen:Carbo
Type % Carbon % Oxygen % Sulfur Heat Content US Deposits
n Mole Ratio

Pennsylvania, New
anthracite 92 0.5 3 1 high
York
Appalachia,
bituminous 80 0.6 8 5 medium
Midwest, Utah

subbituminous 77 0.9 16 1 medium Rocky Mountains

lignite 71 1.0 23 1 low Montana

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There are four distinct classes of coal (Table 1.10.1); their hydrogen and oxygen contents depend on the length of time the coal has
been buried and the pressures and temperatures to which it has been subjected. Lignite, with a hydrogen:carbon ratio of about 1.0
and a high oxygen content, has the lowest ΔHcomb. Anthracite, in contrast, with a hydrogen:carbon ratio of about 0.5 and the lowest
oxygen content, has the highest ΔHcomb and is the highest grade of coal. The most abundant form in the United States is bituminous
coal, which has a high sulfur content because of the presence of small particles of pyrite (FeS2). The combustion of coal releases
the sulfur in FeS2 as SO2, which is a major contributor to acid rain. Table 1.10.2 compares the ΔHcomb per gram of oil, natural gas,
and coal with those of selected organic compounds.
Table 1.10.2 : Enthalpies of Combustion of Common Fuels and Selected Organic Compounds
Fuel ΔHcomb (kJ/g)

dry wood −15

peat −20.8

bituminous coal −28.3

charcoal −35

kerosene −37

C6H6 (benzene) −41.8

crude oil −43

natural gas −50

C2H2 (acetylene) −50.0

CH4 (methane) −55.5

gasoline −84

hydrogen −143

Peat, a precursor to coal, is the partially decayed remains of plants that grow in swampy areas. It is removed from the ground in the
form of soggy bricks of mud that will not burn until they have been dried. Even though peat is a smoky, poor-burning fuel that
gives off relatively little heat, humans have burned it since ancient times (Figure 1.10.4). If a peat bog were buried under many
layers of sediment for a few million years, the peat could eventually be compressed and heated enough to become lignite, the
lowest grade of coal; given enough time and heat, lignite would eventually become anthracite, a much better fuel.

Figure 1.10.4 : A Peat Bog. Peat is a smoky fuel that burns poorly and produces little heat, but it has been used as a fuel since
ancient times.

1.10.3: Converting Coal to Gaseous and Liquid Fuels

Oil and natural gas resources are limited. Current estimates suggest that the known reserves of petroleum will be exhausted in
about 60 years, and supplies of natural gas are estimated to run out in about 120 years. Coal, on the other hand, is relatively

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abundant, making up more than 90% of the world’s fossil fuel reserves. As a solid, coal is much more difficult to mine and ship
than petroleum (a liquid) or natural gas. Consequently, more than 75% of the coal produced each year is simply burned in power
plants to produce electricity. A great deal of current research focuses on developing methods to convert coal to gaseous fuels (coal
gasification) or liquid fuels (coal liquefaction). In the most common approach to coal gasification, coal reacts with steam to
produce a mixture of CO and H2 known as synthesis gas, or syngas:Because coal is 70%–90% carbon by mass, it is approximated
as C in Equation 1.10.1.
C(s) + H2 O(g) → C O(g) + H2(g) ΔH = 131 kJ (1.10.1)

Converting coal to syngas removes any sulfur present and produces a clean-burning mixture of gases.
Syngas is also used as a reactant to produce methane and methanol. A promising approach is to convert coal directly to methane
through a series of reactions:

2C(s) + 2 H2 O(g) → 2CO(g) + 2 H2 (g) ΔH1 = 262 kJ

CO(g) + H2 O(g) → C O2 (g) + H2 (g) ΔH2 = −41 kJ

CO(g) + 3 H2 (g) → C H4 (g) + H2 O(g) ΔH3 = −206 kJ

¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
¯
Overall : 2C(s) + 2 H2 O(g) → C H4 (g) + C O2 (g) ΔHcomb = 15 kJ

Burning a small amount of coal or methane provides the energy consumed by these reactions. Unfortunately, methane produced by
this process is currently significantly more expensive than natural gas. As supplies of natural gas become depleted, however, this
coal-based process may well become competitive in cost.

Measuring crude oil. The standard industrial unit of measure for crude oil is the 42 gal barrel.
Similarly, the techniques available for converting coal to liquid fuels are not yet economically competitive with the production of
liquid fuels from petroleum. Current approaches to coal liquefaction use a catalyst to break the complex network structure of coal
into more manageable fragments. The products are then treated with hydrogen (from syngas or other sources) under high pressure
to produce a liquid more like petroleum. Subsequent distillation, cracking, and reforming can be used to create products similar to
those obtained from petroleum. The total yield of liquid fuels is about 5.5 bbl of crude liquid per ton of coal (1 bbl is 42 gal or 160
L). Although the economics of coal liquefaction are currently even less attractive than for coal gasification, liquid fuels based on
coal are likely to become economically competitive as supplies of petroleum are consumed.

 Example 1.10.1

If bituminous coal is converted to methane by the process in Equation 1.10.1, what is the ratio of the ΔHcomb of the methane
produced to the enthalpy of the coal consumed to produce the methane? (Note that 1 mol of CH4 is produced for every 2 mol
of carbon in coal.)
Given: chemical reaction and ΔHcomb (Table 1.10.2)
Asked for: ratio of ΔHcomb of methane produced to coal consumed
Strategy:

1.10.4 https://chem.libretexts.org/@go/page/42257
 A Write a balanced chemical equation for the conversion of coal to methane. Referring to Table 1.10.2, calculate the ΔHcomb of
methane and carbon.
B Calculate the ratio of the energy released by combustion of the methane to the energy released by combustion of the carbon.
Solution:
A The balanced chemical equation for the conversion of coal to methane is as follows:

2 C(s) + 2 H O(g) → CH (g) + CO (g)

2 4 2

Thus 1 mol of methane is produced for every 2 mol of carbon consumed. The ΔHcomb of 1 mol of methane is

⎛ 16.043 g ⎞ −55.5 kJ
1 mol CH4 ( ) = −890 kJ
⎝ 1 mol CH ⎠ g
4

The ΔHcomb of 2 mol of carbon (as coal) is

12.011 g
−28.3 kJ
2 mol C ( )( ) = −680 kJ
g
1 mol C

B The ratio of the energy released from the combustion of methane to the energy released from the combustion of carbon is
−890 kJ
= 1.31
−680 kJ

The energy released from the combustion of the product (methane) is 131% of that of the reactant (coal). The fuel value of coal
is actually increased by the process!
How is this possible when the law of conservation of energy states that energy cannot be created? The reaction consumes 2 mol
of water (ΔH = −285.8 kJ/mol) but produces only 1 mol of CO2 (ΔH = −393.5 kJ/mol). Part of the difference in
f
∘ ∘
f

potential energy between the two (approximately 180 kJ/mol) is stored in CH4 and can be released during combustion.

 Exercise 1.10.1

Using the data in Table 1.10.2, calculate the mass of hydrogen necessary to provide as much energy during combustion as 1
bbl of crude oil (density approximately 0.75 g/mL).

Answer
36 kg

1.10.4: The Carbon Cycle and the Greenhouse Effect

Even if carbon-based fuels could be burned with 100% efficiency, producing only CO2(g) and H2O(g), doing so could still
potentially damage the environment when carried out on the vast scale required by an industrial society. The amount of CO2
released is so large and is increasing so rapidly that it is apparently overwhelming the natural ability of the planet to remove CO2
from the atmosphere. In turn, the elevated levels of CO2 are thought to be affecting the temperature of the planet through a
mechanism known as the greenhouse effect. As you will see, there is little doubt that atmospheric CO2 levels are increasing, and
the major reason for this increase is the combustion of fossil fuels. There is substantially less agreement, however, on whether the
increased CO2 levels are responsible for a significant increase in temperature.

1.10.5: The Global Carbon Cycle

Figure 1.10.5 illustrates the global carbon cycle, the distribution and flow of carbon on Earth. Normally, the fate of atmospheric
CO2 is to either (1) dissolve in the oceans and eventually precipitate as carbonate rocks or (2) be taken up by plants. The rate of
uptake of CO2 by the ocean is limited by its surface area and the rate at which gases dissolve, which are approximately constant.
The rate of uptake of CO2 by plants, representing about 60 billion metric tons of carbon per year, partly depends on how much of
Earth’s surface is covered by vegetation. Unfortunately, the rapid deforestation for agriculture is reducing the overall amount of
vegetation, and about 60 billion metric tons of carbon are released annually as CO2 from animal respiration and plant decay. The

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amount of carbon released as CO2 every year by fossil fuel combustion is estimated to be about 5.5 billion metric tons. The net
result is a system that is slightly out of balance, experiencing a slow but steady increase in atmospheric CO2 levels (Figure 1.10.6).
As a result, average CO2 levels have increased by about 30% since 1850.

Figure 1.10.5 : The Global Carbon Cycle

Most of Earth’s carbon is found in the crust, where it is stored as calcium and magnesium carbonate in sedimentary rocks. The
oceans also contain a large reservoir of carbon, primarily as the bicarbonate ion (HCO3−). Green plants consume about 60 billion
metric tons of carbon per year as CO2 during photosynthesis, and about the same amount of carbon is released as CO2 annually
from animal and plant respiration and decay. The combustion of fossil fuels releases about 5.5 billion metric tons of carbon per
year as CO2.

Figure 1.10.6 : Changes in Atmospheric CO2 Levels. (a) Average worldwide CO2 levels have increased by about 30% since 1850.
(b) Atmospheric CO2 concentrations measured at Mauna Loa in Hawaii show seasonal variations caused by the removal of CO2
from the atmosphere by green plants during the growing season along with a general increase in CO2 levels.

1.10.6: The Atmospheric Greenhouse Effect

The increasing levels of atmospheric CO2 are of concern because CO2 absorbs thermal energy radiated by the Earth, as do other
gases such as water vapor, methane, and chlorofluorocarbons. Collectively, these substances are called greenhouse gases; they
mimic the effect of a greenhouse by trapping thermal energy in the Earth’s atmosphere, a phenomenon known as the greenhouse
effect (Figure 1.10.7).

1.10.6 https://chem.libretexts.org/@go/page/42257
 Figure 1.10.7 : The Greenhouse Effect. Thermal energy can be trapped in Earth’s atmosphere by gases such as CO2, water vapor,
methane, and chlorofluorocarbons before it can be radiated into space—like the effect of a greenhouse. It is not yet clear how large
an increase in the temperature of Earth’s surface can be attributed to this phenomenon.
Venus is an example of a planet that has a runaway greenhouse effect. The atmosphere of Venus is about 95 times denser than that
of Earth and contains about 95% CO2. Because Venus is closer to the sun, it also receives more solar radiation than Earth does. The
result of increased solar radiation and high CO2 levels is an average surface temperature of about 450°C, which is hot enough to
melt lead.
Data such as those in Figure Figure 1.10.6 indicate that atmospheric levels of greenhouse gases have increased dramatically over
the past 100 years, and it seems clear that the heavy use of fossil fuels by industry is largely responsible. It is not clear, however,
how large an increase in temperature (global warming) may result from a continued increase in the levels of these gases. Estimates
of the effects of doubling the preindustrial levels of CO2 range from a 0°C to a 4.5°C increase in the average temperature of Earth’s
surface, which is currently about 14.4°C. Even small increases, however, could cause major perturbations in our planet’s delicately
balanced systems. For example, an increase of 5°C in Earth’s average surface temperature could cause extensive melting of glaciers
and the Antarctic ice cap. It has been suggested that the resulting rise in sea levels could flood highly populated coastal areas, such
as New York City, Calcutta, Tokyo, Rio de Janeiro, and Sydney. An analysis conducted in 2009 by leading climate researchers
from the US National Oceanic and Atmospheric Administration, Switzerland, and France shows that CO2 in the atmosphere will
remain near peak levels far longer than other greenhouse gases, which dissipate more quickly. The study predicts a rise in sea levels
of approximately 3 ft by the year 3000, excluding the rise from melting glaciers and polar ice caps. According to the analysis,
southwestern North America, the Mediterranean, and southern Africa are projected to face droughts comparable to that of the Dust
Bowl of the 1930s as a result of global climate changes.
The increase in CO2 levels is only one of many trends that can affect Earth’s temperature. In fact, geologic evidence shows that the
average temperature of Earth has fluctuated significantly over the past 400,000 years, with a series of glacial periods (during which
the temperature was 10°C–15°C lower than it is now and large glaciers covered much of the globe) interspersed with relatively
short, warm interglacial periods (Figure 1.10.8). Although average temperatures appear to have increased by 0.5°C in the last
century, the statistical significance of this increase is open to question, as is the existence of a cause-and-effect relationship between
the temperature change and CO2 levels. Despite the lack of incontrovertible scientific evidence, however, many people believe that
we should take steps now to limit CO2 emissions and explore alternative sources of energy, such as solar energy, geothermal energy
from volcanic steam, and nuclear energy, to avoid even the possibility of creating major perturbations in Earth’s environment. In
2010, international delegates met in Cancún, Mexico, and agreed on a broad array of measures that would advance climate
protection. These included the development of low-carbon technologies, providing a framework to reduce deforestation, and aiding
countries in assessing their own vulnerabilities. They avoided, however, contentious issues of assigning emissions reductions
commitments.

1.10.7 https://chem.libretexts.org/@go/page/42257
 Figure 1.10.8 : Average Surface Temperature of Earth over the Past 400,000 Years. The dips correspond to glacial periods, and the
peaks correspond to relatively short, warm interglacial periods. Because of these fluctuations, the statistical significance of the
0.5°C increase in average temperatures observed in the last century is open to question.

 Example 1.10.2

A student at UCLA decided to fly home to New York for Christmas. The round trip was 4500 air miles, and part of the cost of
her ticket went to buy the 100 gal of jet fuel necessary to transport her and her baggage. Assuming that jet fuel is primarily n-
dodecane (C12H26) with a density of 0.75 g/mL, how much energy was expended and how many tons of CO were emitted 2

into the upper atmosphere to get her home and back?

Given: volume and density of reactant in combustion reaction
Asked for: energy expended and mass of CO2 emitted
Strategy:
A After writing a balanced chemical equation for the reaction, calculate ΔH ∘
comb

B Determine the number of moles of dodecane in 100 gal by using the density and molar mass of dodecane and the appropriate
conversion factors.
C Obtain the amount of energy expended by multiplying ΔH by the number of moles of dodecane. Calculate the amount
∘
comb

of CO2 emitted in tons by using mole ratios from the balanced chemical equation and the appropriate conversion factors.
Solution
A We first need to write a balanced chemical equation for the reaction:

2C H (l) + 37 O (g) ⟶ 24 CO (g) + 26 H O(l)

12 26 2 2 2

We can calculate ΔH ∘
comb
using the ΔH values corresponding to each substance in the specified phase (phases are not shown
∘
f

for simplicity):
∘ ∘ ∘
ΔH = ΣmΔH (products) − ΣnΔH (reactants)
comb f f

∘ ∘ ∘ ∘
= [24ΔH (CO ) + 26ΔH (H O)] − [37ΔH (O ) + 2ΔH (C H )]
f 2 f 2 f 2 f 12 26

= [24(−393.5 kJ/mol C O2 ) + 26(−285.8 kJ/mol H2 O)]

−[37(0 kJ/mol O2 ) + 2(−350.9 kJ/mol C12 H26 )]

= −16, 173.0 kJ

According to the balanced chemical equation for the reaction, this value is ΔH
∘
comb
for the combustion of 2 mol of n-
dodecane. So we must divide by 2 to obtain ΔH per mole of n-dodecane:
∘
comb

∘
ΔH = −8, 086.5 kJ/mol C12 H26
comb

B The number of moles of dodecane in 100 gal can be calculated as follows, using density, molar mass, and appropriate
conversion factors:

⎛ 3.785 L ⎞ 1000 mL 0.75 g 1 mol

3
100 gal ( )( )( ) = 1.7 × 10 mol C12 H26
⎝ 1 gal ⎠ L mL 170.34 g

C The total energy released is

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 ∘ 3 7
ΔH = (−8086.5 kJ/ mol )(1.7 × 10 mol ) = −1.4 × 10 kJ
comb

From the balanced chemical equation for the reaction, we see that each mole of dodecane forms 12 mol of CO
2
upon
combustion. Hence the amount of CO emitted is
2

24
⎛ mol CO2 ⎞
44.0 g 1 lb
2 1 tn
3 ⎜ ⎟(
1.7 × 10 mol C12 H26 )( )( ) = 0.99 tn
⎜ ⎟
454 g 2000 lb
1 mol C12 H26 1 mol CO2
⎝ ⎠

 Exercise 1.10.2
Suppose the student in Example 1.10.2 couldn’t afford the plane fare, so she decided to drive home instead. Assume that the
round-trip distance by road was 5572 miles, her fuel consumption averaged 31 mpg, and her fuel was pure isooctane (C8H18,
density = 0.6919 g/mL). How much energy was expended and how many tons of CO2 were produced during her trip?

Answer
2.2 × 107 kJ; 1.6 tons of CO2 (about twice as much as is released by flying)

1.10.7: Summary
Thermochemical concepts can be used to calculate the efficiency of various forms of fuel, which can then be applied to
environmental issues. More than 80% of the energy used by modern society (about 3 × 1017 kJ/yr) is from the combustion of fossil
fuels. Because of their availability, ease of transport, and facile conversion to convenient fuels, natural gas and petroleum are
currently the preferred fuels. Supplies of coal, a complex solid material derived from plants that lived long ago, are much greater,
but the difficulty in transporting and burning a solid makes it less attractive as a fuel. Coal releases the smallest amount of energy
per gram of any fossil fuel, and natural gas the greatest amount. The combustion of fossil fuels releases large amounts of CO2 that
upset the balance of the carbon cycle and result in a steady increase in atmospheric CO2 levels. Because CO2 is a greenhouse gas,
which absorbs heat before it can be radiated from Earth into space, CO2 in the atmosphere can result in increased surface
temperatures (the greenhouse effect). The temperature increases caused by increased CO2 levels because of human activities are,
however, superimposed on much larger variations in Earth’s temperature that have produced phenomena such as the ice ages and
are still poorly understood.

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1.E: Fundamentals of Thermochemistry (Exercises)
These are homework exercises to accompany the Textmap created for "Principles of Modern Chemistry" by Oxtoby et al.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here.

Q1A
A sample of O gas is under an external pressure of 17 atm and contained in a cylinder with a volume of 50 L. The gas is cooled
2

and the resulting volume is 25 L. Calculate the amount of work done on the O gas. 2

Q1B
A system containing oxygen gas is heated at a constant pressure of 40.0 atm so that its volume increases 177 L to 458 L. Express
the amount of work that the system did in kilo-joules.

Q2
The gas mixture inside one of the cylinders of an airplane expands against a constant external pressure of 5.00 atm because of the
growing altitude, from an initial volume of 500 mL (at the end of the compression stroke) to the final volume of 1200 mL.
Calculate the work done on the gas mixture during this process and express it in Joules.

Q3
The following events are based on a true story. A butcher for the local Chinese restaurant needs to defrost a large chunk of beef,
which weights 50 lb and is currently at 0 C . He wants to accomplish this by is going out onto the street and repeatedly drop it onto
∘

the ground. Suppose the potential energy of the meat completely transforms into heat each time it hits the ground, and that energy
can be calculated from

V = mgΔh

where m is mass of the object, g is the acceleration of gravity, and Δh is change in height. If the man is 5 ft tall and he wants to
get the meat to room temperature (25 C), how many times does he have to drop the piece of meat? Assume the environment has no
∘

J
effect on the meat, and that it does not lose any heat. (Specific Heat of the Meat: 0.25 ∘
).
g C

Q4
J
Suppose you have a ball (C p = 0.85
o
) at 25°C, what will its final temperature be if the amount of work equal to dropping it
g C
m
down from a height of 86.6m is done to it ? (g = 9.81 2
)
s

Q7A
The rule of Dulong and Petit shows that the molar heat capacities of most metallic elements group around a certain value “X”
J
at 25oC. By first calculating and showing the molar heat capacities of metals rhenium, silver, lead, tungsten, copper,
K mol
J J J
molybdenum and hafnium (given that the respective specific heat capacities of these metals are 0.14 , 0.23 , 0.13 ,
K g K g K g
J J J J
0.13 , 0.39 , 0.25 and 0.14 ), find the value of “X”. (hint: take the average value of the calculated molar heat
K g K g K g K g

capacities and round off value to nearest whole number).

Q7B
The specific heat capacities of metals aluminum, bismuth, copper, lead, and silver at 25°C are 0.900, 0.123, 0.386, 0.128, and 0.233
J
. Calculate the molar heat capacities of these metals. According to the rule of Dulong and Petit, the molar heat capacities of
g K
J
metallic elements, like these, are approximately 25 .
K mol

1.E.1 https://chem.libretexts.org/@go/page/67021
Q9
An undisclosed volume of water is tightly sealed in a microwave-safe container at room temperature before it is placed in an ice
bath where it is cooled by a student.
a. During the cooling process within the ice bath, state whether (ΔU ), Q, and W of the system are negative, zero, or positive.
Explain your reasoning.
b. After being cooled, the student decides that the water seems too cold so it is placed in the microwave where the container of
water is heated back to room temperature. What are the new signs of (ΔU ), Q, and W during the heating process? Explain your
reasoning.
c. Now determine the signs of (ΔU + ΔU ), (Q + Q ) , and (W + W ), where possible, assuming that the cooling process
1 2 1 2 1 2

was step 1 and the heating process was step 2.

Q11A
Your lab partner slipped a sample of unknown hot metal that is 40.0g, which is initially at 130.0°C into a 100.0 g water that is
initially at 50.0°C. A temperature probe indicates that equilibrium is reached at 60.15°C. Using the specific heat capacity of water
J
4.18 , calculate the specific heat capacity of the unknown metal.
K

Q11B
Let's say you 34.5 grams of some hot metal that is initially at 75°C and you put that metal into 64.0 grams of water that is initially
at 25°C. If the the two objects reach thermal equilibrium at 39°C, what is the specific heat capacity of the metal when the specific
J
heat capacity of water is 4.18 .
K g

Q12
A 10.00 g sample of Aluminum at 60.0 °C and a 30.0 g sample of copper at a temperature of -20.0 °C were thrown simultaneously
into a 50.0 g of water at a temperature of 25.0 °C. What will be the final temperature of the system consisting of the two metal
samples and the water? Assuming that this system is completely isolated from the surroundings. Use the information below for
your calculations.
cs(Al) = 0.900J/(K ⋅ g)

cs(Cu) = 0.385J/(K ⋅ g)

cs( H O) = 4.184J/(K ⋅ g)
2

Q15A
Calculated the heat required to melt 3.00 g of ice and the heat required to change the temperature of water from 0°C to 100°C.
What is the proportionality of the heat necessary to melt ice compared to the heat required to change the temperature of water from
0°C to 100°C? Use values from Table S2 and assume ΔH =334 J g-1 for calculations? Why is the heat positive instead of
f

negative?

Q15B
An observation in the 18th century stated that the heat that raised a certain mass of water from its freezing point to boiling point is
equal to four-thirds of the heat required to melt the same mass of ice. Using the theory behind the observation, estimate the heat
required to melt 10 g of ice, know that the heat capacity of water is 4.18 J/oC.

Q17
For his birthday, his John's parents have given him a compressible oven filled with 0.250 mol argon. If he sets this compressible
oven at 1.00 atm and 273 K and let it contract from a constant external pressure of 0.100 atm until the gas pressure reaches 10.00
atm and the temperature reaches 400 K, what is the work done on the gas, the internal energy change, and the heat absorbed by the
gas?

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Q19
Take 4 moles of ideal, monatomic gas going through expansion processes. The gas was initially put at a pressure of 5.00 atm and a
temperature of 30°C. The gas first goes through isothermal expansion until the volume doubled. An isochoric process follows as
3
the pressure is halved. C v = R
2

a. Build ΔU , W, and Q table for each process.

b. Find the final temperature.

Q20
An apparatus is set up such that an ideal gas is released into vacuum by opening a stopcock, hence allowing it to freely expand (i.e.,
no external force is applied). Calculate ΔU of the system, and prove that the free expansion process is adiabatic i.e no heat transfer.

Q21
A 150 L vessel contains 8.00 moles of neon at 270 K is compressed adiabatically, so that there is no gain nor loss of any heat, and
irreversibly until the final temperature is 470 K. Calculate the change in internal energy, the heat added to the gas, and the work
done on the gas.

Q22
A gas expands at constant external pressure of 3.00 atm until its volume has increased by 9.00 to 15.00 L. During this process, it
absorbs 800J of heat from the surroundings.
a. Calculate the energy change of the gas, ΔU
b. Calculate the work, w, done on the gas in an irreversible adiabatic (q = 0) process connecting the same initial and final state.

Q23
Using the theorem of equipartition of energy, calculate the specific heat capacity at constant pressure C at 25ºC and 1 atm for O
p 2

and CO. Compare the calculated values to the experimental data (O = 29.36, CO = 29.1) and thus calculate the percent of the
2

experimental value that results from vibrational motions. Answer: The percent of C due to vibrational motions is 0.897% for O
p 2

and 0.141% for CO.

Q23B
Using the classical equipartition theorem, calculate the value of C at 298 K and 1 atm for HF(g) and F
p 2
(g), assuming that their
J J
pressure is constant. Then compare your calculation with the experiment values of 29.13 and 31.30 respectively.
K mol K mol
What is the per cent of the measured value that arises from vibrational motions?

Q25
a. Calculate the change of enthalpy when a 69-grams sample of zinc is heated from 753 K to 927 K at a constant pressure of 1
atm.
b. Calculate the change of enthalpy when 3 moles of butane are heated from 204 K to 258 K at a constant pressure of 1 atm.

Q31
What is the change in enthalpy when 8.19 grams of ethane (C 2
H
6
) vaporizes, assuming a normal boiling point and
kJ
ΔHvap = 14.72 .
mol

Q33
J J
The heat capacity C of ice is 38
p and C of water is 75
p . A 24.0 g ice cube at -15 oC is placed into 120 g of water at
K mol K mol
room temperature (25oC). What is the temperature of the water when it reaches equilibrium?

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Q35
Determine the change in enthalpy (ΔH ) for the following chemical reaction
4 NH +5 O ⟶ 4 NO +6 H O
3 (g) 2 (g) (g) 2 (g)

given that:
kJ
O +N ⟶ 2 NO ΔH = +180.5
2 (g) 2 (g) (g)
mol

kJ
2H O ⟶ 2H +O ΔH = +483.64
2 (g) 2 (g) 2 (g)
mol

kJ
3H
2 (g)
+N
2 (g)
⟶ 2 NH
3 (g)
ΔH = −92.22 .
mol

Q37
ΔH of C H (g) from C H (l) to its gaseous form is +33.9 kJ/mol. Which of these two substances absorbs off more heat when 10
6 6 6 6

lbs of the substance is burned? Which of these two substances require less energy when condensed to solid form?

Q39
Calculate the enthalpy change under standard conditions for the reaction:

C H O(l) + 4 O (g) → 3 CO (g) + 3 H O(l)

3 6 2 2 2

given information below:

ΔH°f, O2(g): 0 kJ/mol
ΔH°f, CO2 (g): -393.5 kJ/mol
ΔH°f, H2O(l): -285.83 kJ/mol
ΔH°f, C3H6O(l): -248 kJ/mol

Q47
A 10 gram sample of pure hydrogen is burned completely with excess oxygen to generate liquid water in a constant volume
calorimeter at 25 °C. The amount of heat evolved is 1,420 kJ.
a. Write and balance the chemical equation for the combustion reaction.
b. Calculate the standard change in internal energy for the combustion of 1.00 mole hydrogen to liquid water.
c. Calculate the standard enthalpy change per mole of hydrogen for the same reaction as in part (a).
d. Calculate the standard enthalpy of formation per mole of hydrogen, using data for the standard enthalpies of formation of liquid
water (Table T1).
A consequence of the constant-volume condition is that the heat released corresponds to qv and thus to the internal energy
change ΔU rather than to ΔH under constant pressure conditions.
sys sys

ΔUsys = qv

This comes from the definition of enthalpy

Hsys = Usys + P V

and associated change

ΔHsys = ΔUsys + Δ(P V )

or using the chain rule

0

ΔHsys = ΔUsys + P ΔV + V ΔP

which simplifies to

ΔHsys = ΔUsys + V ΔP

1.E.4 https://chem.libretexts.org/@go/page/67021
 If we assuming ideal gas law for the gases

P V = nRT

or
ΔnRT
ΔP =
V

substituting this into the equation for enthalpy change gives the enthalpy change under constant volume conditions in terms
of changing number of moles

ΔHsys = ΔUsys + Δng RT

or

ΔHsys = qv + Δng RT

where Δn is the change in the number of moles of gases in the reaction.

g

Q49
Carbon dioxide (CO ) is a common byproduct of the combustion of fossil fuels. Estimate the standard enthalpy of formation (
2

ΔH ) of carbon dioxide at 25°C, use Table T1.

f

Q51
Given the table of average bond enthalpies shown below, estimate the enthalpy change ΔH ° for the following reaction:

2 H (g) + O (g) ⟶ 2 H O(l)

2 2 2

Bond Bond Enthalpy (kJ/mol)

H−H 436

H−O 463

O=O 498

Q59
Two quantum states are separated by an energy of 0.6 × 10-21J. Calculate the relative populations of the two quantum states at a
temperature of 33°C.

Q63
By utilizing the Harmonic Oscillator Model, calculate the relative population of the first energy state and the ground state, both at
N
278.15 K , for H . The force constant for H is 510
2 2
m

Q69
A container holds 2 L of gas under 5.00 atm and a ball floating in 10 L of NaOH. As the volume of the gas expands to 20 L, the
ball is turned upside down. This turn is caused by the temperature increase of the NaOH after the gas expands. Assuming that no
heat is lost, the density of NaOH is 2.13 g/cm3 and the specific heat is 4.184 J/g K, calculate the increase in temperature of the
NaOH.

Q69
Some gas in a piston expands against a constant pressure of 1.2 atm from a volume of 3 L to 18 L. The piston turns an egg beater
submerged in 150 g of water. If the water was originally at 25°C, what is its temperature once the gas stops expanding? Assume
that all of heat goes into the water and the specific heat capacity of water is 4.184 J K-1 g-1.

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 CHAPTER OVERVIEW

II: Principles of Thermodynamics (Entropy and Gibbs Energy)

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

The name "thermodynamics" is really a silly name. Think about it; the field deals primarily with the condition of equilibrium, that
is, no change or a "static" situation. The actual field that describes non-equilibration properties is "kinetics" or "dynamics," hence
the more apt term for this field is really "thermostatics." However, since we cannot change a name that has been in use for 150
years, we will stick with it and pretend otherwise.
2.1: The Nature of Spontaneous Processes
2.2: Entropy and Spontaneity - A Molecular Statistical Interpretation
2.3: Entropy and Heat - Experimental Basis of the Second Law of Thermodynamics
2.4: Entropy Changes and Spontaneity
2.5: Entropy Changes in Reversible Processes
2.6: Quantum States, Microstates, and Energy Spreading
2.7: The Third Law of Thermodynamics
2.8: Gibbs Energy
2.E: Principles of Thermodynamics (Exercises)

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curated by LibreTexts.

1
2.1: The Nature of Spontaneous Processes
 Learning Objectives
Distinguish between spontaneous and nonspontaneous processes
Describe the dispersal of matter and energy that accompanies certain spontaneous processes

In this section, consider the differences between two types of changes in a system: Those that occur spontaneously and those that occur only with the continuous input of energy. In doing so,
we’ll gain an understanding as to why some systems are naturally inclined to change in one direction under certain conditions. We’ll also gain insight into how the spontaneity of a process
affects the distribution of energy and matter within the system.

2.1.1: Spontaneous and Nonspontaneous Processes

Processes have a natural tendency to occur in one direction under a given set of conditions. Water will naturally flow downhill, but uphill flow requires outside intervention such as the use of a
pump. A spontaneous process is one that occurs naturally under certain conditions. A nonspontaneous process, on the other hand, will not take place unless it is “driven” by the continual input
of energy from an external source. A process that is spontaneous in one direction under a particular set of conditions is nonspontaneous in the reverse direction. At room temperature and typical
atmospheric pressure, for example, ice will spontaneously melt, but water will not spontaneously freeze.
The spontaneity of a process is not correlated to the speed of the process. A spontaneous change may be so rapid that it is essentially instantaneous or so slow that it cannot be observed over any
practical period of time. To illustrate this concept, consider the decay of radioactive isotopes, a topic more thoroughly treated in the chapter on nuclear chemistry. Radioactive decay is by
definition a spontaneous process in which the nuclei of unstable isotopes emit radiation as they are converted to more stable nuclei. All the decay processes occur spontaneously, but the rates at
which different isotopes decay vary widely. Technetium-99m is a popular radioisotope for medical imaging studies that undergoes relatively rapid decay and exhibits a half-life of about six
hours. Uranium-238 is the most abundant isotope of uranium, and its decay occurs much more slowly, exhibiting a half-life of more than four billion years (Figure 2.1.1).

Figure 2.1.1 : Both U-238 and Tc-99m undergo spontaneous radioactive decay, but at drastically different rates. Over the course of one week, essentially all of a Tc-99m sample and none of a U-
238 sample will have decayed. (CC by 4.0; Morgan Johnson via LibreTexts)
Two curves are shown to represent U-238 and Tc-99m respectively. The vertical axes represents the percentage of isotope remaining and the horizontal axes is the time that has elapsed in days.
As another example, consider the conversion of diamond into graphite (Figure 2.1.2).
C(s, diamond) ⟶ C(s, graphite) (2.1.1)

The phase diagram for carbon indicates that graphite is the stable form of this element under ambient atmospheric pressure, while diamond is the stable allotrope at very high pressures, such as
those present during its geologic formation. Thermodynamic calculations of the sort described in the last section of this chapter indicate that the conversion of diamond to graphite at ambient
pressure occurs spontaneously, yet diamonds are observed to exist, and persist, under these conditions. Though the process is spontaneous under typical ambient conditions, its rate is extremely
slow, and so for all practical purposes diamonds are indeed “forever.” Situations such as these emphasize the important distinction between the thermodynamic and the kinetic aspects of a
process. In this particular case, diamonds are said to be thermodynamically unstable but kinetically stable under ambient conditions.

Figure 2.1.2 : The conversion of carbon from the diamond allotrope to the graphite allotrope is spontaneous at ambient pressure, but its rate is immeasurably slow at low to moderate
temperatures. This process is known as graphitization, and its rate can be increased to easily measurable values at temperatures in the 1000–2000 K range. (credit "diamond" photo: modification
of work by "Fancy Diamonds"/Flickr; credit "graphite" photo: modification of work by images-of-elements.com/carbon.php)
Comparison of diamond and graphite shown in its physical form as well as its molecular arrangement respectively.

2.1.2: Dispersal of Matter and Energy

As we extend our discussion of thermodynamic concepts toward the objective of predicting spontaneity, consider now an isolated system consisting of two flasks connected with a closed valve.
Initially there is an ideal gas on the left and a vacuum on the right (Figure 2.1.3). When the valve is opened, the gas spontaneously expands to fill both flasks. Recalling the definition of
pressure-volume work from the chapter on thermochemistry, note that no work has been done because the pressure in a vacuum is zero.

w = −P ΔV (2.1.2)

=0 (P = 0 in a vaccum) (2.1.3)

Note as well that since the system is isolated, no heat has been exchanged with the surroundings (q = 0). The first law of thermodynamics confirms that there has been no change in the system’s
internal energy as a result of this process.

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 ΔU = q + w (First Law of Thermodynamics)

= 0 +0 = 0 (2.1.4)

The spontaneity of this process is therefore not a consequence of any change in energy that accompanies the process. Instead, the movement of the gas appears to be related to the greater, more
uniform dispersal of matter that results when the gas is allowed to expand. Initially, the system was comprised of one flask containing matter and another flask containing nothing. After the
spontaneous process took place, the matter was distributed both more widely (occupying twice its original volume) and more uniformly (present in equal amounts in each flask).

Figure 2.1.3 : An isolated system consists of an ideal gas in one flask that is connected by a closed valve to a second flask containing a vacuum. Once the valve is opened, the gas spontaneously
becomes evenly distributed between the flasks.
When the valve is closed, all of the gas molecules accumlating only in one side of the flask. The diagram with the open valve shows gas being equally distributed among the two flasks. The
dispersion of the gas is labeled as spontaneous while the reverse is labeled as non spontaneous.
Now consider two objects at different temperatures: object X at temperature TX and object Y at temperature TY, with TX > TY (Figure 2.1.4). When these objects come into contact, heat
spontaneously flows from the hotter object (X) to the colder one (Y). This corresponds to a loss of thermal energy by X and a gain of thermal energy by Y.

qX < 0 and qY = −qX > 0 (2.1.5)

From the perspective of this two-object system, there was no net gain or loss of thermal energy, rather the available thermal energy was redistributed among the two objects. This spontaneous
process resulted in a more uniform dispersal of energy.

Figure 2.1.4 :When two objects at different temperatures come in contact, heat spontaneously flows from the hotter to the colder object.
Two separated blocks. One is labeled X and the other labeled Y. The diagram next to it shows the two blocks in contact with one another.
As illustrated by the two processes described, an important factor in determining the spontaneity of a process is the extent to which it changes the dispersal or distribution of matter and/or
energy. In each case, a spontaneous process took place that resulted in a more uniform distribution of matter or energy.

 Example 2.1.1: Redistribution of Matter during a Spontaneous Process

Describe how matter and energy are redistributed when the following spontaneous processes take place:
a. A solid sublimes.
b. A gas condenses.
c. A drop of food coloring added to a glass of water forms a solution with uniform color.

Solution

Figure 2.1.5 :(credit a: modification of work by Jenny Downing; credit b: modification of work by “Fuzzy Gerdes”/Flickr; credit c: modification of work by Sahar Atwa)
This figure has three photos labeled, “a,” “b,” and “c.” Photo a shows a glass with dry ice in water. There is a thick vapor coming from the top of the glass. Photo b shows water forming
outside of a glass containing cold beverage. Photo c shows a sealed container that holds a red liquid.
a. Sublimation is the conversion of a solid (relatively high density) to a gas (much lesser density). This process yields a much greater dispersal of matter, since the molecules will occupy a
much greater volume after the solid-to-gas transition. However, an input of energy from the surroundings ss required for the molecules to leave the solid phase and enter the gas phase.
b. Condensation is the conversion of a gas (relatively low density) to a liquid (much greater density). This process yields a much lesser dispersal of matter, since the molecules will occupy
a much lesser volume after the gas-to-liquid transition. As the gas molecules move together to form the droplets of liquid, they form intermolecular forces and thus release energy to the
surroundings.
c. The process in question is dilution. The food dye molecules initially occupy a much smaller volume (the drop of dye solution) than they occupy once the process is complete (in the full
glass of water). The process therefore entails a greater dispersal of matter. The process may also yield a more uniform dispersal of matter, since the initial state of the system involves
two regions of different dye concentrations (high in the drop, zero in the water), and the final state of the system contains a single dye concentration throughout. This process can occur
with out a change in energy because the molecules have kinetic energy relative to the temperature of the water, and so will be constantly in motion.

 Exercise 2.1.1
Describe how matter and energy are redistributed when you empty a canister of compressed air into a room.

Answer
This process entails both a greater and more uniform dispersal of matter as the compressed air in the canister is permitted to expand into the lower-pressure air of the room. The process
also requires an input of energy to disrupt the intermolecular forces between the closely-spaced gas molecules that are originally compressed into the container. If you were to touch the
nozzle of the canister, you would notice that it is cold because the exiting molecules are taking energy away from their surroundings, and the canister is part of the surroundings.

Summary
Chemical and physical processes have a natural tendency to occur in one direction under certain conditions. A spontaneous process occurs without the need for a continual input of energy from
some external source, while a nonspontaneous process requires such. Systems undergoing a spontaneous process may or may not experience a gain or loss of energy, but they will experience a

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change in the way matter and/or energy is distributed within the system. In this section we have only discussed nuclear decay, physical changes of pure substances, and macroscopic events such
as water flowing downhill. In the following sections we will discuss mixtures and chemical reactions, situations in which the description of sponteneity becomes more challenging.

Glossary
nonspontaneous process
process that requires continual input of energy from an external source

spontaneous change
process that takes place without a continuous input of energy from an external source

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2.2: Entropy and Spontaneity - A Molecular Statistical Interpretation
 Learning Objectives
The Learning Objective of this Module is to understand the relationship between internal energy and entropy.

We know that the first law of thermodynamics governs changes in the state function we called internal energy (U ) and that changes
in the internal energy (ΔU ) are closely related to changes in the enthalpy (ΔH ), which is a measure of the heat flow between a
system and its surroundings at constant pressure. You also learned previously that the enthalpy change for a chemical reaction can
be calculated using tabulated values of enthalpies of formation. This information, however, does not tell us whether a particular
process or reaction will occur spontaneously.

2.2.1: Spontaneous Reactions

Let’s consider a familiar example of spontaneous change. If a hot frying pan that has just been removed from the stove is allowed
to come into contact with a cooler object, such as cold water in a sink, heat will flow from the hotter object to the cooler one, in this
case usually releasing steam. Eventually both objects will reach the same temperature, at a value between the initial temperatures of
the two objects. This transfer of heat from a hot object to a cooler one obeys the first law of thermodynamics: energy is conserved.
Now consider the same process in reverse. Suppose that a hot frying pan in a sink of cold water were to become hotter while the
water became cooler. As long as the same amount of thermal energy was gained by the frying pan and lost by the water, the first
law of thermodynamics would be satisfied. Yet we all know that such a process cannot occur: heat always flows from a hot object
to a cold one, never in the reverse direction. That is, by itself the magnitude of the heat flow associated with a process does not
predict whether the process will occur spontaneously.
For many years, chemists and physicists tried to identify a single measurable quantity that would enable them to predict whether a
particular process or reaction would occur spontaneously. Initially, many of them focused on enthalpy changes and hypothesized
that an exothermic process would always be spontaneous. But although it is true that many, if not most, spontaneous processes are
exothermic, there are also many spontaneous processes that are not exothermic. For example, at a pressure of 1 atm, ice melts
spontaneously at temperatures greater than 0°C, yet this is an endothermic process because heat is absorbed. Similarly, many salts
(such as NH4NO3, NaCl, and KBr) dissolve spontaneously in water even though they absorb heat from the surroundings as they
dissolve (i.e., ΔH soln> 0 ). Reactions can also be both spontaneous and highly endothermic, like the reaction of barium hydroxide

with ammonium thiocyanate shown in Figure 2.2.1.

Endothermic reaction: very, VERY cool.

Figure 2.2.1 : An Endothermic Reaction. The reaction of barium hydroxide with ammonium thiocyanate is spontaneous but highly
endothermic, so water, one product of the reaction, quickly freezes into slush. When water is placed on a block of wood under the
flask, the highly endothermic reaction that takes place in the flask freezes water that has been placed under the beaker, so the flask
becomes frozen to the wood. For a full video: see www.youtube.com/watch?v=GQkJI-Nq3Os.
Thus enthalpy is not the only factor that determines whether a process is spontaneous. For example, after a cube of sugar has
dissolved in a glass of water so that the sucrose molecules are uniformly dispersed in a dilute solution, they never spontaneously
come back together in solution to form a sugar cube. Moreover, the molecules of a gas remain evenly distributed throughout the
entire volume of a glass bulb and never spontaneously assemble in only one portion of the available volume. To help explain why

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these phenomena proceed spontaneously in only one direction requires an additional state function called entropy (S ), a
thermodynamic property of all substances that is proportional to their degree of disorder.

The direction of a spontaneous process is not governed by the internal energy change nor enthalpy change and thus the First
Law of Thermodynamics cannot predict the direction of a natural process

2.2.2: Probabilities and Microstates

Chemical and physical changes in a system may be accompanied by either an increase or a decrease in the disorder of the system,
corresponding to an increase in entropy (ΔS > 0 ) or a decrease in entropy (ΔS < 0 ), respectively. As with any other state
function, the change in entropy is defined as the difference between the entropies of the final and initial states:
ΔS = Sf − Si (2.2.1)

When a gas expands into a vacuum, its entropy increases because the increased volume allows for greater atomic or molecular
disorder. The greater the number of atoms or molecules in the gas, the greater the disorder. The magnitude of the entropy of a
system depends on the number of microscopic states, or microstates, associated with it (in this case, the number of atoms or
molecules); that is, the greater the number of microstates, the greater the entropy.
How can we express disorder quantitatively? From the example of coins, you can probably see that simple statistics plays a role:
the probability of obtaining three heads and seven tails after tossing ten coins is just the ratio of the number of ways that ten
different coins can be arranged in this way, to the number of all possible arrangements of ten coins.

Using the language of molecular statistics, we say that a collection of coins in which a given fraction of its members are heads-up
constitutes a macroscopic state of the system. Since we do not care which coins are heads-up, there are clearly numerous
configurations of the individual coins which can result in this “macrostate”. Each of these configurations specifies a microscopic
state of the system. The greater the number of microstates that correspond to a given macrostate (or configuration), the greater the
probability of that macrostate. To see what this means, consider the possible outcomes of a toss of four coins (Table 2.2.1):
Table 2.2.1 : Coin Toss Results
macrostate (Configuration) ways probability microstates

0 heads 1 1/16 TTTT

1 head 4 4/16 = 1/4 HTTT THTT TTHT TTTH

HHTT HTHT HTTH THHT

2 heads 6 6/16 = 3/8
TTHH THTH

3 heads 4 4/16 = 1/4 HHHT HTHH HHTH THHH

4 heads 1 1/16 HHHH

A toss of four coins will yield one of the five outcomes (macrostates) listed in the leftmost column of the table. The second column
gives the number of “ways”— that is, the number of head/tail configurations of the set of coins (the number of microstates)— that
can result in the macrostate. The probability of a toss resulting in a particular macrostate is proportional to the number of
microstates corresponding to the macrostate, and is equal to this number, divided by the total number of possible microstates (in
this example, 24 =16). An important assumption here is that all microstates are equally probable; that is, the toss is a “fair” one in
which the many factors that determine the trajectory of each coin operate in an entirely random way.

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 The greater the number of microstates that correspond to a given macrostate, the greater the probability of that macrostate.

2.2.3: Entropy and Microstates

Following the work of Carnot and Clausius, Ludwig Boltzmann developed a molecular-scale statistical model that related the
entropy of a system to the number of microstates possible for the system. A microstate (Ω) is a specific configuration of the
locations and energies of the atoms or molecules that comprise a system like the following:
S = k ln Ω (2.2.2)

Here k is the Boltzmann constant and has a value of 1.38 × 10−23 J/K.
As for other state functions, the change in entropy for a process is the difference between its final (S ) and initial (S ) values:
f i

ΔS = Sf − Si (2.2.3)

= k ln Ωf − k ln Ωi (2.2.4)

Ωf
= k ln (2.2.5)
Ωi

For processes involving an increase in the number of microstates, Ω > Ω , the entropy of the system increases, ΔS > 0 .
f i

Conversely, processes that reduce the number of microstates, Ω < Ω , yield a decrease in system entropy, ΔS < 0 . This
f i

molecular-scale interpretation of entropy provides a link to the probability that a process will occur as illustrated in the next
paragraphs.
Consider the general case of a system comprised of N particles distributed among n boxes. The number of microstates possible for
such a system is nN. For example, distributing four particles among two boxes will result in 24 = 16 different microstates as
illustrated in Figure 2.2.2. Microstates with equivalent particle arrangements (not considering individual particle identities) are
grouped together and are called distributions. The probability that a system will exist with its components in a given distribution is
proportional to the number of microstates within the distribution. Since entropy increases logarithmically with the number of
microstates (Equation 2.2.2), the most probable distribution is therefore the one of greatest entropy.

Figure 2.2.2 : The sixteen microstates associated with placing four particles in two boxes are shown. The microstates are collected
into five distributions—(a), (b), (c), (d), and (e)—based on the numbers of particles in each box.
For this system, the most probable configuration is one of the six microstates associated with distribution (c) where the particles are
evenly distributed between the boxes, that is, a configuration of two particles in each box. The probability of finding the system in
this configuration is
6 3
=
16 8

The least probable configuration of the system is one in which all four particles are in one box, corresponding to distributions (a)
and (e), each with a probability of

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 1

16

The probability of finding all particles in only one box (either the left box or right box) is then
1 1 2 1
( + ) = =
16 16 16 8

As you add more particles to the system, the number of possible microstates increases exponentially (2N). A macroscopic
(laboratory-sized) system would typically consist of moles of particles (N ~ 1023), and the corresponding number of microstates
would be staggeringly huge. Regardless of the number of particles in the system, however, the distributions in which roughly equal
numbers of particles are found in each box are always the most probable configurations.
The previous description of an ideal gas expanding into a vacuum is a macroscopic example of this particle-in-a-box model. For
this system, the most probable distribution is confirmed to be the one in which the matter is most uniformly dispersed or distributed
between the two flasks. The spontaneous process whereby the gas contained initially in one flask expands to fill both flasks equally
therefore yields an increase in entropy for the system.

Figure 2.2.3 : This shows a microstate model describing the flow of heat from a hot object to a cold object. (a) Before the heat flow
occurs, the object comprised of particles A and B contains both units of energy and as represented by a distribution of three
microstates. (b) If the heat flow results in an even dispersal of energy (one energy unit transferred), a distribution of four
microstates results. (c) If both energy units are transferred, the resulting distribution has three microstates.
A similar approach may be used to describe the spontaneous flow of heat. Consider a system consisting of two objects, each
containing two particles, and two units of energy (represented as “*”) in Figure 2.2.3. The hot object is comprised of particles A
and B and initially contains both energy units. The cold object is comprised of particles C and D, which initially has no energy
units. Distribution (a) shows the three microstates possible for the initial state of the system, with both units of energy contained
within the hot object. If one of the two energy units is transferred, the result is distribution (b) consisting of four microstates. If both
energy units are transferred, the result is distribution (c) consisting of three microstates. And so, we may describe this system by a
total of ten microstates. The probability that the heat does not flow when the two objects are brought into contact, that is, that the
system remains in distribution (a), is . More likely is the flow of heat to yield one of the other two distribution, the combined
3

10

probability being . The most likely result is the flow of heat to yield the uniform dispersal of energy represented by distribution
7

10

(b), the probability of this configuration being . As for the previous example of matter dispersal, extrapolating this treatment to
4

10

macroscopic collections of particles dramatically increases the probability of the uniform distribution relative to the other
distributions. This supports the common observation that placing hot and cold objects in contact results in spontaneous heat flow
that ultimately equalizes the objects’ temperatures. And, again, this spontaneous process is also characterized by an increase in
system entropy.

 Example 2.2.1: Determination of ΔS

Consider the system shown here. What is the change in entropy for a process that converts the system from distribution (a) to
(c)?

Solution
We are interested in the following change:

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 The initial number of microstates is one, the final six:
Ωc
ΔS = k ln
Ωa

6
−23
= 1.38 × 10 J/K × ln
1

−23
= 2.47 × 10 J/K

The sign of this result is consistent with expectation; since there are more microstates possible for the final state than for the
initial state, the change in entropy should be positive.

 Exercise 2.2.1

Consider the system shown in Figure 2.2.3. What is the change in entropy for the process where all the energy is transferred
from the hot object (AB) to the cold object (CD)?

Answer
0 J/K

A disordered system has a greater number of possible microstates than does an ordered system, so it has a higher entropy. This is
most clearly seen in the entropy changes that accompany phase transitions, such as solid to liquid or liquid to gas. As you know, a
crystalline solid is composed of an ordered array of molecules, ions, or atoms that occupy fixed positions in a lattice, whereas the
molecules in a liquid are free to move and tumble within the volume of the liquid; molecules in a gas have even more freedom to
move than those in a liquid. Each degree of motion increases the number of available microstates, resulting in a higher entropy.
Thus the entropy of a system must increase during melting (ΔSfus > 0). Similarly, when a liquid is converted to a vapor, the greater
freedom of motion of the molecules in the gas phase means that ΔSvap > 0. Conversely, the reverse processes (condensing a vapor
to form a liquid or freezing a liquid to form a solid) must be accompanied by a decrease in the entropy of the system: ΔS < 0.

 Definition: Entropy

Entropy (S) is a thermodynamic property of all substances that is proportional to their degree of disorder. The greater the
number of possible microstates for a system, the greater the disorder and the higher the entropy.

Disorder is more probable than order because there are so many more ways of achieving it. Thus coins and cards tend to
assume random configurations when tossed or shuffled, and socks and books tend to become more scattered about a teenager’s
room during the course of daily living. But there are some important differences between these large-scale mechanical, or macro
systems, and the collections of sub-microscopic particles that constitute the stuff of chemistry, and which we will refer to here
generically as molecules. Molecules, unlike macro objects, are capable of accepting, storing, and giving up energy in tiny amounts
(quanta), and act as highly efficient carriers and spreaders of thermal energy as they move around. Thus, in chemical systems,
1. We are dealing with huge numbers of particles. This is important because statistical predictions are always more accurate for
larger samples. Thus although for the four tosses there is a good chance (62%) that the H/T ratio will fall outside the range of
0.45 - 0.55, this probability becomes almost zero for 1000 tosses. To express this in a different way, the chances that 1000 gas
molecules moving about randomly in a container would at any instant be distributed in a sufficiently non-uniform manner to
produce a detectable pressure difference between the two halves of a container will be extremely small. If we increase the
number of molecules to a chemically significant number (around 1020, say), then the same probability becomes
indistinguishable from zero.
2. Once the change begins, it proceeds spontaneously. That is, no external agent (a tosser, shuffler, or teenager) is needed to
keep the process going. Gases will spontaneously expand if they are allowed to, and reactions, once started, will proceed toward
equilibrium.
3. Thermal energy is continually being exchanged between the particles of the system, and between the system and the
surroundings. Collisions between molecules result in exchanges of momentum (and thus of kinetic energy) amongst the
particles of the system, and (through collisions with the walls of a container, for example) with the surroundings.

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 4. Thermal energy spreads rapidly and randomly throughout the various energetically accessible microstates of the system.
The direction of spontaneous change is that which results in the maximum possible spreading and sharing of thermal energy.
The importance of these last two points is far greater than you might at first think, but to fully appreciate this, you must recall the
various ways in which thermal energy is stored in molecules.

2.2.4: Sign of Entropy Change

The relationships between entropy, microstates, and matter/energy dispersal described previously allow us to make generalizations
regarding the relative entropies of substances and to predict the sign of entropy changes for chemical and physical processes.
Consider the phase changes illustrated in Figure 2.2.4. In the solid phase, the atoms or molecules are restricted to nearly fixed
positions with respect to each other and are capable of only modest oscillations about these positions. With essentially fixed
locations for the system’s component particles, the number of microstates is relatively small. In the liquid phase, the atoms or
molecules are free to move over and around each other, though they remain in relatively close proximity to one another. This
increased freedom of motion results in a greater variation in possible particle locations, so the number of microstates is
correspondingly greater than for the solid. As a result, S >S
liquid and the process of converting a substance from solid to
solid

liquid (melting) is characterized by an increase in entropy, ΔS > 0 . By the same logic, the reciprocal process (freezing) exhibits a
decrease in entropy, ΔS < 0 .

Figure 2.2.4 : The entropy of a substance increases (ΔS > 0 ) as it transforms from a relatively ordered solid, to a less-ordered
liquid, and then to a still less-ordered gas. The entropy decreases (ΔS < 0 ) as the substance transforms from a gas to a liquid and
then to a solid.
Now consider the vapor or gas phase. The atoms or molecules occupy a much greater volume than in the liquid phase; therefore
each atom or molecule can be found in many more locations than in the liquid (or solid) phase. Consequently, for any substance,
Sgas ≫ Sliquid > Ssolid (2.2.6)

and the processes of vaporization and sublimation likewise involve increases in entropy, ΔS > 0 . Likewise, the reciprocal phase
transitions, condensation and deposition, involve decreases in entropy, ΔS < 0 .
According to kinetic-molecular theory, the temperature of a substance is proportional to the average kinetic energy of its particles.
Raising the temperature of a substance will result in more extensive vibrations of the particles in solids and more rapid translations
of the particles in liquids and gases. At higher temperatures, the distribution of kinetic energies among the atoms or molecules of
the substance is also broader (more dispersed) than at lower temperatures. Thus, the entropy for any substance increases with
temperature (Figure 2.2.5 ).

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 Figure 2.2.5 : Entropy increases as the temperature of a substance is raised, which corresponds to the greater spread of kinetic
energies. When a substance melts or vaporizes, it experiences a significant increase in entropy.
The entropy of a substance is influenced by structure of the particles (atoms or molecules) that comprise the substance. With regard
to atomic substances, heavier atoms possess greater entropy at a given temperature than lighter atoms, which is a consequence of
the relation between a particle’s mass and the spacing of quantized translational energy levels (which is a topic beyond the scope of
our treatment). For molecules, greater numbers of atoms (regardless of their masses) increase the ways in which the molecules can
vibrate and thus the number of possible microstates and the system entropy.
Finally, variations in the types of particles affect the entropy of a system. Compared to a pure substance, in which all particles are
identical, the entropy of a mixture of two or more different particle types is greater. This is because of the additional orientations
and interactions that are possible in a system comprised of nonidentical components. For example, when a solid dissolves in a
liquid, the particles of the solid experience both a greater freedom of motion and additional interactions with the solvent particles.
This corresponds to a more uniform dispersal of matter and energy and a greater number of microstates. The process of dissolution
therefore involves an increase in entropy, ΔS > 0 .
Considering the various factors that affect entropy allows us to make informed predictions of the sign of ΔS for various chemical
and physical processes as illustrated in Example 2.2.2.

 Example 2.2.2: Predicting the Sign of ∆S

Predict the sign of the entropy change for the following processes. Indicate the reason for each of your predictions.
a. One mole liquid water at room temperature ⟶ one mole liquid water at 50 °C
b. Ag (aq) + Cl (aq) ⟶ AgCl(s)
+ −

c. C H (l) + O (g) ⟶ 6 CO (g) + 3 H O(l)

6 6
15

2 2 2 2

d. NH (s) ⟶ NH (l)
3 3

Solution
a. positive, temperature increases
b. negative, reduction in the number of ions (particles) in solution, decreased dispersal of matter
c. negative, net decrease in the amount of gaseous species
d. positive, phase transition from solid to liquid, net increase in dispersal of matter

 Exercise 2.2.2

Predict the sign of the enthalpy change for the following processes. Give a reason for your prediction.
a. NaNO (s) ⟶ Na (aq) + NO (aq)
3
+ −
3

b. the freezing of liquid water

c. CO (s) ⟶ CO (g)
2 2

d. CaCO(s) ⟶ CaO(s) + CO (g) 2

Answer a
Positive; The solid dissolves to give an increase of mobile ions in solution.

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 Answer b
Negative; The liquid becomes a more ordered solid.
Answer c
Positive; The relatively ordered solid becomes a gas.
Answer d
Positive; There is a net production of one mole of gas.

2.2.5: Summary
Entropy (S ) is a state function that can be related to the number of microstates for a system (the number of ways the system can be
arranged) and to the ratio of reversible heat to kelvin temperature. It may be interpreted as a measure of the dispersal or distribution
of matter and/or energy in a system, and it is often described as representing the “disorder” of the system. For a given substance,
Ssolid<S ≪ S
liquid gas in a given physical state at a given temperature, entropy is typically greater for heavier atoms or more
complex molecules. Entropy increases when a system is heated and when solutions form. Using these guidelines, the sign of
entropy changes for some chemical reactions may be reliably predicted.

2.2.6: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

2.2: Entropy and Spontaneity - A Molecular Statistical Interpretation is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by LibreTexts.

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2.3: Entropy and Heat - Experimental Basis of the Second Law of Thermodynamics
 Learning Objectives
The Learning Objective of this Module is to understand the relationship between internal energy and entropy.

2.3.1: Thermodynamic Definition of Entropy

Experiments show that the magnitude of ΔSvap is 80–90 J/(mol•K) for a wide variety of liquids with different boiling points.
However, liquids that have highly ordered structures due to hydrogen bonding or other intermolecular interactions tend to have
significantly higher values of ΔS . For instance, ΔSvap for water is 102 J/(mol•K). Another process that is accompanied by
vap

entropy changes is the formation of a solution. As illustrated in Figure 2.3.1, the formation of a liquid solution from a crystalline
solid (the solute) and a liquid solvent is expected to result in an increase in the number of available microstates of the system and
hence its entropy. Indeed, dissolving a substance such as NaCl in water disrupts both the ordered crystal lattice of NaCl and the
ordered hydrogen-bonded structure of water, leading to an increase in the entropy of the system. At the same time, however, each
dissolved Na ion becomes hydrated by an ordered arrangement of at least six water molecules, and the Cl− ions also cause the
+

water to adopt a particular local structure. Both of these effects increase the order of the system, leading to a decrease in entropy.
The overall entropy change for the formation of a solution therefore depends on the relative magnitudes of these opposing factors.
In the case of an NaCl solution, disruption of the crystalline NaCl structure and the hydrogen-bonded interactions in water is
quantitatively more important, so ΔS soln > 0.

Figure 2.3.1 : The Effect of Solution Formation on Entropy

Dissolving NaCl in water results in an increase in the entropy of the system. Each hydrated ion, however, forms an ordered
arrangement with water molecules, which decreases the entropy of the system. The magnitude of the increase is greater than the
magnitude of the decrease, so the overall entropy change for the formation of an NaCl solution is positive.

 Example 2.3.1
Predict which substance in each pair has the higher entropy and justify your answer.
a. 1 mol of NH3(g) or 1 mol of He(g), both at 25°C
b. 1 mol of Pb(s) at 25°C or 1 mol of Pb(l) at 800°C
Given: amounts of substances and temperature
Asked for: higher entropy
Strategy:
From the number of atoms present and the phase of each substance, predict which has the greater number of available
microstates and hence the higher entropy.
Solution:
a. Both substances are gases at 25°C, but one consists of He atoms and the other consists of NH3 molecules. With four atoms
instead of one, the NH3 molecules have more motions available, leading to a greater number of microstates. Hence we
predict that the NH3 sample will have the higher entropy.

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 b. The nature of the atomic species is the same in both cases, but the phase is different: one sample is a solid, and one is a
liquid. Based on the greater freedom of motion available to atoms in a liquid, we predict that the liquid sample will have the
higher entropy.

 Exercise 2.3.1

Predict which substance in each pair has the higher entropy and justify your answer.
a. 1 mol of He(g) at 10 K and 1 atm pressure or 1 mol of He(g) at 250°C and 0.2 atm
b. a mixture of 3 mol of H2(g) and 1 mol of N2(g) at 25°C and 1 atm or a sample of 2 mol of NH3(g) at 25°C and 1 atm

Answer a
1 mol of He(g) at 250°C and 0.2 atm (higher temperature and lower pressure indicate greater volume and more microstates)
Answer b
a mixture of 3 mol of H2(g) and 1 mol of N2(g) at 25°C and 1 atm (more molecules of gas are present)

This page titled 2.3: Entropy and Heat - Experimental Basis of the Second Law of Thermodynamics is shared under a CC BY-NC-SA 3.0 license
and was authored, remixed, and/or curated by Anonymous.

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2.4: Entropy Changes and Spontaneity
 Learning Objectives
State and explain the second and third laws of thermodynamics
Calculate entropy changes for phase transitions and chemical reactions under standard conditions

2.4.1: Connecting Entropy and Heat to Spontaneity

In the quest to identify a property that may reliably predict the spontaneity of a process, we have identified a very promising
candidate: entropy. Processes that involve an increase in entropy of the system (ΔS > 0 ) are very often spontaneous; however,
sys

examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, we may reach a
significant conclusion regarding the relation between this property and spontaneity. In thermodynamic models, the system and
surroundings comprise everything, that is, the universe, and so the following is true:
ΔSuniv = ΔSsys + ΔSsurr (2.4.1)

To illustrate this relation, consider again the process of heat flow between two objects, one identified as the system and the other as
the surroundings. There are three possibilities for such a process:
1. The objects are at different temperatures, and heat flows from the hotter to the cooler object. This is always observed to occur
spontaneously. Designating the hotter object as the system and invoking the definition of entropy yields the following:
−qrev
ΔSsys = (2.4.2)
Tsys

and
qrev
ΔSsurr = (2.4.3)
Tsurr

The arithmetic signs of qrev denote the loss of heat by the system and the gain of heat by the surroundings. Since Tsys > Tsurr in
this scenario, the magnitude of the entropy change for the surroundings will be greater than that for the system, and so the sum
of ΔSsys and ΔSsurr will yield a positive value for ΔSuniv. This process involves an increase in the entropy of the universe.
2. The objects are at different temperatures, and heat flows from the cooler to the hotter object. This is never observed to occur
spontaneously. Again designating the hotter object as the system and invoking the definition of entropy yields the following:
qrev
ΔSsys = (2.4.4)
Tsys

and
−qrev
ΔSsurr = (2.4.5)
Tsurr

The arithmetic signs of qrev denote the gain of heat by the system and the loss of heat by the surroundings. The magnitude of the
entropy change for the surroundings will again be greater than that for the system, but in this case, the signs of the heat changes
will yield a negative value for ΔSuniv. This process involves a decrease in the entropy of the universe.
3. The temperature difference between the objects is infinitesimally small, T ≈ T sys , and so the heat flow is
surr

thermodynamically reversible. See the previous section’s discussion). In this case, the system and surroundings experience
entropy changes that are equal in magnitude and therefore sum to yield a value of zero for ΔSuniv. This process involves no
change in the entropy of the universe.
These results lead to a profound statement regarding the relation between entropy and spontaneity known as the second law of
thermodynamics: all spontaneous changes cause an increase in the entropy of the universe. A summary of these three relations is
provided in Table 2.4.1.
Table 2.4.1 : The Second Law of Thermodynamics
ΔSuniv > 0 spontaneous

ΔSuniv < 0 nonspontaneous (spontaneous in opposite direction)

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 ΔSuniv = 0 reversible (system is at equilibrium)

 Definition: The Second Law of Thermodynamics

All spontaneous changes cause an increase in the entropy of the universe, i.e.,
ΔSuniv > 0. (2.4.6)

For many realistic applications, the surroundings are vast in comparison to the system. In such cases, the heat gained or lost by the
surroundings as a result of some process represents a very small, nearly infinitesimal, fraction of its total thermal energy. For
example, combustion of a fuel in air involves transfer of heat from a system (the fuel and oxygen molecules undergoing reaction) to
surroundings that are infinitely more massive (the earth’s atmosphere). As a result, q is a good approximation of qrev, and the
surr

second law may be stated as the following:

ΔSuniv = ΔSsys + ΔSsurr (2.4.7)

qsurr
= ΔSsys + (2.4.8)
T

We may use this equation to predict the spontaneity of a process as illustrated in Example 2.4.1.

 Example 2.4.1: Will Ice Spontaneously Melt?

The entropy change for the process

H O(s) ⟶ H O(l)
2 2

is 22.1 J/K and requires that the surroundings transfer 6.00 kJ of heat to the system. Is the process spontaneous at −10.00 °C? Is
it spontaneous at +10.00 °C?
Solution
We can assess the spontaneity of the process by calculating the entropy change of the universe. If ΔSuniv is positive, then the
process is spontaneous. At both temperatures, ΔSsys = 22.1 J/K and qsurr = −6.00 kJ.
At −10.00 °C (263.15 K), the following is true:

ΔSuniv = ΔSsys + ΔSsurr

qsurr
= ΔSsys +
T

3
−6.00 × 10 J
= 22.1 J/K +
263.15 K

= −0.7 J/K

Suniv < 0, so melting is nonspontaneous (not spontaneous) at −10.0 °C.

At 10.00 °C (283.15 K), the following is true:
qsurr
ΔSuniv = ΔSsys +
T

3
−6.00 × 10 J
= 22.1 J/K +
283.15 K

= +0.9 J/K

ΔSuniv > 0 , so melting is spontaneous at 10.00 °C.

Access for free at OpenStax 2.4.2 https://chem.libretexts.org/@go/page/46427

  Exercise 2.4.1

Using this information, determine if liquid water will spontaneously freeze at the same temperatures. What can you say about
the values of ΔS ? univ

Answer
Entropy is a state function, and freezing is the opposite of melting. At −10.00 °C spontaneous, +0.7 J/K; at +10.00 °C
nonspontaneous, −0.9 J/K.

2.4.2: Summary
The second law of thermodynamics states that a spontaneous process increases the entropy of the universe, Suniv > 0 . If
ΔS univ< 0 , the process is nonspontaneous, and if ΔS = 0 , the system is at equilibrium.
univ

2.4.3: Key Equations

∘ ∘ ∘ ∘
ΔS = ΔS = ∑ νS (products) − ∑ ν S (reactants)
298 298 298
qrev
ΔS =
T
ΔSuniv = ΔSsys + ΔSsurr
qsurr
ΔSuniv = ΔSsys + ΔSsurr = ΔSsys +
T

2.4.4: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

This page titled 2.4: Entropy Changes and Spontaneity is shared under a CC BY 4.0 license and was authored, remixed, and/or curated by
OpenStax.

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2.5: Entropy Changes in Reversible Processes
 Learning Objectives

You are expected to be able to define and explain the significance of terms identified in bold.
A reversible process is one carried out in infinitesimal steps after which, when undone, both the system and surroundings
(that is, the world) remain unchanged (see the example of gas expansion-compression below). Although true reversible
change cannot be realized in practice, it can always be approximated.
As a process is carried out in a more reversible manner, the value of w approaches its maximum possible value, and q
approaches its minimum possible value.
Although q is not a state function, the quotient qrev/T is, and is known as the entropy.

A change is said to occur reversibly when it can be carried out in a series of infinitesimal steps, each one of which can be undone
by making a similarly minute change to the conditions that bring the change about. For example, the reversible expansion of a gas
can be achieved by reducing the external pressure in a series of infinitesimal steps; reversing any step will restore the system and
the surroundings to their previous state. Similarly, heat can be transferred reversibly between two bodies by changing the
temperature difference between them in infinitesimal steps each of which can be undone by reversing the temperature difference.
The most widely cited example of an irreversible change is the free expansion of a gas into a vacuum. Although the system can
always be restored to its original state by recompressing the gas, this would require that the surroundings perform work on the gas.
Since the gas does no work on the surrounding in a free expansion (the external pressure is zero, so P ΔV = 0 ,) there will be a
permanent change in the surroundings. Another example of irreversible change is the conversion of mechanical work into frictional
heat; there is no way, by reversing the motion of a weight along a surface, that the heat released due to friction can be restored to
the system.

2.24 L , 10 atm 2.24 L , 1 atm

EXPANSION COMPRESSION

1 Stage

-20 L - atm +202 L - atm

2 Stages

-28 L - atm +119 L - atm

3 Stages

-33 L - atm +85L - atm

Infinite Stages
P (Reversible) P
-52 L - atm +52 L - atm
(maximum work) (minimum work)
V V

Figure 2.5.1 : Reversible vs. Irreversible Expansions and Compressions. (CC BY-NC; Ümit Kaya)
These diagrams show the same expansion and compression ±ΔV carried out in different numbers of steps ranging from a single
step at the top to an "infinite" number of steps at the bottom. As the number of steps increases, the processes become less
irreversible; that is, the difference between the work done in expansion and that required to re-compress the gas diminishes. In the
limit of an ”infinite” number of steps (bottom), these work terms are identical, and both the system and surroundings (the “world”)
are unchanged by the expansion-compression cycle. In all other cases the system (the gas) is restored to its initial state, but the
surroundings are forever changed.

2.5.1 https://chem.libretexts.org/@go/page/46426
  Definition: Reversible Changes

A reversible change is one carried out in such as way that, when undone, both the system and surroundings (that is, the world)
remain unchanged.

It should go without saying, of course, that any process that proceeds in infinitesimal steps would take infinitely long to occur, so
thermodynamic reversibility is an idealization that is never achieved in real processes, except when the system is already at
equilibrium, in which case no change will occur anyway! So why is the concept of a reversible process so important?
The answer can be seen by recalling that the change in the internal energy that characterizes any process can be distributed in an
infinity of ways between heat flow across the boundaries of the system and work done on or by the system, as expressed by the
First Law of thermodynamics

ΔU = q + w. (2.5.1)

Each combination of q and w represents a different pathway between the initial and final states. It can be shown that as a process
such as the expansion of a gas is carried out in successively longer series of smaller steps, the absolute value of q approaches a
minimum, and that of w approaches a maximum that is characteristic of the particular process. Thus when a process is carried out
reversibly, the w-term in Equation 2.5.1 has its greatest possible value, and the q-term is at its smallest. These special quantities
wmax and q
min (which we denote as q and pronounce “q-reversible”) have unique values for any given process and are therefore
rev

state functions.

2.5.1: Work and Reversibility

Changes in entropy (ΔS ), together with changes in enthalpy (ΔH ), enable us to predict in which direction a chemical or physical
change will occur spontaneously. Before discussing how to do so, however, we must understand the difference between a reversible
process and an irreversible one. In a reversible process, every intermediate state between the extremes is an equilibrium state,
regardless of the direction of the change. In contrast, an irreversible process is one in which the intermediate states are not
equilibrium states, so change occurs spontaneously in only one direction. As a result, a reversible process can change direction at
any time, whereas an irreversible process cannot. When a gas expands reversibly against an external pressure such as a piston, for
example, the expansion can be reversed at any time by reversing the motion of the piston; once the gas is compressed, it can be
allowed to expand again, and the process can continue indefinitely. In contrast, the expansion of a gas into a vacuum (P = 0 ) isext

irreversible because the external pressure is measurably less than the internal pressure of the gas. No equilibrium states exist, and
the gas expands irreversibly. When gas escapes from a microscopic hole in a balloon into a vacuum, for example, the process is
irreversible; the direction of airflow cannot change.
Because work done during the expansion of a gas depends on the opposing external pressure (w = P ΔV ), work done in a
ext

reversible process is always equal to or greater than work done in a corresponding irreversible process: w ≥ w
rev . Whether a
irrev

process is reversible or irreversible, the first law of thermodynamics holds (Equation 2.5.1). Because U is a state function, the
magnitude of ΔU does not depend on reversibility and is independent of the path taken. So
ΔU = qrev + wrev (2.5.2)

= qirrev + wirrev (2.5.3)

Work done in a reversible process is always equal to or greater than work done in a corresponding irreversible process:
wrev ≥ wirrev (2.5.4)

In other words, ΔU for a process is the same whether that process is carried out in a reversible manner or an irreversible one. We
now return to our earlier definition of entropy, using the magnitude of the heat flow for a reversible process (q ) to define entropy
rev

quantitatively.

2.5.2 https://chem.libretexts.org/@go/page/46426
 ΔU
q W Reversible process;
maximum work performed

q W Real (irreversible) process;

some work performed

q Limiting irreversible process;

no work performed

Figure 2.5.2 : Note that the reversible condition implies w

max and q . The impossibility of extracting all of the internal energy as
min

work is essentially a statement of the Second Law. (CC BY-NC; Ümit Kaya)
For a process that reversibly exchanges a quantity of heat q rev with the surroundings, the entropy change is defined as
qrev
ΔS = (2.5.5)
T

This is the basic way of evaluating ΔS for constant-temperature processes such as phase changes, or the isothermal expansion of a
gas. For processes in which the temperature is not constant such as heating or cooling of a substance, the equation must be
integrated over the required temperature range, as discussed below.

 Q&A: If no real process can take place reversibly, what use is an expression involving q rev ?

This is a rather fine point that you should understand: although transfer of heat between the system and surroundings is
impossible to achieve in a truly reversible manner, this idealized pathway is only crucial for the definition of ΔS ; by virtue of
its being a state function, the same value of ΔS will apply when the system undergoes the same net change via any pathway.
For example, the entropy change a gas undergoes when its volume is doubled at constant temperature will be the same
regardless of whether the expansion is carried out in 1000 tiny steps (as reversible as patience is likely to allow) or by a single-
step (as irreversible a pathway as you can get!) expansion into a vacuum (Figure 2.5.1).

Entropy is an extensive quantity; that is, it is proportional to the quantity of matter in a system; thus 100 g of metallic copper has
twice the entropy of 50 g at the same temperature. This makes sense because the larger piece of copper contains twice as many
quantized energy levels able to contain the thermal energy.

 Entropy and "disorder"

Entropy is still described, particularly in older textbooks, as a measure of disorder. In a narrow technical sense this is correct,
since the spreading and sharing of thermal energy does have the effect of randomizing the disposition of thermal energy within
a system. But to simply equate entropy with “disorder” without further qualification is extremely misleading because it is far
too easy to forget that entropy (and thermodynamics in general) applies only to molecular-level systems capable of exchanging
thermal energy with the surroundings. Carrying these concepts over to macro systems may yield compelling analogies, but it is
no longer science. It is far better to avoid the term “disorder” altogether in discussing entropy.

2.5.3 https://chem.libretexts.org/@go/page/46426
2.5.2: ΔS sys for an Isothermal Expansion (or Compression)
As a substance becomes more dispersed in space, the thermal energy it carries is also spread over a larger volume, leading to an
increase in its entropy. Because entropy, like energy, is an extensive property, a dilute solution of a given substance may well
possess a smaller entropy than the same volume of a more concentrated solution, but the entropy per mole of solute (the molar
entropy) will of course always increase as the solution becomes more dilute.
For gaseous substances, the volume and pressure are respectively direct and inverse measures of concentration. For an ideal gas
that expands at a constant temperature (meaning that it absorbs heat from the surroundings to compensate for the work it does
during the expansion), the increase in entropy is given by
V2
ΔS = R ln( ) (2.5.6)
V1

Note: If the gas is allowed to cool during the expansion, the relation becomes more complicated and will best be discussed in a
more advanced course.
Because the pressure of an ideal gas is inversely proportional to its volume, i.e.,
nRT
P = (2.5.7)
V

we can easily alter Equation 2.5.6 to express the entropy change associated with a change in the pressure of an ideal gas:
P1
ΔS = R ln( ) (2.5.8)
P2

Also the concentration c = n/V for an ideal gas is proportional to pressure

P = cRT (2.5.9)

we can expressing the entropy change directly in concentrations, we have the similar relation
c1
ΔS = R ln( ) (2.5.10)
c2

Although these equations strictly apply only to perfect gases and cannot be used at all for liquids and solids, it turns out that in a
dilute solution, the solute can often be treated as a gas dispersed in the volume of the solution, so the last equation can actually give
a fairly accurate value for the entropy of dilution of a solution. We will see later that this has important consequences in
determining the equilibrium concentrations in a homogeneous reaction mixture.

2.5.3: The Relationship between Internal Energy and Entropy

Because the quantity of heat transferred (q ) is directly proportional to the absolute temperature of an object (T ) (q ∝ T ), the
rev rev

hotter the object, the greater the amount of heat transferred. Moreover, adding heat to a system increases the kinetic energy of the
component atoms and molecules and hence their disorder (ΔS ∝ q ). Combining these relationships for any reversible process,
rev

qrev = T ΔS (2.5.11)

and
qrev
ΔS = (2.5.12)
T

Because the numerator (qrev) is expressed in units of energy (joules), the units of ΔS are joules/kelvin (J/K). Recognizing that the
work done in a reversible process at constant pressure is
wrev = −P ΔV , (2.5.13)

we can express Equation 2.5.3 as follows:

ΔU = qrev + wrev (2.5.14)

= T ΔS − P ΔV (2.5.15)

2.5.4 https://chem.libretexts.org/@go/page/46426
Thus the change in the internal energy of the system is related to the change in entropy, the absolute temperature, and the P V work
done.
To illustrate the use of Equation 2.5.12 and Equation 2.5.15, we consider two reversible processes before turning to an irreversible
process. When a sample of an ideal gas is allowed to expand reversibly at constant temperature, heat must be added to the gas
during expansion to keep its T constant (Figure 2.5.5). The internal energy of the gas does not change because the temperature of
the gas does not change; that is, ΔU = 0 and qrev = −wrev. During expansion, ΔV > 0, so the gas performs work on its surroundings:

wrev = −P ΔV < 0. (2.5.16)

According to Equation 2.5.15, this means that q must increase during expansion; that is, the gas must absorb heat from the
rev

surroundings during expansion, and the surroundings must give up that same amount of heat. The entropy change of the system is
therefore
qrev
ΔSsys = + (2.5.17)
T

and the entropy change of the surroundings is

qrev
ΔSsurr = − . (2.5.18)
T

The corresponding change in entropy of the universe is then as follows:

ΔSuniv = ΔSsys + ΔSsurr (2.5.19)

qrev qrev
= + (− ) (2.5.20)
T T

=0 (2.5.21)

Thus no change in ΔS univ has occurred.

Figure 2.5.5 : Expansion of Gas at Constant Temperature. (CC BY-SA-NC; Anonymous by request)
In the initial state (top), the temperatures of a gas and the surroundings are the same. During the reversible expansion of the gas,
heat must be added to the gas to maintain a constant temperature. Thus the internal energy of the gas does not change, but work is
performed on the surroundings. In the final state (bottom), the temperature of the surroundings is lower because the gas has
absorbed heat from the surroundings during expansion.
Now consider the reversible melting of a sample of ice at 0°C and 1 atm. The enthalpy of fusion of ice is 6.01 kJ/mol, which means
that 6.01 kJ of heat are absorbed reversibly from the surroundings when 1 mol of ice melts at 0°C, as illustrated in Figure 2.5.6.
The surroundings constitute a sample of low-density carbon foam that is thermally conductive, and the system is the ice cube that
has been placed on it. The direction of heat flow along the resulting temperature gradient is indicated with an arrow. From Equation
2.5.12, we see that the entropy of fusion of ice can be written as follows:

qrev ΔHfus
ΔSfus = = (2.5.22)
T T

2.5.5 https://chem.libretexts.org/@go/page/46426
 Figure 2.5.6 : Thermograms Showing That Heat Is Absorbed from the Surroundings When Ice Melts at 0°C
By convention, a thermogram shows cold regions in blue, warm regions in red, and thermally intermediate regions in green. When
an ice cube (the system, dark blue) is placed on the corner of a square sample of low-density carbon foam with very high thermal
conductivity, the temperature of the foam is lowered (going from red to green). As the ice melts, a temperature gradient appears,
ranging from warm to very cold. An arrow indicates the direction of heat flow from the surroundings (red and green) to the ice
cube. The amount of heat lost by the surroundings is the same as the amount gained by the ice, so the entropy of the universe does
not change.
In this case,
6.01 kJ/mol
ΔSf us = (2.5.23)
273 K

= 22.0 J/(mol ∙ K) (2.5.24)

= ΔSsys . (2.5.25)

The amount of heat lost by the surroundings is the same as the amount gained by the ice, so
qrev
ΔSsurr = (2.5.26)
T

−6.01 kJ/mol
= (2.5.27)
273 K

= −22.0 J/(mol ∙ K). (2.5.28)

Once again, we see that the entropy of the universe does not change:

ΔSuniv = ΔSsys + ΔSsurr (2.5.29)

= 22.0 J/(mol ∙ K) − 22.0 J/(mol ∙ K) (2.5.30)

=0 (2.5.31)

In these two examples of reversible processes, the entropy of the universe is unchanged. This is true of all reversible processes and
constitutes part of the second law of thermodynamics: the entropy of the universe remains constant in a reversible process, whereas
the entropy of the universe increases in an irreversible (spontaneous) process.

 The Second Law of Thermodynamics

The entropy of the universe increases during a spontaneous process. It also increases during an observable non-spontaneous
process.

As an example of an irreversible process, consider the entropy changes that accompany the spontaneous and irreversible transfer of
heat from a hot object to a cold one, as occurs when lava spewed from a volcano flows into cold ocean water. The cold substance,
the water, gains heat (q > 0), so the change in the entropy of the water can be written as ΔScold = q/Tcold. Similarly, the hot
substance, the lava, loses heat (q < 0), so its entropy change can be written as ΔShot = −q/Thot, where Tcold and Thot are the
temperatures of the cold and hot substances, respectively. The total entropy change of the universe accompanying this process is
therefore

2.5.6 https://chem.libretexts.org/@go/page/46426
 ΔSuniv = ΔScold + ΔShot (2.5.32)

q q
= + (− ) (2.5.33)
Tcold Thot

The numerators on the right side of Equation 2.5.33 are the same in magnitude but opposite in sign. Whether ΔSuniv is positive or
negative depends on the relative magnitudes of the denominators. By definition, Thot > Tcold, so −q/Thot must be less than q/Tcold,
and ΔSuniv must be positive. As predicted by the second law of thermodynamics, the entropy of the universe increases during this
irreversible process. Any process for which ΔSuniv is positive is, by definition, a spontaneous one that will occur as written.
Conversely, any process for which ΔSuniv approaches zero will not occur spontaneously as written but will occur spontaneously in
the reverse direction. We see, therefore, that heat is spontaneously transferred from a hot substance, the lava, to a cold substance,
the ocean water. In fact, if the lava is hot enough (e.g., if it is molten), so much heat can be transferred that the water is converted to
steam (Figure 2.5.7).

Figure 2.5.7 : Spontaneous Transfer of Heat from a Hot Substance to a Cold Substance
When molten lava flows into cold ocean water, so much heat is spontaneously transferred to the water that steam is produced.

 Example 2.5.1: Tin Pest

Tin has two allotropes with different structures. Gray tin (α-tin) has a structure similar to that of diamond, whereas white tin (β-
tin) is denser, with a unit cell structure that is based on a rectangular prism. At temperatures greater than 13.2°C, white tin is
the more stable phase, but below that temperature, it slowly converts reversibly to the less dense, powdery gray phase. This
phenomenon was argued to plagued Napoleon’s army during his ill-fated invasion of Russia in 1812: the buttons on his
soldiers’ uniforms were made of tin and disintegrated during the Russian winter, adversely affecting the soldiers’ health (and
morale). The conversion of white tin to gray tin is exothermic, with ΔH = −2.1 kJ/mol at 13.2°C.
a. What is ΔS for this process?
b. Which is the more highly ordered form of tin—white or gray?
Given: ΔH and temperature
Asked for: ΔS and relative degree of order
Strategy:
Use Equation 2.5.12 to calculate the change in entropy for the reversible phase transition. From the calculated value of ΔS,
predict which allotrope has the more highly ordered structure.

Solution
a. We know from Equation 2.5.12 that the entropy change for any reversible process is the heat transferred (in joules) divided
by the temperature at which the process occurs. Because the conversion occurs at constant pressure, and ΔH and ΔU are
essentially equal for reactions that involve only solids, we can calculate the change in entropy for the reversible phase
transition where qrev = ΔH. Substituting the given values for ΔH and temperature in kelvins (in this case, T = 13.2°C =
286.4 K),
qrev (−2.1 kJ/mol)(1000 J/kJ)
ΔS = = = −7.3 J/(mol ⋅ K)
T 286.4 K

2.5.7 https://chem.libretexts.org/@go/page/46426
 b. The fact that ΔS < 0 means that entropy decreases when white tin is converted to gray tin. Thus gray tin must be the more
highly ordered structure.

tin pest, transformation of beta tin into …

Video 2.5.1 : Time lapse tin pest reaction. Beta tin to alpha tin transformation, time lapse video of sample maintained at -40 C. 20
shots per hour.

Note: Whether failing buttons were indeed a contributing factor in the failure of the invasion remains disputed; critics of the theory
point out that the tin used would have been quite impure and thus more tolerant of low temperatures. Laboratory tests provide
evidence that the time required for unalloyed tin to develop significant tin pest damage at lowered temperatures is about 18 months,
which is more than twice the length of Napoleon's Russian campaign. It is clear though that some of the regiments employed in the
campaign had tin buttons and that the temperature reached sufficiently low values (at least -40 °C) to facilitate tin pest.

 Exercise 2.5.1: Sulfur

Elemental sulfur exists in two forms: an orthorhombic form (Sα), which is stable below 95.3°C, and a monoclinic form (Sβ),
which is stable above 95.3°C. The conversion of orthorhombic sulfur to monoclinic sulfur is endothermic, with
ΔH = 0.401 kJ/mol at 1 atm.

a. What is ΔS for this process?

b. Which is the more highly ordered form of sulfur—Sα or Sβ?

Answer a
1.09 J/(mol•K)
Answer b
Sα

2.5.8 https://chem.libretexts.org/@go/page/46426
2.5.4: Summary
During a spontaneous process, the entropy of the universe increases.
qrev
ΔS =
T

A reversible process is one for which all intermediate states between extremes are equilibrium states; it can change direction at any
time. In contrast, an irreversible process occurs in one direction only. The change in entropy of the system or the surroundings is
the quantity of heat transferred divided by the temperature. The second law of thermodynamics states that in a reversible process,
the entropy of the universe is constant, whereas in an irreversible process, such as the transfer of heat from a hot object to a cold
object, the entropy of the universe increases.

2.5: Entropy Changes in Reversible Processes is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

2.5.9 https://chem.libretexts.org/@go/page/46426
2.6: Quantum States, Microstates, and Energy Spreading
 Learning Objectives
Explain how entropy is a measure of the degree of the spreading and sharing of thermal energy within a system.
Explain why the entropy of a substance increases with its molecular weight and complexity and with temperature.
Explain why entropy increases as the pressure or concentration becomes smaller.
Explain why entropies of gases are much larger than those of condensed phases.

Entropy is a measure of the degree of spreading and sharing of thermal energy within a system. This “spreading and sharing” can
be spreading of the thermal energy into a larger volume of space or its sharing amongst previously inaccessible microstates of the
system. Entropy is an extensive quantity; that is, it is proportional to the quantity of matter in a system; thus 100 g of metallic
copper has twice the entropy of 50 g at the same temperature. This makes sense because the larger piece of copper contains twice
as many quantized energy levels able to contain the thermal energy.
Thermal energy is the portion of a molecule's energy that is proportional to its temperature, and thus relates to motion at the
molecular scale. What kinds of molecular motions are possible? For monatomic molecules, there is only one: actual movement
from one location to another, which we call translation. Since there are three directions in space, all molecules possess three modes
of translational motion.
For polyatomic molecules, two additional kinds of motions are possible. One of these is rotation; a linear molecule such as CO2 in
which the atoms are all laid out along the x-axis can rotate along the y- and z-axes, while molecules having less symmetry can
rotate about all three axes. Thus linear molecules possess two modes of rotational motion, while non-linear ones have three
rotational modes. Finally, molecules consisting of two or more atoms can undergo internal vibrations. For freely moving molecules
in a gas, the number of vibrational modes or patterns depends on both the number of atoms and the shape of the molecule, and it
increases rapidly as the molecule becomes more complicated.

10-17J 300 J 30 J

translation rotation vibration

Figure 2.6.1 : Relative Energy levels for translation (left), rotation (middle) and vibration (right). (CC BY-NC; Ümit Kaya based off
of figure by Stephen Lower)
The relative populations of the quantized translational, rotational, and vibrational energy states of a typical diatomic molecule are
depicted by the thickness of the lines in this schematic (not-to-scale!) diagram. The colored shading indicates the total thermal
energy available at a given temperature. The numbers at the top show order-of-magnitude spacings between adjacent levels. It is
readily apparent that virtually all the thermal energy resides in translational states.
Notice the greatly different spacing of the three kinds of energy levels in Figure 2.6.1. This is extremely important because it
determines the number of energy quanta that a molecule can accept, and, as Figure 2.6.2 demonstrates, the number of different
ways this energy can be distributed amongst the molecules.

2.6.1 https://chem.libretexts.org/@go/page/46487
 7
4
6
5 3
4
3 2
thermal
2 energy
1
1
0 0

The quantity of energy indicated by the vertical arrow In molecules with more widely-spaced
can be distributed in three ways in a collection of molecules energy levels there are fewer ways of
whose allowed energy levels are spaced as shown here distributing the same total energy

Figure 2.6.2 : The more closely spaced the quantized energy states of a molecule, the greater will be the number of ways in which a
given quantity of thermal energy can be shared amongst a collection of these molecules. (CC BY-NC; Ümit Kaya based off
of figure by Stephen Lower)

The spacing of molecular energy states becomes closer as the mass and number of bonds in the molecule increases, so we can
generally say that the more complex the molecule, the greater the density of its energy states.

At the atomic and molecular level, all energy is quantized; each particle possesses discrete states of kinetic energy and is able to
accept thermal energy only in packets whose values correspond to the energies of one or more of these states. Polyatomic
molecules can store energy in rotational and vibrational motions, and all molecules (even monatomic ones) will possess
translational kinetic energy (thermal energy) at all temperatures above absolute zero. The energy difference between adjacent
translational states is so minute that translational kinetic energy can be regarded as continuous (non-quantized) for most practical
purposes.
The number of ways in which thermal energy can be distributed amongst the allowed states within a collection of molecules is
easily calculated from simple statistics, but we will confine ourselves to an example here. Suppose that we have a system consisting
of three molecules and three quanta of energy to share among them. We can give all the kinetic energy to any one molecule, leaving
the others with none, we can give two units to one molecule and one unit to another, or we can share out the energy equally and
give one unit to each molecule. All told, there are ten possible ways of distributing three units of energy among three identical
molecules as shown here:

0
Molecule a b c a b c a b c a b c a b c a b c a b c a b c a b c a b c

Microstate 1 2 3 4 5 6 7 8 9 10
Configuration i ii iii

Figure 2.6.3 . (CC BY-NC; Ümit Kaya based off of figure by Stephen Lower)
Each of these ten possibilities represents a distinct microstate that will describe the system at any instant in time. Those microstates
that possess identical distributions of energy among the accessible quantum levels (and differ only in which particular molecules
occupy the levels) are known as configurations. Because all microstates are equally probable, the probability of any one
configuration is proportional to the number of microstates that can produce it. Thus in the system shown above, the configuration
labeled ii will be observed 60% of the time, while iii will occur only 10% of the time.
As the number of molecules and the number of quanta increases, the number of accessible microstates grows explosively; if 1000
quanta of energy are shared by 1000 molecules, the number of available microstates will be around 10600— a number that greatly

2.6.2 https://chem.libretexts.org/@go/page/46487
exceeds the number of atoms in the observable universe! The number of possible configurations (as defined above) also increases,
but in such a way as to greatly reduce the probability of all but the most probable configurations. Thus for a sample of a gas large
enough to be observable under normal conditions, only a single configuration (energy distribution amongst the quantum
states) need be considered; even the second-most-probable configuration can be neglected.
The bottom line: any collection of molecules large enough in numbers to have chemical significance will have its thermal energy
distributed over an unimaginably large number of microstates. The number of microstates increases exponentially as more energy
states ("configurations" as defined above) become accessible owing to
Addition of energy quanta (higher temperature),
Increase in the number of molecules (resulting from dissociation, for example).
the volume of the system increases (which decreases the spacing between energy states, allowing more of them to be populated
at a given temperature.)

2.6.1: Spontaneous Process: Heat Death

Energy is conserved; if you lift a book off the table, and let it fall, the total amount of energy in the world remains unchanged. All
you have done is transferred it from the form in which it was stored within the glucose in your body to your muscles, and then to
the book (that is, you did work on the book by moving it up against the earth’s gravitational field). After the book has fallen, this
same quantity of energy exists as thermal energy (heat) in the book and table top.
What has changed, however, is the availability of this energy. Once the energy has spread into the huge number of thermal
microstates in the warmed objects, the probability of its spontaneously (that is, by chance) becoming un-dispersed is essentially
zero. Thus although the energy is still “there”, it is forever beyond utilization or recovery. The profundity of this conclusion was
recognized around 1900, when it was first described at the “heat death” of the world. This refers to the fact that every spontaneous
process (essentially every change that occurs) is accompanied by the “dilution” of energy. The obvious implication is that all of the
molecular-level kinetic energy will be spread out completely, and nothing more will ever happen.

2.6.2: Spontaneous Process: Gases Expansions

Everybody knows that a gas, if left to itself, will tend to expand and fill the volume within which it is confined completely and
uniformly. What “drives” this expansion? At the simplest level it is clear that with more space available, random motions of the
individual molecules will inevitably disperse them throughout the space. But as we mentioned above, the allowed energy states that
molecules can occupy are spaced more closely in a larger volume than in a smaller one. The larger the volume available to the gas,
the greater the number of microstates its thermal energy can occupy. Since all such states within the thermally accessible range of
energies are equally probable, the expansion of the gas can be viewed as a consequence of the tendency of thermal energy to be
spread and shared as widely as possible. Once this has happened, the probability that this sharing of energy will reverse itself (that
is, that the gas will spontaneously contract) is so minute as to be unthinkable.

barrier

concentrated dilute

Figure 2.6.4 : (CC BY-NC; Ümit Kaya based off of figure by Stephen Lower)
Imagine a gas initially confined to one half of a box (Figure 2.6.4). The barrier is then removed so that it can expand into the full
volume of the container. We know that the entropy of the gas will increase as the thermal energy of its molecules spreads into the
enlarged space. In terms of the spreading of thermal energy, Figure Figure 2.6.5 may be helpful. The tendency of a gas to expand is
due to the more closely-spaced thermal energy states in the larger volume .

2.6.3 https://chem.libretexts.org/@go/page/46487
 (1) (2) (3)

Figure 2.6.5 : The pink shading represents the thermally-accessible range of microstates for a given temperature. (CC BY-NC; Ümit
Kaya based off of figure by Stephen Lower)

2.6.3: Spontaneous Process: Mixing and dilution

Mixing and dilution really amount to the same thing, especially for ideal gases. Replace the pair of containers shown above with
one containing two kinds of molecules in the separate sections (Figure 2.6.6). When we remove the barrier, the "red" and "blue"
molecules will each expand into the space of the other. (Recall Dalton's Law that "each gas is a vacuum to the other gas").
However, notice that although each gas underwent an expansion, the overall process amounts to what we call "mixing".

unmixed mixed

Figure 2.6.6 : Mixing of a gas. (CC BY-NC; Ümit Kaya based off of figure by Stephen Lower)
What is true for gaseous molecules can, in principle, apply also to solute molecules dissolved in a solvent. But bear in mind that
whereas the enthalpy associated with the expansion of a perfect gas is by definition zero, ΔH's of mixing of two liquids or of
dissolving a solute in a solvent have finite values which may limit the miscibility of liquids or the solubility of a solute.
But what's really dramatic is that when just one molecule of a second gas is introduced into the container ( in Figure 2.6.5), an
unimaginably huge number of new configurations become possible, greatly increasing the number of microstates that are thermally
accessible (as indicated by the pink shading above).

2.6.4: Spontaneous Process: Thermal Equilibrium

Just as gases spontaneously change their volumes from “smaller-to-larger”, the flow of heat from a warmer body to a cooler one
always operates in the direction “warmer-to-cooler” because this allows thermal energy to populate a larger number of energy
microstates as new ones are made available by bringing the cooler body into contact with the warmer one; in effect, the thermal
energy becomes more “diluted”.

2.6.4 https://chem.libretexts.org/@go/page/46487
 hot cold combined
(a) (b)

Figure 2.6.7 : Part a of the figure is a schematic depiction of the thermal energy states in two separated identical bodies at different
temperatures indicated by shading. (CC BY-NC; Ümit Kaya based off of figure by Stephen Lower)
When the bodies are brought into thermal contact (b), thermal energy flows from the higher occupied levels in the warmer object
into the unoccupied levels of the cooler one until equal numbers are occupied in both bodies, bringing them to the same
temperature. As you might expect, the increase in the amount of energy spreading and sharing is proportional to the amount of heat
transferred q, but there is one other factor involved, and that is the temperature at which the transfer occurs. When a quantity of
heat q passes into a system at temperature T, the degree of dilution of the thermal energy is given by
q
(2.6.1)
T

To understand why we have to divide by the temperature, consider the effect of very large and very small values of T in the
denominator of Equation 2.6.1. If the body receiving the heat is initially at a very low temperature, relatively few thermal energy
states are initially occupied, so the amount of energy spreading into vacant states can be very great. Conversely, if the temperature
is initially large, more thermal energy is already spread around within it, and absorption of the additional energy will have a
relatively small effect on the degree of thermal disorder within the body.

2.6.5: Summary
Entropy is a measure of the degree of spreading and sharing of thermal energy within a system. This “spreading and sharing” can
be spreading of the thermal energy into a larger volume of space or its sharing amongst previously inaccessible microstates of the
system. The following box shows how this concept applies to a number of common processes.

 Observations and Explanations in terms of Entropy changes

A deck of cards is shuffled, or 100 coins, initially heads up, are randomly tossed.

Source of Entropy Increase of System

This has nothing to do with entropy because macro objects are unable to exchange thermal energy with the surroundings
within the time scale of the process

Two identical blocks of copper, one at 20°C and the other at 40°C, are placed in contact.

Source of Entropy Increase of System

The cooler block contains more unoccupied microstates, so heat flows from the warmer block until equal numbers of
microstates are populated in the two blocks.

A gas expands isothermally to twice its initial volume.

Source of Entropy Increase of System

A constant amount of thermal energy spreads over a larger volume of space

1 mole of water is heated by 1C°.

Source of Entropy Increase of System

2.6.5 https://chem.libretexts.org/@go/page/46487
 The increased thermal energy makes additional microstates accessible. (The increase is by a factor of about
1020,000,000,000,000, 000,000,000.)

Equal volumes of two gases are allowed to mix.

Source of Entropy Increase of System

The effect is the same as allowing each gas to expand to twice its volume; the thermal energy in each is now spread over a
larger volume.

One mole of dihydrogen, H2, is placed in a container and heated to 3000K.

Source of Entropy Increase of System

Some of the H dissociates to H atoms because at this temperature there are more thermally accessible microstates in the 2
2

moles of H atoms.

The above reaction mixture is cooled to 300 K.

Source of Entropy Increase of System

The composition shifts back to virtually all H because this molecule contains more thermally accessible microstates at low
2

temperatures.

This page titled 2.6: Quantum States, Microstates, and Energy Spreading is shared under a CC BY 3.0 license and was authored, remixed, and/or
curated by Stephen Lower via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is
available upon request.

2.6.6 https://chem.libretexts.org/@go/page/46487
2.7: The Third Law of Thermodynamics
 Learning Objectives
The absolute entropy of a pure substance at a given temperature is the sum of all the entropy it would acquire on warming
from absolute zero (where S = 0 ) to the particular temperature.
Calculate entropy changes for phase transitions and chemical reactions under standard conditions

The atoms, molecules, or ions that compose a chemical system can undergo several types of molecular motion, including
translation, rotation, and vibration (Figure 2.7.1). The greater the molecular motion of a system, the greater the number of possible
microstates and the higher the entropy. A perfectly ordered system with only a single microstate available to it would have an
entropy of zero. The only system that meets this criterion is a perfect crystal at a temperature of absolute zero (0 K), in which each
component atom, molecule, or ion is fixed in place within a crystal lattice and exhibits no motion (ignoring quantum zero point
motion).

Figure 2.7.1 : Molecular Motions. Vibrational, rotational, and translational motions of a carbon dioxide molecule are illustrated
here. Only a perfectly ordered, crystalline substance at absolute zero would exhibit no molecular motion (classically; there will
always be motion quantum mechanically) and have zero entropy. In practice, this is an unattainable ideal. (CC BY-SA-NC;
Anonymous by request)
This system may be described by a single microstate, as its purity, perfect crystallinity and complete lack of motion (at least
classically, quantum mechanics argues for constant motion) means there is but one possible location for each identical atom or
molecule comprising the crystal (Ω = 1 ). According to the Boltzmann equation, the entropy of this system is zero.

S = k ln Ω

= k ln(1)

=0

In practice, absolute zero is an ideal temperature that is unobtainable, and a perfect single crystal is also an ideal that cannot be
achieved. Nonetheless, the combination of these two ideals constitutes the basis for the third law of thermodynamics: the entropy of
any perfectly ordered, crystalline substance at absolute zero is zero.

 Definition: Third Law of Thermodynamics

The entropy of a pure, perfect crystalline substance at 0 K is zero.

The third law of thermodynamics has two important consequences: it defines the sign of the entropy of any substance at
temperatures above absolute zero as positive, and it provides a fixed reference point that allows us to measure the absolute entropy
of any substance at any temperature. In this section, we examine two different ways to calculate ΔS for a reaction or a physical
change. The first, based on the definition of absolute entropy provided by the third law of thermodynamics, uses tabulated values of
absolute entropies of substances. The second, based on the fact that entropy is a state function, uses a thermodynamic cycle similar
to those discussed previously.

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2.7.1: Standard-State Entropies
One way of calculating ΔS for a reaction is to use tabulated values of the standard molar entropy (S ), which is the entropy of 1
o

mol of a substance under standard pressure (1 bar). Often the standard molar entropy is given at 298 K and is often demarked as
ΔS
o
298
. The units of S are J/(mol•K). Unlike enthalpy or internal energy, it is possible to obtain absolute entropy values by
o

measuring the entropy change that occurs between the reference point of 0 K (corresponding to S = 0 ) and 298 K (Tables T1 and
T2).
As shown in Table 2.7.1, for substances with approximately the same molar mass and number of atoms, S values fall in the order
o

o o o
S (gas) ≫ S (liquid) > S (solid). (2.7.1)

For instance, S for liquid water is 70.0 J/(mol•K), whereas S for water vapor is 188.8 J/(mol•K). Likewise, S is 260.7
o o o

J/(mol•K) for gaseous I and 116.1 J/(mol•K) for solid I . This order makes qualitative sense based on the kinds and extents of
2 2

motion available to atoms and molecules in the three phases (Figure 2.7.1). The correlation between physical state and absolute
entropy is illustrated in Figure 2.7.2, which is a generalized plot of the entropy of a substance versus temperature.

Figure 2.7.2 : A Generalized Plot of Entropy versus Temperature for a Single Substance. Absolute entropy increases steadily with
increasing temperature until the melting point is reached, where it jumps suddenly as the substance undergoes a phase change from
a highly ordered solid to a disordered liquid (ΔSfus). The entropy again increases steadily with increasing temperature until the
boiling point is reached, where it jumps suddenly as the liquid undergoes a phase change to a highly disordered gas (ΔSvap). (CC
BY-SA-NC; anonymous).

2.7.2: The Third Law Lets us Calculate Absolute Entropies

The absolute entropy of a substance at any temperature above 0 K must be determined by calculating the increments of heat q
required to bring the substance from 0 K to the temperature of interest, and then summing the ratios q/T . Two kinds of
experimental measurements are needed:
1. The enthalpies associated with any phase changes the substance may undergo within the temperature range of interest. Melting
of a solid and vaporization of a liquid correspond to sizeable increases in the number of microstates available to accept thermal
energy, so as these processes occur, energy will flow into a system, filling these new microstates to the extent required to
maintain a constant temperature (the freezing or boiling point); these inflows of thermal energy correspond to the heats of
fusion and vaporization. The entropy increase associated with transition at temperature T is
ΔHf usion
. (2.7.2)
T

2. The heat capacity C of a phase expresses the quantity of heat required to change the temperature by a small amount ΔT , or
more precisely, by an infinitesimal amount dT . Thus the entropy increase brought about by warming a substance over a range

2.7.2 https://chem.libretexts.org/@go/page/46428
 of temperatures that does not encompass a phase transition is given by the sum of the quantities C dT

T
for each increment of
temperature dT . This is of course just the integral
T
Cp
S0→T = ∫ dt (2.7.3)
0
T

Because the heat capacity is itself slightly temperature dependent, the most precise determinations of absolute entropies require that
the functional dependence of C on T be used in the integral in Equation 2.7.3, i.e.,:
T
Cp (T )
S0→T = ∫ dt. (2.7.4)
0
T

When this is not known, one can take a series of heat capacity measurements over narrow temperature increments ΔT and measure
the area under each section of the curve. The area under each section of the plot represents the entropy change associated with
heating the substance through an interval ΔT . To this must be added the enthalpies of melting, vaporization, and of any solid-solid
phase changes.

Figure 2.7.3 : Heat capacity/temperature as a function of temperature. (CC BY; Stephan Lower)
Values of C for temperatures near zero are not measured directly, but can be estimated from quantum theory. The cumulative areas
p

from 0 K to any given temperature (Figure 2.7.3) are then plotted as a function of T , and any phase-change entropies such as
Hvap
Svap = (2.7.5)
Tb

are added to obtain the absolute entropy at temperature T . As shown in Figure 2.7.2 above, the entropy of a substance increases
with temperature, and it does so for two reasons:
As the temperature rises, more microstates become accessible, allowing thermal energy to be more widely dispersed. This is
reflected in the gradual increase of entropy with temperature.
The molecules of solids, liquids, and gases have increasingly greater freedom to move around, facilitating the spreading and
sharing of thermal energy. Phase changes are therefore accompanied by massive and discontinuous increase in the entropy.

2.7.3: Calculating ΔS sys

We can make careful calorimetric measurements to determine the temperature dependence of a substance’s entropy and to derive
absolute entropy values under specific conditions. Standard entropies are given the label S for values determined for one mole
o
298

of substance at a pressure of 1 bar and a temperature of 298 K. The standard entropy change (ΔS ) for any process may be o

computed from the standard entropies of its reactant and product species like the following:
o o o
ΔS = ∑ νS (products) − ∑ ν S (reactants) (2.7.6)
298 298

Here, ν represents stoichiometric coefficients in the balanced equation representing the process. For example, ΔS
o
for the
following reaction at room temperature

mA + nB ⟶ xC + yD (2.7.7)

is computed as the following:

o o o o o
ΔS = [x S (C) + y S (D)] − [m S (A) + nS (B)] (2.7.8)
298 298 298 298

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Table 2.7.1 lists some standard entropies at 298.15 K. You can find additional standard entropies in Tables T1 and T2
Table 2.7.1 : Standard Molar Entropy Values of Selected Substances at 25°C
Gases Liquids Solids

Substance S
o
[J/(mol•K)] Substance S
o
[J/(mol•K)] Substance S
o
[J/(mol•K)]

He 126.2 H2O 70.0 C (diamond) 2.4

H2 130.7 CH3OH 126.8 C (graphite) 5.7

Ne 146.3 Br2 152.2 LiF 35.7

Ar 154.8 CH3CH2OH 160.7 SiO2 (quartz) 41.5

Kr 164.1 C6H6 173.4 Ca 41.6

Xe 169.7 CH3COCl 200.8 Na 51.3

H2O 188.8 C6H12 (cyclohexane) 204.4 MgF2 57.2

N2 191.6 C8H18 (isooctane) 329.3 K 64.7

O2 205.2 NaCl 72.1

CO2 213.8 KCl 82.6

I2 260.7 I2 116.1

A closer examination of Table 2.7.1 also reveals that substances with similar molecular structures tend to have similar S values. o

Among crystalline materials, those with the lowest entropies tend to be rigid crystals composed of small atoms linked by strong,
highly directional bonds, such as diamond (S = 2.4 J/(mol ∙ K) ). In contrast, graphite, the softer, less rigid allotrope of carbon,
o

has a higher S (5.7 J/(mol•K)) due to more disorder (microstates) in the crystal. Soft crystalline substances and those with larger
o

atoms tend to have higher entropies because of increased molecular motion and disorder. Similarly, the absolute entropy of a
substance tends to increase with increasing molecular complexity because the number of available microstates increases with
molecular complexity. For example, compare the S values for CH3OH(l) and CH3CH2OH(l). Finally, substances with strong
o

hydrogen bonds have lower values of S , which reflects a more ordered structure.
o

Entropy increases with softer, less rigid solids, solids that contain larger atoms, and solids
with complex molecular structures.
To calculate ΔS for a chemical reaction from standard molar entropies, we use the familiar “products minus reactants” rule, in
o

which the absolute entropy of each reactant and product is multiplied by its stoichiometric coefficient in the balanced chemical
equation. Example 2.7.1 illustrates this procedure for the combustion of the liquid hydrocarbon isooctane (C H ; 2,2,4- 8 18

trimethylpentane).

 Example 2.7.1

Use the data in Table 2.7.1 to calculate ΔS

o
for the reaction of liquid isooctane with O (g)
2
to give CO (g)
2
and H O(g)
2
at
298 K.
Given: standard molar entropies, reactants, and products
Asked for: ΔS°
Strategy:
Write the balanced chemical equation for the reaction and identify the appropriate quantities in Table 2.7.1. Subtract the sum
of the absolute entropies of the reactants from the sum of the absolute entropies of the products, each multiplied by their
appropriate stoichiometric coefficients, to obtain ΔS for the reaction. o

Solution:
The balanced chemical equation for the complete combustion of isooctane (C 8
H
18
) is as follows:
25
C H (l) + O (g) ⟶ 8 CO (g) + 9 H O(g)
8 18 2 2 2 2

2.7.4 https://chem.libretexts.org/@go/page/46428
We calculate ΔS for the reaction using the “products minus reactants” rule, where m and n are the stoichiometric coefficients
o

of each product and each reactant:

o o o
ΔSrxn = ∑ m S (products) − ∑ nS (reactants)

25
o o o o
= [8 S (C O2 ) + 9 S (H2 O)] − [ S (C8 H18 ) + S (O2 )]
2

= {[8 mol C O2 × 213.8 J/(mol ⋅ K)] + [9 mol H2 O × 188.8 J/(mol ⋅ K)]}

25
− {[1 mol C8 H18 × 329.3 J/(mol ⋅ K)] + [ mol O2 × 205.2 J/(mol ⋅ K)]}
2

= 515.3 J/K

ΔS is positive, as expected for a combustion reaction in which one large hydrocarbon molecule is converted to many
o

molecules of gaseous products.

 Exercise 2.7.1
Use the data in Table 2.7.1 to calculate ΔS
o
for the reaction of H (g)
2
with liquid benzene (C 6
H
6
) to give cyclohexane (
C H
6
) at 298 K.
12

Answer
-361.1 J/K

 Example 2.7.2: Determination of ΔS°

Calculate the standard entropy change for the following process at 298 K:

H O(g) ⟶ H O(l)
2 2

Solution
The value of the standard entropy change at room temperature, ΔS o
298
, is the difference between the standard entropy of the
product, H2O(l), and the standard entropy of the reactant, H2O(g).
o o o
ΔS =S (H O(l)) − S (H O(g))
298 298 2 298 2

−1 −1 −1 −1
= (70.0 J mol K ) − (188.8 Jmol K )

−1 −1
= −118.8 J mol K

The value for ΔS o

298
is negative, as expected for this phase transition (condensation), which the previous section discussed.

 Exercise 2.7.2

Calculate the standard entropy change for the following process at 298 K:

H (g) + C H (g) ⟶ C H (g)

2 2 4 2 6

Answer
−120.6 J mol−1 K−1

 Example 2.7.3: Determination of ΔS°

Calculate the standard entropy change for the combustion of methanol, CH3OH at 298 K:

2 CH OH(l) + 3 O (g) ⟶ 2 CO (g) + 4 H O(l)

3 2 2 2

Solution

2.7.5 https://chem.libretexts.org/@go/page/46428
 The value of the standard entropy change is equal to the difference between the standard entropies of the products and the
entropies of the reactants scaled by their stoichiometric coefficients. The standard entropy of formations are found in Table
2.7.1.

o o
ΔS = ΔS
298

o o
= ∑ νS (products) − ∑ ν S (reactants)
298 298

o o o o
= 2S (CO (g)) + 4 S (H O(l))] − [2 S (CH OH(l)) + 3 S (O (g))]
298 2 298 2 298 3 298 2

= [(2 × 213.8) + (4 × 70.0)] − [(2 × 126.8) + (3 × 205.03)]

= −161.6 J/mol ⋅ K

 Exercise 2.7.3

Calculate the standard entropy change for the following reaction at 298 K:

Ca (OH) (s) ⟶ CaO(s) + H O(l)

2 2

Answer
24.7 J/mol•K

2.7.4: Summary
Energy values, as you know, are all relative, and must be defined on a scale that is completely arbitrary; there is no such thing as
the absolute energy of a substance, so we can arbitrarily define the enthalpy or internal energy of an element in its most stable form
at 298 K and 1 atm pressure as zero. The same is not true of the entropy; since entropy is a measure of the “dilution” of thermal
energy, it follows that the less thermal energy available to spread through a system (that is, the lower the temperature), the smaller
will be its entropy. In other words, as the absolute temperature of a substance approaches zero, so does its entropy. This principle is
the basis of the Third law of thermodynamics, which states that the entropy of a perfectly-ordered solid at 0 K is zero.
In practice, chemists determine the absolute entropy of a substance by measuring the molar heat capacity (C ) as a function of p

temperature and then plotting the quantity C /T versus T . The area under the curve between 0 K and any temperature T is the
p

absolute entropy of the substance at T . In contrast, other thermodynamic properties, such as internal energy and enthalpy, can be
evaluated in only relative terms, not absolute terms.
The second law of thermodynamics states that a spontaneous process increases the entropy of the universe, Suniv > 0. If ΔSuniv < 0,
the process is nonspontaneous, and if ΔSuniv = 0, the system is at equilibrium. The third law of thermodynamics establishes the zero
for entropy as that of a perfect, pure crystalline solid at 0 K. With only one possible microstate, the entropy is zero. We may
compute the standard entropy change for a process by using standard entropy values for the reactants and products involved in the
process.

2.7.5: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook

2.7: The Third Law of Thermodynamics is shared under a CC BY license and was authored, remixed, and/or curated by LibreTexts.

2.7.6 https://chem.libretexts.org/@go/page/46428
2.8: Gibbs Energy
 Learning Objectives
To understand the relationship between Gibbs free energy and work.

One of the major goals of chemical thermodynamics is to establish criteria for predicting whether a particular reaction or process
will occur spontaneously. We have developed one such criterion, the change in entropy of the universe: if ΔS univ> 0 for a process

or a reaction, then the process will occur spontaneously as written. Conversely, if ΔS univ < 0 , a process cannot occur

spontaneously; if ΔS univ = 0 , the system is at equilibrium. The sign of ΔS is a universally applicable and infallible indicator
univ

of the spontaneity of a reaction. Unfortunately, using ΔS univ requires that we calculate ΔS for both a system and its
surroundings. This is not particularly useful for two reasons: we are normally much more interested in the system than in the
surroundings, and it is difficult to make quantitative measurements of the surroundings (i.e., the rest of the universe). A criterion of
spontaneity that is based solely on the state functions of a system would be much more convenient and is provided by a new state
function: the Gibbs free energy.

2.8.1: Gibbs Energy and Spontaneity

The Gibbs energy (also known as the Gibbs function) is defined as

Gsys = Hsys – T Ssys (2.8.1)

in which S refers to the entropy of the system. Since H , T and S are all state functions, so is G. Thus for any change in state, we
can expand Equation 2.8.1 to

ΔGsys = ΔHsys – T ΔSsys (2.8.2)

How does this simple equation relate to the entropy change of the universe ΔS that we know is the sole criterion for
univ

spontaneous change from the second law of thermodynamics? Starting with the definition
ΔSuniv = ΔSsurr + ΔSsys (2.8.3)

we would first like to get rid of ΔS . How can a chemical reaction (a change in the system) affect the entropy of the
surr

surroundings? Because most reactions are either exothermic or endothermic, they are accompanied by heat q across the system
p

boundary (we are considering constant pressure processes). The enthalpy change of the reaction ΔH is the "flow" of heat into
sys

the system from the surroundings under constant pressure, so the heat "withdrawn" from the surroundings will be – q . p

From the thermodynamic definition of entropy, the change of the entropy of the surroundings will be
qp ΔHsys
ΔSsurr =– =– . (2.8.4)
T T

We can therefore rewrite Equation 2.8.3 as

– ΔHsys
ΔSuniv = + ΔSsys (2.8.5)
T

Multiplying through by – T , we obtain

– T ΔSuniv = ΔHsys – T ΔSsys (2.8.6)

which expresses the entropy change of the universe in terms of thermodynamic properties of the system exclusively.
If – T ΔSuniv is denoted by ΔG, then we have Equation 2.8.2 which defines the Gibbs energy change for the process.

2.8.1 https://chem.libretexts.org/@go/page/46429
The criterion for predicting spontaneity is based on (ΔG), the change in G, at constant temperature and pressure. Although very
few chemical reactions actually occur under conditions of constant temperature and pressure, most systems can be brought back to
the initial temperature and pressure without significantly affecting the value of thermodynamic state functions such as G. At
constant temperature and pressure,
ΔG = ΔH − T ΔS (2.8.7)

where all thermodynamic quantities are those of the system. Recall that at constant pressure, ΔH = q , whether a process is
reversible or irreversible, and
T ΔS = qrev . (2.8.8)

Using these expressions, we can reduce Equation 2.8.7 to

ΔG = q − qrev . (2.8.9)

Thus ΔG is the difference between the heat released during a process (via a reversible or an irreversible path) and the heat released
for the same process occurring in a reversible manner. Under the special condition in which a process occurs reversibly, q = q rev

and ΔG = 0 . As we shall soon see, if ΔG is zero, the system is at equilibrium, and there will be no net change.
What about processes for which ΔG ≠ 0 ? To understand how the sign of ΔG for a system determines the direction in which
change is spontaneous, we can rewrite the relationship between ΔS and q , discussed earlier.
rev

qrev
ΔS =
T

with the definition of ΔH in terms of qrev

qrev = ΔH

to obtain
ΔHsys
ΔSsurr = − (2.8.10)
T

Thus the entropy change of the surroundings is related to the enthalpy change of the system. We have stated that for a spontaneous
reaction, ΔS univ> 0 , so substituting we obtain

ΔSuniv = ΔSsys + ΔSsurr > 0

ΔHsys
= ΔSsys − >0
T

Multiplying both sides of the inequality by −T reverses the sign of the inequality; rearranging,

ΔHsys − T ΔSsys < 0 (2.8.11)

which is equal to ΔG (Equation 2.8.7). We can therefore see that for a spontaneous process, ΔG sys <0 .
The relationship between the entropy change of the surroundings and the heat gained or lost by the system provides the key
connection between the thermodynamic properties of the system and the change in entropy of the universe. The relationship shown
in Equation 2.8.7 allows us to predict spontaneity by focusing exclusively on the thermodynamic properties and temperature of the
system. We predict that highly exothermic processes (ΔH ≪ 0 ) that increase the entropy of a system (ΔS ≫ 0 ) would sys

therefore occur spontaneously. An example of such a process is the decomposition of ammonium nitrate fertilizer. Ammonium
nitrate was also used to destroy the Murrah Federal Building in Oklahoma City, Oklahoma, in 1995. For a system at constant
temperature and pressure, we can summarize the following results:
If ΔG < 0 , the process occurs spontaneously.
If ΔG = 0 , the system is at equilibrium.
If ΔG > 0 , the process is not spontaneous as written but occurs spontaneously in the reverse direction.
To further understand how the various components of ΔG dictate whether a process occurs spontaneously, we now look at a simple
and familiar physical change: the conversion of liquid water to water vapor.

2.8.2 https://chem.libretexts.org/@go/page/46429
 Example 2.8.1: Vaporizing Water

At Room Temperature (100 °C)

If the conversion of liquid water to water vapor is carried out at 1 atm and the normal boiling point of 100.00 °C (373.15 K),
we can calculate ΔG from the experimentally measured value of ΔH (40.657 kJ/mol). For vaporizing 1 mol of water,
vap

ΔH = 40, 657; J, so the process is highly endothermic. From the definition of ΔS (Equation 2.8.10), we know that for 1 mol

of water,
ΔHvap
ΔSvap =
Tb

40,657 J
=
373.15 K

= 108.96 J/K

Hence there is an increase in the disorder of the system. At the normal boiling point of water,

ΔG100∘ C = ΔH100∘ C − T ΔS100∘ C

= 40,657 J − [(373.15 K)(108.96 J/K)]

=0 J

The energy required for vaporization offsets the increase in entropy of the system. Thus ΔG = 0 , and the liquid and vapor are
in equilibrium, as is true of any liquid at its boiling point under standard conditions.
Above Room Temperature (110 °C)
Now suppose we were to superheat 1 mol of liquid water to 110°C. The value of ΔG for the vaporization of 1 mol of water at
110°C, assuming that ΔH and ΔS do not change significantly with temperature, becomes
ΔG110∘ C = ΔH − T ΔS

= 40,657 J − [(383.15 K)(108.96 J/K)]

= −1,091 J

Since ΔG < 0 , the vaporization of water is predicted to occur spontaneously and irreversibly at 110 °C.
Below Room Temperature (90 °C)
We can also calculate ΔG for the vaporization of 1 mol of water at a temperature below its normal boiling point—for example,
90°C—making the same assumptions:
ΔG90∘ C = ΔH − T ΔS

= 40,657 J − [(363.15 K)(108.96 J/K)]

= 1,088 J

Since ΔG > 0 , water does not spontaneously convert to water vapor at 90 °C. When using all the digits in the calculator
display in carrying out our calculations, ΔG110°C = 1090 J = −ΔG90°C, as we would predict.
Equilibrium Temperature
We can also calculate the temperature at which liquid water is in equilibrium with water vapor. Inserting the values of ΔH and
ΔS into the definition of ΔG (Equation 2.8.7), setting ΔG = 0 , and solving for T ,

0 = 40, 657 J − T (108.96 J/K)

T = 373.15 K

Thus ΔG = 0 at T = 373.15 K and 1 atm, which indicates that liquid water and water vapor are in equilibrium; this
temperature is called the normal boiling point of water.
At temperatures greater than 373.15 K, ΔG is negative, and water evaporates spontaneously and irreversibly. Below 373.15 K,
ΔG is positive, and water does not evaporate spontaneously. Instead, water vapor at a temperature less than 373.15 K and 1

2.8.3 https://chem.libretexts.org/@go/page/46429
 atm will spontaneously and irreversibly condense to liquid water. Figure 2.8.1 shows how the ΔH and T ΔS terms vary with
temperature for the vaporization of water. When the two lines cross, ΔG = 0 , and ΔH = T ΔS.

ΔGvap = 0
(liquid and vapor phases in equilibrium)
50.00

45.00 ΔHvap ΔGvap < 0

kJ / mol (liquid water
ΔGvap > 0 evaporates)
40.00
(water vapor
condenses)
35.00
TΔSvap

30.00
300 325 350 375 400 425 450
Temperature (K)

Figure 2.8.1 : Temperature Dependence of ΔH and TΔS for the Vaporization of Water. Both ΔH and TΔS are temperature
dependent, but the lines have opposite slopes and cross at 373.15 K at 1 atm, where ΔH = TΔS. Because ΔG = ΔH − TΔS, at
this temperature ΔG = 0, indicating that the liquid and vapor phases are in equilibrium. The normal boiling point of water is
therefore 373.15 K. Above the normal boiling point, the T ΔS term is greater than ΔH, making ΔG < 0; hence, liquid water
evaporates spontaneously. Below the normal boiling point, the ΔH term is greater than T ΔS , making ΔG > 0. Thus liquid
water does not evaporate spontaneously, but water vapor spontaneously condenses to liquid. (CC BY-NC; Ümit Kaya)

A similar situation arises in the conversion of liquid egg white to a solid when an egg is boiled. The major component of egg white
is a protein called albumin, which is held in a compact, ordered structure by a large number of hydrogen bonds. Breaking them
requires an input of energy (ΔH > 0 ), which converts the albumin to a highly disordered structure in which the molecules
aggregate as a disorganized solid (ΔS > 0 ). At temperatures greater than 373 K, the T ΔS term dominates, and ΔG < 0 , so the
conversion of a raw egg to a hard-boiled egg is an irreversible and spontaneous process above 373 K.
Figure 2.8.1
ΔH ΔS −T ΔS ΔG

- + - -
(exothermic) (products more disordered) (favors spontaneity) (spontaneous at all T)

-
(spontaneous) at low T
- - +
+
(exothermic) (products less disordered) (opposes spontaneity)
(non-spontaneous) at high T
"Enthalpically-driven process"
+
(non-spontaneous) at low T
+ + -
-
(endothermic) (products more disordered) (favors spontaneity)
(spontaneous) at high T
"Entropically-driven process"

+ - + +
(endothermic) (products less disordered) (opposes spontaneity) (non-spontaneous at all T)

2.8.2: Enthalpically vs. Entropically Driving Reactions

Some textbooks and teachers say that the free energy, and thus the spontaneity of a reaction, depends on both the enthalpy and
entropy changes of a reaction, and they sometimes even refer to reactions as "energy driven" or "entropy driven" depending on
whether ΔH or the T ΔS term dominates. This is technically correct, but misleading because it disguises the important fact that
ΔS , which this equation expresses in an indirect way, is the only criterion of spontaneous change.
total

2.8.4 https://chem.libretexts.org/@go/page/46429
Consider the following possible states for two different types of molecules with some attractive force:

Entropically favored state q Enthalpically favored state

(assuming some attractive force)

Figure 2.8.2 : An enthalpic favored reaction. (CC BY-NC; Ümit Kaya)

There would appear to be greater entropy on the left (state 1) than on the right (state 2). Thus the entropic change for the reaction as
written (i.e. going to the right) would be (-) in magnitude, and the energetic contribution to the free energy change would be (+)
(i.e. unfavorable) for the reaction as written.
In going to the right, there is an attractive force and the molecules adjacent to each other is a lower energy state (heat energy, q, is
liberated). To go to the left, we have to overcome this attractive force (input heat energy) and the left direction is unfavorable with
regard to heat energy q. The change in enthalpy is (-) in going to the right (q released), and this enthalpy change is negative (-) in
going to the right (and (+) in going to the left). This reaction as written, is therefore, enthalpically favorable and entropically
unfavorable. Hence, It is enthalpically driven.
From Table 2.8.1, it would appear that we might be able to get the reaction to go to the right at low temperatures (lower
temperature would minimize the energetic contribution of the entropic change). Looking at the same process from an opposite
direction:

Enthalpically favored state q Entropically favored state

(assuming some attractive force)

Figure 2.8.3 : An entropically favored reaction. (CC BY-NC; Ümit Kaya)

This reaction as written, is entropically favorable, and enthalpically unfavorable; it is entropically driven. From Table 2.8.1, it
would appear that we might be able to get the reaction to go to the right at high temperatures (high temperature would increase the
energetic contribution of the entropic change).

2.8.3: The Relationship between ΔG and Work

In the previous subsection, we learned that the value of ΔG allows us to predict the spontaneity of a physical or a chemical change.
In addition, the magnitude of ΔG for a process provides other important information. The change in Gibbs energy is equal to the
maximum amount of work that a system can perform on the surroundings while undergoing a spontaneous change (at constant
temperature and pressure):
ΔG = wmax . (2.8.12)

To see why this is true, let’s look again at the relationships among free energy, enthalpy, and entropy expressed in Equation 2.8.7.
We can rearrange this equation as follows:
ΔH = ΔG + T ΔS (2.8.13)

This equation tells us that when energy is released during an exothermic process (ΔH < 0 ), such as during the combustion of a
fuel, some of that energy can be used to do work (ΔG < 0 ), while some is used to increase the entropy of the universe (
T ΔS > 0 ). Only if the process occurs infinitely slowly in a perfectly reversible manner will the entropy of the universe be

unchanged. Because no real system is perfectly reversible, the entropy of the universe increases during all processes that produce
energy. As a result, no process that uses stored energy can ever be 100% efficient; that is, ΔH will never equal ΔG because ΔS
has a positive value.

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One of the major challenges facing engineers is to maximize the efficiency of converting stored energy to useful work or
converting one form of energy to another. As indicated in Table 2.8.2, the efficiencies of various energy-converting devices vary
widely. For example, an internal combustion engine typically uses only 25%–30% of the energy stored in the hydrocarbon fuel to
perform work; the rest of the stored energy is released in an unusable form as heat. In contrast, gas–electric hybrid engines, now
used in several models of automobiles, deliver approximately 50% greater fuel efficiency. A large electrical generator is highly
efficient (approximately 99%) in converting mechanical to electrical energy, but a typical incandescent light bulb is one of the least
efficient devices known (only approximately 5% of the electrical energy is converted to light). In contrast, a mammalian liver cell
is a relatively efficient machine and can use fuels such as glucose with an efficiency of 30%–50%.
Table 2.8.2 : Approximate Thermodynamic Efficiencies of Various Devices
Device Energy Conversion Approximate Efficiency (%)

large electrical generator mechanical → electrical 99

chemical battery chemical → electrical 90

home furnace chemical → heat 65

small electric tool electrical → mechanical 60

space shuttle engine chemical → mechanical 50

mammalian liver cell chemical → chemical 30–50

spinach cell light → chemical 30

internal combustion engine chemical → mechanical 25–30

fluorescent light electrical → light 20

solar cell light → electricity 10

incandescent light bulb electricity → light 5

yeast cell chemical → chemical 2–4

2.8.4: Standard Free-Energy Change

We have seen that there is no way to measure absolute enthalpies, although we can measure changes in enthalpy (ΔH) during a
chemical reaction. Because enthalpy is one of the components of Gibbs free energy, we are consequently unable to measure
absolute free energies; we can measure only changes in free energy. The standard free-energy change (ΔG°) is the change in free
energy when one substance or a set of substances in their standard states is converted to one or more other substances, also in their
standard states. The standard free-energy change can be calculated from the definition of free energy, if the standard enthalpy and
entropy changes are known, using Equation 2.8.14:
ΔG° = ΔH ° − T ΔS° (2.8.14)

If ΔS° and ΔH° for a reaction have the same sign, then the sign of ΔG depends on the relative magnitudes of the ΔH° and TΔS°
o

terms. It is important to recognize that a positive value of ΔG for a reaction does not mean that no products will form if the
o

reactants in their standard states are mixed; it means only that at equilibrium the concentrations of the products will be less than the
concentrations of the reactants.

A positive ΔG means that the equilibrium constant is less than 1.

o

 Example 2.8.1
Calculate the standard free-energy change (ΔG°) at 25°C for the reaction

H (g) + O (g) −
↽⇀
− H O (l)
2 2 2 2

At 25°C, the standard enthalpy change (ΔH°) is −187.78 kJ/mol, and the absolute entropies of the products and reactants are:
S°(H2O2) = 109.6 J/(mol•K),
S°(O2) = 205.2 J/(mol•K), and

2.8.6 https://chem.libretexts.org/@go/page/46429
 S°(H2) = 130.7 J/(mol•K).
Is the reaction spontaneous as written?
Given: balanced chemical equation, ΔH° and S° for reactants and products
Asked for: spontaneity of reaction as written
Strategy:
A. Calculate ΔS° from the absolute molar entropy values given.
B. Use Equation 2.8.14, the calculated value of ΔS°, and other data given to calculate ΔG for the reaction.
o

C. Use the value of ΔG to determine whether the reaction is spontaneous as written.

o

Solution
A To calculate ΔG for the reaction, we need to know ΔH°, ΔS°, and T. We are given ΔH°, and we know that T = 298.15 K.
o

We can calculate ΔS° from the absolute molar entropy values provided using the “products minus reactants” rule:
∘ ∘ ∘ ∘
ΔS =S (H2 O2 ) − [ S (O2 ) + S (H2 )]

= [1 mol H2 O2 × 109.6 J/(mol ⋅ K)]

− {[ 1 mol H2 × 130.7 J/(mol ⋅ K)] + [ 1 mol O2 × 205.2 J/(mol ⋅ K)]}

= −226.3 J/K (per mole of H2 O2 )

As we might expect for a reaction in which 2 mol of gas is converted to 1 mol of a much more ordered liquid, ΔS° is very
negative for this reaction.
B Substituting the appropriate quantities into Equation 2.8.14,
∘ ∘ ∘
ΔG = ΔH − T ΔS

= −187.78 kJ/mol − (298.15 K)[−226.3 J/(mol ⋅ K) × 1 kJ/1000 J]

= −187.78 kJ/mol + 67.47 kJ/mol

= −120.31 kJ/mol

The negative value of ΔG indicates that the reaction is spontaneous as written. Because ΔS° and ΔH° for this reaction have
o

the same sign, the sign of ΔG depends on the relative magnitudes of the ΔH° and TΔS° terms. In this particular case, the
o

enthalpy term dominates, indicating that the strength of the bonds formed in the product more than compensates for the
unfavorable ΔS° term and for the energy needed to break bonds in the reactants.

 Exercise 2.8.1
Calculate the standard free-energy change (ΔG°) at 25°C for the reaction

2 H (g) + N (g) −
↽⇀
− N H (l).
2 2 2 4

At 25°C, the standard enthalpy change (ΔH°) is 50.6 kJ/mol, and the absolute entropies of the products and reactants are S°
(N2H4) = 121.2 J/(mol•K), S°(N2) = 191.6 J/(mol•K), and S°(H2) = 130.7 J/(mol•K). Is the reaction spontaneous as written?

Answer
149.5 kJ/mol; no

Tabulated values of standard free energies of formation allow chemists to calculate the values of ΔG for a wide variety of
o

chemical reactions rather than having to measure them in the laboratory. The standard free energy of formation (ΔG )of a ∘
f

compound is the change in free energy that occurs when 1 mol of a substance in its standard state is formed from the component
elements in their standard states. By definition, the standard free energy of formation of an element in its standard state is zero at
298.15 K. One mole of Cl2 gas at 298.15 K, for example, has ΔG = 0 . The standard free energy of formation of a compound can
∘
f

2.8.7 https://chem.libretexts.org/@go/page/46429
be calculated from the standard enthalpy of formation (ΔH∘f) and the standard entropy of formation (ΔS∘f) using the definition of
free energy:
o o o
ΔG = ΔH − T ΔS (2.8.15)
f f f

Using standard free energies of formation to calculate the standard free energy of a reaction is analogous to calculating standard
enthalpy changes from standard enthalpies of formation using the familiar “products minus reactants” rule:
o o o
ΔGrxn = ∑ mΔG (products) − ∑ nΔG (reactants) (2.8.16)
f f

where m and n are the stoichiometric coefficients of each product and reactant in the balanced chemical equation. A very large
negative ΔG indicates a strong tendency for products to form spontaneously from reactants; it does not, however, necessarily
o

indicate that the reaction will occur rapidly. To make this determination, we need to evaluate the kinetics of the reaction.

 "Products minus Reactants" Rule

The ΔG of a reaction can be calculated from tabulated ΔG values (Table T1) using the “products minus reactants” rule.
o o
f

 Example 2.8.2

Calculate ΔG for the reaction of isooctane with oxygen gas to give carbon dioxide and water. Use the following data:
o

ΔG°f(isooctane) = −353.2 kJ/mol,

ΔG°f(CO2) = −394.4 kJ/mol, and
ΔG°f(H2O) = −237.1 kJ/mol.
Is the reaction spontaneous as written?
Given: balanced chemical equation and values of ΔG°f for isooctane, CO2, and H2O
Asked for: spontaneity of reaction as written
Strategy:
Use the “products minus reactants” rule to obtain ΔG∘rxn, remembering that ΔG°f for an element in its standard state is zero.
From the calculated value, determine whether the reaction is spontaneous as written.

Solution
The balanced chemical equation for the reaction is as follows:
25
C H (l) + O (g) ⟶ 8 CO (g) + 9 H O(l)
8 18 2 2 2 2

We are given ΔG∘f

values for all the products and reactants except O2(g). Because oxygen gas is an element in its standard
state, ΔG∘f (O2) is zero. Using the “products minus reactants” rule,
25
∘ ∘ ∘ ∘ ∘
ΔG = [8ΔG (C O2 ) + 9ΔG (H2 O)] − [1ΔG (C8 H18 ) + ΔG (O2 )]
f f f f
2

= [(8 mol)(−394.4 kJ/mol) + (9 mol)(−237.1 kJ/mol)]

25
− [(1 mol)(−353.2 kJ/mol) + ( mol) (0 kJ/mol)]
2

= −4935.9 kJ (per mol of C8 H18 )

Because ΔG is a large negative number, there is a strong tendency for the spontaneous formation of products from reactants
o

(though not necessarily at a rapid rate). Also notice that the magnitude of ΔG is largely determined by the ΔG∘f of the stable
o

products: water and carbon dioxide.

2.8.8 https://chem.libretexts.org/@go/page/46429
  Exercise 2.8.2
Calculate ΔG for the reaction of benzene with hydrogen gas to give cyclohexane using the following data
o

ΔG∘f(benzene) = 124.5 kJ/mol

ΔG∘f (cyclohexane) = 217.3 kJ/mol.
Is the reaction spontaneous as written?

Answer
92.8 kJ; no

Calculated values of ΔG are extremely useful in predicting whether a reaction will occur spontaneously if the reactants and
o

products are mixed under standard conditions. We should note, however, that very few reactions are actually carried out under
standard conditions, and calculated values of ΔG may not tell us whether a given reaction will occur spontaneously under
o

nonstandard conditions. What determines whether a reaction will occur spontaneously is the free-energy change (ΔG) under the
actual experimental conditions, which are usually different from ΔG°. If the ΔH and TΔS terms for a reaction have the same sign,
for example, then it may be possible to reverse the sign of ΔG by changing the temperature, thereby converting a reaction that is
not thermodynamically spontaneous, having Keq < 1, to one that is, having a Keq > 1, or vice versa. Because ΔH and ΔS usually do
not vary greatly with temperature in the absence of a phase change, we can use tabulated values of ΔH° and ΔS° to calculate ΔG o

at various temperatures, as long as no phase change occurs over the temperature range being considered.

In the absence of a phase change, neither ΔH nor ΔS vary greatly with temperature.

 Example 2.8.3
Calculate (a) ΔG and (b) ΔG300°C for the reaction N2(g)+3H2(g)⇌2NH3(g), assuming that ΔH and ΔS do not change between
o

25°C and 300°C. Use these data:

S°(N2) = 191.6 J/(mol•K),
S°(H2) = 130.7 J/(mol•K),
S°(NH3) = 192.8 J/(mol•K), and
ΔH∘f (NH3) = −45.9 kJ/mol.
Given: balanced chemical equation, temperatures, S° values, and ΔH∘f for NH3
Asked for: ΔG and ΔG at 300°C
o

Strategy:
A. Convert each temperature to kelvins. Then calculate ΔS° for the reaction. Calculate ΔH° for the reaction, recalling that
ΔH∘f for any element in its standard state is zero.
B. Substitute the appropriate values into Equation 2.8.14 to obtain ΔG for the reaction.
o

C. Assuming that ΔH and ΔS are independent of temperature, substitute values into Equation 2.8.7 to obtain ΔG for the
reaction at 300°C.

Solution
A To calculate ΔG for the reaction using Equation 2.8.14, we must know the temperature as well as the values of ΔS° and
o

ΔH°. At standard conditions, the temperature is 25°C, or 298 K. We can calculate ΔS° for the reaction from the absolute molar
entropy values given for the reactants and the products using the “products minus reactants” rule:

2.8.9 https://chem.libretexts.org/@go/page/46429
 ∘ ∘ ∘ ∘
ΔSrxn = 2 S (NH3 ) − [ S (N2 ) + 3 S (H2 )]

= [ 2 mol NH3 × 192.8 J/(mol ⋅ K)]

− {[ 1 mol N2 × 191.6 J/(mol ⋅ K)] + [ 3 mol H2 × 130.7 J/(mol ⋅ K)]}

= −198.1 J/K (per mole of N )

2

We can also calculate ΔH° for the reaction using the “products minus reactants” rule. The value of ΔH∘f (NH3) is given, and
ΔH∘f is zero for both N2 and H2:
∘ ∘ ∘ ∘
ΔHrxn = 2ΔH (NH3 ) − [ΔH (N2 ) + 3ΔH (H2 )]
f f f

= [2 × (−45.9 kJ/mol)] − [(1 × 0 kJ/mol) + (3 × 0 kJ/mol)]

= −91.8 kJ(per mole of N )

2

B Inserting the appropriate values into Equation 2.8.14

∘ ∘ ∘
ΔGrxn = ΔH − T ΔS

= (−91.8 kJ) − (298 K)(−198.1 J/K)(1 kJ/1000 J)

= −32.7 kJ (per mole of N )

2

C To calculate ΔG for this reaction at 300°C, we assume that ΔH and ΔS are independent of temperature (i.e., ΔH300°C = H°
and ΔS300°C = ΔS°) and insert the appropriate temperature (573 K) into Equation 2.8.7:
ΔG300∘ C = ΔH300∘ C − (573 K)(ΔS300∘ C )

∘ ∘
= ΔH − (573 K)ΔS

= (−91.8 kJ) − (573 K)(−198.1 J/K)(1 kJ/1000 J)

= 21.7 kJ (per mole of N )

2

In this example, changing the temperature has a major effect on the thermodynamic spontaneity of the reaction. Under standard
conditions, the reaction of nitrogen and hydrogen gas to produce ammonia is thermodynamically spontaneous, but in practice,
it is too slow to be useful industrially. Increasing the temperature in an attempt to make this reaction occur more rapidly also
changes the thermodynamics by causing the −TΔS° term to dominate, and the reaction is no longer spontaneous at high
temperatures; that is, its Keq is less than one. This is a classic example of the conflict encountered in real systems between
thermodynamics and kinetics, which is often unavoidable.

 Exercise 2.8.3

Calculate
a. ΔG° and
b. ΔG 750°C

for the following reaction

2 NO(g) + O (g) −
↽⇀
− 2 NO (g)
2 2

which is important in the formation of urban smog. Assume that ΔH and ΔS do not change between 25.0°C and 750°C and
use these data:
S°(NO) = 210.8 J/(mol•K),
S°(O2) = 205.2 J/(mol•K),
S°(NO2) = 240.1 J/(mol•K),
ΔH∘f(NO2) = 33.2 kJ/mol, and
ΔH∘f (NO) = 91.3 kJ/mol.

Answer a
−72.5 kJ/mol of O 2

2.8.10 https://chem.libretexts.org/@go/page/46429
 Answer b
33.8 kJ/mol of O 2

The effect of temperature on the spontaneity of a reaction, which is an important factor in the design of an experiment or an
industrial process, depends on the sign and magnitude of both ΔH° and ΔS°. The temperature at which a given reaction is at
equilibrium can be calculated by setting ΔG = 0 in Equation 2.8.14, as illustrated in Example 2.8.4.
o

 Example 2.8.4

As you saw in Example 2.8.3, the reaction of nitrogen and hydrogen gas to produce ammonia is one in which ΔH° and ΔS° are
both negative. Such reactions are predicted to be thermodynamically spontaneous at low temperatures but nonspontaneous at
high temperatures. Use the data in Example 2.8.3 to calculate the temperature at which this reaction changes from spontaneous
to nonspontaneous, assuming that ΔH° and ΔS° are independent of temperature.
Given: ΔH° and ΔS°
Asked for: temperature at which reaction changes from spontaneous to nonspontaneous
Strategy:
Set ΔG equal to zero in Equation 2.8.14 and solve for T, the temperature at which the reaction becomes nonspontaneous.
o

Solution
In Example 2.8.3, we calculated that ΔH° is −91.8 kJ/mol of N2 and ΔS° is −198.1 J/K per mole of N2, corresponding to ΔG o

= −32.7 kJ/mol of N2 at 25°C. Thus the reaction is indeed spontaneous at low temperatures, as expected based on the signs of
ΔH° and ΔS°. The temperature at which the reaction becomes nonspontaneous is found by setting ΔG equal to zero and
o

rearranging Equation 2.8.14 to solve for T:

∘ ∘ ∘
ΔG = ΔH − T ΔS =0

∘ ∘
ΔH = T ΔS

∘
ΔH (−91.8 kJ)(1000 J/kJ)
T = = = 463 K
ΔS ∘ −198.1 J/K

This is a case in which a chemical engineer is severely limited by thermodynamics. Any attempt to increase the rate of reaction
of nitrogen with hydrogen by increasing the temperature will cause reactants to be favored over products above 463 K.

 Exercise 2.8.4
As you found in the exercise in Example 2.8.3, ΔH° and ΔS° are both negative for the reaction of nitric oxide and oxygen to
form nitrogen dioxide. Use those data to calculate the temperature at which this reaction changes from spontaneous to
nonspontaneous.

Answer
792.6 K

2.8.5: Summary
The change in Gibbs free energy, which is based solely on changes in state functions, is the criterion for predicting the
spontaneity of a reaction.
Free-energy change

ΔG = ΔH − T ΔS

Standard free-energy change

2.8.11 https://chem.libretexts.org/@go/page/46429
 ΔG° = ΔH ° − T ΔS°

We can predict whether a reaction will occur spontaneously by combining the entropy, enthalpy, and temperature of a system in a
new state function called Gibbs free energy (G). The change in free energy (ΔG) is the difference between the heat released during
a process and the heat released for the same process occurring in a reversible manner. If a system is at equilibrium, ΔG = 0. If the
process is spontaneous, ΔG < 0. If the process is not spontaneous as written but is spontaneous in the reverse direction, ΔG > 0. At
constant temperature and pressure, ΔG is equal to the maximum amount of work a system can perform on its surroundings while
undergoing a spontaneous change. The standard free-energy change (ΔG°) is the change in free energy when one substance or a set
of substances in their standard states is converted to one or more other substances, also in their standard states. The standard free
energy of formation (ΔG∘f), is the change in free energy that occurs when 1 mol of a substance in its standard state is formed from
the component elements in their standard states. Tabulated values of standard free energies of formation are used to calculate ΔG o

for a reaction.

2.8.6: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Mike Blaber (Florida State University)

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2.E: Principles of Thermodynamics (Exercises)
These are homework exercises to accompany the Textmap created for "Principles of Modern Chemistry" by Oxtoby et al.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here.

2.E.1: Q3
Write detailed calculation down for each question involved in gambling,
a. How many “microstates” are there for the cards that come up from five random cards each from a separate deck?
b. What is the probability of getting 5 queens of hearts?
c. What is the probability of getting any specific hand of five cards?

2.E.2: Q5
Is the above reaction spontaneous under 1 atm and room temperature? If so, what are the driving factors?

3 NO(g) −
↽⇀
− N O(g) + NO (g)
2 2

2.E.3: Q9
For each of the following scenarios predict the system's entropy change whether it is ΔS < 0 , ΔS = 0 , or ΔS > 0 .
a. Increasing the amount of quarters being flipped from 2 to 4.
b. Moving a child from a 30 ft. × 30 ft. room to a 5 ft. × 5 ft. room to play in .
c. Increasing the temperature of a non-ideal polyatomic gas.

2.E.4: Q10
Determine whether the change in entropy for the processes listed down below are positive or negative:
a. condensing of iodine gas into a solid
b. diffusion of an ideal gas

2.E.5: Q11
Osmium melts at 3,027 °C and has an enthalpy change of fusion of 31.0 kJ/mol. Calculate the entropy of fusion of osmium.

2.E.6: Q13
Trouton's Rule is used to estimate the molar enthalpy of vaporization. What is iodine's enthalpy of vaporization if its normal boiling
point is 184.4oC?

2.E.7: Q15
If 0.250 mol Argon is expanded reversibly and isothermally at 400 K in its compressible oven from an initial volume of 12.0 L to a
final volume of 30.0 L, what will the ∆U, q, w, ∆H, and ∆S for the gas?

2.E.8: Q17
Consider this. Exactly 2 moles of ice undergoes three different processes.
I. heated reversibly at atmospheric pressure from temperature X to 0 °C, then
II. melted reversibly at 0 °C. Finally
III. it was heated reversibly at atmospheric pressure up to an unknown temperature Y.
Find temperature X & Y and identify ΔS surr .
Given:
ΔHfus = 6007 J.mol-1
-1 -1
C (ice) = 38 J.K .mol
p

-1 -1
C (water) = 75 J.K .mol
p

-1
ΔS = 12.034 J.K
I

2.E.1 https://chem.libretexts.org/@go/page/69603
 ΔSIII = 136 J.K-1

2.E.9: Q18
Suppose 2 moles of water at standard temperature (25°C) and pressure is spontaneously evaporated by allowing it to fall onto a
nickel plate maintained at 125°C. Calculate ΔS for the water, ΔS for the nickel plate, and ΔS if C
total = 75.4 J/(K.mol)
p( H O)(l)
2

and C = 36.0 J/(K.mol). Take ΔH = 40.68 KJ/mol for water and its boiling point of 100°C.
p( H O)(g)
2
vap

2.E.10: Q19
A 181.49 g sample of lead at 97.0oC initially is added to a coffee cup calorimeter that contains 150.0 g water which is at 24.7oC.
The equilibrium temperature is 29.4oC, assuming that there is no heat lost to the calorimeter or the environment. The molar heat
capacity of lead (Cp(Pb)) is 26.4 J K-1 mol-1 and that of water (Cp(H2O)) is 75.2 J K-1 mol-1. What is ΔS for the lead sample, ΔS
for the water sample, and ΔS for this process?
total

2.E.11: Q20
Copper has a heat capacity of 38.5 J K-1 mol-1, approximately independent of temperature between 0°C to 100°C. Calculate the
enthalpy and entropy change of 5.00 moles of copper as it is cooled at atmospheric pressure from 100°C to 0°C.

2.E.12: Q23
The alkaline earth metals react with oxygen to give the following compounds:

2 Be(g) + O (g) ⟶ 2 BeO(s)

2

2 Mg(g) + O (g) ⟶ 2 MgO(s)

2

2 Ca(g) + O (g) ⟶ 2 CaO(s)

2

Compute ΔS for each reaction, and identify a periodic trend about the entropy.

2.E.13: Q27
Is the entropy change in the reaction positive, negative or zero and why?

CH (g) + 2 O (g) ⟶ CO (g) + 2 H O(l)

4 2 2 2

Hint: You don't need to actually calculate the change in entropy to determine whether the change in entropy is positive or negative.
Think about it conceptually.

2.E.14: Q33
At 25.0°C the reaction below is not spontaneous.

2 H O(g) ⟶ 2 H (g) + O (g)

2 2 2

with ΔG = +228.59 kJ

mol

If the above reaction were coupled with the following nonspontaneous reaction, could it be made to proceed? Why or Why not?

3 H (g) + N (g) −
↽⇀
− 2 NH (g)
2 2 3

with ΔG = −16.48 mol

kJ

2.E.15: Q35A
A reaction at constant temperature and pressure is spontaneous if ΔG < 0 and nonspontaneous if ΔG > 0 . Over what range of
temperatures is each of the following processes spontaneous? Assume that all gases are at a pressure of 1 atm. (Hint: Use Tables T1
to calculate ΔH and ΔS (assumed independent of temperature and equal to ΔH and ΔS , respectively, and then use the
∘ ∘

definition of ΔG).
a. Photosynthesis, a reaction of how plants produce food for themselves and animals, and convert carbon dioxide into water:

2.E.2 https://chem.libretexts.org/@go/page/69603
 6 CO (g) + 6 H O(l) + light ⟶ C H O (s) + 6 O (g)
2 2 6 12 6 2

b. The combustion reaction of propane, found in gas grills and some fireplaces:

C H (g) + 5 O (g) ⟶ 3 CO (g) + 4 H O(l)

3 8 2 2 2

c. Methane burning in O gas.

2

CH (g) + 2 O (g) ⟶ CO (g) + 2 H O(l)

4 2 2 2

2.E.16: Q35B
Over what temperatures are these reactions spontaneous (under constant pressure and temperature)? You may need to use Table 1.
a. S(s, rhombic) + Zn(s) → ZnS(s, sphalerite)
b. 2 Cu(s) + Cl → 2 CuCl(s)
2

c. 4 Al(s) + 3 O (g) → 2 Al O (s)

2 2 3

2.E.17: Q37
Determine if the following reaction is spontaneous at 25°C by evaluating ∆H°rxn, ∆S°rxn and ∆G°rxn.

N H (l) + O (g) ⟶ N (g) + 2 H O(l)

2 4 2 2 2

2.E.18: Q39
A thermodynamic engine operates cyclically and reversibly between two temperatures reservoirs, absorbing heat from the high-
temperature bath at 600 K and discarding heat to low-temperature bath at 300 K.
a. What is the thermodynamic efficiency of the engine?
b. How much heat is absorbed from the high-temperature bath if -1800 J of heat is discarded to the low-temperature bath during
each cycle?
c. How much work does the engine perform in one cycle of operation?

2.E.19: Q41
Acetone (C H O ) is an volatile liquid with a normal boiling point of 56°C and a molar enthalpy of vaporization of 29.1 kJ mol-1.
3 6

What is the molar entropy of vaporization of acetone under 1 atm of pressure?

2.E.20: Q53
Under standard conditions and 25°C, you have this reversible process

Sn(s, white) ⟶ Sn(s, gray)

a. Is the change in entropy (ΔS ) for this reaction positive or negative? Calculate the change in entropy using Table T1.
b. Calculate (ΔS ) for the reaction if ΔH for this reaction is -2.1 kJ/mol.

2.E.21: Q59
Compute the ΔG for the following reaction the reaction. The
∘
f
ΔG
∘
f
of H2SO3 (aq) is -537.81 kJ mol-1, the ΔG
∘
f
of SO2 (g) is
-300.19 kJ mol-1, and the ΔG of H2O (g) is -120.42 kJ mol-1.
∘
f

H SO (aq) ⟶ H O(g) + SO (g)

2 3 2 2

2.E.22: Q61
Professor Nesral wants to create some water through the combustion of hydrogen. This reaction is depicted as follows:

2 H (g) + O (g) ⟶ 2 H O(g)

2 2 2

Is this reaction spontaneous? Prove it by calculating ΔG at 298.15K. Suppose that Nesral asks his friend in El Azizia, Libya,
∘

where the temperature is around 57 C (330K), to perform the same reaction. Calculate the Gibbs energy for this value and
∘

compare it to ΔG . ∘

2.E.3 https://chem.libretexts.org/@go/page/69603
Relevant Information:
J
Entropy Values (S ;∘
)
mol K

Hydrogen: 130.6
Water: 188.7
Oxygen: 205.6
kJ
Enthalpy Values(H ; ∘
)
mol

ΔH
∘
f
Water: −241.826

2.E.23: Q63A
The concentration of sodium in the plasma is approximately 0.14 M. While in the fluid outside of the plasma, sodium concentration
is about 0.5 M.
a. In what direction will the sodium ions spontaneously move past the cell wall?
b. The spontaneous process of movement in part a is called "passive transport". Movement in the opposite direction is called
"active transport" and requires work to happen. Calculate the amount of free energy required to move 5 moles of Na+ by active
transport (non-spontaneous direction) at 273 K.

2.E.24: Q63B
For a hypothetical nerve cell, the sodium ion concentration is 0.015 M outside the cell and 0.00045 M inside the cell. Active
transport involves using proteins and chemical energy stored in ATP to move the ions in a thermodynamically unfavorable
direction. Assuming that conditions in the cell allow the hydrolysis of a single ATP molecule to give 2.05×10-18 J of usable enegy.
How many molecules of ATP would be needed to move 0.005 moles of sodium ions using active transport at standard conditions?
You can assume that the sodium ion concentrations remain constant.

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 SECTION OVERVIEW

Unit II: Physical Equilibria

Macroscopic quantities of matter can exist in only one of three states: Gas, Liquid or Solid. The following are not states of matter:
electricity, gels, powders, plasmas, supercritical fluids or your mother's apple pie. Only two aspects determine the state of matter
for a specific system/chemical: 1) The (intermolecular) forces within the sample and 2) the conditions outside the sample (e.g.
temperature, pressure etc).

III: Solids, Liquids, and Phase Transitions

3.1: Bulk Properties of Gases, Liquids, and Solids - Molecular Interpretation
3.2: Intermolecular Forces - Origins in Molecular Structure
3.3: Intermolecular Forces in Liquids
3.4: Phase Equilibrium
3.5: Phase Transitions
3.6: Phase Diagrams
3.7: Clausius-Clapeyron Equation
3.8: The Solid State
3.9: Bonding in Metals
3.E: Solids, Liquids, and Phase Transitions (Exercises)

IV: Solutions
4.0: Types of Solutions - Some Terminology
4.1: Composition of Solutions
4.2: Nature of Dissolved Species
4.3: Phase Equilibrium in Solutions - Nonvolatile Solutes
4.4: Phase Equilibrium in Solutions - Volatile Solutes
4.5: Separating Volatile Solutions - Distillation
4.6: Colloidal Suspensions
4.E: Solutions (Exercises)

Unit II: Physical Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
 CHAPTER OVERVIEW

III: Solids, Liquids, and Phase Transitions

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

3.1: Bulk Properties of Gases, Liquids, and Solids - Molecular Interpretation

3.2: Intermolecular Forces - Origins in Molecular Structure
3.3: Intermolecular Forces in Liquids
3.4: Phase Equilibrium
3.5: Phase Transitions
3.6: Phase Diagrams
3.7: Clausius-Clapeyron Equation
3.8: The Solid State
3.9: Bonding in Metals
3.E: Solids, Liquids, and Phase Transitions (Exercises)

This page titled III: Solids, Liquids, and Phase Transitions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by Delmar Larsen.

1
3.1: Bulk Properties of Gases, Liquids, and Solids - Molecular Interpretation
 Learning Objectives
To describe the unique properties of liquids.
To know how and why the vapor pressure of a liquid varies with temperature.
To understand that the equilibrium vapor pressure of a liquid depends on the temperature and the intermolecular forces
present.

Although you have been introduced to some of the interactions that hold molecules together in a liquid, we have not yet discussed
the consequences of those interactions for the bulk properties of liquids. We now turn our attention to four unique properties of
liquids that intimately depend on the nature of intermolecular interactions:
1. surface tension,
2. capillary action,
3. viscosity, and
4. boiling point.

3.1.1: Surface Tension

If liquids tend to adopt the shapes of their containers, then why do small amounts of water on a freshly waxed car form raised
droplets instead of forming a thin, continuous film? The answer lies in a property called surface tension, which depends on
intermolecular forces. Surface tension is the energy required to increase the surface area of a liquid by a unit amount and varies
greatly from liquid to liquid based on the nature of the intermolecular forces, e.g., water with hydrogen bonds has a surface tension
of 7.29 × 10 J/m (at 20°C), while mercury with metallic (electrostatic) bonds has as surface tension that is 6.5-times greater:
−2 2

J/ m (at 20°C).
−1 2
4.86 × 10

Figure 3.1.1 presents a microscopic view of a liquid droplet. A typical molecule in the interior of the droplet is surrounded by other
molecules that exert attractive forces from all directions. Consequently, there is no net force on the molecule that would cause it to
move in a particular direction. In contrast, a molecule on the surface experiences a net attraction toward the drop because there are
no molecules on the outside to balance the forces exerted by adjacent molecules in the interior. Because a sphere has the smallest
possible surface area for a given volume, intermolecular attractive interactions between water molecules cause the droplet to adopt
a spherical shape. This maximizes the number of attractive interactions and minimizes the number of water molecules at the
surface. Hence raindrops are almost spherical, and drops of water on a waxed (nonpolar) surface, which does not interact strongly
with water, form round beads. A dirty car is covered with a mixture of substances, some of which are polar. Attractive interactions
between the polar substances and water cause the water to spread out into a thin film instead of forming beads.

Figure 3.1.1 : A Representation of Surface Tension in a Liquid. Molecules at the surface of water experience a net attraction to
other molecules in the liquid, which holds the surface of the bulk sample together. In contrast, those in the interior experience
uniform attractive forces. (CC BY-SA-NC; anonymous)
The same phenomenon holds molecules together at the surface of a bulk sample of water, almost as if they formed a skin. When
filling a glass with water, the glass can be overfilled so that the level of the liquid actually extends above the rim. Similarly, a
sewing needle or a paper clip can be placed on the surface of a glass of water where it “floats,” even though steel is much denser

3.1.1 https://chem.libretexts.org/@go/page/43103
than water. Many insects take advantage of this property to walk on the surface of puddles or ponds without sinking. This is better
demonstrated in the zero-gravity conditions of space (Figure 3.1.2).

Wringing out Water on the ISS - for Scie…

Scie…

Figure 3.1.2 : The Effects of the High Surface Tension of Liquid Water. The Full video can be found at https://youtu.be/o8TssbmY-
GM.
Such phenomena are manifestations of surface tension, which is defined as the energy required to increase the surface area of a
liquid by a specific amount. Surface tension is therefore measured as energy per unit area, such as joules per square meter (J/m2).
The values of the surface tension of some representative liquids are listed in Table 3.1.2. Note the correlation between the surface
tension of a liquid and the strength of the intermolecular forces: the stronger the intermolecular forces, the higher the surface
tension. For example, water, with its strong intermolecular hydrogen bonding, has one of the highest surface tension values of any
liquid, whereas low-boiling-point organic molecules, which have relatively weak intermolecular forces, have much lower surface
tensions. Mercury is an apparent anomaly, but its very high surface tension is due to the presence of strong metallic bonding.
Table 3.1.2 : Surface Tension, Viscosity, Vapor Pressure (at 25°C Unless Otherwise Indicated), and Normal Boiling Points of Common
Liquids
Surface Tension (× 10−3
Substance Viscosity (mPa•s) Vapor Pressure (mmHg) Normal Boiling Point (°C)
J/m2)

Organic Compounds

diethyl ether 17 0.22 531 34.6

n-hexane 18 0.30 149 68.7

acetone 23 0.31 227 56.5

ethanol 22 1.07 59 78.3

ethylene glycol 48 16.1 ~0.08 198.9

Liquid Elements

bromine 41 0.94 218 58.8

mercury 486 1.53 0.0020 357

Water

0°C 75.6 1.79 4.6 —

20°C 72.8 1.00 17.5 —

60°C 66.2 0.47 149 —

100°C 58.9 0.28 760 —

Adding soaps and detergents that disrupt the intermolecular attractions between adjacent water molecules can reduce the surface
tension of water. Because they affect the surface properties of a liquid, soaps and detergents are called surface-active agents, or
surfactants. In the 1960s, US Navy researchers developed a method of fighting fires aboard aircraft carriers using “foams,” which
are aqueous solutions of fluorinated surfactants. The surfactants reduce the surface tension of water below that of fuel, so the

3.1.2 https://chem.libretexts.org/@go/page/43103
fluorinated solution is able to spread across the burning surface and extinguish the fire. Such foams are now used universally to
fight large-scale fires of organic liquids.

 Surface Energies and Surface Tension

Any material - solid, liquid or (non-ideal) gas - wants to bond to itself. This is why condensed phase materials "sticks" together
in the first place. However, a surface disrupts this bonding, and so incurs an energy penalty. This is why liquids in zero gravity
ball up into spherical drops (Figure 3.1.2) - the sphere is the shape with the lowest surface area for a fixed volume. We can
describe this surface energy with dimensions of energy per unit area, which is the amount of extra energy needed to create new
surface or extend a surface (e.g., cracking a solid or parting a liquid). Hence, surface tension is typically given in J/m2 units
(Table 3.1.2).

3.1.2: Capillary Action

Intermolecular forces also cause a phenomenon called capillary action, which is the tendency of a polar liquid to rise against
gravity into a small-diameter tube (a capillary), as shown in Figure 3.1.3. When a glass capillary is put into a dish of water, water
is drawn up into the tube. The height to which the water rises depends on the diameter of the tube and the temperature of the water
but not on the angle at which the tube enters the water. The smaller the diameter, the higher the liquid rises. The height of the water
does not depend on the angle at which the capillary is tilted.

Figure 3.1.3 : The Phenomenon of Capillary Action. Capillary action seen as water climbs to different levels in glass tubes of
different diameters. (Dr. Clay Robinson, PhD, West Texas A&M University)
Capillary action is the net result of two opposing sets of forces: cohesive forces, which are the intermolecular forces that hold a
liquid together, and adhesive forces, which are the attractive forces between a liquid and the substance that composes the capillary.

Cohesive forces bind molecules of the same type together

Adhesive forces bind a substance to a surface

Water has both strong adhesion to glass, which contains polar SiOH groups, and strong intermolecular cohesion. When a glass
capillary is put into water, the surface tension due to cohesive forces constricts the surface area of water within the tube, while
adhesion between the water and the glass creates an upward force that maximizes the amount of glass surface in contact with the
water. If the adhesive forces are stronger than the cohesive forces, as is the case for water, then the liquid in the capillary rises to
the level where the downward force of gravity exactly balances this upward force. If, however, the cohesive forces are stronger
than the adhesive forces, as is the case for mercury and glass, the liquid pulls itself down into the capillary below the surface of the
bulk liquid to minimize contact with the glass (part (a) in Figure 3.1.4). The upper surface of a liquid in a tube is called the
meniscus, and the shape of the meniscus depends on the relative strengths of the cohesive and adhesive forces. In liquids such as
water, the meniscus is concave; in liquids such as mercury, however, which have very strong cohesive forces and weak adhesion to
glass, the meniscus is convex (Figure 3.1.4b).

3.1.3 https://chem.libretexts.org/@go/page/43103
 Figure 3.1.4 : The Phenomenon of Capillary Action. Capillary action of water compared to mercury, in each case with respect to a
polar surface such as glass. (a) This drawing illustrates the shape of the meniscus and the relative height of a mercury column when
a glass capillary is put into liquid mercury. The meniscus is convex and the surface of the liquid inside the tube is lower than the
level of the liquid outside the tube. (b) Because water adheres strongly to the polar surface of glass, it has a concave meniscus,
whereas mercury, which does not adhere to the glass, has a convex meniscus. (CC BY-SA 3.0; MesserWoland via Wikipedia)
Fluids and nutrients are transported up the stems of plants or the trunks of trees by capillary action. Plants contain tiny rigid tubes
composed of cellulose, to which water has strong adhesion. Because of the strong adhesive forces, nutrients can be transported
from the roots to the tops of trees that are more than 50 m tall. Cotton towels are also made of cellulose; they absorb water because
the tiny tubes act like capillaries and “wick” the water away from your skin. The moisture is absorbed by the entire fabric, not just
the layer in contact with your body.

Polar substances are drawn up a glass capillary and generally have concave meniscuses
and nonpolar substances general avoid the capillary and exhibit convex meniscuses.

3.1.3: Viscosity
Viscosity (η) is the resistance of a liquid to flow. Some liquids, such as gasoline, ethanol, and water, flow very readily and hence
have a low viscosity. Others, such as motor oil, molasses, and maple syrup, flow very slowly and have a high viscosity. The two
most common methods for evaluating the viscosity of a liquid are
1. to measure the time it takes for a quantity of liquid to flow through a narrow vertical tube and
2. to measure the time it takes steel balls to fall through a given volume of the liquid.
The higher the viscosity, the slower the liquid flows through the tube and the steel balls fall. Viscosity is expressed in units of the
poise (mPa•s); the higher the number, the higher the viscosity. The viscosities of some representative liquids are listed in Table
3.1.1 and show a correlation between viscosity and intermolecular forces. Because a liquid can flow only if the molecules can

move past one another with minimal resistance, strong intermolecular attractive forces make it more difficult for molecules to
move with respect to one another. The addition of a second hydroxyl group to ethanol, for example, which produces ethylene
glycol (HOCH2CH2OH), increases the viscosity 15-fold. This effect is due to the increased number of hydrogen bonds that can
form between hydroxyl groups in adjacent molecules, resulting in dramatically stronger intermolecular attractive forces.

Comparison of structures of ethanol (left) with ethylene glycol (right). (CC BY-SA-NC; anonymous)
There is also a correlation between viscosity and molecular shape. Liquids consisting of long, flexible molecules tend to have
higher viscosities than those composed of more spherical or shorter-chain molecules. The longer the molecules, the easier it is for

3.1.4 https://chem.libretexts.org/@go/page/43103
them to become “tangled” with one another, making it more difficult for them to move past one another. London dispersion forces
also increase with chain length. Due to a combination of these two effects, long-chain hydrocarbons (such as motor oils) are highly
viscous.

Viscosity increases as intermolecular interactions or molecular size increases.

 Application: Motor Oils

Motor oils and other lubricants demonstrate the practical importance of controlling viscosity. The oil in an automobile engine
must effectively lubricate under a wide range of conditions, from subzero starting temperatures to the 200°C that oil can reach
in an engine in the heat of the Mojave Desert in August. Viscosity decreases rapidly with increasing temperatures because the
kinetic energy of the molecules increases, and higher kinetic energy enables the molecules to overcome the attractive forces
that prevent the liquid from flowing (Table 3.1.3). As a result, an oil that is thin enough to be a good lubricant in a cold engine
will become too “thin” (have too low a viscosity) to be effective at high temperatures.

Oil viscosity in severe frost

Viscosity of motor Oils. youtu.be/V5a4kP-5Jiw

The viscosity of motor oils is described by an SAE (Society of Automotive Engineers) rating ranging from SAE 5 to SAE 50 for
engine oils: the lower the number, the lower the viscosity. So-called single-grade oils can cause major problems. If they are viscous
enough to work at high operating temperatures (SAE 50, for example), then at low temperatures, they can be so viscous that a car is
difficult to start or an engine is not properly lubricated. Consequently, most modern oils are multigrade, with designations such as
SAE 20W/50 (a grade used in high-performance sports cars), in which case the oil has the viscosity of an SAE 20 oil at subzero
temperatures (hence the W for winter) and the viscosity of an SAE 50 oil at high temperatures. These properties are achieved by a
careful blend of additives that modulate the intermolecular interactions in the oil, thereby controlling the temperature dependence
of the viscosity. Many of the commercially available oil additives “for improved engine performance” are highly viscous materials
that increase the viscosity and effective SAE rating of the oil, but overusing these additives can cause the same problems
experienced with highly viscous single-grade oils.
Table 3.1.3 : Dynamic Viscosity (N s/m2)
Temperature (oC)
SAE
0 20 50 100

10 0.31 0.079 0.020 0.005

20 0.72 0.170 0.033 0.007

30 1.53 0.310 0.061 0.010

40 2.61 0.430 0.072 0.012

3.1.5 https://chem.libretexts.org/@go/page/43103
 Temperature (oC)
SAE
0 20 50 100

50 3.82 0.630 0.097 0.015

 Example 3.1.1

Based on the nature and strength of the intermolecular cohesive forces and the probable nature of the liquid–glass adhesive
forces, predict what will happen when a glass capillary is put into a beaker of SAE 20 motor oil. Will the oil be pulled up into
the tube by capillary action or pushed down below the surface of the liquid in the beaker? What will be the shape of the
meniscus (convex or concave)? (Hint: the surface of glass is lined with Si–OH groups.)
Given: substance and composition of the glass surface
Asked for: behavior of oil and the shape of meniscus
Strategy:
A. Identify the cohesive forces in the motor oil.
B. Determine whether the forces interact with the surface of glass. From the strength of this interaction, predict the behavior of
the oil and the shape of the meniscus.
Solution:
A Motor oil is a nonpolar liquid consisting largely of hydrocarbon chains. The cohesive forces responsible for its high boiling
point are almost solely London dispersion forces between the hydrocarbon chains.
B Such a liquid cannot form strong interactions with the polar Si–OH groups of glass, so the surface of the oil inside the
capillary will be lower than the level of the liquid in the beaker. The oil will have a convex meniscus similar to that of mercury.

 Exercise 3.1.1

Predict what will happen when a glass capillary is put into a beaker of ethylene glycol. Will the ethylene glycol be pulled up
into the tube by capillary action or pushed down below the surface of the liquid in the beaker? What will be the shape of the
meniscus (convex or concave)?

Answer
Capillary action will pull the ethylene glycol up into the capillary. The meniscus will be concave.

 Oddity of Science: Superfluid Helium-4

Superfluid helium-4 is the superfluid form of helium-4, an isotope of the element helium. A superfluid is a state of matter in
which the matter behaves like a fluid with zero viscosity. The substance, which looks like a normal liquid, flows without
friction past any surface, which allows it to continue to circulate over obstructions and through pores in containers which hold
it, subject only to its own inertia.

The liquid helium is in the superfluid phase. A thin invisible film creeps up the inside wall of the cup and down on the outside.
A drop forms. It will fall off into the liquid helium below. This will repeat until the cup is empty - provided the liquid remains
superfluid. (Public Domain; Alfred Leitner).

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 Many ordinary fluids, like alcohol or petroleum, creep up solid walls, driven by their surface tension. However, in the case of
superfluid helium-4, the flow of the liquid in the layer is not restricted by its viscosity but by a critical velocity which is about
20 cm/s. This is a fairly high velocity so superfluid helium can flow relatively easily up the wall of containers, over the top,
and down to the same level as the surface of the liquid inside the container. In a container, lifted above the liquid level, it forms
visible droplets as seen above.

3.1.4: Boiling Points

The vapor pressure of a liquid is defined as the pressure exerted by a vapor in equilibrium with its condensed phases (solid or
liquid) at a given temperature in a closed system (discussed in more detail in next Sections of Chapter). As the temperature of a
liquid increases, the vapor pressure of the liquid increases until it equals the external pressure, or the atmospheric pressure in the
case of an open container. Bubbles of vapor begin to form throughout the liquid, and the liquid begins to boil. The temperature at
which a liquid boils at exactly 1 atm pressure is the normal boiling point of the liquid. For water, the normal boiling point is exactly
100°C. The normal boiling points of the other liquids in Figure 3.1.8 are represented by the points at which the vapor pressure
curves cross the line corresponding to a pressure of 1 atm.

Figure 3.1.8 : The Vapor Pressures of Several Liquids as a Function of Temperature. The point at which the vapor pressure curve
crosses the P = 1 atm line (dashed) is the normal boiling point of the liquid. (CC BY-SA-NC; anonymous)
Although we usually cite the normal boiling point of a liquid, the actual boiling point depends on the pressure. At a pressure
greater than 1 atm, water boils at a temperature greater than 100°C because the increased pressure forces vapor molecules above
the surface to condense. Hence the molecules must have greater kinetic energy to escape from the surface. Conversely, at pressures
less than 1 atm, water boils below 100°C.
Table 3.1.4 : The Boiling Points of Water at Various Locations on Earth
Place Altitude above Sea Level (ft) Atmospheric Pressure (mmHg) Boiling Point of Water (°C)

Mt. Everest, Nepal/Tibet 29,028 240 70

Bogota, Colombia 11,490 495 88

Denver, Colorado 5280 633 95

Washington, DC 25 759 100

Dead Sea, Israel/Jordan −1312 799 101.4

Typical variations in atmospheric pressure at sea level are relatively small, causing only minor changes in the boiling point of
water. For example, the highest recorded atmospheric pressure at sea level is 813 mmHg, recorded during a Siberian winter; the
lowest sea-level pressure ever measured was 658 mmHg in a Pacific typhoon. At these pressures, the boiling point of water
changes minimally, to 102°C and 96°C, respectively. At high altitudes, on the other hand, the dependence of the boiling point of
water on pressure becomes significant. Table 3.1.4 lists the boiling points of water at several locations with different altitudes. At
an elevation of only 5000 ft, for example, the boiling point of water is already lower than the lowest ever recorded at sea level. The

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lower boiling point of water has major consequences for cooking everything from soft-boiled eggs (a “three-minute egg” may well
take four or more minutes in the Rockies and even longer in the Himalayas) to cakes (cake mixes are often sold with separate high-
altitude instructions). Conversely, pressure cookers, which have a seal that allows the pressure inside them to exceed 1 atm, are
used to cook food more rapidly by raising the boiling point of water and thus the temperature at which the food is being cooked.

As pressure increases, the boiling point of a liquid increases and vice versa.

 Example 3.1.2: Boiling Mercury

Use Figure 3.1.8 to estimate the following.
a. the boiling point of water in a pressure cooker operating at 1000 mmHg
b. the pressure required for mercury to boil at 250°C

What does the LIQUID METAL Mercur

Mercur…
…

Mercury boils at 356 °C at room pressure. To see video go to www.youtube.com/watch?v=0iizsbXWYoo

Given: data in Figure 3.1.8, pressure, and boiling point
Asked for: corresponding boiling point and pressure
Strategy:
A. To estimate the boiling point of water at 1000 mmHg, refer to Figure 3.1.8 and find the point where the vapor pressure curve of
water intersects the line corresponding to a pressure of 1000 mmHg.
B. To estimate the pressure required for mercury to boil at 250°C, find the point where the vapor pressure curve of mercury
intersects the line corresponding to a temperature of 250°C.
Solution:
a. The vapor pressure curve of water intersects the P = 1000 mmHg line at about 110°C; this is therefore the boiling point of water
at 1000 mmHg.
b. The vertical line corresponding to 250°C intersects the vapor pressure curve of mercury at P ≈ 75 mmHg. Hence this is the
pressure required for mercury to boil at 250°C.

 Exercise 3.1.2: Boiling Ethylene Glycol

Ethylene glycol is an organic compound primarily used as a raw material in the manufacture of polyester fibers and fabric
industry, and polyethylene terephthalate resins (PET) used in bottling. Use the data in Figure 3.1.8 to estimate the following.
a. the normal boiling point of ethylene glycol
b. the pressure required for diethyl ether to boil at 20°C.

Answer a
200°C
Answer b

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 450 mmHg

3.1.5: Summary
Surface tension, capillary action, boiling points, and viscosity are unique properties of liquids that depend on the nature of
intermolecular interactions. Surface tension is the energy required to increase the surface area of a liquid by a given amount. The
stronger the intermolecular interactions, the greater the surface tension. Surfactants are molecules, such as soaps and detergents,
that reduce the surface tension of polar liquids like water. Capillary action is the phenomenon in which liquids rise up into a
narrow tube called a capillary. It results when cohesive forces, the intermolecular forces in the liquid, are weaker than adhesive
forces, the attraction between a liquid and the surface of the capillary. The shape of the meniscus, the upper surface of a liquid in a
tube, also reflects the balance between adhesive and cohesive forces. The viscosity of a liquid is its resistance to flow. Liquids that
have strong intermolecular forces tend to have high viscosities. The boiling point of a liquid is the temperature when the vapor
pressure of the liquid equals the external pressure, or the atmospheric pressure in the case of an open container.

3.1.6: Contributors and Attributions

Modified by Joshua Halpern (Howard University)

This page titled 3.1: Bulk Properties of Gases, Liquids, and Solids - Molecular Interpretation is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by Delmar Larsen.

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3.2: Intermolecular Forces - Origins in Molecular Structure
 Learning Objectives
To describe the intermolecular forces in liquids.

The properties of liquids are intermediate between those of gases and solids, but are more similar to solids. In contrast to
intramolecular forces, such as the covalent bonds that hold atoms together in molecules and polyatomic ions, intermolecular forces
hold molecules together in a liquid or solid. Intermolecular forces are generally much weaker than covalent bonds. For example, it
requires 927 kJ to overcome the intramolecular forces and break both O–H bonds in 1 mol of water, but it takes only about 41 kJ to
overcome the intermolecular attractions and convert 1 mol of liquid water to water vapor at 100°C. (Despite this seemingly low
value, the intermolecular forces in liquid water are among the strongest such forces known!) Given the large difference in the
strengths of intra- and intermolecular forces, changes between the solid, liquid, and gaseous states almost invariably occur for
molecular substances without breaking covalent bonds.

The properties of liquids are intermediate between those of gases and solids but are more similar to solids.

Intermolecular forces determine bulk properties such as the melting points of solids and the boiling points of liquids. Liquids boil
when the molecules have enough thermal energy to overcome the intermolecular attractive forces that hold them together, thereby
forming bubbles of vapor within the liquid. Similarly, solids melt when the molecules acquire enough thermal energy to overcome
the intermolecular forces that lock them into place in the solid.

3.2.1: Coulombic Interactions

Through various experiments, Charles Augustin de Coulomb found a way to explain the interactions between charged particles,
which in turn helped to explain where the stabilities and instabilities of various particles come from. While the entities that hold
atoms together within a molecule can be attributed to bonds, the forces that create these bonds can be explained by Coulomb
Forces. Thus, the physical basis behind the bonding of two atoms can be explained.
Coulomb’s findings indicate that like charges repel each other and unlike charges attract one another. Thus electrons, which are
negatively charged, repel each other but attract protons. Likewise, protons repel each other.

FQ-q Fq-Q
+q +Q

FQ-q Fq-Q
+q -Q

The absolute value of the force F between two point charges q and Q relates to the distance between the point charges and to the
simple product of their charges. The diagram shows that like charges repel each other, and opposite charges attract each other. (CC
BY-NC; Ümit Kaya)
Each atom is made up of a nucleus in the center, which consists of a number of protons and neutrons, depending upon the element
in question. Surrounding the nucleus are electrons that float around the nucleus in what can be thought of as a cloud. As two atoms
approach one another, the protons of one atom attract the electrons of the other atom. Similarly, the protons of the other atom attract
the electrons of the first atom. As a result, the simultaneous attraction of the components from one atom to another create a bond.
This interaction can be summarized mathematically and is known as Coulombic forces:
q1 q2
F =k (3.2.1)
2
r

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In this mathematical representation of Coulomb's observations,
F is the electrical force acting between two atoms
with q and q representing the magnitude of the charges of each atom,
1 2

r is the distance between the two atoms.

and k is a constant.
From Equation 3.2.1, the electrostatic force between two charges is inversely proportional to the square of the distance separating
the two atoms.

3.2.2: Ion–Ion Interactions

The interactions between ions (ion - ion interactions or charge-charge interactions) are the easiest to understand since such
interactions are just a simple application of Coulombic forces (Equation 3.2.1). This specific interaction operates over relatively
long distances in the gas phase and is responsible for the attraction of opposite charge ions and the repulsion of like charged ions.

+
Na F-
H H

230 pm 74 pm
670 kJ 435 kJ

Figure 3.2.1 : Ion-Ion attraction in NaF (left) exceeds the covalent bond energy of H (right). (CC BY-NC; Ümit Kaya)
2

Coulombic forces are also involved in all forms of chemical bonding; when they act between separate charged particles they are
especially strong. Thus the energy required to pull a mole of Na and F ions apart in the sodium fluoride crystal is greater than
+ –

that needed to break the a covalent bonds of a mole of H . The effects of ion-ion attraction are seen most directly in salts such as
2

NaF and NaCl that consist of oppositely-charged ions arranged in inter-penetrating crystal lattices.

According to Coulomb's Law the force between two charged particles is given by
q1 q2
F = (3.2.2)
4πϵ0 r2

ion-ion Force

Instead of using SI units, chemists often prefer to express atomic-scale distances in picometers and charges as electron charge (±1,
±2, etc.) Using these units, the proportionality constant 1/4πϵ works out to 2.31 × 10 J pm . The sign of F determines whether
16

the force will be attractive (–) or repulsive (+); notice that the latter is the case whenever the two q's have the same sign. Two
oppositely-charged particles flying about in a vacuum will be attracted toward each other, and the force becomes stronger and
stronger as they approach until eventually they will stick together and a considerable amount of energy will be required to separate
them.

Figure 3.2.2 : Ion - Ion Interactions in the Gas Phase. (Gary L. Bertrand).
They form an ion-pair, a new particle which has a positively-charged area and a negatively-charged area. There are fairly strong
interactions between these ion pairs and free ions, so that these clusters tend to grow, and they will eventually fall out of the gas
phase as a liquid or solid (depending on the temperature).

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 Equation 3.2.2 is an example of an inverse square law; the force falls off as the square of the distance. A similar law governs
the manner in which the illumination falls off as you move away from a point light source; recall this the next time you walk
away from a street light at night, and you will have some feeling for what an inverse square law means.

The stronger the attractive force acting between two particles, the greater the amount of work required to separate them. Work
represents a flow of energy, so the foregoing statement is another way of saying that when two particles move in response to a
force, their potential energy is lowered. This work is found by integrating the negative of the force function with respect to distance
over the distance moved. Thus the energy that must be supplied in order to completely separate two oppositely-charged particles
initially at a distance r is given by
0

∞
q1 q2 q1 q2
w = −∫ dr = − (3.2.3)
2
ro 4πϵ0 r 4πϵ0 ro

hence, the potential (Vion−ion ) responsible for the ion-ion force is

q1 q2
Vion−ion = (3.2.4)
4π ϵ0 r

ion-ion potential

 Example 3.2.1

When sodium chloride is melted, some of the ion pairs vaporize and form neutral NaCl dimers. How much energy would be
released when one mole of Na and Cl ions are brought together to generate dimers in this way? The bondlength of NaCl is
+ –

237 pm.

Solution
The interactions involved in forming NaCl dimers is the ion-ion forces with a potential energy given by Equation 3.2.4.
However, this is the energy of interaction for one pair of Na and Cl ion and needs to be scaled by a mole. So the energy
+ –

released will be
E = Na V (NaCl)

q1 q2
= Na
4π ϵ0 r

The r in this equation is the distance between the two ions, which is the bondlength of 237 pm (237 × 10 −12
m ).
−19 −19
(+1.6 × 10 C )(−1.6 × 10 C)
23 9 2 2
E = (6.022 × 10 ) (8.987 × 10 N m / C )
−12
 237 × 10 m
1/4πϵo

=– 584 kJ/mol

This is not the energy needed to separate one mole of NaCl since that is a lattice and has more than pairwise interactions and
require addressing the geometric orientation of the lattice (see Madelung Constants for more details).

Intermolecular forces are electrostatic in nature; that is, they arise from the electrostatic interaction between positively and
negatively charged species. Like covalent and ionic bonds, intermolecular interactions are the sum of both attractive and repulsive
components. Because electrostatic interactions fall off rapidly with increasing distance between molecules, intermolecular
interactions are most important for solids and liquids, where the molecules are close together. These interactions become important
for gases only at very high pressures, where they are responsible for the observed deviations from the ideal gas law at high
pressures (i.e., real gases).

3.2.3: Ion-Dipole Interactions

A dipole that is close to a positive or negative ion will orient itself so that the end whose partial charge is opposite to the ion charge
will point toward the ion. This kind of interaction is very important in aqueous solutions of ionic substances; H2O is a highly polar

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molecule, so that in a solution of sodium chloride, for example, the Na+ ions will be enveloped by a shell of water molecules with
their oxygen-ends pointing toward these ions, while H2O molecules surrounding the Cl– ions will have their hydrogen ends
directed inward. As a consequence of ion-dipole interactions, all ionic species in aqueous solution are hydrated; this is what is
denoted by the suffix in formulas such as K+(aq), etc.

H
+ -
Na δ O δ+

240 pm H
84 kJ

Figure 3.2.3 : Ion - Dipole Interaction. (CC BY-NC; Ümit Kaya)

The strength of ion-dipole attraction depends on the magnitude of the dipole moment and on the charge density of the ion. This
latter quantity is just the charge of the ion divided by its volume. Owing to their smaller sizes, positive ions tend to have larger
charge densities than negative ions, and they should be more strongly hydrated in aqueous solution. The hydrogen ion, being
nothing more than a bare proton of extremely small volume, has the highest charge density of any ion; it is for this reason that it
exists entirely in its hydrated form H3O+ in water.
Since there is now both attractive and repulsive interactions and they both get weaker as the ion and dipole distance increases while
also approaching each other in strength, the net ion-dipole is an inverse square relationship as shown in Equation 3.2.5.
−| q1 | μ2
E ∝ (3.2.5)
2
r

ion-dipole potential

ris the distance of separation.

qis the charge of the ion ( only the magnitude of the charge is shown here.)
μ is the permanent dipole moment of the polar molecule.

′ ⃗
μ⃗ = q d (3.2.6)

where q is the partial charge of each end of the dipole and d is the separation between the charges within the dipole
′

 Ion-Ion vs. Ion-Dipole potentials

There are several differences between ion-ion potential (Equation 3.2.4 ) and the ion-dipole potential (Equation 3.2.5 )
interactions.
First, the potential of ion/dipole interactions are negative and net interaction will always be attractive, since the attraction of
the opposite dipole to the ion will make it closer than the dipole with the like charge. By using the absolute value of the
charge of the ion, and placing a negative sign in front of the equation, this results in a lowering of the potential energy (μ is
positive).
Second, the potential drops off quicker in Equation 3.2.5, where it is an inverse square relationship to the radius (1/r ), 2

while a simple charge-charge interaction (Equation 3.2.4) has a linear inverse relationship (1/r). This means the ion-dipole
are a shorter range interaction and diminish more rapidly the father the polar molecule is from the ion.
Third, note that the units of the two equations are the same, as μ has the units of charge X distance. However, the distance
in μ is the distance between the dipoles of the polar molecule, while the distance denoted by the "r" is the distance between
the ion and the dipole.

It needs to be understood that the molecules in a solution are rotating and vibrating and actual systems are quite complicated
(Figure 3.2.4). What is important to realize is that these interactions are Coulombic in nature and how the mathematical equations
describe this in terms of the magnitude of the charges and their distances from each other. In this course we will not be calculating
dipole moments or the magnitudes of them, but understanding how to read the equations, and developing qualitative
understandings that allow us to predict trends.

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 Figure 3.2.4 : Ion-Dipole Interactions in the gas phase. (Gary L. Bertrand).

3.2.4: Dipole–Dipole Interactions

Polar covalent bonds behave as if the bonded atoms have localized fractional charges that are equal but opposite (i.e., the two
bonded atoms generate a dipole). If the structure of a molecule is such that the individual bond dipoles do not cancel one another,
then the molecule has a net dipole moment. Molecules with net dipole moments tend to align themselves so that the positive end of
one dipole is near the negative end of another and vice versa, as shown in part (a) in Figure 3.2.1.

Figure 3.2.5 : Attractive and Repulsive Dipole–Dipole Interactions. (a and b) Molecular orientations in which the positive end of
one dipole (δ ) is near the negative end of another (δ ) (and vice versa) produce attractive interactions. (c and d) Molecular
+ −

orientations that juxtapose the positive or negative ends of the dipoles on adjacent molecules produce repulsive interactions.
These arrangements are more stable than arrangements in which two positive or two negative ends are adjacent (Figure 3.2.1c).
Hence dipole–dipole interactions, such as those in Figure 3.2.5b, are attractive intermolecular interactions, whereas those in Figure
3.2.5d are repulsive intermolecular interactions. Because molecules in a liquid move freely and continuously, molecules always

experience both attractive and repulsive dipole–dipole interactions simultaneously, as shown in Figure 3.2.2. On average, however,
the attractive interactions dominate.

Figure 3.2.6 : Both Attractive and Repulsive Dipole–Dipole Interactions Occur in a Liquid Sample with Many Molecules
Because each end of a dipole possesses only a fraction of the charge of an electron, dipole–dipole interactions are substantially
weaker than the interactions between two ions, each of which has a charge of at least ±1, or between a dipole and an ion, in which
one of the species has at least a full positive or negative charge. In addition, the attractive interaction between dipoles falls off
much more rapidly with increasing distance than do the ion–ion interactions. Recall that the attractive energy between two ions is
proportional to 1/r, where r is the distance between the ions. Doubling the distance (r → 2r) decreases the attractive energy by one-
half.

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In contrast, the energy of the interaction of two dipoles is proportional to 1/r6, so doubling the distance between the dipoles
decreases the strength of the interaction by 26, or 64-fold:
2 2
2μ μ 1
A B
V =− (3.2.7)
2 6
3(4πϵ0 ) r kB T

Thus a substance such as HCl, which is partially held together by dipole–dipole interactions, is a gas at room temperature and 1 atm
pressure, whereas NaCl, which is held together by interionic interactions, is a high-melting-point solid. Within a series of
compounds of similar molar mass, the strength of the intermolecular interactions increases as the dipole moment of the molecules
increases, as shown in Table 3.2.1. Using what we learned about predicting relative bond polarities from the electronegativities of
the bonded atoms, we can make educated guesses about the relative boiling points of similar molecules.
Table 3.2.1 : Relationships between the Dipole Moment and the Boiling Point for Organic Compounds of Similar Molar Mass
Compound Molar Mass (g/mol) Dipole Moment (D) Boiling Point (K)

C3H6 (cyclopropane) 42 0 240

CH3OCH3 (dimethyl ether) 46 1.30 248

CH3CN (acetonitrile) 41 3.9 355

The attractive energy between two ions is proportional to 1/r, whereas the attractive energy between two dipoles is
proportional to 1/r6.

 Example 3.2.2

Arrange ethyl methyl ether (CH OCH CH ), 2-methylpropane [isobutane, (CH

3 2 3 3
) CHCH
2 3
], and acetone (CH 3
COCH
3
) in
order of increasing boiling points. Their structures are as follows:

Given: compounds
Asked for: order of increasing boiling points

Strategy:
Compare the molar masses and the polarities of the compounds. Compounds with higher molar masses and that are polar will
have the highest boiling points.

Solution:
The three compounds have essentially the same molar mass (58–60 g/mol), so we must look at differences in polarity to predict
the strength of the intermolecular dipole–dipole interactions and thus the boiling points of the compounds. The first compound,
2-methylpropane, contains only C–H bonds, which are not very polar because C and H have similar electronegativities. It
should therefore have a very small (but nonzero) dipole moment and a very low boiling point. Ethyl methyl ether has a
structure similar to H2O; it contains two polar C–O single bonds oriented at about a 109° angle to each other, in addition to
relatively nonpolar C–H bonds. As a result, the C–O bond dipoles partially reinforce one another and generate a significant
dipole moment that should give a moderately high boiling point. Acetone contains a polar C=O double bond oriented at about

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 120° to two methyl groups with nonpolar C–H bonds. The C–O bond dipole therefore corresponds to the molecular dipole,
which should result in both a rather large dipole moment and a high boiling point. Thus we predict the following order of
boiling points: 2-methylpropane < ethyl methyl ether < acetone. This result is in good agreement with the actual data: 2-
methylpropane, boiling point = −11.7°C, and the dipole moment (μ) = 0.13 D; methyl ethyl ether, boiling point = 7.4°C and μ
= 1.17 D; acetone, boiling point = 56.1°C and μ = 2.88 D.

 Exercise 3.2.1
Arrange carbon tetrafluoride (CF4), ethyl methyl sulfide (CH3SC2H5), dimethyl sulfoxide [(CH3)2S=O], and 2-methylbutane
[isopentane, (CH3)2CHCH2CH3] in order of decreasing boiling points.

Answer
dimethyl sulfoxide (boiling point = 189.9°C) > ethyl methyl sulfide (boiling point = 67°C) > 2-methylbutane (boiling point
= 27.8°C) > carbon tetrafluoride (boiling point = −128°C)

3.2.5: London Dispersion Forces

Thus far we have considered only interactions between polar molecules, but other factors must be considered to explain why many
nonpolar molecules, such as bromine, benzene, and hexane, are liquids at room temperature, and others, such as iodine and
naphthalene, are solids. Even the noble gases can be liquefied or solidified at low temperatures, high pressures, or both (Table
3.2.2).

What kind of attractive forces can exist between nonpolar molecules or atoms? This question was answered by Fritz London
(1900–1954), a German physicist who later worked in the United States. In 1930, London proposed that temporary fluctuations in
the electron distributions within atoms and nonpolar molecules could result in the formation of short-lived instantaneous dipole
moments, which produce attractive forces called London dispersion forces between otherwise nonpolar substances.
Table 3.2.2 : Normal Melting and Boiling Points of Some Elements and Nonpolar Compounds
Substance Molar Mass (g/mol) Melting Point (°C) Boiling Point (°C)

Ar 40 −189.4 −185.9

Xe 131 −111.8 −108.1

N2 28 −210 −195.8

O2 32 −218.8 −183.0

F2 38 −219.7 −188.1

I2 254 113.7 184.4

CH4 16 −182.5 −161.5

Consider a pair of adjacent He atoms, for example. On average, the two electrons in each He atom are uniformly distributed around
the nucleus. Because the electrons are in constant motion, however, their distribution in one atom is likely to be asymmetrical at
any given instant, resulting in an instantaneous dipole moment. As shown in part (a) in Figure 3.2.3, the instantaneous dipole
moment on one atom can interact with the electrons in an adjacent atom, pulling them toward the positive end of the instantaneous
dipole or repelling them from the negative end. The net effect is that the first atom causes the temporary formation of a dipole,
called an induced dipole, in the second. Interactions between these temporary dipoles cause atoms to be attracted to one another.
These attractive interactions are weak and fall off rapidly with increasing distance. London was able to show with quantum
mechanics that the attractive energy between molecules due to temporary dipole–induced dipole interactions falls off as 1/r6.
Doubling the distance therefore decreases the attractive energy by 26, or 64-fold.

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 Figure 3.2.3 : Instantaneous Dipole Moments. The formation of an instantaneous dipole moment on one He atom (a) or an H2
molecule (b) results in the formation of an induced dipole on an adjacent atom or molecule.
Instantaneous dipole–induced dipole interactions between nonpolar molecules can produce intermolecular attractions just as they
produce interatomic attractions in monatomic substances like Xe. This effect, illustrated for two H2 molecules in part (b) in Figure
3.2.3, tends to become more pronounced as atomic and molecular masses increase (Table 3.2.2). For example, Xe boils at

−108.1°C, whereas He boils at −269°C. The reason for this trend is that the strength of London dispersion forces is related to the
ease with which the electron distribution in a given atom can be perturbed. In small atoms such as He, the two 1s electrons are held
close to the nucleus in a very small volume, and electron–electron repulsions are strong enough to prevent significant asymmetry in
their distribution. In larger atoms such as Xe, however, the outer electrons are much less strongly attracted to the nucleus because
of filled intervening shells. As a result, it is relatively easy to temporarily deform the electron distribution to generate an
instantaneous or induced dipole. The ease of deformation of the electron distribution in an atom or molecule is called its
polarizability. Because the electron distribution is more easily perturbed in large, heavy species than in small, light species, we say
that heavier substances tend to be much more polarizable than lighter ones.

For similar substances, London dispersion forces get stronger with increasing molecular
size.
The polarizability of a substance also determines how it interacts with ions and species that possess permanent dipoles. Thus
London dispersion forces are responsible for the general trend toward higher boiling points with increased molecular mass and
greater surface area in a homologous series of compounds, such as the alkanes (part (a) in Figure 3.2.4). The strengths of London
dispersion forces also depend significantly on molecular shape because shape determines how much of one molecule can interact
with its neighboring molecules at any given time. For example, part (b) in Figure 3.2.4 shows 2,2-dimethylpropane (neopentane)
and n-pentane, both of which have the empirical formula C5H12. Neopentane is almost spherical, with a small surface area for
intermolecular interactions, whereas n-pentane has an extended conformation that enables it to come into close contact with other
n-pentane molecules. As a result, the boiling point of neopentane (9.5°C) is more than 25°C lower than the boiling point of n-
pentane (36.1°C).

3.2.8 https://chem.libretexts.org/@go/page/43104
 Figure 3.2.4 : Mass and Surface Area Affect the Strength of London Dispersion Forces. (a) In this series of four simple alkanes,
larger molecules have stronger London forces between them than smaller molecules and consequently higher boiling points. (b)
Linear n-pentane molecules have a larger surface area and stronger intermolecular forces than spherical neopentane molecules. As
a result, neopentane is a gas at room temperature, whereas n-pentane is a volatile liquid.
All molecules, whether polar or nonpolar, are attracted to one another by London dispersion forces in addition to any other
attractive forces that may be present. In general, however, dipole–dipole interactions in small polar molecules are significantly
stronger than London dispersion forces, so the former predominate.

 Example 3.2.2

Arrange n-butane, propane, 2-methylpropane [isobutene, (CH3)2CHCH3], and n-pentane in order of increasing boiling points.
Given: compounds
Asked for: order of increasing boiling points

Strategy:
Determine the intermolecular forces in the compounds and then arrange the compounds according to the strength of those
forces. The substance with the weakest forces will have the lowest boiling point.

Solution:
The four compounds are alkanes and nonpolar, so London dispersion forces are the only important intermolecular forces.
These forces are generally stronger with increasing molecular mass, so propane should have the lowest boiling point and n-
pentane should have the highest, with the two butane isomers falling in between. Of the two butane isomers, 2-methylpropane
is more compact, and n-butane has the more extended shape. Consequently, we expect intermolecular interactions for n-butane
to be stronger due to its larger surface area, resulting in a higher boiling point. The overall order is thus as follows, with actual
boiling points in parentheses: propane (−42.1°C) < 2-methylpropane (−11.7°C) < n-butane (−0.5°C) < n-pentane (36.1°C).

 Exercise 3.2.2

Arrange GeH4, SiCl4, SiH4, CH4, and GeCl4 in order of decreasing boiling points.

Answer
GeCl4 (87°C) > SiCl4 (57.6°C) > GeH4 (−88.5°C) > SiH4 (−111.8°C) > CH4 (−161°C)

3.2.6: Summary
Intermolecular forces are electrostatic in nature and include van der Waals forces and hydrogen bonds. Molecules in liquids are
held to other molecules by intermolecular interactions, which are weaker than the intramolecular interactions that hold the atoms
together within molecules and polyatomic ions. Transitions between the solid and liquid or the liquid and gas phases are due to
changes in intermolecular interactions but do not affect intramolecular interactions. The three major types of intermolecular
interactions are dipole–dipole interactions, London dispersion forces (these two are often referred to collectively as van der Waals

3.2.9 https://chem.libretexts.org/@go/page/43104
forces), and hydrogen bonds. Dipole–dipole interactions arise from the electrostatic interactions of the positive and negative ends
of molecules with permanent dipole moments; their strength is proportional to the magnitude of the dipole moment and to 1/r6,
where r is the distance between dipoles. London dispersion forces are due to the formation of instantaneous dipole moments in
polar or nonpolar molecules as a result of short-lived fluctuations of electron charge distribution, which in turn cause the temporary
formation of an induced dipole in adjacent molecules. Like dipole–dipole interactions, their energy falls off as 1/r6. Larger atoms
tend to be more polarizable than smaller ones because their outer electrons are less tightly bound and are therefore more easily
perturbed.

This page titled 3.2: Intermolecular Forces - Origins in Molecular Structure is shared under a CC BY-NC-SA 4.0 license and was authored,
remixed, and/or curated by Delmar Larsen.

3.2.10 https://chem.libretexts.org/@go/page/43104
3.3: Intermolecular Forces in Liquids
 Learning Objectives
To describe the intermolecular forces in liquids.

3.3.1: Hydrogen Bonds

Molecules with hydrogen atoms bonded to electronegative atoms such as O, N, and F (and to a much lesser extent Cl and S) tend to
exhibit unusually strong intermolecular interactions. These result in much higher boiling points than are observed for substances in
which London dispersion forces dominate, as illustrated for the covalent hydrides of elements of groups 14–17 in Figure 3.3.1.
Methane and its heavier congeners in group 14 form a series whose boiling points increase smoothly with increasing molar mass.
This is the expected trend in nonpolar molecules, for which London dispersion forces are the exclusive intermolecular forces. In
contrast, the hydrides of the lightest members of groups 15–17 have boiling points that are more than 100°C greater than predicted
on the basis of their molar masses. The effect is most dramatic for water: if we extend the straight line connecting the points for
H2Te and H2Se to the line for period 2, we obtain an estimated boiling point of −130°C for water! Imagine the implications for life
on Earth if water boiled at −130°C rather than 100°C.

Figure 3.3.1 : The Effects of Hydrogen Bonding on Boiling Points. These plots of the boiling points of the covalent hydrides of the
elements of groups 14–17 show that the boiling points of the lightest members of each series for which hydrogen bonding is
possible (HF, NH3, and H2O) are anomalously high for compounds with such low molecular masses.
Why do strong intermolecular forces produce such anomalously high boiling points and other unusual properties, such as high
enthalpies of vaporization and high melting points? The answer lies in the highly polar nature of the bonds between hydrogen and
very electronegative elements such as O, N, and F. The large difference in electronegativity results in a large partial positive charge
on hydrogen and a correspondingly large partial negative charge on the O, N, or F atom. Consequently, H–O, H–N, and H–F bonds
have very large bond dipoles that can interact strongly with one another. Because a hydrogen atom is so small, these dipoles can
also approach one another more closely than most other dipoles. The combination of large bond dipoles and short dipole–dipole
distances results in very strong dipole–dipole interactions called hydrogen bonds, as shown for ice in Figure 3.3.2. A hydrogen
bond is usually indicated by a dotted line between the hydrogen atom attached to O, N, or F (the hydrogen bond donor) and the
atom that has the lone pair of electrons (the hydrogen bond acceptor). Because each water molecule contains two hydrogen atoms
and two lone pairs, a tetrahedral arrangement maximizes the number of hydrogen bonds that can be formed. In the structure of ice,
each oxygen atom is surrounded by a distorted tetrahedron of hydrogen atoms that form bridges to the oxygen atoms of adjacent
water molecules. The bridging hydrogen atoms are not equidistant from the two oxygen atoms they connect, however. Instead, each
hydrogen atom is 101 pm from one oxygen and 174 pm from the other. In contrast, each oxygen atom is bonded to two H atoms at
the shorter distance and two at the longer distance, corresponding to two O–H covalent bonds and two O⋅⋅⋅H hydrogen bonds from

3.3.1 https://chem.libretexts.org/@go/page/43105
adjacent water molecules, respectively. The resulting open, cagelike structure of ice means that the solid is actually slightly less
dense than the liquid, which explains why ice floats on water rather than sinks.

Figure 3.3.2 : The Hydrogen-Bonded Structure of Ice

Each water molecule accepts two hydrogen bonds from two other water molecules and donates two hydrogen atoms to form
hydrogen bonds with two more water molecules, producing an open, cagelike structure. The structure of liquid water is very
similar, but in the liquid, the hydrogen bonds are continually broken and formed because of rapid molecular motion.

 It takes two to tango...

Hydrogen bond formation requires both a hydrogen bond donor and a hydrogen bond acceptor.

Because ice is less dense than liquid water, rivers, lakes, and oceans freeze from the top down. In fact, the ice forms a protective
surface layer that insulates the rest of the water, allowing fish and other organisms to survive in the lower levels of a frozen lake or
sea. If ice were denser than the liquid, the ice formed at the surface in cold weather would sink as fast as it formed. Bodies of water
would freeze from the bottom up, which would be lethal for most aquatic creatures. The expansion of water when freezing also
explains why automobile or boat engines must be protected by “antifreeze” and why unprotected pipes in houses break if they are
allowed to freeze.

 Example 3.3.1

Considering CH3OH, C2H6, Xe, and (CH3)3N, which can form hydrogen bonds with themselves? Draw the hydrogen-bonded
structures.
Given: compounds
Asked for: formation of hydrogen bonds and structure
Strategy:
A. Identify the compounds with a hydrogen atom attached to O, N, or F. These are likely to be able to act as hydrogen bond
donors.
B. Of the compounds that can act as hydrogen bond donors, identify those that also contain lone pairs of electrons, which
allow them to be hydrogen bond acceptors. If a substance is both a hydrogen donor and a hydrogen bond acceptor, draw a
structure showing the hydrogen bonding.
Solution:
A Of the species listed, xenon (Xe), ethane (C2H6), and trimethylamine [(CH3)3N] do not contain a hydrogen atom attached to
O, N, or F; hence they cannot act as hydrogen bond donors.
B The one compound that can act as a hydrogen bond donor, methanol (CH3OH), contains both a hydrogen atom attached to O
(making it a hydrogen bond donor) and two lone pairs of electrons on O (making it a hydrogen bond acceptor); methanol can
thus form hydrogen bonds by acting as either a hydrogen bond donor or a hydrogen bond acceptor. The hydrogen-bonded
structure of methanol is as follows:

3.3.2 https://chem.libretexts.org/@go/page/43105
  Exercise 3.3.1

Considering CH CO3 2
H , (CH
3
) N
3
, NH , and CH
3 3
F , which can form hydrogen bonds with themselves? Draw the hydrogen-
bonded structures.

Answer
CH CO H
3 2
and NH ; 3

Although hydrogen bonds are significantly weaker than covalent bonds, with typical dissociation energies of only 15–25 kJ/mol,
they have a significant influence on the physical properties of a compound. Compounds such as HF can form only two hydrogen
bonds at a time as can, on average, pure liquid NH3. Consequently, even though their molecular masses are similar to that of water,
their boiling points are significantly lower than the boiling point of water, which forms four hydrogen bonds at a time.

 Example 3.3.2

Arrange C60 (buckminsterfullerene, which has a cage structure), NaCl, He, Ar, and N2O in order of increasing boiling points.

Spinning Buckminsterfullerene (C ). (CC BY-SA 3.0; unported; Sponk).

60

Given: compounds
Asked for: order of increasing boiling points
Strategy:
Identify the intermolecular forces in each compound and then arrange the compounds according to the strength of those forces.
The substance with the weakest forces will have the lowest boiling point.
Solution:
Electrostatic interactions are strongest for an ionic compound, so we expect NaCl to have the highest boiling point. To predict
the relative boiling points of the other compounds, we must consider their polarity (for dipole–dipole interactions), their ability

3.3.3 https://chem.libretexts.org/@go/page/43105
to form hydrogen bonds, and their molar mass (for London dispersion forces). Helium is nonpolar and by far the lightest, so it
should have the lowest boiling point. Argon and N2O have very similar molar masses (40 and 44 g/mol, respectively), but N2O
is polar while Ar is not. Consequently, N2O should have a higher boiling point. A C60 molecule is nonpolar, but its molar mass
is 720 g/mol, much greater than that of Ar or N2O. Because the boiling points of nonpolar substances increase rapidly with
molecular mass, C60 should boil at a higher temperature than the other nonionic substances. The predicted order is thus as
follows, with actual boiling points in parentheses:
He (−269°C) < Ar (−185.7°C) < N2O (−88.5°C) < C60 (>280°C) < NaCl (1465°C).

 Exercise 3.3.2
Arrange 2,4-dimethylheptane, Ne, CS2, Cl2, and KBr in order of decreasing boiling points.

Answer
KBr (1435°C) > 2,4-dimethylheptane (132.9°C) > CS2 (46.6°C) > Cl2 (−34.6°C) > Ne (−246°C)

 Special Properties of Water

Besides mercury, water has the highest surface tension for all liquids. Water's high surface tension is due to the hydrogen
bonding in water molecules. Water also has an exceptionally high heat of vaporization. Vaporization occurs when a liquid
changes to a gas, which makes it an endothermic reaction. Water's heat of vaporization is 41 kJ/mol. Vapor pressure is
inversely related to intermolecular forces, so those with stronger intermolecular forces have a lower vapor pressure. Water has
very strong intermolecular forces, hence the low vapor pressure, but it's even lower compared to larger molecules with low
vapor pressures.
Viscosity is the property of fluid having high resistance to flow. We normally think of liquids like honey or motor oil being
viscous, but when compared to other substances with like structures, water is viscous. Liquids with stronger intermolecular
interactions are usually more viscous than liquids with weak intermolecular interactions.
Cohesion is intermolecular forces between like molecules; this is why water molecules are able to hold themselves together
in a drop. Water molecules are very cohesive because of the molecule's polarity. This is why you can fill a glass of water
just barely above the rim without it spilling.
Because of water's polarity, it is able to dissolve or dissociate many particles. Oxygen has a slightly negative charge, while the
two hydrogens have a slightly positive charge. The slightly negative particles of a compound will be attracted to water's
hydrogen atoms, while the slightly positive particles will be attracted to water's oxygen molecule; this causes the compound to
dissociate.
Besides the explanations above, we can look to some attributes of a water molecule to provide some more reasons of water's
uniqueness:
Forgetting fluorine, oxygen is the most electronegative non-noble gas element, so while forming a bond, the electrons are
pulled towards the oxygen atom rather than the hydrogen. This creates two polar bonds, which make the water molecule
more polar than the bonds in the other hydrides in the group.
A 104.5° bond angle creates a very strong dipole.
Water has hydrogen bonding which probably is a vital aspect in water's strong intermolecular interaction

3.3.4 https://chem.libretexts.org/@go/page/43105
 Figure 3.3.3 : Young boy with father ice fish. The fish do not freeze below the ice surface of the lake due to the unique
properties of water. (Public Domain; U.S. Fish and Wildlife Service).
The properties of water make it suitable for organisms to survive in during differing weather conditions. Water expands as it
freezes, which explains why ice is able to float on liquid water. During the winter when lakes begin to freeze, the surface of the
water freezes and then moves down toward deeper water; this explains why people can ice skate on or fall through a frozen
lake. If ice was not able to float, the lake would freeze from the bottom up killing all ecosystems living in the lake. However
ice floats, so the fish are able to survive under the surface of the ice during the winter. The surface of ice above a lake also
shields lakes from the cold temperature outside and insulates the water beneath it, allowing the lake under the frozen ice to stay
liquid and maintain a temperature adequate for the ecosystems living in the lake to survive.

3.3.2: Summary
Intermolecular forces are electrostatic in nature and include van der Waals forces and hydrogen bonds. Molecules in liquids are
held to other molecules by intermolecular interactions, which are weaker than the intramolecular interactions that hold the atoms
together within molecules and polyatomic ions. Transitions between the solid and liquid or the liquid and gas phases are due to
changes in intermolecular interactions but do not affect intramolecular interactions. The three major types of intermolecular
interactions are dipole–dipole interactions, London dispersion forces (these two are often referred to collectively as van der Waals
forces), and hydrogen bonds. Dipole–dipole interactions arise from the electrostatic interactions of the positive and negative ends
of molecules with permanent dipole moments; their strength is proportional to the magnitude of the dipole moment and to 1/r6,
where r is the distance between dipoles. London dispersion forces are due to the formation of instantaneous dipole moments in
polar or nonpolar molecules as a result of short-lived fluctuations of electron charge distribution, which in turn cause the temporary
formation of an induced dipole in adjacent molecules. Like dipole–dipole interactions, their energy falls off as 1/r6. Larger atoms
tend to be more polarizable than smaller ones because their outer electrons are less tightly bound and are therefore more easily
perturbed. Hydrogen bonds are especially strong dipole–dipole interactions between molecules that have hydrogen bonded to a
highly electronegative atom, such as O, N, or F. The resulting partially positively charged H atom on one molecule (the hydrogen
bond donor) can interact strongly with a lone pair of electrons of a partially negatively charged O, N, or F atom on adjacent
molecules (the hydrogen bond acceptor). Because of strong O⋅⋅⋅H hydrogen bonding between water molecules, water has an
unusually high boiling point, and ice has an open, cagelike structure that is less dense than liquid water.

This page titled 3.3: Intermolecular Forces in Liquids is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
Delmar Larsen.

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3.4: Phase Equilibrium
 Learning Objectives
To know how and why the vapor pressure of a liquid varies with temperature.
To understand that the equilibrium vapor pressure of a liquid depends on the temperature and the intermolecular forces
present.
To understand that the relationship between pressure, enthalpy of vaporization, and temperature is given by the Clausius-
Clapeyron equation.

Nearly all of us have heated a pan of water with the lid in place and shortly thereafter heard the sounds of the lid rattling and hot
water spilling onto the stovetop. When a liquid is heated, its molecules obtain sufficient kinetic energy to overcome the forces
holding them in the liquid and they escape into the gaseous phase. By doing so, they generate a population of molecules in the
vapor phase above the liquid that produces a pressure—the vapor pressure of the liquid. In the situation we described, enough
pressure was generated to move the lid, which allowed the vapor to escape. If the vapor is contained in a sealed vessel, however,
such as an unvented flask, and the vapor pressure becomes too high, the flask will explode (as many students have unfortunately
discovered). In this section, we describe vapor pressure in more detail and explain how to quantitatively determine the vapor
pressure of a liquid.

3.4.1: Evaporation and Condensation

Because the molecules of a liquid are in constant motion, we can plot the fraction of molecules with a given kinetic energy (KE)
against their kinetic energy to obtain the kinetic energy distribution of the molecules in the liquid (Figure 3.4.1), just as we did for
a gas. As for gases, increasing the temperature increases both the average kinetic energy of the particles in a liquid and the range of
kinetic energy of the individual molecules. If we assume that a minimum amount of energy (E ) is needed to overcome the
0

intermolecular attractive forces that hold a liquid together, then some fraction of molecules in the liquid always has a kinetic energy
greater than E . The fraction of molecules with a kinetic energy greater than this minimum value increases with increasing
0

temperature. Any molecule with a kinetic energy greater than E has enough energy to overcome the forces holding it in the liquid
0

and escape into the vapor phase. Before it can do so, however, a molecule must also be at the surface of the liquid, where it is
physically possible for it to leave the liquid surface; that is, only molecules at the surface can undergo evaporation (or
vaporization), where molecules gain sufficient energy to enter a gaseous state above a liquid’s surface, thereby creating a vapor
pressure.

Figure 3.4.1 : The Distribution of the Kinetic Energies of the Molecules of a Liquid at Two Temperatures. Just as with gases,
increasing the temperature shifts the peak to a higher energy and broadens the curve. Only molecules with a kinetic energy greater
than E0 can escape from the liquid to enter the vapor phase, and the proportion of molecules with KE > E0 is greater at the higher
temperature. (CC BY-SA-NC; Anonymous by request)
Graph of fraction of molecules with a particular kinetic energy against kinetic energy. Green line is temperature at 400 kelvin,
purple line is temperature at 300 kelvin.

3.4.1 https://chem.libretexts.org/@go/page/43106
To understand the causes of vapor pressure, consider the apparatus shown in Figure 3.4.2. When a liquid is introduced into an
evacuated chamber (part (a) in Figure 3.4.2), the initial pressure above the liquid is approximately zero because there are as yet no
molecules in the vapor phase. Some molecules at the surface, however, will have sufficient kinetic energy to escape from the liquid
and form a vapor, thus increasing the pressure inside the container. As long as the temperature of the liquid is held constant, the
fraction of molecules with KE > E will not change, and the rate at which molecules escape from the liquid into the vapor phase
0

will depend only on the surface area of the liquid phase.

Figure 3.4.2 : Vapor Pressure. (a) When a liquid is introduced into an evacuated chamber, molecules with sufficient kinetic energy
escape from the surface and enter the vapor phase, causing the pressure in the chamber to increase. (b) When sufficient molecules
are in the vapor phase for a given temperature, the rate of condensation equals the rate of evaporation (a steady state is reached),
and the pressure in the container becomes constant. (CC BY-SA-NC; Anonymous by request)
As soon as some vapor has formed, a fraction of the molecules in the vapor phase will collide with the surface of the liquid and
reenter the liquid phase in a process known as condensation (part (b) in Figure 3.4.2). As the number of molecules in the vapor
phase increases, the number of collisions between vapor-phase molecules and the surface will also increase. Eventually, a steady
state will be reached in which exactly as many molecules per unit time leave the surface of the liquid (vaporize) as collide with it
(condense). At this point, the pressure over the liquid stops increasing and remains constant at a particular value that is
characteristic of the liquid at a given temperature. The rates of evaporation and condensation over time for a system such as this are
shown graphically in Figure 3.4.3.

Figure 3.4.3 : The Relative Rates of Evaporation and Condensation as a Function of Time after a Liquid Is Introduced into a Sealed
Chamber. The rate of evaporation depends only on the surface area of the liquid and is essentially constant. The rate of
condensation depends on the number of molecules in the vapor phase and increases steadily until it equals the rate of evaporation.
(CC BY-SA-NC; Anonymous by request)
Graph of rate against time. The green line is evaporation while the pruple line is condensation. Dynamic equilibrium is established
when the evaporation and condensation rates are equal.

3.4.2: Equilibrium Vapor Pressure

Two opposing processes (such as evaporation and condensation) that occur at the same rate and thus produce no net change in a
system, constitute a dynamic equilibrium. In the case of a liquid enclosed in a chamber, the molecules continuously evaporate and

3.4.2 https://chem.libretexts.org/@go/page/43106
condense, but the amounts of liquid and vapor do not change with time. The pressure exerted by a vapor in dynamic equilibrium
with a liquid is the equilibrium vapor pressure of the liquid.
If a liquid is in an open container, however, most of the molecules that escape into the vapor phase will not collide with the surface
of the liquid and return to the liquid phase. Instead, they will diffuse through the gas phase away from the container, and an
equilibrium will never be established. Under these conditions, the liquid will continue to evaporate until it has “disappeared.” The
speed with which this occurs depends on the vapor pressure of the liquid and the temperature. Volatile liquids have relatively high
vapor pressures and tend to evaporate readily; nonvolatile liquids have low vapor pressures and evaporate more slowly. Although
the dividing line between volatile and nonvolatile liquids is not clear-cut, as a general guideline, we can say that substances with
vapor pressures greater than that of water (Figure 3.4.4) are relatively volatile, whereas those with vapor pressures less than that of
water are relatively nonvolatile. Thus diethyl ether (ethyl ether), acetone, and gasoline are volatile, but mercury, ethylene glycol,
and motor oil are nonvolatile.

Figure 3.4.4 : The Vapor Pressures of Several Liquids as a Function of Temperature. The point at which the vapor pressure curve
crosses the P = 1 atm line (dashed) is the normal boiling point of the liquid. (CC BY-SA-NC; Anonymous by request)
The equilibrium vapor pressure of a substance at a particular temperature is a characteristic of the material, like its molecular mass,
melting point, and boiling point. It does not depend on the amount of liquid as long as at least a tiny amount of liquid is present in
equilibrium with the vapor. The equilibrium vapor pressure does, however, depend very strongly on the temperature and the
intermolecular forces present, as shown for several substances in Figure 3.4.4. Molecules that can hydrogen bond, such as ethylene
glycol, have a much lower equilibrium vapor pressure than those that cannot, such as octane. The nonlinear increase in vapor
pressure with increasing temperature is much steeper than the increase in pressure expected for an ideal gas over the corresponding
temperature range. The temperature dependence is so strong because the vapor pressure depends on the fraction of molecules that
have a kinetic energy greater than that needed to escape from the liquid, and this fraction increases exponentially with temperature.
As a result, sealed containers of volatile liquids are potential bombs if subjected to large increases in temperature. The gas tanks on
automobiles are vented, for example, so that a car won’t explode when parked in the sun. Similarly, the small cans (1–5 gallons)
used to transport gasoline are required by law to have a pop-off pressure release.

Volatile substances have low boiling points and relatively weak intermolecular
interactions; nonvolatile substances have high boiling points and relatively strong
intermolecular interactions.

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 Vapor Pressure & Boiling Point

A Video Discussing Vapor Pressure and Boiling Points. Video Source: Vapor Pressure & Boiling Point(opens in new window)
[youtu.be]
The exponential rise in vapor pressure with increasing temperature in Figure 3.4.4 allows us to use natural logarithms to express
the nonlinear relationship as a linear one.

−ΔHvap 1
ln P = ( ) +C (3.4.1)
R T

where
ln P is the natural logarithm of the vapor pressure,
ΔHvap is the enthalpy of vaporization,
R is the universal gas constant [8.314 J/(mol•K)],

T is the temperature in kelvins, and

C is the y-intercept, which is a constant for any given line.

Plotting ln P versus the inverse of the absolute temperature (1/T ) is a straight line with a slope of −ΔHvap/R. Equation 3.4.1,
called the Clausius–Clapeyron Equation, can be used to calculate the ΔH of a liquid from its measured vapor pressure at two or
vap

more temperatures. The simplest way to determine ΔH is to measure the vapor pressure of a liquid at two temperatures and
vap

insert the values of P and T for these points into Equation 3.4.2, which is derived from the Clausius–Clapeyron equation:

P1 −ΔHvap 1 1
ln( ) = ( − ) (3.4.2)
P2 R T1 T2

Conversely, if we know ΔHvap and the vapor pressure P at any temperature T , we can use Equation 3.4.2 to calculate the vapor
1 1

pressure P at any other temperature T , as shown in Example 3.4.1.

2 2

The Clausius-Clapeyron Equation

3.4.4 https://chem.libretexts.org/@go/page/43106
A Video Discussing the Clausius-Clapeyron Equation. Video Link: The Clausius-Clapeyron Equation(opens in new window)
[youtu.be]

 Example 3.4.1: Vapor Pressure of Mercury

The experimentally measured vapor pressures of liquid Hg at four temperatures are listed in the following table:
experimentally measured vapor pressures of liquid Hg at four temperatures
T (°C) 80.0 100 120 140

P (torr) 0.0888 0.2729 0.7457 1.845

From these data, calculate the enthalpy of vaporization (ΔHvap) of mercury and predict the vapor pressure of the liquid at
160°C. (Safety note: mercury is highly toxic; when it is spilled, its vapor pressure generates hazardous levels of mercury
vapor.)
Given: vapor pressures at four temperatures
Asked for: ΔHvap of mercury and vapor pressure at 160°C

Strategy:
A. Use Equation 3.4.2 to obtain ΔHvap directly from two pairs of values in the table, making sure to convert all values to the
appropriate units.
B. Substitute the calculated value of ΔHvap into Equation 3.4.2 to obtain the unknown pressure (P2).

Solution:
A The table gives the measured vapor pressures of liquid Hg for four temperatures. Although one way to proceed would be to
plot the data using Equation 3.4.1 and find the value of ΔHvap from the slope of the line, an alternative approach is to use
Equation 3.4.2 to obtain ΔHvap directly from two pairs of values listed in the table, assuming no errors in our measurement. We
therefore select two sets of values from the table and convert the temperatures from degrees Celsius to kelvin because the
equation requires absolute temperatures. Substituting the values measured at 80.0°C (T1) and 120.0°C (T2) into Equation 3.4.2
gives

0.7457 T orr −ΔHvap 1 1

ln( ) = ( − )
0.0888 T orr 8.314 J/mol ⋅ K (120 + 273) K (80.0 + 273) K

−ΔHvap
−4 −1
ln(8.398) = (−2.88 × 10 K )
8.314 J/mol ⋅ K

−4 −1
2.13 = −ΔHvap (−3.46 × 10 )J ⋅ mol

ΔHvap = 61, 400 J/mol = 61.4 kJ/mol

B We can now use this value of ΔHvap to calculate the vapor pressure of the liquid (P2) at 160.0°C (T2):

−61, 400 J/mol

P2 1 1
ln( ) = ( − )
0.0888 torr −1 (160 + 273) K (80.0 + 273) K
8.314 J/mol K

Using the relationship e ln x

=x , we have
P2
ln( ) = 3.86
0.0888 T orr

P2
3.86
=e = 47.5
0.0888 T orr

P2 = 4.21T orr

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 At 160°C, liquid Hg has a vapor pressure of 4.21 torr, substantially greater than the pressure at 80.0°C, as we would expect.

 Exercise 3.4.1: Vapor Pressure of Nickel

The vapor pressure of liquid nickel at 1606°C is 0.100 torr, whereas at 1805°C, its vapor pressure is 1.000 torr. At what
temperature does the liquid have a vapor pressure of 2.500 torr?

Answer
1896°C

3.4.3: Boiling Points

As the temperature of a liquid increases, the vapor pressure of the liquid increases until it equals the external pressure, or the
atmospheric pressure in the case of an open container. Bubbles of vapor begin to form throughout the liquid, and the liquid begins
to boil. The temperature at which a liquid boils at exactly 1 atm pressure is the normal boiling point of the liquid. For water, the
normal boiling point is exactly 100°C. The normal boiling points of the other liquids in Figure 3.4.4 are represented by the points
at which the vapor pressure curves cross the line corresponding to a pressure of 1 atm. Although we usually cite the normal boiling
point of a liquid, the actual boiling point depends on the pressure. At a pressure greater than 1 atm, water boils at a temperature
greater than 100°C because the increased pressure forces vapor molecules above the surface to condense. Hence the molecules
must have greater kinetic energy to escape from the surface. Conversely, at pressures less than 1 atm, water boils below 100°C.
Table 3.4.1 : The Boiling Points of Water at Various Locations on Earth
Place Altitude above Sea Level (ft) Atmospheric Pressure (mmHg) Boiling Point of Water (°C)

Mt. Everest, Nepal/Tibet 29,028 240 70

Bogota, Colombia 11,490 495 88

Denver, Colorado 5280 633 95

Washington, DC 25 759 100

Dead Sea, Israel/Jordan −1312 799 101.4

Typical variations in atmospheric pressure at sea level are relatively small, causing only minor changes in the boiling point of
water. For example, the highest recorded atmospheric pressure at sea level is 813 mmHg, recorded during a Siberian winter; the
lowest sea-level pressure ever measured was 658 mmHg in a Pacific typhoon. At these pressures, the boiling point of water
changes minimally, to 102°C and 96°C, respectively. At high altitudes, on the other hand, the dependence of the boiling point of
water on pressure becomes significant. Table 3.4.1 lists the boiling points of water at several locations with different altitudes. At
an elevation of only 5000 ft, for example, the boiling point of water is already lower than the lowest ever recorded at sea level. The
lower boiling point of water has major consequences for cooking everything from soft-boiled eggs (a “three-minute egg” may well
take four or more minutes in the Rockies and even longer in the Himalayas) to cakes (cake mixes are often sold with separate high-
altitude instructions). Conversely, pressure cookers, which have a seal that allows the pressure inside them to exceed 1 atm, are
used to cook food more rapidly by raising the boiling point of water and thus the temperature at which the food is being cooked.

As pressure increases, the boiling point of a liquid increases and vice versa.

 Example 3.4.2: Boiling Mercury

Use Figure 3.4.4 to estimate the following.

a. the boiling point of water in a pressure cooker operating at 1000 mmHg
b. the pressure required for mercury to boil at 250°C

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 Mercury boils at 356 °C at room pressure. To see video go to www.youtube.com/watch?v=0iizsbXWYoo
Given: Data in Figure 3.4.4, pressure, and boiling point
Asked for: corresponding boiling point and pressure

Strategy:
A. To estimate the boiling point of water at 1000 mmHg, refer to Figure 3.4.4 and find the point where the vapor pressure
curve of water intersects the line corresponding to a pressure of 1000 mmHg.
B. To estimate the pressure required for mercury to boil at 250°C, find the point where the vapor pressure curve of mercury
intersects the line corresponding to a temperature of 250°C.

Solution:
a. A The vapor pressure curve of water intersects the P = 1000 mmHg line at about 110°C; this is therefore the boiling point
of water at 1000 mmHg.
b. B The vertical line corresponding to 250°C intersects the vapor pressure curve of mercury at P ≈ 75 mmHg. Hence this is
the pressure required for mercury to boil at 250°C.

 Exercise 3.4.2: Boiling Ethlyene Glycol

Ethylene glycol is an organic compound primarily used as a raw material in the manufacture of polyester fibers and fabric
industry, and polyethylene terephthalate resins (PET) used in bottling. Use the data in Figure 3.4.4 to estimate the following.
a. the normal boiling point of ethylene glycol
b. the pressure required for diethyl ether to boil at 20°C.

Answer a
200°C
Answer b
450 mmHg

3.4.4: Summary
Because the molecules of a liquid are in constant motion and possess a wide range of kinetic energies, at any moment some fraction
of them has enough energy to escape from the surface of the liquid to enter the gas or vapor phase. This process, called
vaporization or evaporation, generates a vapor pressure above the liquid. Molecules in the gas phase can collide with the liquid
surface and reenter the liquid via condensation. Eventually, a steady state is reached in which the number of molecules
evaporating and condensing per unit time is the same, and the system is in a state of dynamic equilibrium. Under these conditions,
a liquid exhibits a characteristic equilibrium vapor pressure that depends only on the temperature. We can express the nonlinear
relationship between vapor pressure and temperature as a linear relationship using the Clausius–Clapeyron equation. This
equation can be used to calculate the enthalpy of vaporization of a liquid from its measured vapor pressure at two or more
temperatures. Volatile liquids are liquids with high vapor pressures, which tend to evaporate readily from an open container;
nonvolatile liquids have low vapor pressures. When the vapor pressure equals the external pressure, bubbles of vapor form within
the liquid, and it boils. The temperature at which a substance boils at a pressure of 1 atm is its normal boiling point.

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3.4.5: Contributors and Attributions
Modified by Joshua Halpern (Howard University)

This page titled 3.4: Phase Equilibrium is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Delmar Larsen.
11.5: Vapor Pressure is licensed CC BY-NC-SA 3.0.

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3.5: Phase Transitions
 Learning Objectives
To calculate the energy changes that accompany phase changes.

We take advantage of changes between the gas, liquid, and solid states to cool a drink with ice cubes (solid to liquid), cool our
bodies by perspiration (liquid to gas), and cool food inside a refrigerator (gas to liquid and vice versa). We use dry ice, which is
solid CO2, as a refrigerant (solid to gas), and we make artificial snow for skiing and snowboarding by transforming a liquid to a
solid. In this section, we examine what happens when any of the three forms of matter is converted to either of the other two. These
changes of state are often called phase changes. The six most common phase changes are shown in Figure 3.5.1.

Figure 3.5.1 : Enthalpy changes that accompany phase transitions are indicated by purple and green arrows. (CC BY-SA-NC;
anoymous)
Purple arrows indicate heatingfrom solid to gas, solid to liquid, and liquid to gas. Green arrows indicate cooling from gas to solid,
gas to liquid, and liquid to solid.

3.5.1: Energy Changes That Accompany Phase Changes

Phase changes are always accompanied by a change in the energy of a system. For example, converting a liquid, in which the
molecules are close together, to a gas, in which the molecules are, on average, far apart, requires an input of energy (heat) to give
the molecules enough kinetic energy to allow them to overcome the intermolecular attractive forces. The stronger the attractive
forces, the more energy is needed to overcome them. Solids, which are highly ordered, have the strongest intermolecular
interactions, whereas gases, which are very disordered, have the weakest. Thus any transition from a more ordered to a less ordered
state (solid to liquid, liquid to gas, or solid to gas) requires an input of energy; it is endothermic. Conversely, any transition from a
less ordered to a more ordered state (liquid to solid, gas to liquid, or gas to solid) releases energy; it is exothermic. The energy
change associated with each common phase change is shown in Figure 3.5.1.

ΔH is positive for any transition from a more ordered to a less ordered state and negative
for a transition from a less ordered to a more ordered state.
Previously, we defined the enthalpy changes associated with various chemical and physical processes. The melting points and
molar enthalpies of fusion (ΔH ), the energy required to convert from a solid to a liquid, a process known as fusion (or
f us

melting), as well as the normal boiling points and enthalpies of vaporization (ΔH ) of selected compounds are listed in Table
vap

3.5.1.

Table 3.5.1 : Melting and Boiling Points and Enthalpies of Fusion and Vaporization for Selected Substances. Values given under 1 atm. of
external pressure.

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 Substance Melting Point (°C) ΔHfus (kJ/mol) Boiling Point (°C) ΔHvap (kJ/mol)

N2 −210.0 0.71 −195.8 5.6

HCl −114.2 2.00 −85.1 16.2

Br2 −7.2 10.6 58.8 30.0

CCl4 −22.6 2.56 76.8 29.8

CH3CH2OH (ethanol) −114.1 4.93 78.3 38.6

CH3(CH2)4CH3 (n-
−95.4 13.1 68.7 28.9
hexane)

H2O 0 6.01 100 40.7

Na 97.8 2.6 883 97.4

NaF 996 33.4 1704 176.1

The substances with the highest melting points usually have the highest enthalpies of fusion; they tend to be ionic compounds that
are held together by very strong electrostatic interactions. Substances with high boiling points are those with strong intermolecular
interactions that must be overcome to convert a liquid to a gas, resulting in high enthalpies of vaporization. The enthalpy of
vaporization of a given substance is much greater than its enthalpy of fusion because it takes more energy to completely separate
molecules (conversion from a liquid to a gas) than to enable them only to move past one another freely (conversion from a solid to
a liquid).

Less energy is needed to allow molecules to move past each other than to separate them
totally.

Figure 3.5.2 : The Sublimation of solid iodine. When solid iodine is heated at ordinary atmospheric pressure, it sublimes. When the
I2 vapor comes in contact with a cold surface, it deposits I2 crystals. Figure used with permission from Wikipedia.
The direct conversion of a solid to a gas, without an intervening liquid phase, is called sublimation. The amount of energy required
to sublime 1 mol of a pure solid is the enthalpy of sublimation (ΔHsub). Common substances that sublime at standard temperature
and pressure (STP; 0°C, 1 atm) include CO2 (dry ice); iodine (Figure 3.5.2); naphthalene, a substance used to protect woolen
clothing against moths; and 1,4-dichlorobenzene. As shown in Figure 3.5.1, the enthalpy of sublimation of a substance is the sum
of its enthalpies of fusion and vaporization provided all values are at the same T; this is an application of Hess’s law.
ΔHsub = ΔHf us + ΔHvap (3.5.1)

Fusion, vaporization, and sublimation are endothermic processes; they occur only with the absorption of heat. Anyone who has
ever stepped out of a swimming pool on a cool, breezy day has felt the heat loss that accompanies the evaporation of water from
the skin. Our bodies use this same phenomenon to maintain a constant temperature: we perspire continuously, even when at rest,
losing about 600 mL of water daily by evaporation from the skin. We also lose about 400 mL of water as water vapor in the air we
exhale, which also contributes to cooling. Refrigerators and air-conditioners operate on a similar principle: heat is absorbed from
the object or area to be cooled and used to vaporize a low-boiling-point liquid, such as ammonia or the chlorofluorocarbons (CFCs)
and the hydrofluorocarbons (HCFCs). The vapor is then transported to a different location and compressed, thus releasing and

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dissipating the heat. Likewise, ice cubes efficiently cool a drink not because of their low temperature but because heat is required to
convert ice at 0°C to liquid water at 0°C.

3.5.2: Temperature Curves

The processes on the right side of Figure 3.5.1—freezing, condensation, and deposition, which are the reverse of fusion,
sublimation, and vaporization—are exothermic. Thus heat pumps that use refrigerants are essentially air-conditioners running in
reverse. Heat from the environment is used to vaporize the refrigerant, which is then condensed to a liquid in coils within a house
to provide heat. The energy changes that occur during phase changes can be quantified by using a heating or cooling curve.

3.5.2.1: Heating Curves

Figure 3.5.3 shows a heating curve, a plot of temperature versus heating time, for a 75 g sample of water. The sample is initially ice
at 1 atm and −23°C; as heat is added, the temperature of the ice increases linearly with time. The slope of the line depends on both
the mass of the ice and the specific heat (Cs) of ice, which is the number of joules required to raise the temperature of 1 g of ice by
1°C. As the temperature of the ice increases, the water molecules in the ice crystal absorb more and more energy and vibrate more
vigorously. At the melting point, they have enough kinetic energy to overcome attractive forces and move with respect to one
another. As more heat is added, the temperature of the system does not increase further but remains constant at 0°C until all the ice
has melted. Once all the ice has been converted to liquid water, the temperature of the water again begins to increase. Now,
however, the temperature increases more slowly than before because the specific heat capacity of water is greater than that of ice.
When the temperature of the water reaches 100°C, the water begins to boil. Here, too, the temperature remains constant at 100°C
until all the water has been converted to steam. At this point, the temperature again begins to rise, but at a faster rate than seen in
the other phases because the heat capacity of steam is less than that of ice or water.

Figure 3.5.3 : A Heating Curve for Water. This plot of temperature shows what happens to a 75 g sample of ice initially at 1 atm
and −23°C as heat is added at a constant rate: A–B: heating solid ice; B–C: melting ice; C–D: heating liquid water; D–E:
vaporizing water; E–F: heating steam.
Thus the temperature of a system does not change during a phase change. In this example, as long as even a tiny amount of ice is
present, the temperature of the system remains at 0°C during the melting process, and as long as even a small amount of liquid
water is present, the temperature of the system remains at 100°C during the boiling process. The rate at which heat is added does
not affect the temperature of the ice/water or water/steam mixture because the added heat is being used exclusively to overcome the
attractive forces that hold the more condensed phase together. Many cooks think that food will cook faster if the heat is turned up
higher so that the water boils more rapidly. Instead, the pot of water will boil to dryness sooner, but the temperature of the water
does not depend on how vigorously it boils.

The temperature of a sample does not change during a phase change.

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If heat is added at a constant rate, as in Figure 3.5.3, then the length of the horizontal lines, which represents the time during which
the temperature does not change, is directly proportional to the magnitude of the enthalpies associated with the phase changes. In
Figure 3.5.3, the horizontal line at 100°C is much longer than the line at 0°C because the enthalpy of vaporization of water is
several times greater than the enthalpy of fusion.
A superheated liquid is a sample of a liquid at the temperature and pressure at which it should be a gas. Superheated liquids are not
stable; the liquid will eventually boil, sometimes violently. The phenomenon of superheating causes “bumping” when a liquid is
heated in the laboratory. When a test tube containing water is heated over a Bunsen burner, for example, one portion of the liquid
can easily become too hot. When the superheated liquid converts to a gas, it can push or “bump” the rest of the liquid out of the test
tube. Placing a stirring rod or a small piece of ceramic (a “boiling chip”) in the test tube allows bubbles of vapor to form on the
surface of the object so the liquid boils instead of becoming superheated. Superheating is the reason a liquid heated in a smooth cup
in a microwave oven may not boil until the cup is moved, when the motion of the cup allows bubbles to form.

3.5.2.2: Cooling Curves

The cooling curve, a plot of temperature versus cooling time, in Figure 3.5.4 plots temperature versus time as a 75 g sample of
steam, initially at 1 atm and 200°C, is cooled. Although we might expect the cooling curve to be the mirror image of the heating
curve in Figure 3.5.3, the cooling curve is not an identical mirror image. As heat is removed from the steam, the temperature falls
until it reaches 100°C. At this temperature, the steam begins to condense to liquid water. No further temperature change occurs
until all the steam is converted to the liquid; then the temperature again decreases as the water is cooled. We might expect to reach
another plateau at 0°C, where the water is converted to ice; in reality, however, this does not always occur. Instead, the temperature
often drops below the freezing point for some time, as shown by the little dip in the cooling curve below 0°C. This region
corresponds to an unstable form of the liquid, a supercooled liquid. If the liquid is allowed to stand, if cooling is continued, or if a
small crystal of the solid phase is added (a seed crystal), the supercooled liquid will convert to a solid, sometimes quite suddenly.
As the water freezes, the temperature increases slightly due to the heat evolved during the freezing process and then holds constant
at the melting point as the rest of the water freezes. Subsequently, the temperature of the ice decreases again as more heat is
removed from the system.

Figure 3.5.4 : A Cooling Curve for Water. This plot of temperature shows what happens to a 75 g sample of steam initially at 1 atm
and 200°C as heat is removed at a constant rate: A–B: cooling steam; B–C: condensing steam; C–D: cooling liquid water to give a
supercooled liquid; D–E: warming the liquid as it begins to freeze; E–F: freezing liquid water; F–G: cooling ice.
Supercooling effects have a huge impact on Earth’s climate. For example, supercooling of water droplets in clouds can prevent the
clouds from releasing precipitation over regions that are persistently arid as a result. Clouds consist of tiny droplets of water, which
in principle should be dense enough to fall as rain. In fact, however, the droplets must aggregate to reach a certain size before they
can fall to the ground. Usually a small particle (a nucleus) is required for the droplets to aggregate; the nucleus can be a dust
particle, an ice crystal, or a particle of silver iodide dispersed in a cloud during seeding (a method of inducing rain). Unfortunately,
the small droplets of water generally remain as a supercooled liquid down to about −10°C, rather than freezing into ice crystals that

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are more suitable nuclei for raindrop formation. One approach to producing rainfall from an existing cloud is to cool the water
droplets so that they crystallize to provide nuclei around which raindrops can grow. This is best done by dispersing small granules
of solid CO2 (dry ice) into the cloud from an airplane. Solid CO2 sublimes directly to the gas at pressures of 1 atm or lower, and the
enthalpy of sublimation is substantial (25.3 kJ/mol). As the CO2 sublimes, it absorbs heat from the cloud, often with the desired
results.

The Thermodynamics of Phase Changes

A Video Discussing the Thermodynamics of Phase Changes. Video Source: The Thermodynamics of Phase Changes,
YouTube(opens in new window) [youtu.be]

 Example 3.5.1: Cooling Tea

If a 50.0 g ice cube at 0.0°C is added to 500 mL of tea at 20.0°C, what is the temperature of the tea when the ice cube has just
melted? Assume that no heat is transferred to or from the surroundings. The density of water (and iced tea) is 1.00 g/mL over
the range 0°C–20°C, the specific heats of liquid water and ice are 4.184 J/(g•°C) and 2.062 J/(g•°C), respectively, and the
enthalpy of fusion of ice is 6.01 kJ/mol.
Given: mass, volume, initial temperature, density, specific heats, and ΔH f us

Asked for: final temperature

Strategy
Substitute the given values into the general equation relating heat gained (by the ice) to heat lost (by the tea) to obtain the final
temperature of the mixture.

Solution
When two substances or objects at different temperatures are brought into contact, heat will flow from the warmer one to the
cooler. The amount of heat that flows is given by

q = m Cs ΔT

where q is heat, m is mass, C is the specific heat, and ΔT is the temperature change. Eventually, the temperatures of the two
s

substances will become equal at a value somewhere between their initial temperatures. Calculating the temperature of iced tea
after adding an ice cube is slightly more complicated. The general equation relating heat gained and heat lost is still valid, but
in this case we also have to take into account the amount of heat required to melt the ice cube from ice at 0.0°C to liquid water
at 0.0°C.
The amount of heat gained by the ice cube as it melts is determined by its enthalpy of fusion in kJ/mol:

q = nΔHf us

For our 50.0 g ice cube:

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 1 mol
qice = 50.0g ⋅ ⋅ 6.01 kJ/mol
18.02 g

= 16.7 kJ

Thus, when the ice cube has just melted, it has absorbed 16.7 kJ of heat from the tea. We can then substitute this value into the
first equation to determine the change in temperature of the tea:
1.00 g
qtea = −16, 700J = 500mL ⋅ ⋅ 4.184J/(g ∙ °C )ΔT
1 mL

ΔT = −7.98°C = Tf − Ti

Tf = 12.02°C

This would be the temperature of the tea when the ice cube has just finished melting; however, this leaves the melted ice still at
0.0°C. We might more practically want to know what the final temperature of the mixture of tea will be once the melted ice has
come to thermal equilibrium with the tea. To determine this, we can add one more step to the calculation by plugging in to the
general equation relating heat gained and heat lost again:
qice = −qtea

qice = mice Cs ΔT = 50.0g ⋅ 4.184J/(g ∙ °C ) ⋅ (Tf − 0.0°C )

= 209.2J/°C ⋅ Tf

qtea = mtea Cs ΔT = 500g ⋅ 4.184J/(g ∙ °C ) ⋅ (Tf − 12.02°C ) = 2092J/°C ⋅ Tf − 25, 150J

209.2J/°C ⋅ Tf = −2092J/°C ⋅ Tf + 25, 150J

2301.2J/°C ⋅ Tf = 25, 150J

Tf = 10.9°C

The final temperature is in between the initial temperatures of the tea (12.02 °C) and the melted ice (0.0 °C), so this answer
makes sense. In this example, the tea loses much more heat in melting the ice than in mixing with the cold water, showing the
importance of accounting for the heat of phase changes!

 Exercise 3.5.1: Death by Freezing

Suppose you are overtaken by a blizzard while ski touring and you take refuge in a tent. You are thirsty, but you forgot to bring
liquid water. You have a choice of eating a few handfuls of snow (say 400 g) at −5.0°C immediately to quench your thirst or
setting up your propane stove, melting the snow, and heating the water to body temperature before drinking it. You recall that
the survival guide you leafed through at the hotel said something about not eating snow, but you cannot remember why—after
all, it’s just frozen water. To understand the guide’s recommendation, calculate the amount of heat that your body will have to
supply to bring 400 g of snow at −5.0°C to your body’s internal temperature of 37°C. Use the data in Example 3.5.1

Answer
200 kJ (4.1 kJ to bring the ice from −5.0°C to 0.0°C, 133.6 kJ to melt the ice at 0.0°C, and 61.9 kJ to bring the water from
0.0°C to 37°C), which is energy that would not have been expended had you first melted the snow.

3.5.3: Summary
Fusion, vaporization, and sublimation are endothermic processes, whereas freezing, condensation, and deposition are exothermic
processes. Changes of state are examples of phase changes, or phase transitions. All phase changes are accompanied by changes
in the energy of a system. Changes from a more-ordered state to a less-ordered state (such as a liquid to a gas) are endothermic.
Changes from a less-ordered state to a more-ordered state (such as a liquid to a solid) are always exothermic. The conversion of a
solid to a liquid is called fusion (or melting). The energy required to melt 1 mol of a substance is its enthalpy of fusion (ΔHfus).
The energy change required to vaporize 1 mol of a substance is the enthalpy of vaporization (ΔHvap). The direct conversion of a
solid to a gas is sublimation. The amount of energy needed to sublime 1 mol of a substance is its enthalpy of sublimation (ΔHsub)

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and is the sum of the enthalpies of fusion and vaporization. Plots of the temperature of a substance versus heat added or versus
heating time at a constant rate of heating are called heating curves. Heating curves relate temperature changes to phase transitions.
A superheated liquid, a liquid at a temperature and pressure at which it should be a gas, is not stable. A cooling curve is not
exactly the reverse of the heating curve because many liquids do not freeze at the expected temperature. Instead, they form a
supercooled liquid, a metastable liquid phase that exists below the normal melting point. Supercooled liquids usually crystallize
on standing, or adding a seed crystal of the same or another substance can induce crystallization.

This page titled 3.5: Phase Transitions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Delmar Larsen.
11.4: Phase Changes is licensed CC BY-NC-SA 3.0.

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3.6: Phase Diagrams
 Learning Objectives
To understand the basics of a one-component phase diagram as a function of temperature and pressure in a closed system.
To be able to identify the triple point, the critical point, and four regions: solid, liquid, gas, and a supercritical fluid.

The state exhibited by a given sample of matter depends on the identity, temperature, and pressure of the sample. A phase diagram
is a graphic summary of the physical state of a substance as a function of temperature and pressure in a closed system.

3.6.1: Introduction
A typical phase diagram consists of discrete regions that represent the different phases exhibited by a substance (Figure 3.6.1).
Each region corresponds to the range of combinations of temperature and pressure over which that phase is stable. The combination
of high pressure and low temperature (upper left of Figure 3.6.1) corresponds to the solid phase, whereas the gas phase is favored
at high temperature and low pressure (lower right). The combination of high temperature and high pressure (upper right)
corresponds to a supercritical fluid.

Figure 3.6.1 : A Typical Phase Diagram for a Substance That Exhibits Three Phases—Solid, Liquid, and Gas—and a Supercritical
Region

The solid phase is favored at low temperature and high pressure; the gas phase is favored at high temperature and low pressure.

The lines in a phase diagram correspond to the combinations of temperature and pressure at which two phases can coexist in
equilibrium. In Figure 3.6.1, the line that connects points A and D separates the solid and liquid phases and shows how the melting
point of a solid varies with pressure. The solid and liquid phases are in equilibrium all along this line; crossing the line horizontally
corresponds to melting or freezing. The line that connects points A and B is the vapor pressure curve of the liquid, which we
discussed in Section 11.5. It ends at the critical point, beyond which the substance exists as a supercritical fluid. The line that
connects points A and C is the vapor pressure curve of the solid phase. Along this line, the solid is in equilibrium with the vapor
phase through sublimation and deposition. Finally, point A, where the solid/liquid, liquid/gas, and solid/gas lines intersect, is the
triple point; it is the only combination of temperature and pressure at which all three phases (solid, liquid, and gas) are in
equilibrium and can therefore exist simultaneously. Because no more than three phases can ever coexist, a phase diagram can never
have more than three lines intersecting at a single point.
Remember that a phase diagram, such as the one in Figure 3.6.1, is for a single pure substance in a closed system, not for a liquid
in an open beaker in contact with air at 1 atm pressure. In practice, however, the conclusions reached about the behavior of a
substance in a closed system can usually be extrapolated to an open system without a great deal of error.

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3.6.2: The Phase Diagram of Water
Figure 3.6.2 shows the phase diagram of water and illustrates that the triple point of water occurs at 0.01°C and 0.00604 atm (4.59
mmHg). Far more reproducible than the melting point of ice, which depends on the amount of dissolved air and the atmospheric
pressure, the triple point (273.16 K) is used to define the absolute (Kelvin) temperature scale. The triple point also represents the
lowest pressure at which a liquid phase can exist in equilibrium with the solid or vapor. At pressures less than 0.00604 atm,
therefore, ice does not melt to a liquid as the temperature increases; the solid sublimes directly to water vapor. Sublimation of water
at low temperature and pressure can be used to “freeze-dry” foods and beverages. The food or beverage is first cooled to subzero
temperatures and placed in a container in which the pressure is maintained below 0.00604 atm. Then, as the temperature is
increased, the water sublimes, leaving the dehydrated food (such as that used by backpackers or astronauts) or the powdered
beverage (as with freeze-dried coffee).

Figure 3.6.2 : Two Versions of the Phase Diagram of Water. (a) In this graph with linear temperature and pressure axes, the
boundary between ice and liquid water is almost vertical. (b) This graph with an expanded scale illustrates the decrease in melting
point with increasing pressure. (The letters refer to points discussed in Example 3.6.1 ).
The phase diagram for water illustrated in Figure 3.6.2b shows the boundary between ice and water on an expanded scale. The
melting curve of ice slopes up and slightly to the left rather than up and to the right as in Figure 3.6.1; that is, the melting point of
ice decreases with increasing pressure; at 100 MPa (987 atm), ice melts at −9°C. Water behaves this way because it is one of the
few known substances for which the crystalline solid is less dense than the liquid (others include antimony and bismuth).
Increasing the pressure of ice that is in equilibrium with water at 0°C and 1 atm tends to push some of the molecules closer
together, thus decreasing the volume of the sample. The decrease in volume (and corresponding increase in density) is smaller for a
solid or a liquid than for a gas, but it is sufficient to melt some of the ice.
In Figure 3.6.2b point A is located at P = 1 atm and T = −1.0°C, within the solid (ice) region of the phase diagram. As the pressure
increases to 150 atm while the temperature remains the same, the line from point A crosses the ice/water boundary to point B,
which lies in the liquid water region. Consequently, applying a pressure of 150 atm will melt ice at −1.0°C. We have already
indicated that the pressure dependence of the melting point of water is of vital importance. If the solid/liquid boundary in the phase
diagram of water were to slant up and to the right rather than to the left, ice would be denser than water, ice cubes would sink,
water pipes would not burst when they freeze, and antifreeze would be unnecessary in automobile engines.

 Ice Skating: An Incorrect Hypothesis of Phase Transitions

Until recently, many textbooks described ice skating as being possible because the pressure generated by the skater’s blade is
high enough to melt the ice under the blade, thereby creating a lubricating layer of liquid water that enables the blade to slide
across the ice. Although this explanation is intuitively satisfying, it is incorrect, as we can show by a simple calculation.

3.6.2 https://chem.libretexts.org/@go/page/43108
 Pressure from ice skates on ice. from wikihow.com.
Recall that pressure (P) is the force (F) applied per unit area (A):
F
P =
A

To calculate the pressure an ice skater exerts on the ice, we need to calculate only the force exerted and the area of the skate
blade. If we assume a 75.0 kg (165 lb) skater, then the force exerted by the skater on the ice due to gravity is

F = mg

where m is the mass and g is the acceleration due to Earth’s gravity (9.81 m/s2). Thus the force is
2 2
F = (75.0 kg)(9.81 m/ s ) = 736 (kg ∙ m)/ s = 736N

If we assume that the skate blades are 2.0 mm wide and 25 cm long, then the area of the bottom of each blade is
−3 −2 −4 2
A = (2.0 × 10 m)(25 × 10 m) = 5.0 × 10 m

If the skater is gliding on one foot, the pressure exerted on the ice is
736 N
6 2 6
P = = 1.5 × 10 N /m = 1.5 × 10 P a = 15 atm
−4 2
5.0 × 10 m

The pressure is much lower than the pressure needed to decrease the melting point of ice by even 1°C, and experience indicates
that it is possible to skate even when the temperature is well below freezing. Thus pressure-induced melting of the ice cannot
explain the low friction that enables skaters (and hockey pucks) to glide. Recent research indicates that the surface of ice,
where the ordered array of water molecules meets the air, consists of one or more layers of almost liquid water. These layers,
together with melting induced by friction as a skater pushes forward, appear to account for both the ease with which a skater
glides and the fact that skating becomes more difficult below about −7°C, when the number of lubricating surface water layers
decreases.

 Example 3.6.1: Water

Referring to the phase diagram of water in Figure 3.6.2:

a. predict the physical form of a sample of water at 400°C and 150 atm.
b. describe the changes that occur as the sample in part (a) is slowly allowed to cool to −50°C at a constant pressure of 150
atm.
Given: phase diagram, temperature, and pressure
Asked for: physical form and physical changes

Strategy:
A. Identify the region of the phase diagram corresponding to the initial conditions and identify the phase that exists in this
region.
B. Draw a line corresponding to the given pressure. Move along that line in the appropriate direction (in this case cooling) and
describe the phase changes.

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 Solution:
a. A Locate the starting point on the phase diagram in part (a) in Figure 3.6.2. The initial conditions correspond to point A,
which lies in the region of the phase diagram representing water vapor. Thus water at T = 400°C and P = 150 atm is a gas.
b. B Cooling the sample at constant pressure corresponds to moving left along the horizontal line in part (a) in Figure 3.6.2.
At about 340°C (point B), we cross the vapor pressure curve, at which point water vapor will begin to condense and the
sample will consist of a mixture of vapor and liquid. When all of the vapor has condensed, the temperature drops further,
and we enter the region corresponding to liquid water (indicated by point C). Further cooling brings us to the melting curve,
the line that separates the liquid and solid phases at a little below 0°C (point D), at which point the sample will consist of a
mixture of liquid and solid water (ice). When all of the water has frozen, cooling the sample to −50°C takes us along the
horizontal line to point E, which lies within the region corresponding to solid water. At P = 150 atm and T = −50°C,
therefore, the sample is solid ice.

 Exercise 3.6.2

Referring to the phase diagram of water in Figure 3.6.2, predict the physical form of a sample of water at −0.0050°C as the
pressure is gradually increased from 1.0 mmHg to 218 atm.

Answer
The sample is initially a gas, condenses to a solid as the pressure increases, and then melts when the pressure is increased
further to give a liquid.

3.6.3: The Phase Diagram of Carbon Dioxide

In contrast to the phase diagram of water, the phase diagram of CO2 (Figure 3.6.3) has a more typical melting curve, sloping up
and to the right. The triple point is −56.6°C and 5.11 atm, which means that liquid CO2 cannot exist at pressures lower than 5.11
atm. At 1 atm, therefore, solid CO2 sublimes directly to the vapor while maintaining a temperature of −78.5°C, the normal
sublimation temperature. Solid CO2 is generally known as dry ice because it is a cold solid with no liquid phase observed when it is
warmed.

Dry ice (CO 2

) sublimed in air under room temperature and pressure. from Wikipedia.
(s)

Also notice the critical point at 30.98°C and 72.79 atm. Supercritical carbon dioxide is emerging as a natural refrigerant, making it
a low carbon (and thus a more environmentally friendly) solution for domestic heat pumps.

3.6.4 https://chem.libretexts.org/@go/page/43108
 Figure 3.6.3 : The Phase Diagram of Carbon Dioxide. Note the critical point, the triple point, and the normal sublimation
temperature in this diagram.
The triple point is at -57.57 degrees C and 5.11 atm. The critical point is at 30.98 degree C and 72.79 atm.

3.6.4: The Critical Point

As the phase diagrams above demonstrate, a combination of high pressure and low temperature allows gases to be liquefied. As we
increase the temperature of a gas, liquefaction becomes more and more difficult because higher and higher pressures are required to
overcome the increased kinetic energy of the molecules. In fact, for every substance, there is some temperature above which the gas
can no longer be liquefied, regardless of pressure. This temperature is the critical temperature (Tc), the highest temperature at which
a substance can exist as a liquid. Above the critical temperature, the molecules have too much kinetic energy for the intermolecular
attractive forces to hold them together in a separate liquid phase. Instead, the substance forms a single phase that completely
occupies the volume of the container. Substances with strong intermolecular forces tend to form a liquid phase over a very large
temperature range and therefore have high critical temperatures. Conversely, substances with weak intermolecular interactions have
relatively low critical temperatures. Each substance also has a critical pressure (Pc), the minimum pressure needed to liquefy it at
the critical temperature. The combination of critical temperature and critical pressure is called the critical point. The critical
temperatures and pressures of several common substances are listed in Figure 3.6.1.
Figure 3.6.1 : Critical Temperatures and Pressures of Some Simple Substances
Substance Tc (°C) Pc (atm)

NH3 132.4 113.5

CO2 31.0 73.8

CH3CH2OH (ethanol) 240.9 61.4

He −267.96 2.27

Hg 1477 1587

CH4 −82.6 46.0

N2 −146.9 33.9

H2O 374.0 217.7

High-boiling-point, nonvolatile liquids have high critical temperatures and vice versa.

3.6.5: Supercritical Fluids

3.6.5 https://chem.libretexts.org/@go/page/43108
 Phase Diagrams

A Video Discussing Phase Diagrams. Video Source: Phase Diagrams(opens in new window) [youtu.be]

This page titled 3.6: Phase Diagrams is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Delmar Larsen.
11.6: Phase Diagrams is licensed CC BY-NC-SA 3.0.

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3.7: Clausius-Clapeyron Equation
 Learning Objectives
Apply the Clausius-Clapeyron equation to estimate the vapor pressure at any temperature.
Estimate the heat of phase transition from the vapor pressures measured at two temperatures.

The vaporization curves of most liquids have similar shapes with the vapor pressure steadily increasing as the temperature
increases (Figure 3.7.1).

Figure 3.7.1 : The Vapor Pressures of Several Liquids as a Function of Temperature. The point at which the vapor pressure curve
crosses the P = 1 atm line (dashed) is the normal boiling point of the liquid. (CC BY-SA-NC 3.0; Anonymous)
A good approach is to find a mathematical model for the pressure increase as a function of temperature. Experiments showed that
the vapor pressure P and temperature T are related,
ΔHvap
P ∝ exp(− ) (3.7.1)
RT

where ΔH vap is the Enthalpy (heat) of Vaporization and R is the gas constant (8.3145 J mol-1 K-1).
A simple relationship can be found by integrating Equation 3.7.1 between two pressure-temperature endpoints:

P1 ΔHvap 1 1
ln( ) = ( − ) (3.7.2)
P2 R T2 T1

where P and P are the vapor pressures at two temperatures T and T . Equation 3.7.2 is known as the Clausius-Clapeyron
1 2 1 2

Equation and allows us to estimate the vapor pressure at another temperature, if the vapor pressure is known at some temperature,
and if the enthalpy of vaporization is known.

 Alternative Formulation
The order of the temperatures in Equation 3.7.2 matters as the Clausius-Clapeyron Equation is sometimes written with a
negative sign (and switched order of temperatures):
P1 ΔHvap 1 1
ln( ) =− ( − ) (3.7.3)
P2 R T1 T2

3.7.1 https://chem.libretexts.org/@go/page/96724
  Example 3.7.1: Vapor Pressure of Water

The vapor pressure of water is 1.0 atm at 373 K, and the enthalpy of vaporization is 40.7 kJ mol-1. Estimate the vapor pressure
at temperature 363 and 383 K respectively.

Solution
Using the Clausius-Clapeyron equation (Equation 3.7.3), we have:
40, 700 1 1
P363 = 1.0 exp[− ( )( − )]
8.3145 363 K 373 K

= 0.697 atm

40, 700 1 1
P383 = 1.0 exp[− ( )( − )]
8.3145 383 K 373 K

= 1.409 atm

Note that the increase in vapor pressure from 363 K to 373 K is 0.303 atm, but the increase from 373 to 383 K is 0.409 atm.
The increase in vapor pressure is not a linear process.

Discussion
We can use the Clausius-Clapeyron equation to construct the entire vaporization curve. There is a deviation from experimental
value, that is because the enthalpy of vaporization varies slightly with temperature.

The Clausius-Clapeyron equation can be also applied to sublimation; the following example shows its application in estimating the
heat of sublimation.

 Example 3.7.2: Sublimation of Ice

The vapor pressures of ice at 268 K and 273 K are 2.965 and 4.560 torr respectively. Estimate the heat of sublimation of ice.

Solution
The enthalpy of sublimation is ΔHsub . Use a piece of paper and derive the Clausius-Clapeyron equation so that you can get
the form:
P273
R ln( )
P268
ΔHsub =
1 1
−
268 K 273 K

4.560
8.3145 ln( )
2.965
=
1 1
−
268 K 273 K

−1
= 52, 370 J mol

Note that the heat of sublimation is the sum of heat of melting (6,006 J/mol at 0°C and 101 kPa) and the heat of vaporization
(45,051 J/mol at 0 °C).

3.7.2 https://chem.libretexts.org/@go/page/96724
  Exercise 3.7.2

Show that the vapor pressure of ice at 274 K is higher than that of water at the same temperature. Note the curve of
vaporization is also called the curve of evaporization.

 Example 3.7.3: Vaporization of Ethanol

Calculate ΔH vap for ethanol, given vapor pressure at 40 oC = 150 torr. The normal boiling point for ethanol is 78 oC.

Solution
Recognize that we have TWO sets of (P , T ) data:
Set 1: (150 torr at 40+273K)
Set 2: (760 torr at 78+273K)
We then directly use these data in Equation 3.7.3

150 −ΔHvap 1 1
ln( ) = [ − ]
760 8.314 313 351

−ΔHvap 1 1
ln 150 − ln 760 = [ − ]
8.314 313 351

−ΔHvap
−1.623 = [0.0032 − 0.0028]
8.314

Then solving for ΔH vap

4
ΔHvap = 3.90 × 10 joule/mole

= 39.0 kJ/mole

 Advanced Note

It is important to not use the Clausius-Clapeyron equation for the solid to liquid transition. That requires the use of the more
general Clapeyron equation
¯
dP ΔH
=
dT ¯
T ΔV

where ΔH ¯
and ΔV¯ is the molar change in enthalpy (the enthalpy of fusion in this case) and volume respectively between the
two phases in the transition.

This page titled 3.7: Clausius-Clapeyron Equation is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
Delmar Larsen.
Clausius-Clapeyron Equation by Albert Censullo, Chung (Peter) Chieh is licensed CC BY-NC-SA 4.0.

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3.8: The Solid State
 Learning Objectives
Define and describe the bonding and properties of ionic, molecular, metallic, and covalent network crystalline solids
Describe the main types of crystalline solids: ionic solids, metallic solids, covalent network solids, and molecular solids
Explain the ways in which crystal defects can occur in a solid

When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which the atoms, ions, or molecules are
arranged in a definite repeating pattern. It is also possible for a liquid to freeze before its molecules become arranged in an orderly
pattern. The resulting materials are called amorphous solids or noncrystalline solids (or, sometimes, glasses). The particles of such
solids lack an ordered internal structure and are randomly arranged (Figure 3.8.1).

Figure 3.8.1 : The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline solids) or randomly
(amorphous).
The crystalline arrangement shows many circles drawn in rows and stacked together tightly. The amorphous arrangement shows
many circles spread slightly apart and in no organized pattern.
Metals and ionic compounds typically form ordered, crystalline solids. Substances that consist of large molecules, or a mixture of
molecules whose movements are more restricted, often form amorphous solids. For examples, candle waxes are amorphous solids
composed of large hydrocarbon molecules. Some substances, such as boron oxide (Figure 3.8.2), can form either crystalline or
amorphous solids, depending on the conditions under which it is produced. Also, amorphous solids may undergo a transition to the
crystalline state under appropriate conditions.

Figure 3.8.2 : (a) Diboron trioxide, B2O3, is normally found as a white, amorphous solid (a glass), which has a high degree of
disorder in its structure. (b) By careful, extended heating, it can be converted into a crystalline form of B2O3, which has a very
ordered arrangement.
The first structure of diboron trioxide shows five identical and separated hexagonal rings. The second structure of diboron trioxide
shows a more interconnected structure with four large rings forming a more stable structure.
Crystalline solids are generally classified according the nature of the forces that hold its particles together. These forces are
primarily responsible for the physical properties exhibited by the bulk solids. The following sections provide descriptions of the

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major types of crystalline solids: ionic, metallic, covalent network, and molecular.

3.8.1: Ionic Solids

Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and negative ions that are held together by
electrostatic attractions, which can be quite strong (Figure 3.8.3). Many ionic crystals also have high melting points. This is due to
the very strong attractions between the ions—in ionic compounds, the attractions between full charges are (much) larger than those
between the partial charges in polar molecular compounds. This will be looked at in more detail in a later discussion of lattice
energies. Although they are hard, they also tend to be brittle, and they shatter rather than bend. Ionic solids do not conduct
electricity; however, they do conduct when molten or dissolved because their ions are free to move. Many simple compounds
formed by the reaction of a metallic element with a nonmetallic element are ionic.

Figure 3.8.3 : Sodium chloride is an ionic solid.

A cube composed of purple and green spheres is shown. The cube has dimensions of three by three spheres. The purple spheres are
slightly larger than the green spheres.

3.8.2: Metallic Solids

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms Figure 3.8.4. The structure of metallic
crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such
a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk
properties. All exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many are very hard and quite
strong. Because of their malleability (the ability to deform under pressure or hammering), they do not shatter and, therefore, make
useful construction materials. The melting points of the metals vary widely. Mercury is a liquid at room temperature, and the alkali
metals melt below 200 °C. Several post-transition metals also have low melting points, whereas the transition metals melt at
temperatures above 1000 °C. These differences reflect differences in strengths of metallic bonding among the metals.

Figure 3.8.4 : Copper is a metallic solid.

3.8.3: Covalent Network Solids

Covalent network solids include crystals of diamond, silicon, some other nonmetals, and some covalent compounds such as silicon
dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds. The
atoms in these solids are held together by a network of covalent bonds, as shown in Figure 3.8.5. To break or to melt a covalent
network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically
characterized by hardness, strength, and high melting points. For example, diamond is one of the hardest substances known and
melts above 3500 °C.

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 Figure 3.8.5 . A covalent crystal contains a three-dimensional network of covalent bonds, as illustrated by the structures of
diamond, silicon dioxide, silicon carbide, and graphite. Graphite is an exceptional example, composed of planar sheets of covalent
crystals that are held together in layers by noncovalent forces. Unlike typical covalent solids, graphite is very soft and electrically
conductive.
The complex three dimensional structure of diamond, silicon dioxide, silicon carbide and graphite is shown along with a a smaller
repeating unit of the structure shown above each structure.

3.8.4: Molecular Solids

Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 3.8.6, are composed of neutral molecules. The
strengths of the attractive forces between the units present in different crystals vary widely, as indicated by the melting points of the
crystals. Small symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have weak attractive forces and form
molecular solids with very low melting points (below −200 °C). Substances consisting of larger, nonpolar molecules have larger
attractive forces and melt at higher temperatures. Molecular solids composed of molecules with permanent dipole moments (polar
molecules) melt at still higher temperatures. Examples include ice (melting point, 0 °C) and table sugar (melting point, 185 °C).

Figure 3.8.6 : Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular solid with a melting point of −78
°C. Iodine (I2) consists of larger, nonpolar molecules and forms a molecular solid that melts at 114 °C.
On the left, many red and grey molecules are densely stacked in a 3-D drawing to represent carbon dioxide. On the right, purple
molecules are scattered randomly to represent iodine.

3.8.5: Properties of Solids

A crystalline solid, like those listed in Table 3.8.1 has a precise melting temperature because each atom or molecule of the same
type is held in place with the same forces or energy. Thus, the attractions between the units that make up the crystal all have the
same strength and all require the same amount of energy to be broken. The gradual softening of an amorphous material differs
dramatically from the distinct melting of a crystalline solid. This results from the structural nonequivalence of the molecules in the
amorphous solid. Some forces are weaker than others, and when an amorphous material is heated, the weakest intermolecular
attractions break first. As the temperature is increased further, the stronger attractions are broken. Thus amorphous materials soften
over a range of temperatures.
Table 3.8.1 : Types of Crystalline Solids and Their Properties

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 Type of Solid Type of Particles Type of Attractions Properties Examples

hard, brittle, conducts

electricity as a liquid but
ionic ions ionic bonds NaCl, Al2O3
not as a solid, high to very
high melting points

shiny, malleable, ductile,

conducts heat and
atoms of electropositive
metallic metallic bonds electricity well, variable Cu, Fe, Ti, Pb, U
elements
hardness and melting
temperature

atoms of electronegative very hard, not conductive,

covalent network covalent bonds C (diamond), SiO2, SiC
elements very high melting points

variable hardness, variable

molecular molecules (or atoms) IMFs brittleness, not conductive, H2O, CO2, I2, C12H22O11
low melting points

 Graphene: Material of the Future

Carbon is an essential element in our world. The unique properties of carbon atoms allow the existence of carbon-based life
forms such as ourselves. Carbon forms a huge variety of substances that we use on a daily basis, including those shown in
Figure 3.8.7. You may be familiar with diamond and graphite, the two most common allotropes of carbon. (Allotropes are
different structural forms of the same element.) Diamond is one of the hardest-known substances, whereas graphite is soft
enough to be used as pencil lead. These very different properties stem from the different arrangements of the carbon atoms in
the different allotropes.

Figure 3.8.7 : Diamond is extremely hard because of the strong bonding between carbon atoms in all directions. Graphite (in
pencil lead) rubs off onto paper due to the weak attractions between the carbon layers. An image of a graphite surface shows
the distance between the centers of adjacent carbon atoms. (credit left photo: modification of work by Steve Jurvetson; credit
middle photo: modification of work by United States Geological Survey)
A close up of a piece of diamond shows a three dimensional sturcture of a complex network of well bonded carbon atoms. A
close up of a graphite shows several layers of carbon sheets. Each sheet is composed of a repeated and connected hexagonal
structure of carbon atoms. The third diagram shows that the distance between the center of atoms is 1.4 times 10 to the power
of negative 10 meters.
You may be less familiar with a recently discovered form of carbon: graphene. Graphene was first isolated in 2004 by using
tape to peel off thinner and thinner layers from graphite. It is essentially a single sheet (one atom thick) of graphite. Graphene,
illustrated in Figure 3.8.8, is not only strong and lightweight, but it is also an excellent conductor of electricity and heat. These

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 properties may prove very useful in a wide range of applications, such as vastly improved computer chips and circuits, better
batteries and solar cells, and stronger and lighter structural materials. The 2010 Nobel Prize in Physics was awarded to Andre
Geim and Konstantin Novoselov for their pioneering work with graphene.

Figure 3.8.8 : Graphene sheets can be formed into buckyballs, nanotubes, and stacked layers.
A sheet of interconnected hexagonal rings is shown at the top. Below it, a bukcyball is shown which is a sphere is composed of
hexagonal rings. In the lower middle image, a nanotube is shown that is made by rolling a graphene sheet into a tube. In the
lower right image, stacked sheets made up of four horizontal sheets composed of joined, hexagonal rings is shown.

3.8.6: Crystal Defects

In a crystalline solid, the atoms, ions, or molecules are arranged in a definite repeating pattern, but occasional defects may occur in
the pattern. Several types of defects are known, as illustrated in Figure 3.8.9. Vacancies are defects that occur when positions that
should contain atoms or ions are vacant. Less commonly, some atoms or ions in a crystal may occupy positions, called interstitial
sites, located between the regular positions for atoms. Other distortions are found in impure crystals, as, for example, when the
cations, anions, or molecules of the impurity are too large to fit into the regular positions without distorting the structure. Trace
amounts of impurities are sometimes added to a crystal (a process known as doping) in order to create defects in the structure that
yield desirable changes in its properties. For example, silicon crystals are doped with varying amounts of different elements to
yield suitable electrical properties for their use in the manufacture of semiconductors and computer chips.

Figure 3.8.9 : Types of crystal defects include vacancies, interstitial atoms, and substitutions impurities.

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Summary
Some substances form crystalline solids consisting of particles in a very organized structure; others form amorphous
(noncrystalline) solids with an internal structure that is not ordered. The main types of crystalline solids are ionic solids, metallic
solids, covalent network solids, and molecular solids. The properties of the different kinds of crystalline solids are due to the types
of particles of which they consist, the arrangements of the particles, and the strengths of the attractions between them. Because
their particles experience identical attractions, crystalline solids have distinct melting temperatures; the particles in amorphous
solids experience a range of interactions, so they soften gradually and melt over a range of temperatures. Some crystalline solids
have defects in the definite repeating pattern of their particles. These defects (which include vacancies, atoms or ions not in the
regular positions, and impurities) change physical properties such as electrical conductivity, which is exploited in the silicon
crystals used to manufacture computer chips.

Glossary
amorphous solid
(also, noncrystalline solid) solid in which the particles lack an ordered internal structure

covalent network solid

solid whose particles are held together by covalent bonds

crystalline solid
solid in which the particles are arranged in a definite repeating pattern

interstitial sites
spaces between the regular particle positions in any array of atoms or ions

ionic solid
solid composed of positive and negative ions held together by strong electrostatic attractions

metallic solid
solid composed of metal atoms

molecular solid
solid composed of neutral molecules held together by intermolecular forces of attraction

vacancy
defect that occurs when a position that should contain an atom or ion is vacant

This page titled 3.8: The Solid State is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Delmar Larsen.
10.5: The Solid State of Matter by OpenStax is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

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3.9: Bonding in Metals
In the early 1900's, Paul Drüde came up with the "sea of electrons" metallic bonding theory by modeling metals as a mixture of
atomic cores (atomic cores = positive nuclei + inner shell of electrons) and valence electrons. Metallic bonds occur among metal
atoms. Whereas ionic bonds join metals to non-metals, metallic bonding joins a bulk of metal atoms. A sheet of aluminum foil and
a copper wire are both places where you can see metallic bonding in action.
Metals tend to have high melting points and boiling points suggesting strong bonds between the atoms. Even a soft metal like
sodium (melting point 97.8°C) melts at a considerably higher temperature than the element (neon) which precedes it in the Periodic
Table. Sodium has the electronic structure 1s22s22p63s1. When sodium atoms come together, the electron in the 3s atomic orbital of
one sodium atom shares space with the corresponding electron on a neighboring atom to form a molecular orbital - in much the
same sort of way that a covalent bond is formed.
The difference, however, is that each sodium atom is being touched by eight other sodium atoms - and the sharing occurs between
the central atom and the 3s orbitals on all of the eight other atoms. Each of these eight is in turn being touched by eight sodium
atoms, which in turn are touched by eight atoms - and so on and so on, until you have taken in all the atoms in that lump of sodium.
All of the 3s orbitals on all of the atoms overlap to give a vast number of molecular orbitals that extend over the whole piece of
metal. There have to be huge numbers of molecular orbitals, of course, because any orbital can only hold two electrons.
The electrons can move freely within these molecular orbitals, and so each electron becomes detached from its parent atom. The
electrons are said to be delocalized. The metal is held together by the strong forces of attraction between the positive nuclei and the
delocalized electrons (Figure 3.9.1).

Figure 3.9.1 : Metallic Bonding: The Electron Sea Model: Positive atomic nuclei (orange circles) surrounded by a sea of
delocalized electrons (yellow circles).
This is sometimes described as "an array of positive ions in a sea of electrons". If you are going to use this view, beware! Is a metal
made up of atoms or ions? It is made of atoms. Each positive center in the diagram represents all the rest of the atom apart from the
outer electron, but that electron has not been lost - it may no longer have an attachment to a particular atom, but it's still there in the
structure. Sodium metal is therefore written as Na, not Na . +

 Example 3.9.1: Metallic bonding in magnesium

Use the sea of electrons model to explain why Magnesium has a higher melting point (650 °C) than sodium (97.79 °C).

Solution
If you work through the same argument above for sodium with magnesium, you end up with stronger bonds and hence a higher
melting point.
Magnesium has the outer electronic structure 3s2. Both of these electrons become delocalized, so the "sea" has twice the
electron density as it does in sodium. The remaining "ions" also have twice the charge (if you are going to use this particular
view of the metal bond) and so there will be more attraction between "ions" and "sea".
More realistically, each magnesium atom has 12 protons in the nucleus compared with sodium's 11. In both cases, the nucleus
is screened from the delocalized electrons by the same number of inner electrons - the 10 electrons in the 1s2 2s2 2p6 orbitals.

3.9.1 https://chem.libretexts.org/@go/page/96758
 That means that there will be a net pull from the magnesium nucleus of 2+, but only 1+ from the sodium nucleus.
So not only will there be a greater number of delocalized electrons in magnesium, but there will also be a greater attraction for
them from the magnesium nuclei. Magnesium atoms also have a slightly smaller radius than sodium atoms, and so the
delocalized electrons are closer to the nuclei. Each magnesium atom also has twelve near neighbors rather than sodium's eight.
Both of these factors increase the strength of the bond still further.
Note: Transition metals tend to have particularly high melting points and boiling points. The reason is that they can involve the
3d electrons in the delocalization as well as the 4s. The more electrons you can involve, the stronger the attractions tend to be.

 Bulk properties of metals

Metals have several qualities that are unique, such as the ability to conduct electricity and heat, a low ionization energy, and a
low electronegativity (so they will give up electrons easily to form cations). Their physical properties include a lustrous (shiny)
appearance, and they are malleable and ductile. Metals have a crystal structure but can be easily deformed. In this model, the
valence electrons are free, delocalized, mobile, and not associated with any particular atom. This model may account for:
Conductivity: Since the electrons are free, if electrons from an outside source were pushed into a metal wire at one end
(Figure 3.9.2), the electrons would move through the wire and come out at the other end at the same rate (conductivity is
the movement of charge).

Figure 3.9.2 : The "sea of electrons" is free to flow about the crystal of positive metal ions. These flowing electron can conduct
electrical change when an electric field is applied (e.g., a battery). (CC-BY-SA; OpenStax and Rafaelgarcia).
Malleability and Ductility: The electron-sea model of metals not only explains their electrical properties but their
malleability and ductility as well. The sea of electrons surrounding the protons acts like a cushion, and so when the metal is
hammered on, for instance, the overall composition of the structure of the metal is not harmed or changed. The protons may
be rearranged but the sea of electrons with adjust to the new formation of protons and keep the metal intact. When one layer
of ions in an electron sea moves along one space with respect to the layer below it, the crystal structure does not fracture
but is only deformed (Figure 3.9.3).

Figure 3.9.3 : Malleability of metals originate from each of moving layer of atoms with respect to each other. The final
situation is much the same as the initial. Thus if we hit a metal with a hammer, the crystals do not shatter, but merely change
their shape, This is very different from the behavior of ionic crystals.
Heat capacity: This is explained by the ability of free electrons to move about the solid.
Luster: The free electrons can absorb photons in the "sea," so metals are opaque-looking. Electrons on the surface can
bounce back light at the same frequency that the light hits the surface, therefore the metal appears to be shiny.
However, these observations are only qualitative, and not quantitative, so they cannot be tested. The "Sea of Electrons" theory
stands today only as an oversimplified model of how metallic bonding works.

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In a molten metal, the metallic bond is still present, although the ordered structure has been broken down. The metallic bond is not
fully broken until the metal boils. That means that boiling point is actually a better guide to the strength of the metallic bond than
melting point is. On melting, the bond is loosened, not broken. The strength of a metallic bond depends on three things:
1. The number of electrons that become delocalized from the metal
2. The charge of the cation (metal).
3. The size of the cation.
A strong metallic bond will be the result of more delocalized electrons, which causes the effective nuclear charge on electrons on
the cation to increase, in effect making the size of the cation smaller. Metallic bonds are strong and require a great deal of energy to
break, and therefore metals have high melting and boiling points. A metallic bonding theory must explain how so much bonding
can occur with such few electrons (since metals are located on the left side of the periodic table and do not have many electrons in
their valence shells). The theory must also account for all of a metal's unique chemical and physical properties.

3.9.1: Expanding the Range of Bonding Possible

Previously, we argued that bonding between atoms can classified as range of possible bonding between ionic bonds (fully charge
transfer) and covalent bonds (fully shared electrons). When two atoms of slightly differing electronegativities come together to
form a covalent bond, one atom attracts the electrons more than the other; this is called a polar covalent bond. However, simple
“ionic” and “covalent” bonding are idealized concepts and most bonds exist on a two-dimensional continuum described by the van
Arkel-Ketelaar Triangle (Figure 3.9.4).

Figure 3.9.4 : van Arkel-Ketelaar Triangle plots the difference in electronegativity (Δχ) and the average electronegativity in a bond
(∑ χ ). the top region is where bonds are mostly ionic, the lower left region is where bonding is metallic, and the lower right region
is where the bonding is covalent.
Bond triangles or van Arkel–Ketelaar triangles (named after Anton Eduard van Arkel and J. A. A. Ketelaar) are triangles used for
showing different compounds in varying degrees of ionic, metallic and covalent bonding. In 1941 van Arkel recognized three
extreme materials and associated bonding types. Using 36 main group elements, such as metals, metalloids and non-metals, he
placed ionic, metallic and covalent bonds on the corners of an equilateral triangle, as well as suggested intermediate species. The
bond triangle shows that chemical bonds are not just particular bonds of a specific type. Rather, bond types are interconnected and
different compounds have varying degrees of different bonding character (for example, polar covalent bonds).

3.9.3 https://chem.libretexts.org/@go/page/96758
 A1/S2.4.1/2 What is the van Arkel-Ketel…
Arkel-Ketel…

Video 3.9.1 : What is the van Arkel-Ketelaar Triangle of Bonding?

Using electronegativity - two compound average electronegativity on x-axis of Figure 3.9.4.
χA + χB
∑χ = (3.9.1)
2

and electronegativity difference on y-axis,

Δχ = | χA − χB | (3.9.2)

we can rate the dominant bond between the compounds. On the right side of Figure 3.9.4 (from ionic to covalent) should be
compounds with varying difference in electronegativity. The compounds with equal electronegativity, such as Cl (chlorine) are
2

placed in the covalent corner, while the ionic corner has compounds with large electronegativity difference, such as NaCl (table
salt). The bottom side (from metallic to covalent) contains compounds with varying degree of directionality in the bond. At one
extreme is metallic bonds with delocalized bonding and at the other are covalent bonds in which the orbitals overlap in a particular
direction. The left side (from ionic to metallic) is meant for delocalized bonds with varying electronegativity difference.

 The Three Extremes in bonding

In general:
Metallic bonds have low Δχ and low average ∑ χ.
Ionic bonds have moderate-to-high Δχ and moderate values of average ∑ χ.
Covalent bonds have moderate to high average ∑ χ and can exist with moderately low Δχ.

 Example 3.9.2

Use the tables of electronegativities (Table A2) and Figure 3.9.4 to estimate the following values
difference in electronegativity (Δχ)
average electronegativity in a bond (∑ χ)
percent ionic character
likely bond type
for the selected compounds:
a. AsH (e.g., in arsine AsH )
b. SrLi
c. KF.

Solution
a: AsH

3.9.4 https://chem.libretexts.org/@go/page/96758
 The electronegativity of As is 2.18
The electronegativity of H is 2.22
Using Equations 3.9.1 and 3.9.2:
χA + χB
∑χ =
2

2.18 + 2.22
=
2

= 2.2

Δχ = χA − χB

= 2.18 − 2.22

= 0.04

From Figure 3.9.4, the bond is fairly nonpolar and has a low ionic character (10% or less)
The bonding is in the middle of a covalent bond and a metallic bond
b: SrLi
The electronegativity of Sr is 0.95
The electronegativity of Li is 0.98
Using Equations 3.9.1 and 3.9.2:
χA + χB
∑χ =
2

0.95 + 0.98
=
2

= 0.965

Δχ = χA − χB

= 0.98 − 0.95

= 0.025

From Figure 3.9.4, the bond is fairly nonpolar and has a low ionic character (~3% or less)
The bonding is likely metallic.
c: KF
The electronegativity of K is 0.82
The electronegativity of F is 3.98
Using Equations 3.9.1 and 3.9.2:
χA + χB
∑χ =
2

0.82 + 3.98
=
2

= 2.4

Δχ = χA − χB

= |0.82 − 3.98|

= 3.16

From Figure 3.9.4, the bond is fairly polar and has a high ionic character (~75%)
The bonding is likely ionic.

3.9.5 https://chem.libretexts.org/@go/page/96758
  Exercise 3.9.2

Contrast the bonding of NaCl and silicon tetrafluoride.

Answer
NaCl is an ionic crystal structure, and an electrolyte when dissolved in water; Δχ = 1.58, average ∑ χ = 1.79 , while
silicon tetrafluoride is covalent (molecular, non-polar gas; Δχ = 2.08, average ∑ χ = 2.94.

3.9.2: Contributors and Attributions

Jim Clark (Chemguide.co.uk)
Daniel James Berger
Wikipedia
Ed Vitz (Kutztown University), John W. Moore (UW-Madison), Justin Shorb (Hope College), Xavier Prat-Resina (University of
Minnesota Rochester), Tim Wendorff, and Adam Hahn.

This page titled 3.9: Bonding in Metals is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Delmar Larsen.
Metallic Bonding by Jim Clark is licensed CC BY-NC 4.0.

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3.E: Solids, Liquids, and Phase Transitions (Exercises)
These are homework exercises to accompany the Textmap created for "Principles of Modern Chemistry" by Oxtoby et al.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here.

3.E.1: Q.1
If a substance has relatively strong intermolecular forces, a high melting point, and is not easily compressed, will this substance be
a solid, liquid, or gas?

3.E.2: Q.3
An unknown sample at 25 o
C had a volume of 3.00 × 10 14
μm
3
and a mass of 3.20 × 10 3
g .
g
a. Is this sample most likely in a gaseous state or a condensed one? Why? (HINT: The density of water is 1.000 ).
mL

b. After completing mass spectroscopy the molar mass of the material was found to be 127 g mol-1, what is the molar volume at
25 C from using the answer in part (a).
o

3.E.3: Q.6A
If the volume of a substance changes from 300 cm to 313 cm when it is heated from 25
3 3 o
C to 40
o
C , is the substance ideal gas,
nearly ideal gas, or condensed?

3.E.4: Q.6B
Cooling a sample of matter from 130° to 50° at a constant pressure causes its volume to increase from 769.1 to 930.1 cm3. Classify
the material as nearly ideal gas, a non ideal gas, or condensed.

3.E.5: Q.7
The molar volume of a substance is the volume occupied by one mole of the substance. The molar volume of a typical solid or
3 3 3

liquid is 10 cm

mol
to 100 cm

mol
, while the molar volume of a gas under the same conditions is about 24, 000 . What does the cm

mol

similarity of the molar volumes of solid and liquid forms of the same substance suggest? What does the great difference of the the
molar volumes of solid/liquid and gas forms of the same substance suggest?

3.E.6: Q.9
Suppose you have to choose between solid I
2
and solid NH Cl
4
to fill your cushion and you prefer softer cushions, which one
would you choose and why?

3.E.7: Q.11
The diffusion constant is defined as the amount of substance that when diffusing from a region of high concentration to that of a
low concentration goes through each unit of cross section per unit time. What happens to the diffusion constant, at constant
temperature, as density of a liquid decreases, as the density of a solid increases, and as the density of a gas decreases? Explain the
phenomena.

3.E.8: Q.15
For the following chemicals list attractive intermolecular forces that you expect to see with each chemical. Of the forces you listed
for each example, rank the intermolecular forces from strongest to weakest.
a. He
b. H O
2

c. NaCl
d. CH 4

e. CO
f. O2

3.E.1 https://chem.libretexts.org/@go/page/69604
3.E.9: Q.17
Which of the the following will be most strongly attracted to a lithium ion:
a. fluoride ion
b. a molecule of hydrogen fluoride
c. atom of Argon

3.E.10: Q.19
Estimate the bond length of He , Ar , and Xe from the potential energy curves below. For each interacting pair, identify the
2 2 2

attractive and repulsive distances. What are the intermolecular forces exist in each of the pair of molecules? Order the potential
interactions in term of strength of intermolecular forces.

3.E.11: Q.23
Arrange the following substances in order of decreasing normal boiling points and explain the rationale.
a. CH 3
CH CH CH CH
2 2 2 3

b. CH 3
CH CH CH OH
2 2 2

c. CH 4

d. CH 3
CH(CH )CH CH
3 2 3

3.E.12: Q.24
You are given four beakers A, B, C, and D with four different chemicals. You forgot to label the beakers, so to identify them you
boiled them to find their normal boiling points. The order of the boiling points came out to be B>D>A>C. If the chemicals in the
beakers were HF (Hydrogen Fluoride), Ar (Argon), Cesium Chloride CsCl and Hydrochloric Acid HCl, assign the chemicals to
their respective beakers and give the reasoning behind your answer.

3.E.13: Q.25
Like a normal human being, Kris enjoys breathing. But unfortunately for Kris, she is clinically paranoid, and feels as though she's
breathing in a little too much ethanol. To calm Kris down, you say that as a vapor, ethanol exists, to an extent, as a dimer, (
(CH CH OH) ), in which two CH CH OH molecules are held together by hydrogen bonds. Propose and draw a reasonable
3 2 2 3 2

structure for this dimer to help Kris deal with her problems.

3.E.14: Q.25
Acetic acid (CH COOH ) forms a dimer in the gas phase, where two acetic acid molecules are held together by hydrogen bonds.
3

Draw a reasonable structure for this dimer.

3.E.2 https://chem.libretexts.org/@go/page/69604
3.E.15: Q.26
Hypochlorous acid (HOCl) is a similar compound to HOF , which is the simplest possible compound that allows comparison
between fluoride and oxygen in their abilities to form hydrogen bonds. Although Cl attracts electrons more strongly than O, solid
HOCl cannot form H−Cl bonds. Draw the proposed structure for chains of HOCl molecules in the crystalline state. The bond

angle for HOCl is 103 . o

3.E.16: Q.27
How do the boiling points of hydrogen halides differ from that of hydrogen fluoride (HF). Explain your reasoning. Answer: HF
has a much higher boiling point (20 C ) compared to the other hydrogen halides. This is because HF is capable of forming
o

hydrogen bonding within its compounds.

3.E.17: Q.31
Oxygen is stored at a temperature of 105 K and a pressure of 3.356 atm. If the volume of the container is 2.5 L, calculate the
number of moles of oxygen in the container. Compare this number of moles to the number of moles in the same container at
standard pressure and 298 K. Is it fewer, more, or unchanged?

3.E.18: Q.35
Consider the reaction at 25ºC.

CaC (s) + 2 H O(l) ⟶ C H (g) + Ca (OH) (s)

2 2 2 2 2

If the total pressure is 0.9124 atm and the vapor pressure of water at this temperature is 0.0313 atm. What is the mass of acetylene (
C H ) per liter of "wet" acetylene collected by this reaction (i.e., collected over a pool of water)? Assume all gases behave ideally.
2 2

3.E.19: Q.39
The highest value of sea-level pressure on Earth occurs in Siberia where the Siberian High often allows water to boil at 80oC.
Using chart 10.16 on page 431 of the text book, what can the fraction of pressure be in this location?

3.E.20: Q.41
Water (H O ) has a melting point of 0.00°C and a boiling point of 100.0°C. Benzene (C H ) has a melting point of 5.5°C and a
2 6 6

boiling point of 80.1°C. At 20.0°C, which of the two substances would be expected to have a greater surface tension? Explain?

3.E.21: Q.43
g g
At gallium’s melting point of 302.91K, its density is 6.095 . The density of solid gallium under standard conditions is 5.91
cm
3
cm
3
.
When Ga is at 301.91K and pressure is strongly increased, will Ga undergo a phase change?

3.E.22: Q.45
Given the information below, sketch the phase diagram of Nitrogen:
Triple point: 0.1252 bar, -210°C
Normal boiling point: 1 bar, -195.8°C
Normal melting point: 1 bar, -210°C

3.E.23: Q.47
Use the phase diagram of water to determine whether water is a solid, a liquid, or a gas at each of the following combinations of
temperature and pressure.
a. 1 atm and 20 Co

b. 0.006 atm and 100 C o

c. 210 atm and 100 C o

d. 10 atm and 50 C o

3.E.3 https://chem.libretexts.org/@go/page/69604
 Figure used with permission (CK-12 Foundation – Christopher Auyeung)

3.E.24: Q.53
What phase does candle wax exist in? How about butter?

3.E.25: Q.59
The equilibrium vapor pressure of water at 19 C is 0.02168 atm. A humidifier is placed in a room with a volume of 180m and
o 3

operates until the the room becomes saturated with water vapor. Initially there is no water vapor in water vapor in the air. Assuming
that the room is closed completely from the outside such that water vapor cannot escape, calculate the mass of water that has
passed into the air.

3.E.26: Q.65
A cooling bath is a mixture that is primarily liquid which is kept at a constant, low temperature. While in the lab, Po’lah accidently
severed its hand after trying to make some mac and cheese. As a result it had to immediately transfer its hand to a cooling bath to
sufficiently preserve it but not so that it could be of some use later on. In order to achieve this, the cooling bath had to be kept at
around 0 C . The only liquids it had access to were water and methanol, both at room temperature, and the only cooling agents that
∘

it had were liquid nitrogen and dry ice (solid carbon dioxide). What combination did Po’lah use and why?
Relevant Information:
Carbon Dioxide: sublimes at −78.5 ∘
C

Nitrogen: boils at −195.8 C ∘

Water: freezes at 0 C∘

Ethanol: freezes at −143.7 C ∘

3.E.27: Q.71
The melting points of the chlorides of third period elements are: NaCl = 1074 K, MgCl = 987 K , AlCl = 465 K ,
2 3

SiCl = 204.4 K, PCl = 179 K . Based on the applicable intermolecular forces present in each compound, explain this trend in
4 3

melting points.

3.E.28: Q.71
Why are the melting points of NaCl (801 °C) and MgCl (714 °C) so much higher than the melting points of SCl (-122 °C) and
2 2

Cl (-101.5 °C)? Explain answer in terms of intermolecular forces and identify any potential forces involved.
2

This page titled 3.E: Solids, Liquids, and Phase Transitions (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by Delmar Larsen.

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 CHAPTER OVERVIEW

IV: Solutions

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

In chemistry, a solution is a homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance
dissolved in another substance, known as a solvent.
4.0: Types of Solutions - Some Terminology
4.1: Composition of Solutions
4.2: Nature of Dissolved Species
4.3: Phase Equilibrium in Solutions - Nonvolatile Solutes
4.4: Phase Equilibrium in Solutions - Volatile Solutes
4.5: Separating Volatile Solutions - Distillation
4.6: Colloidal Suspensions
4.E: Solutions (Exercises)

IV: Solutions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
4.0: Types of Solutions - Some Terminology
 Learning Objectives
To understand how enthalpy and entropy changes affect solution formation.
To use the magnitude of the changes in both enthalpy and entropy to predict whether a given solute–solvent combination
will spontaneously form a solution.

In all solutions, whether gaseous, liquid, or solid, the substance present in the greatest amount is the solvent, and the substance or
substances present in lesser amounts are the solute(s). The solute does not have to be in the same physical state as the solvent, but
the physical state of the solvent usually determines the state of the solution. As long as the solute and solvent combine to give a
homogeneous solution, the solute is said to be soluble in the solvent. Table 4.0.1 lists some common examples of gaseous, liquid,
and solid solutions and identifies the physical states of the solute and solvent in each.
Table 4.0.1 : Types of Solutions
Solution Solute Solvent Examples

gas gas gas air, natural gas

liquid gas liquid seltzer water (CO gas in water)

2

alcoholic beverage (ethanol in

liquid liquid liquid
water), gasoline

liquid solid liquid tea, salt water

solid gas solid H

2
in Pd (used for H storage)
2

mercury in silver or gold

solid solid liquid
(amalgam often used in dentistry)

The formation of a solution from a solute and a solvent is a physical process, not a chemical one. That is, both solute and solvent
can be recovered in chemically unchanged forms using appropriate separation methods. For example, solid zinc nitrate dissolves in
water to form an aqueous solution of zinc nitrate:
2 + −
Zn(NO ) (s) + H O(l) → Zn (aq) + 2 NO (aq)
3 2 2 3

Because Zn(NO ) can be recovered easily by evaporating the water, this is a physical process. In contrast, metallic zinc appears
3 2

to dissolve in aqueous hydrochloric acid. In fact, the two substances undergo a chemical reaction to form an aqueous solution of
zinc chloride with evolution of hydrogen gas:
+ − 2 + −
Zn(s) + 2 H (aq) + 2 Cl (aq) → Zn (aq) + 2 Cl (aq) + H (g)
2

Dissolution of a solute in a solvent to form a solution typically does not involve a

chemical transformation and largely consist of breaking intermolecular forces rather than
covalent bonds.
When the solution evaporates, we do not recover metallic zinc, so we cannot say that metallic zinc is soluble in aqueous
hydrochloric acid because it is chemically transformed when it dissolves. The dissolution of a solute in a solvent to form a solution
does not involve a chemical transformation.

 Mercury Amalgams: Examples of solid Solutions

An amalgam is an alloy of mercury with another metal. It may be a liquid, a soft paste or a solid, depending upon the
proportion of mercury. These alloys are formed through metallic bonding, with the electrostatic attractive force of the
conduction electrons working to bind all the positively charged metal ions together into a crystal lattice structure. Almost all
metals can form amalgams with mercury including aluminum (Video 4.0.1), the notable exceptions being iron, platinum,
tungsten, and tantalum. Silver-mercury amalgams are important in dentistry, and gold-mercury amalgam is used in the
extraction of gold from ore.

4.0.1 https://chem.libretexts.org/@go/page/42439
 Aluminum and Mercury

Video 4.0.1 : Aluminum dissolving into Mercury.

Substances that form a single homogeneous phase in all proportions are said to be completely miscible in one another. Ethanol and
water are miscible, just as mixtures of gases are miscible. If two substances are essentially insoluble in each other, such as oil and
water, they are immiscible. Examples of gaseous solutions that we have already discussed include Earth’s atmosphere.

4.0: Types of Solutions - Some Terminology is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.
13.1: Types of Solutions - Some Terminology is licensed CC BY-NC-SA 4.0.

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4.1: Composition of Solutions
 Learning Objectives
To describe the concentration of a solution in the way that is most appropriate for a particular problem or application.
To be familiar with the different units used to express the concentrations of a solution.

There are several different ways to quantitatively describe the concentration of a solution. For example, molarity is a useful way to
describe solution concentrations for reactions that are carried out in solution. Mole fractions are used not only to describe gas
concentrations but also to determine the vapor pressures of mixtures of similar liquids. Example 4.1.1 reviews the methods for
calculating the molarity and mole fraction of a solution when the masses of its components are known.

 Example 4.1.1: Molarity and Mole Fraction

Commercial vinegar is essentially a solution of acetic acid in water. A bottle of vinegar has 3.78 g of acetic acid per 100.0 g of
solution. Assume that the density of the solution is 1.00 g/mL.
a. What is its molarity?
b. What is its mole fraction?
Given: mass of substance and mass and density of solution
Asked for: molarity and mole fraction
Strategy:
A. Calculate the number of moles of acetic acid in the sample. Then calculate the number of liters of solution from its mass
and density. Use these results to determine the molarity of the solution.
B. Determine the mass of the water in the sample and calculate the number of moles of water. Then determine the mole
fraction of acetic acid by dividing the number of moles of acetic acid by the total number of moles of substances in the
sample.
Solution:
A: The molarity is the number of moles of acetic acid per liter of solution. We can calculate the number of moles of acetic acid
as its mass divided by its molar mass.
3.78 g CH CO H
3 2
moles CH CO H =
3 2
60.05 g /mol

= 0.0629 mol

The volume of the solution equals its mass divided by its density.
mass
volume =
density

100.0 g solution
= = 100 mL
1.00 g /mL

Then calculate the molarity directly.

moles CH CO H
3 2
molarity of CH CO H =
3 2
liter solution

0.0629 mol CH CO H
3 2
= = 0.629 M CH CO H
3 2
(100 mL )(1 L/1000 mL )

This result makes intuitive sense. If 100.0 g of aqueous solution (equal to 100 mL) contains 3.78 g of acetic acid, then 1 L of
solution will contain 37.8 g of acetic acid, which is a little more than mole. Keep in mind, though, that the mass and volume
1

of a solution are related by its density; concentrated aqueous solutions often have densities greater than 1.00 g/mL.

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 B: To calculate the mole fraction of acetic acid in the solution, we need to know the number of moles of both acetic acid and
water. The number of moles of acetic acid is 0.0629 mol, as calculated in part (a). We know that 100.0 g of vinegar contains
3.78 g of acetic acid; hence the solution also contains (100.0 g − 3.78 g) = 96.2 g of water. We have
96.2 g H O
2
moles H O = = 5.34 mol H O
2 2
18.02 g /mol

The mole fraction χ of acetic acid is the ratio of the number of moles of acetic acid to the total number of moles of substances
present:
moles CH CO H
3 2
χCH CO2 H =
3
moles CH CO H + moles H O
3 2 2

0.0629 mol
=
0.0629 mol + 5.34 mol

−2
= 0.0116 = 1.16 × 10

This answer makes sense, too. There are approximately 100 times as many moles of water as moles of acetic acid, so the ratio
should be approximately 0.01.

 Exercise 4.1.1: Molarity and Mole Fraction

A solution of HCl gas dissolved in water (sold commercially as “muriatic acid,” a solution used to clean masonry surfaces) has
20.22 g of HCl per 100.0 g of solution, and its density is 1.10 g/mL.
a. What is its molarity?
b. What is its mole fraction?

Answer a
6.10 M HCl
Answer b
χH C l = 0.111

The concentration of a solution can also be described by its molality (m), the number of moles of solute per kilogram of solvent:
moles solute
molality (m) = (4.1.1)
kilogram solvent

Molality, therefore, has the same numerator as molarity (the number of moles of solute) but a different denominator (kilogram of
solvent rather than liter of solution). For dilute aqueous solutions, the molality and molarity are nearly the same because dilute
solutions are mostly solvent. Thus because the density of water under standard conditions is very close to 1.0 g/mL, the volume of
1.0 kg of H O under these conditions is very close to 1.0 L, and a 0.50 M solution of KBr in water, for example, has
2

approximately the same concentration as a 0.50 m solution.

Another common way of describing concentration is as the ratio of the mass of the solute to the total mass of the solution. The
result can be expressed as mass percentage, parts per million (ppm), or parts per billion (ppb):
mass of solute
mass percentage = × 100 (4.1.2)
mass of solution

mass of solute 6
parts per million (ppm) = × 10 (4.1.3)
mass of solution

mass of solute 9
parts per billion (ppb) = × 10 (4.1.4)
mass of solution

In the health sciences, the concentration of a solution is often expressed as parts per thousand (ppt), indicated as a proportion. For
example, adrenalin, the hormone produced in high-stress situations, is available in a 1:1000 solution, or one gram of adrenalin per

4.1.2 https://chem.libretexts.org/@go/page/43412
1000 g of solution.
The labels on bottles of commercial reagents often describe the contents in terms of mass percentage. Sulfuric acid, for example, is
sold as a 95% aqueous solution, or 95 g of H SO per 100 g of solution. Parts per million and parts per billion are used to describe
2 4

concentrations of highly dilute solutions. These measurements correspond to milligrams and micrograms of solute per kilogram of
solution, respectively. For dilute aqueous solutions, this is equal to milligrams and micrograms of solute per liter of solution
(assuming a density of 1.0 g/mL).

 Example 4.1.2: Molarity and Mass

Several years ago, millions of bottles of mineral water were contaminated with benzene at ppm levels. This incident received a
great deal of attention because the lethal concentration of benzene in rats is 3.8 ppm. A 250 mL sample of mineral water has
12.7 ppm of benzene. Because the contaminated mineral water is a very dilute aqueous solution, we can assume that its density
is approximately 1.00 g/mL.
a. What is the molarity of the solution?
b. What is the mass of benzene in the sample?
Given: volume of sample, solute concentration, and density of solution
Asked for: molarity of solute and mass of solute in 250 mL
Strategy:
A. Use the concentration of the solute in parts per million to calculate the molarity.
B. Use the concentration of the solute in parts per million to calculate the mass of the solute in the specified volume of
solution.
Solution:
a. A To calculate the molarity of benzene, we need to determine the number of moles of benzene in 1 L of solution. We know
that the solution contains 12.7 ppm of benzene. Because 12.7 ppm is equivalent to 12.7 mg/1000 g of solution and the density
of the solution is 1.00 g/mL, the solution contains 12.7 mg of benzene per liter (1000 mL). The molarity is therefore
moles
molarity =
liter solution

1 g
1 mol
(12.7 mg ) ( )( )
1000 mg 78.114 g

=
1.00 L

−4
= 1.63 × 10 M

b. B We are given that there are 12.7 mg of benzene per 1000 g of solution, which is equal to 12.7 mg/L of solution. Hence the
mass of benzene in 250 mL (250 g) of solution is

(12.7 mg benzene)(250 mL )
mass of benzene =
1000 mL

= 3.18 mg

−3
= 3.18 × 10 g benzene

 Exercise 4.1.2: Molarity of Lead Solution

The maximum allowable concentration of lead in drinking water is 9.0 ppb.

a. What is the molarity of Pb in a 9.0 ppb aqueous solution?
2 +

b. Use your calculated concentration to determine how many grams of Pb 2 +

are in an 8 oz glass of water.

Answer a
4.3 × 10−8 M

4.1.3 https://chem.libretexts.org/@go/page/43412
 Answer b
2 × 10−6 g

How do chemists decide which units of concentration to use for a particular application? Although molarity is commonly used to
express concentrations for reactions in solution or for titrations, it does have one drawback—molarity is the number of moles of
solute divided by the volume of the solution, and the volume of a solution depends on its density, which is a function of
temperature. Because volumetric glassware is calibrated at a particular temperature, typically 20°C, the molarity may differ from
the original value by several percent if a solution is prepared or used at a significantly different temperature, such as 40°C or 0°C.
For many applications this may not be a problem, but for precise work these errors can become important. In contrast, mole
fraction, molality, and mass percentage depend on only the masses of the solute and solvent, which are independent of temperature.
Mole fraction is not very useful for experiments that involve quantitative reactions, but it is convenient for calculating the partial
pressure of gases in mixtures, as discussed previously. Mole fractions are also useful for calculating the vapor pressures of certain
types of solutions. Molality is particularly useful for determining how properties such as the freezing or boiling point of a solution
vary with solute concentration. Because mass percentage and parts per million or billion are simply different ways of expressing
the ratio of the mass of a solute to the mass of the solution, they enable us to express the concentration of a substance even when
the molecular mass of the substance is unknown. Units of ppb or ppm are also used to express very low concentrations, such as
those of residual impurities in foods or of pollutants in environmental studies.
Table 4.1.1 summarizes the different units of concentration and typical applications for each. When the molar mass of the solute
and the density of the solution are known, it becomes relatively easy with practice to convert among the units of concentration we
have discussed, as illustrated in Example 4.1.3.
Table 4.1.1 : Different Units for Expressing the Concentrations of Solutions*
Unit Definition Application

Used for quantitative reactions in solution and

molarity (M) moles of solute/liter of solution (mol/L) titrations; mass and molecular mass of solute
and volume of solution are known.
Used for partial pressures of gases and vapor
mole fraction (χ) moles of solute/total moles present (mol/mol) pressures of some solutions; mass and
molecular mass of each component are known.
Used in determining how colligative properties
molality (m) moles of solute/kg of solvent (mol/kg) vary with solute concentration; masses and
molecular mass of solute are known.
Useful when masses are known but molecular
mass percentage (%) [mass of solute (g)/mass of solution (g)] × 100
masses are unknown.
Used in the health sciences, ratio solutions are
[mass of solute/mass of solution] × 103 (g
parts per thousand (ppt) typically expressed as a proportion, such as
solute/kg solution)
1:1000.

[mass of solute/mass of solution] × 106 (mg Used for trace quantities; masses are known but
parts per million (ppm)
solute/kg solution) molecular masses may be unknown.

[mass of solute/mass of solution] × 109 (µg Used for trace quantities; masses are known but
parts per billion (ppb)
solute/kg solution) molecular masses may be unknown.

*The molarity of a solution is temperature dependent, but the other units shown in this table are independent of temperature.

 Example 4.1.3: Vodka

Vodka is essentially a solution of ethanol in water. Typical vodka is sold as “80 proof,” which means that it contains 40.0%
ethanol by volume. The density of pure ethanol is 0.789 g/mL at 20°C. If we assume that the volume of the solution is the sum
of the volumes of the components (which is not strictly correct), calculate the following for the ethanol in 80-proof vodka.
a. the mass percentage
b. the mole fraction

4.1.4 https://chem.libretexts.org/@go/page/43412
 c. the molarity
d. the molality
Given: volume percent and density
Asked for: mass percentage, mole fraction, molarity, and molality
Strategy:
A. Use the density of the solute to calculate the mass of the solute in 100.0 mL of solution. Calculate the mass of water in
100.0 mL of solution.
B. Determine the mass percentage of solute by dividing the mass of ethanol by the mass of the solution and multiplying by
100.
C. Convert grams of solute and solvent to moles of solute and solvent. Calculate the mole fraction of solute by dividing the
moles of solute by the total number of moles of substances present in solution.
D. Calculate the molarity of the solution: moles of solute per liter of solution. Determine the molality of the solution by
dividing the number of moles of solute by the kilograms of solvent.
Solution:
The key to this problem is to use the density of pure ethanol to determine the mass of ethanol (C H C H OH), abbreviated as 3 2

EtOH, in a given volume of solution. We can then calculate the number of moles of ethanol and the concentration of ethanol in
any of the required units. A Because we are given a percentage by volume, we assume that we have 100.0 mL of solution. The
volume of ethanol will thus be 40.0% of 100.0 mL, or 40.0 mL of ethanol, and the volume of water will be 60.0% of 100.0 mL,
or 60.0 mL of water. The mass of ethanol is obtained from its density:

0.789 g
mass of EtOH = (40.0 mL ) ( ) = 31.6 g EtOH
mL

If we assume the density of water is 1.00 g/mL, the mass of water is 60.0 g. We now have all the information we need to
calculate the concentration of ethanol in the solution.
B The mass percentage of ethanol is the ratio of the mass of ethanol to the total mass of the solution, expressed as a percentage:
mass of EtOH
%EtOH = ( ) (100)
mass of solution

31.6 g EtOH
=( ) (100)
31.6 g EtOH + 60.0 g H2 O

= 34.5%

C The mole fraction of ethanol is the ratio of the number of moles of ethanol to the total number of moles of substances in the
solution. Because 40.0 mL of ethanol has a mass of 31.6 g, we can use the molar mass of ethanol (46.07 g/mol) to determine
the number of moles of ethanol in 40.0 mL:

⎛ 1 mol ⎞
moles CH CH OH = (31.6 g CH CH OH )
3 2 3 2
⎝ 46.07 g CH CH OH ⎠
3 2

= 0.686 mol CH CH OH
3 2

Similarly, the number of moles of water is

⎛ 1 mol H O ⎞
2
moles H O = (60.0 g H O ) = 3.33 mol H O
2 2 2
⎝ 18.02 g H O ⎠
2

The mole fraction of ethanol is thus

0.686 mol
χCH CH2 OH
= = 0.171
3

0.686 mol + 3.33 mol

4.1.5 https://chem.libretexts.org/@go/page/43412
D The molarity of the solution is the number of moles of ethanol per liter of solution. We already know the number of moles of
ethanol per 100.0 mL of solution, so the molarity is

0.686 mol 1000 mL

MCH CH OH =( )( ) = 6.86 M
3 2
L
100 mL

The molality of the solution is the number of moles of ethanol per kilogram of solvent. Because we know the number of moles
of ethanol in 60.0 g of water, the calculation is again straightforward:
1000 g
0.686 mol EtOH 11.4 mol EtOH
mCH CH OH =( )( ) = = 11.4 m
3 2
60.0 g H2 O kg kg H2 O

 Exercise 4.1.3: Toluene/Benzene Solution

A solution is prepared by mixing 100.0 mL of toluene with 300.0 mL of benzene. The densities of toluene and benzene are
0.867 g/mL and 0.874 g/mL, respectively. Assume that the volume of the solution is the sum of the volumes of the
components. Calculate the following for toluene.
a. mass percentage
b. mole fraction
c. molarity
d. molality

Answer a
mass percentage toluene = 24.8%
Answer b
χtoluene = 0.219

Answer c
2.35 M toluene
Answer d
3.59 m toluene

Measures of Concentration

A Video Discussing Different Measures of Concentration. Video Link: Measures of Concentration, YouTube (opens in new
window) [youtu.be]

4.1.6 https://chem.libretexts.org/@go/page/43412
 Converting Units of Concentration

A Video Discussing how to Convert Measures of Concentration. Video Link: Converting Units of Concentration, YouTube(opens
in new window) [youtu.be]

4.1.1: Summary
Different units are used to express the concentrations of a solution depending on the application. The concentration of a solution is
the quantity of solute in a given quantity of solution. It can be expressed in several ways: molarity (moles of solute per liter of
solution); mole fraction, the ratio of the number of moles of solute to the total number of moles of substances present; mass
percentage, the ratio of the mass of the solute to the mass of the solution times 100; parts per thousand (ppt), grams of solute per
kilogram of solution; parts per million (ppm), milligrams of solute per kilogram of solution; parts per billion (ppb), micrograms of
solute per kilogram of solution; and molality (m), the number of moles of solute per kilogram of solvent.

4.1: Composition of Solutions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
13.4: Ways of Expressing Concentration by Anonymous is licensed CC BY-NC-SA 3.0.

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4.2: Nature of Dissolved Species
 Learning Objectives
To understand how enthalpy and entropy changes affect solution formation.
To use the magnitude of the changes in both enthalpy and entropy to predict whether a given solute–solvent combination
will spontaneously form a solution.

In all solutions, whether gaseous, liquid, or solid, the substance present in the greatest amount is the solvent, and the substance or
substances present in lesser amounts are the solute(s). The solute does not have to be in the same physical state as the solvent, but
the physical state of the solvent usually determines the state of the solution. As long as the solute and solvent combine to give a
homogeneous solution, the solute is said to be soluble in the solvent. Table 4.2.1 lists some common examples of gaseous, liquid,
and solid solutions and identifies the physical states of the solute and solvent in each.
Table 4.2.1 : Types of Solutions
Solution Solute Solvent Examples

gas gas gas air, natural gas

liquid gas liquid seltzer water (CO gas in water)

2

alcoholic beverage (ethanol in

liquid liquid liquid
water), gasoline

liquid solid liquid tea, salt water

solid gas solid H2 in Pd (used for H storage)

2

mercury in silver or gold

solid solid liquid
(amalgam often used in dentistry)

solid solid solid alloys and other "solid solutions"

4.2.1: Forming a Solution

The formation of a solution from a solute and a solvent is a physical process, not a chemical one. That is, both solute and solvent
can be recovered in chemically unchanged forms using appropriate separation methods. For example, solid zinc nitrate dissolves in
water to form an aqueous solution of zinc nitrate:
2 + −
Zn(NO ) (s) + H O(l) → Zn (aq) + 2 NO (aq) (4.2.1)
3 2 2 3

Because Zn(N O ) can be recovered easily by evaporating the water, this is a physical process. In contrast, metallic zinc appears
3 2

to dissolve in aqueous hydrochloric acid. In fact, the two substances undergo a chemical reaction to form an aqueous solution of
zinc chloride with evolution of hydrogen gas:
+ − 2 + −
Zn(s) + 2 H (aq) + 2 Cl (aq) → Zn (aq) + 2 Cl (aq) + H (g) (4.2.2)
2

When the solution evaporates, we do not recover metallic zinc, so we cannot say that metallic zinc is soluble in aqueous
hydrochloric acid because it is chemically transformed when it dissolves. The dissolution of a solute in a solvent to form a solution
does not involve a chemical transformation (that it is a physical change).

Dissolution of a solute in a solvent to form a solution does not involve a chemical

transformation.
Substances that form a single homogeneous phase in all proportions are said to be completely miscible in one another. Ethanol and
water are miscible, just as mixtures of gases are miscible. If two substances are essentially insoluble in each other, such as oil and
water, they are immiscible. Examples of gaseous solutions that we have already discussed include Earth’s atmosphere.

4.2.2: The Role of Enthalpy in Solution Formation

Energy is required to overcome the intermolecular interactions in a solute, which can be supplied only by the new interactions that
occur in the solution, when each solute particle is surrounded by particles of the solvent in a process called solvation (or hydration

4.2.1 https://chem.libretexts.org/@go/page/43413
when the solvent is water). Thus all of the solute–solute interactions and many of the solvent–solvent interactions must be disrupted
for a solution to form. In this section, we describe the role of enthalpy in this process.
Because enthalpy is a state function, we can use a thermochemical cycle to analyze the energetics of solution formation. The
process occurs in three discrete steps, indicated by ΔH , ΔH , and ΔH in Figure 4.2.2. The overall enthalpy change in the
1 2 3

formation of the solution (ΔH ) is the sum of the enthalpy changes in the three steps:
soln

ΔHsoln = ΔH1 + ΔH2 + ΔH3 (4.2.3)

When a solvent is added to a solution, steps 1 and 2 are both endothermic because energy is required to overcome the
intermolecular interactions in the solvent (ΔH ) and the solute (ΔH ). Because ΔH is positive for both steps 1 and 2, the solute–
1 2

solvent interactions (ΔH ) must be stronger than the solute–solute and solvent–solvent interactions they replace in order for the
3

dissolution process to be exothermic (ΔH < 0 ). When the solute is an ionic solid, ΔH corresponds to the lattice energy that
soln 2

must be overcome to form a solution. The higher the charge of the ions in an ionic solid, the higher the lattice energy.
Consequently, solids that have very high lattice energies, such as M gO (−3791 kJ/mol), are generally insoluble in all solvents.

Figure 4.2.2 : Enthalpy Changes That Accompany the Formation of a Solution. Solvation can be an exothermic or endothermic
process depending on the nature of the solute and solvent. In both cases, step 1, separation of the solvent particles, is energetically
uphill (ΔH1 > 0), as is step 2, separation of the solute particles (ΔH2 > 0). In contrast, energy is released in step 3 (ΔH < 0)3

because of interactions between the solute and solvent. (a) When ΔH is larger in magnitude than the sum of ΔH and ΔH , the
3 1 2

overall process is exothermic (ΔH < 0), as shown in the thermochemical cycle. (b) When ΔH is smaller in magnitude than
sol n 3

the sum of ΔH and ΔH , the overall process is endothermic (ΔH

1 2 > 0).
sol n

A positive value for ΔH soln does not mean that a solution will not form. Whether a given process, including formation of a
solution, occurs spontaneously depends on whether the total energy of the system is lowered as a result. Enthalpy is only one of the
contributing factors. A high ΔH is usually an indication that the substance is not very soluble. Instant cold packs used to treat
soln

athletic injuries, for example, take advantage of the large positive ΔH of ammonium nitrate during dissolution (+25.7 kJ/mol),
soln

which produces temperatures less than 0°C (Figure 4.2.3).

4.2.2 https://chem.libretexts.org/@go/page/43413
 Figure 4.2.3 : Commercial Cold Packs for Treating Injuries. These packs contain solid N H N O and water in separate
4 3

compartments. When the seal between the compartments is broken, the N H N O dissolves in the water. Because ΔH
4 3 for sol n

NH NO4 is much greater than zero, heat is absorbed by the cold pack during the dissolution process, producing local
3

temperatures less than 0°C.

4.2.3: Entropy and Solution Formation

The enthalpy change that accompanies a process is important because processes that release substantial amounts of energy tend to
occur spontaneously. A second property of any system, its entropy, is also important in helping us determine whether a given
process occurs spontaneously. We will discuss entropy in more detail elsewhere, but for now we can state that entropy (S ) is a
thermodynamic property of all substances that is proportional to their degree of disorder. A perfect crystal at 0 K, whose atoms are
regularly arranged in a perfect lattice and are motionless, has an entropy of zero. In contrast, gases have large positive entropies
because their molecules are highly disordered and in constant motion at high speeds.
The formation of a solution disperses molecules, atoms, or ions of one kind throughout a second substance, which generally
increases the disorder and results in an increase in the entropy of the system. Thus entropic factors almost always favor formation
of a solution. In contrast, a change in enthalpy may or may not favor solution formation. The London dispersion forces that hold
cyclohexane and n-hexane together in pure liquids, for example, are similar in nature and strength. Consequently, ΔH should soln

be approximately zero, as is observed experimentally. Mixing equal amounts of the two liquids, however, produces a solution in
which the n-hexane and cyclohexane molecules are uniformly distributed over approximately twice the initial volume. In this case,
the driving force for solution formation is not a negative ΔH but rather the increase in entropy due to the increased disorder in
soln

the mixture. All spontaneous processes with ΔH ≥ 0 are characterized by an increase in entropy. In other cases, such as mixing oil
with water, salt with gasoline, or sugar with hexane, the enthalpy of solution is large and positive, and the increase in entropy
resulting from solution formation is not enough to overcome it. Thus in these cases a solution does not form.

All spontaneous processes with ΔH ≥ 0 are characterized by an increase in entropy.

Table 4.2.2 summarizes how enthalpic factors affect solution formation for four general cases. The column on the far right uses the
relative magnitudes of the enthalpic contributions to predict whether a solution will form from each of the four. Keep in mind that
in each case entropy favors solution formation. In two of the cases the enthalpy of solution is expected to be relatively small and
can be either positive or negative. Thus the entropic contribution dominates, and we expect a solution to form readily. In the other
two cases the enthalpy of solution is expected to be large and positive. The entropic contribution, though favorable, is usually too
small to overcome the unfavorable enthalpy term. Hence we expect that a solution will not form readily.
Table 4.2.2 : Relative Changes in Enthalpies for Different Solute–Solvent Combinations*
ΔH1 (separation of ΔH2 (separation of ΔH3 (solute–solvent ΔHsoln (ΔH + ΔH +
1 2 Result of Mixing Solute
solvent molecules) solute particles) interactions) ΔH )3 and Solvent†

large; positive large; positive large; negative small; positive or negative solution will usually form

small; positive large; positive small; negative large; positive solution will not form

large; positive small; positive small; negative large; positive solution will not form

small; positive small; positive small; negative small; positive or negative solution will usually form

4.2.3 https://chem.libretexts.org/@go/page/43413
 ΔH1 (separation of ΔH2 (separation of ΔH3 (solute–solvent ΔHsoln (ΔH + ΔH +
1 2 Result of Mixing Solute
solvent molecules) solute particles) interactions) ΔH )
3 and Solvent†

*ΔH , ΔH , and ΔH refer to the processes indicated in the thermochemical cycle shown in Figure 4.2.2.
1 2 3

†In all four cases, entropy increases.

In contrast to liquid solutions, the intermolecular interactions in gases are weak (they are considered to be nonexistent in ideal
gases). Hence mixing gases is usually a thermally neutral process (ΔH ≈ 0 ), and the entropic factor due to the increase in
soln

disorder is dominant (Figure 4.2.4). Consequently, all gases dissolve readily in one another in all proportions to form solutions.

Figure 4.2.4 : Formation of a Solution of Two Gases. (top) Pure samples of two different gases are in separate bulbs. (bottom)
When the connecting stopcock is opened, diffusion causes the two gases to mix together and form a solution. Even though ΔH sol n

is zero for the process, the increased entropy of the solution (the increased disorder) versus that of the separate gases favors
solution formation.

 Example 4.2.1

Considering LiCl, benzoic acid (C 6

H CO H
5 2
), and naphthalene, which will be most soluble and which will be least soluble in
water?

Given: three compounds

Asked for: relative solubilities in water
Strategy: Assess the relative magnitude of the enthalpy change for each step in the process shown in Figure 4.2.2. Then use
Table 4.2.2 to predict the solubility of each compound in water and arrange them in order of decreasing solubility.

Solution:
The first substance, LiCl, is an ionic compound, so a great deal of energy is required to separate its anions and cations and
overcome the lattice energy (ΔH2 is far greater than zero in Equation 4.2.1). Because water is a polar substance, the

4.2.4 https://chem.libretexts.org/@go/page/43413
 interactions between both Li+ and Cl− ions and water should be favorable and strong. Thus we expect ΔH to be far less than
3

zero, making LiCl soluble in water. In contrast, naphthalene is a nonpolar compound, with only London dispersion forces
holding the molecules together in the solid state. We therefore expect ΔH to be small and positive. We also expect the
2

interaction between polar water molecules and nonpolar naphthalene molecules to be weak ΔH ≈ 0 . Hence we do not expect
3

naphthalene to be very soluble in water, if at all. Benzoic acid has a polar carboxylic acid group and a nonpolar aromatic ring.
We therefore expect that the energy required to separate solute molecules (ΔH2) will be greater than for naphthalene and less
than for LiCl. The strength of the interaction of benzoic acid with water should also be intermediate between those of LiCl and
naphthalene. Hence benzoic acid is expected to be more soluble in water than naphthalene but less soluble than LiCl. We thus
predict LiCl to be the most soluble in water and naphthalene to be the least soluble.

 Exercise 4.2.1

Considering ammonium chloride, cyclohexane, and ethylene glycol (H OC H 2 C H2 OH ), which will be most soluble and
which will be least soluble in benzene?

Answer
The most soluble is cyclohexane; the least soluble is ammonium chloride.

4.2.4: Summary
Solutions are homogeneous mixtures of two or more substances whose components are uniformly distributed on a microscopic
scale. The component present in the greatest amount is the solvent, and the components present in lesser amounts are the solute(s).
The formation of a solution from a solute and a solvent is a physical process, not a chemical one. Substances that are miscible, such
as gases, form a single phase in all proportions when mixed. Substances that form separate phases are immiscible. Solvation is the
process in which solute particles are surrounded by solvent molecules. When the solvent is water, the process is called hydration.
The overall enthalpy change that accompanies the formation of a solution, ΔH , is the sum of the enthalpy change for breaking
soln

the intermolecular interactions in both the solvent and the solute and the enthalpy change for the formation of new solute–solvent
interactions. Exothermic (ΔH soln< 0 ) processes favor solution formation. In addition, the change in entropy, the degree of

disorder of the system, must be considered when predicting whether a solution will form. An increase in entropy (a decrease in
order) favors dissolution.

4.2: Nature of Dissolved Species is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
13.1: The Solution Process is licensed CC BY-NC-SA 3.0.

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4.3: Phase Equilibrium in Solutions - Nonvolatile Solutes
 Learning Objectives
To describe the relationship between solute concentration and the physical properties of a solution.
To understand that the total number of nonvolatile solute particles determines the decrease in vapor pressure, increase in
boiling point, and decrease in freezing point of a solution versus the pure solvent.

Many of the physical properties of solutions differ significantly from those of the pure substances discussed in earlier chapters, and
these differences have important consequences. For example, the limited temperature range of liquid water (0°C–100°C) severely
limits its use. Aqueous solutions have both a lower freezing point and a higher boiling point than pure water. Probably one of the
most familiar applications of this phenomenon is the addition of ethylene glycol (“antifreeze”) to the water in an automobile
radiator. This solute lowers the freezing point of the water, preventing the engine from cracking in very cold weather from the
expansion of pure water on freezing. Antifreeze also enables the cooling system to operate at temperatures greater than 100°C
without generating enough pressure to explode.
Changes in the freezing point and boiling point of a solution depend primarily on the number of solute particles present rather than
the kind of particles. Such properties of solutions are called colligative properties (from the Latin colligatus, meaning “bound
together” as in a quantity). As we will see, the vapor pressure and osmotic pressure of solutions are also colligative properties.

 Counting Concentrations and Effective Concentrations

When we determine the number of particles in a solution, it is important to remember that not all solutions with the same
molarity contain the same concentration of solute particles. Consider, for example, 0.01 M aqueous solutions of sucrose, NaCl,
and CaCl . Because sucrose dissolves to give a solution of neutral molecules, the concentration of solute particles in a 0.01 M
2

sucrose solution is 0.01 M. In contrast, both NaCl and CaCl are ionic compounds that dissociate in water to yield solvated
2

ions. As a result, a 0.01 M aqueous solution of NaCl contains 0.01 M Na ions and 0.01 M Cl ions, for a total particle
+ −

concentration of 0.02 M. Similarly, the CaCl solution contains 0.01 M Ca ions and 0.02 M Cl ions, for a total particle
2
2 + −

concentration of 0.03 M. These values are correct for dilute solutions, where the dissociation of the compounds to form
separately solvated ions is complete.
At higher concentrations (typically >1 M), especially with salts of small, highly charged ions (such as Mg or Al ), or in
2 + 3 +

solutions with less polar solvents, dissociation to give separate ions is often incomplete. The sum of the concentrations of the
dissolved solute particles dictates the physical properties of a solution. In the following discussion, we must therefore keep the
chemical nature of the solute firmly in mind. A greater discussion of this is below.

4.3.1: Vapor Pressure of Solutions and Raoult’s Law For Nonvolatile Solutes
Adding a nonvolatile solute, one whose vapor pressure is too low to measure readily, to a volatile solvent decreases the vapor
pressure of the solvent. We can understand this phenomenon qualitatively by examining Figure 4.3.1, which is a schematic diagram
of the surface of a solution of glucose in water. In an aqueous solution of glucose, a portion of the surface area is occupied by
nonvolatile glucose molecules rather than by volatile water molecules. As a result, fewer water molecules can enter the vapor phase
per unit time, even though the surface water molecules have the same kinetic energy distribution as they would in pure water. At
the same time, the rate at which water molecules in the vapor phase collide with the surface and reenter the solution is unaffected.
The net effect is to shift the dynamic equilibrium between water in the vapor and the liquid phases, decreasing the vapor pressure
of the solution compared with the vapor pressure of the pure solvent.

4.3.1 https://chem.libretexts.org/@go/page/43416
 Figure 4.3.1 : A Model Depicting Why the Vapor Pressure of a Solution of Glucose Is Less Than the Vapor Pressure of Pure Water.
(a) When water or any volatile solvent is in a closed container, water molecules move into and out of the liquid phase at the same
rate in a dynamic equilibrium. (b) If a nonvolatile solute such as glucose is added, some fraction of the surface area is occupied by
solvated solute molecules. As a result, the rate at which water molecules evaporate is decreased, although initially their rate of
condensation is unchanged. (c) When the glucose solution reaches equilibrium, the concentration of water molecules in the vapor
phase, and hence the vapor pressure, is less than that of pure water. (CC BY-NC-SA; anonymous)
Figure 4.3.2 shows two beakers, one containing pure water and one containing an aqueous glucose solution, in a sealed chamber.
We can view the system as having two competing equilibria: water vapor will condense in both beakers at the same rate, but water
molecules will evaporate more slowly from the glucose solution because fewer water molecules are at the surface. Eventually all of
the water will evaporate from the beaker containing the liquid with the higher vapor pressure (pure water) and condense in the
beaker containing the liquid with the lower vapor pressure (the glucose solution). If the system consisted of only a beaker of water
inside a sealed container, equilibrium between the liquid and vapor would be achieved rather rapidly, and the amount of liquid
water in the beaker would remain constant.

Figure 4.3.2 : Transfer of Water to a Beaker Containing a Glucose Solution. (top) One beaker contains an aqueous solution of
glucose, and the other contains pure water. If they are placed in a sealed chamber, the lower vapor pressure of water in the glucose
solution results in a net transfer of water from the beaker containing pure water to the beaker containing the glucose solution.
(bottom) Eventually, all of the water is transferred to the beaker that has the glucose solution. (CC BY-NC-SA; anonymous)
If the particles of a solute are essentially the same size as those of the solvent and both solute and solvent have roughly equal
probabilities of being at the surface of the solution, then the effect of a solute on the vapor pressure of the solvent is proportional to
the number of sites occupied by solute particles at the surface of the solution. Doubling the concentration of a given solute causes
twice as many surface sites to be occupied by solute molecules, resulting in twice the decrease in vapor pressure. The relationship
between solution composition and vapor pressure is therefore
0
PA = χA P (4.3.1)
A

where P is the vapor pressure of component A of the solution (in this case the solvent), χ is the mole fraction of A in solution,
A A

and P is the vapor pressure of pure A . Equation 4.3.1 is known as Raoult’s law, after the French chemist who developed it. If the
0
A

solution contains only a single nonvolatile solute (B ), then we can relate the mole fraction of the solvent to the solute

χA + χB = 1

and we can substitute χ A = 1 − χB into Equation 4.3.1 to obtain

0
PA = (1 − χB )P
A

0 0
=P − χB P
A A

Rearranging and defining ΔP A =P

A
0
− PA , we obtain a relationship between the decrease in vapor pressure and the mole fraction
of nonvolatile solute:

4.3.2 https://chem.libretexts.org/@go/page/43416
 0
P − PA = ΔPA (4.3.2)
A

0
= χB P (4.3.3)
A

We can solve vapor pressure problems in either of two ways: by using Equation 4.3.1 to calculate the actual vapor pressure above a
solution of a nonvolatile solute, or by using Equation 4.3.3 to calculate the decrease in vapor pressure caused by a specified
amount of a nonvolatile solute.

 Example 4.3.1: Anti-Freeze

Ethylene glycol (HOCH CH OH ), the major ingredient in commercial automotive antifreeze, increases the boiling point of
2 2

radiator fluid by lowering its vapor pressure. At 100°C, the vapor pressure of pure water is 760 mmHg. Calculate the vapor
pressure of an aqueous solution containing 30.2% ethylene glycol by mass, a concentration commonly used in climates that do
not get extremely cold in winter.
Given: identity of solute, percentage by mass, and vapor pressure of pure solvent
Asked for: vapor pressure of solution
Strategy:
A. Calculate the number of moles of ethylene glycol in an arbitrary quantity of water, and then calculate the mole fraction of
water.
B. Use Raoult’s law (Equation 4.3.1) to calculate the vapor pressure of the solution.
Solution:
A A 30.2% solution of ethylene glycol contains 302 g of ethylene glycol per kilogram of solution; the remainder (698 g) is
water. To use Raoult’s law to calculate the vapor pressure of the solution, we must know the mole fraction of water. Thus we
must first calculate the number of moles of both ethylene glycol (EG) and water present:

1 mol
moles EG = (302 g )( ) = 4.87 mol EG
62.07 g

1 mol
moles H O = (698 g )( ) = 38.7 mol H2 O
2
18.02 g

The mole fraction of water is thus

38.7 mol H2 O
χH O = = 0.888
2

38.7 mol H2 O + 4.87 mol EG

B From Raoult’s law (Equation 4.3.1), the vapor pressure of the solution is
0
PH O = (χH O )(P )
2 2 H2 O

= (0.888)(760 mmH g) = 675 mmH g

Alternatively, we could solve this problem by calculating the mole fraction of ethylene glycol and then using Equation 4.3.3 to
calculate the resulting decrease in vapor pressure:
4.87 mol EG
χEG =
4.87 mol EG + 38.7 mol H2 O

= 0.112

0
ΔPH O = (χEG )(P )
2 H O
2

= (0.112)(760 mmH g) = 85.1 mmH g

0
PH O =P − ΔPH O = 760 mmH g − 85.1 mmH g = 675 mmH g
2 H O 2
2

The same result is obtained using either method.

4.3.3 https://chem.libretexts.org/@go/page/43416
  Exercise 4.3.1
Seawater is an approximately 3.0% aqueous solution of NaCl by mass with about 0.5% of other salts by mass. Calculate the
decrease in the vapor pressure of water at 25°C caused by this concentration of NaCl, remembering that 1 mol of NaCl
produces 2 mol of solute particles. The vapor pressure of pure water at 25°C is 23.8 mmHg.

Answer
0.45 mmHg. This may seem like a small amount, but it constitutes about a 2% decrease in the vapor pressure of water and
accounts in part for the higher humidity in the north-central United States near the Great Lakes, which are freshwater lakes.
The decrease therefore has important implications for climate modeling.

4.3.2: Boiling Point Elevation

Recall that the normal boiling point of a substance is the temperature at which the vapor pressure equals 1 atm. If a nonvolatile
solute lowers the vapor pressure of a solvent, it must also affect the boiling point. Because the vapor pressure of the solution at a
given temperature is less than the vapor pressure of the pure solvent, achieving a vapor pressure of 1 atm for the solution requires a
higher temperature than the normal boiling point of the solvent. Thus the boiling point of a solution is always greater than that of
the pure solvent. We can see why this must be true by comparing the phase diagram for an aqueous solution with the phase diagram
for pure water (Figure 4.3.4). The vapor pressure of the solution is less than that of pure water at all temperatures. Consequently,
the liquid–vapor curve for the solution crosses the horizontal line corresponding to P = 1 atm at a higher temperature than does
the curve for pure water.

Figure 4.3.4 : Phase Diagrams of Pure Water and an Aqueous Solution of a Nonvolatile Solute. The vaporization curve for the
solution lies below the curve for pure water at all temperatures, which results in an increase in the boiling point and a decrease in
the freezing point of the solution. (CC BY-NC-SA; anonymous)

The boiling point of a solution with a nonvolatile solute is always greater than the boiling
point of the pure solvent.
The magnitude of the increase in the boiling point is related to the magnitude of the decrease in the vapor pressure. As we have just
discussed, the decrease in the vapor pressure is proportional to the concentration of the solute in the solution. Hence the magnitude
of the increase in the boiling point must also be proportional to the concentration of the solute (Figure 4.3.5).

4.3.4 https://chem.libretexts.org/@go/page/43416
 Figure 4.3.5 : Vapor Pressure Decrease and Boiling Point Increase as Functions of the Mole Fraction of a Nonvolatile Solute. (CC
BY-NC-SA; anonymous)
We can define the boiling point elevation (ΔT ) as the difference between the boiling points of the solution and the pure solvent:
b

0
ΔTb = Tb − T (4.3.4)
b

where T is the boiling point of the solution and

b T
b
0
is the boiling point of the pure solvent. We can express the relationship
between ΔT and concentration as follows
b

ΔTb = m Kb (4.3.5)

where m is the concentration of the solute expressed in molality, and K is the molal boiling point elevation constant of the
b

solvent, which has units of °C/m. Table 4.3.1 lists characteristic K values for several commonly used solvents. For relatively
b

dilute solutions, the magnitude of both properties is proportional to the solute concentration.
Table 4.3.1 : Boiling Point Elevation Constants (Kb) and Freezing Point Depression Constants (Kf) for Some Solvents
Solvent Boiling Point (°C) Kb (°C/m) Freezing Point (°C) Kf (°C/m)

acetic acid 117.90 3.22 16.64 3.63

benzene 80.09 2.64 5.49 5.07

d-(+)-camphor 207.4 4.91 178.8 37.8

carbon disulfide 46.2 2.42 −112.1 3.74

carbon tetrachloride 76.8 5.26 −22.62 31.4

chloroform 61.17 3.80 −63.41 4.60

nitrobenzene 210.8 5.24 5.70 6.87

water 100.00 0.51 0.00 1.86

The concentration of the solute is typically expressed as molality rather than mole fraction or molarity for two reasons. First,
because the density of a solution changes with temperature, the value of molarity also varies with temperature. If the boiling point
depends on the solute concentration, then by definition the system is not maintained at a constant temperature. Second, molality
and mole fraction are proportional for relatively dilute solutions, but molality has a larger numerical value (a mole fraction can be
only between zero and one). Using molality allows us to eliminate nonsignificant zeros.
According to Table 4.3.1, the molal boiling point elevation constant for water is 0.51°C/m. Thus a 1.00 m aqueous solution of a
nonvolatile molecular solute such as glucose or sucrose will have an increase in boiling point of 0.51°C, to give a boiling point of
100.51°C at 1.00 atm. The increase in the boiling point of a 1.00 m aqueous NaCl solution will be approximately twice as large as
that of the glucose or sucrose solution because 1 mol of NaCl produces 2 mol of dissolved ions. Hence a 1.00 m NaCl solution
will have a boiling point of about 101.02°C.

4.3.5 https://chem.libretexts.org/@go/page/43416
  Example 4.3.3

In Example 4.3.1, we calculated that the vapor pressure of a 30.2% aqueous solution of ethylene glycol at 100°C is 85.1
mmHg less than the vapor pressure of pure water. We stated (without offering proof) that this should result in a higher boiling
point for the solution compared with pure water. Now that we have seen why this assertion is correct, calculate the boiling
point of the aqueous ethylene glycol solution.
Given: composition of solution
Asked for: boiling point
Strategy:
Calculate the molality of ethylene glycol in the 30.2% solution. Then use Equation 4.3.5 to calculate the increase in boiling
point.
Solution:
From Example 4.3.1, we know that a 30.2% solution of ethylene glycol in water contains 302 g of ethylene glycol (4.87 mol)
per 698 g of water. The molality of the solution is thus
1000 g
4.87 mol
molality of ethylene glycol = ( )( )
698 g H2 O 1 kg

= 6.98 m

From Equation 4.3.5, the increase in boiling point is therefore

ΔTb = mKb

= (6.98 m )(0.51°C / m )

= 3.6°C

The boiling point of the solution is thus predicted to be 104°C. With a solute concentration of almost 7 m, however, the
assumption of a dilute solution used to obtain Equation 4.3.5 may not be valid.

 Exercise 4.3.3

Assume that a tablespoon (5.00 g) of NaCl is added to 2.00 L of water at 20.0°C, which is then brought to a boil to cook
spaghetti. At what temperature will the water boil?

Answer
100.04°C, or 100°C to three significant figures. (Recall that 1 mol of NaCl produces 2 mol of dissolved particles. The
small increase in temperature means that adding salt to the water used to cook pasta has essentially no effect on the cooking
time.)

4.3.3: Freezing Point Depression

The phase diagram in Figure 4.3.4 shows that dissolving a nonvolatile solute in water not only raises the boiling point of the water
but also lowers its freezing point. The solid–liquid curve for the solution crosses the line corresponding to P = 1 atm at a lower
temperature than the curve for pure water.
We can understand this result by imagining that we have a sample of water at the normal freezing point temperature, where there is
a dynamic equilibrium between solid and liquid. Water molecules are continuously colliding with the ice surface and entering the
solid phase at the same rate that water molecules are leaving the surface of the ice and entering the liquid phase. If we dissolve a
nonvolatile solute such as glucose in the liquid, the dissolved glucose molecules will reduce the number of collisions per unit time
between water molecules and the ice surface because some of the molecules colliding with the ice will be glucose. Glucose,
though, has a very different structure than water, and it cannot fit into the ice lattice. Consequently, the presence of glucose
molecules in the solution can only decrease the rate at which water molecules in the liquid collide with the ice surface and solidify.
Meanwhile, the rate at which the water molecules leave the surface of the ice and enter the liquid phase is unchanged. The net

4.3.6 https://chem.libretexts.org/@go/page/43416
effect is to cause the ice to melt. The only way to reestablish a dynamic equilibrium between solid and liquid water is to lower the
temperature of the system, which decreases the rate at which water molecules leave the surface of the ice crystals until it equals the
rate at which water molecules in the solution collide with the ice.
By analogy to our treatment of boiling point elevation,the freezing point depression (ΔT ) is defined as the difference between the
f

freezing point of the pure solvent and the freezing point of the solution:
0
ΔTf = T − Tf (4.3.6)
f

where T is the freezing point of the pure solvent and T is the freezing point of the solution.
0
f
f

The order of the terms is reversed compared with Equation 4.3.4 to express the freezing point depression as a positive number. The
relationship between ΔT and the solute concentration is given by an equation analogous to Equation 4.3.5:
f

ΔTf = m Kf (4.3.7)

where m is the molality of the solution and K is the molal freezing point depression constant for the solvent (in units of °C/m).
f

Like K , each solvent has a characteristic value of K (see Table 4.3.1). Freezing point depression depends on the total number of
b f

dissolved nonvolatile solute particles, just as with boiling point elevation. Thus an aqueous NaCl solution has twice as large a
freezing point depression as a glucose solution of the same molality.
People who live in cold climates use freezing point depression to their advantage in many ways. For example, salt is used to melt
ice and snow on roads and sidewalks, ethylene glycol is added to engine coolant water to prevent an automobile engine from being
destroyed, and methanol is added to windshield washer fluid to prevent the fluid from freezing.

The decrease in vapor pressure, increase in boiling point, and decrease in freezing point of a solution versus a pure liquid all
depend on the total number of dissolved nonvolatile solute particles.

 Example 4.3.4: Salting the Roads

In colder regions of the United States, NaCl or CaCl is often sprinkled on icy roads in winter to melt the ice and make
2

driving safer. Use the data in the Figure below to estimate the concentrations of two saturated solutions at 0°C, one of NaCl
and one of CaCl , and calculate the freezing points of both solutions to see which salt is likely to be more effective at melting
2

ice.

Solubilities of Several Inorganic and Organic Solids in Water as a Function of Temperature. Solubility may increase or
decrease with temperature; the magnitude of this temperature dependence varies widely among compounds. (CC BY-NC-SA;
anonymous)
Given: solubilities of two compounds
Asked for: concentrations and freezing points

4.3.7 https://chem.libretexts.org/@go/page/43416
Strategy:
A. Estimate the solubility of each salt in 100 g of water from the figure. Determine the number of moles of each in 100 g and
calculate the molalities.
B. Determine the concentrations of the dissolved salts in the solutions. Substitute these values into Equation 4.3.7 to calculate
the freezing point depressions of the solutions.
Solution:
A. From Figure above, we can estimate the solubilities of NaCl and CaCl to be about 36 g and 60 g, respectively, per 100 g
2

of water at 0°C. The corresponding concentrations in molality are

⎛ 36 g N aC l ⎞ ⎛
1 mol N aC l ⎞ 1000 g
mN aC l = ( ) = 6.2 m
⎝ 100 g H2 O ⎠ ⎝ 58.44 g N aC l ⎠ 1 kg

⎛ 60 g C aC l2 ⎞ ⎛
1 mol C aC l2 ⎞ 1000 g
mC aC l2 = ( ) = 5.4 m
⎝ 100 g H2 O ⎠ ⎝
110.98 g C aC l2 ⎠
1kg

The lower formula mass of NaCl more than compensates for its lower solubility, resulting in a saturated solution that has a
slightly higher concentration than CaCl . 2

B. Because these salts are ionic compounds that dissociate in water to yield two and three ions per formula unit of NaCl and
CaCl , respectively, the actual concentrations of the dissolved species in the two saturated solutions are 2 × 6.2 m = 12 m for
2

NaCl and 3 × 5.4 m = 16 m for CaCl . The resulting freezing point depressions can be calculated using Equation 4.3.7:
2

NaCl : ΔTf = m Kf = (12 m )(1.86°C / m ) = 22°C

CaCl : ΔTf = m Kf = (16 m )(1.86°C / m ) = 30°C

2

Because the freezing point of pure water is 0°C, the actual freezing points of the solutions are −22°C and −30°C, respectively.
Note that CaCl is substantially more effective at lowering the freezing point of water because its solutions contain three ions
2

per formula unit. In fact, CaCl is the salt usually sold for home use, and it is also often used on highways.
2

Because the solubilities of both salts decrease with decreasing temperature, the freezing point can be depressed by only a
certain amount, regardless of how much salt is spread on an icy road. If the temperature is significantly below the minimum
temperature at which one of these salts will cause ice to melt (say −35°C), there is no point in using salt until it gets warmer

 Exercise 4.3.4

Calculate the freezing point of the 30.2% solution of ethylene glycol in water whose vapor pressure and boiling point we
calculated in Examples 4.3.1 and 4.3.3.

Answer
−13.0°C

 Example 4.3.5

Arrange these aqueous solutions in order of decreasing freezing points: 0.1 m KCl , 0.1 m glucose, 0.1 m SrCl
2
, 0.1 m
ethylene glycol, 0.1 m benzoic acid, and 0.1 m HCl.
Given: molalities of six solutions
Asked for: relative freezing points
Strategy:
A. Identify each solute as a strong, weak, or nonelectrolyte, and use this information to determine the number of solute
particles produced.

4.3.8 https://chem.libretexts.org/@go/page/43416
 B. Multiply this number by the concentration of the solution to obtain the effective concentration of solute particles. The
solution with the highest effective concentration of solute particles has the largest freezing point depression.
Solution:
A Because the molal concentrations of all six solutions are the same, we must focus on which of the substances are strong
electrolytes, which are weak electrolytes, and which are nonelectrolytes to determine the actual numbers of particles in
solution. KCl, SrCl , and HCl are strong electrolytes, producing two, three, and two ions per formula unit, respectively.
2

Benzoic acid is a weak electrolyte (approximately one particle per molecule), and glucose and ethylene glycol are both
nonelectrolytes (one particle per molecule).
B The molalities of the solutions in terms of the total particles of solute are: KCl and HCl, 0.2 m; SrC l , 0.3 m; glucose and
2

ethylene glycol, 0.1 m; and benzoic acid, 0.1–0.2 m. Because the magnitude of the decrease in freezing point is proportional to
the concentration of dissolved particles, the order of freezing points of the solutions is: glucose and ethylene glycol (highest
freezing point, smallest freezing point depression) > benzoic acid > HCl = KCl > SrCl . 2

 Exercise 4.3.5
Arrange these aqueous solutions in order of increasing freezing points: 0.2 m NaCl, 0.3 m acetic acid, 0.1 m CaCl , and 0.2 m
2

sucrose.

Answer
0.2 m NaCl (lowest freezing point) < 0.3 m acetic acid ≈ 0.1 m CaCl < 0.2 m sucrose (highest freezing point)
2

Colligative properties can also be used to determine the molar mass of an unknown compound. One method that can be carried out
in the laboratory with minimal equipment is to measure the freezing point of a solution with a known mass of solute. This method
is accurate for dilute solutions (≤1% by mass) because changes in the freezing point are usually large enough to measure accurately
and precisely. By comparing K and K values in Table 4.3.1, we see that changes in the boiling point are smaller than changes in
b f

the freezing point for a given solvent. Boiling point elevations are thus more difficult to measure precisely. For this reason, freezing
point depression is more commonly used to determine molar mass than is boiling point elevation. Because of its very large value of
K (37.8°C/m), d-(+)-camphor (Table 4.3.1) is often used to determine the molar mass of organic compounds by this method.
f

 Example 4.3.6: Sulfur

A 7.08 g sample of elemental sulfur is dissolved in 75.0 g of C S to create a solution whose freezing point is −113.5°C. Use
2

these data to calculate the molar mass of elemental sulfur and thus the formula of the dissolved Sn molecules (i.e., what is the
value of n ?).
Given: masses of solute and solvent and freezing point
Asked for: molar mass and number of S atoms per molecule
Strategy:
A. Use Equation 4.3.6, the measured freezing point of the solution, and the freezing point of C S from Table 4.3.1 to
2

calculate the freezing point depression. Then use Equation 4.3.7 and the value of K from Table 4.3.1 to calculate the
f

molality of the solution.

B. From the calculated molality, determine the number of moles of solute present.

4.3.9 https://chem.libretexts.org/@go/page/43416
 C. Use the mass and number of moles of the solute to calculate the molar mass of sulfur in solution. Divide the result by the
molar mass of atomic sulfur to obtain n , the number of sulfur atoms per mole of dissolved sulfur.
Solution:
A The first step is to calculate the freezing point depression using Equation 4.3.6:
0
ΔTf = T − Tf = −112.1°C − (−113.5°C ) = 1.4°C
f

Then Equation 4.3.7 gives

ΔTf 1.4° C
m = = = 0.37 m
Kf
3.74° C /m

B The total number of moles of solute present in the solution is

⎛ 0.37mol ⎞ 1kg
moles solute = (75.0 g) ( ) = 0.028 mol
⎝ kg ⎠ 1000 g

C We now know that 0.708 g of elemental sulfur corresponds to 0.028 mol of solute. The molar mass of dissolved sulfur is thus
7.08 g
molar mass = = 260 g/mol
0.028 mol

The molar mass of atomic sulfur is 32 g/mol, so there must be 260/32 = 8.1 sulfur atoms per mole, corresponding to a formula
of S .
8

 Exercise 4.3.6

One of the byproducts formed during the synthesis of C is a deep red solid containing only carbon. A solution of 205 mg of
60

this compound in 10.0 g of C C l has a freezing point of −23.38°C. What are the molar mass and most probable formula of the
4

substance?

Answer
847 g/mol; C 70

4.3.4: Osmotic Pressure

Osmotic pressure is a colligative property of solutions that is observed using a semipermeable membrane, a barrier with pores small
enough to allow solvent molecules to pass through but not solute molecules or ions. The net flow of solvent through a
semipermeable membrane is called osmosis (from the Greek osmós, meaning “push”). The direction of net solvent flow is always
from the side with the lower concentration of solute to the side with the higher concentration.
Osmosis can be demonstrated using a U-tube like the one shown in Figure 4.3.6, which contains pure water in the left arm and a
dilute aqueous solution of glucose in the right arm. A net flow of water through the membrane occurs until the levels in the arms
eventually stop changing, which indicates that equilibrium has been reached. The osmotic pressure (Π ) of the glucose solution is
the difference in the pressure between the two sides, in this case the heights of the two columns. Although the semipermeable
membrane allows water molecules to flow through in either direction, the rate of flow is not the same in both directions because the
concentration of water is not the same in the two arms. The net flow of water through the membrane can be prevented by applying
a pressure to the right arm that is equal to the osmotic pressure of the glucose solution.

4.3.10 https://chem.libretexts.org/@go/page/43416
 Figure 4.3.6 : Osmotic Pressure. (a) A dilute solution of glucose in water is placed in the right arm of a U-tube, and the left arm is
filled to the same height with pure water; a semipermeable membrane separates the two arms. Because the flow of pure solvent
through the membrane from left to right (from pure water to the solution) is greater than the flow of solvent in the reverse direction,
the level of liquid in the right tube rises. (b) At equilibrium, the pressure differential, equal to the osmotic pressure of the solution (
Π sol n), equalizes the flow rate of solvent in both directions. (c) Applying an external pressure equal to the osmotic pressure of the
original glucose solution to the liquid in the right arm reverses the flow of solvent and restores the original situation. (CC BY-NC-
SA; anonymous)
Just as with any other colligative property, the osmotic pressure of a solution depends on the concentration of dissolved solute
particles. Osmotic pressure obeys a law that resembles the ideal gas equation:
nRT
Π = = M RT (4.3.8)
V

where M is the number of moles of solute per unit volume of solution (i.e., the molarity of the solution), R is the ideal gas
constant, and T is the absolute temperature.
As shown in Example 4.3.7, osmotic pressures tend to be quite high, even for rather dilute solutions.

 Example 4.3.7

When placed in a concentrated salt solution, certain yeasts are able to produce high internal concentrations of glycerol to
counteract the osmotic pressure of the surrounding medium. Suppose that the yeast cells are placed in an aqueous solution
containing 4.0% NaCl by mass; the solution density is 1.02 g/mL at 25°C.
a. Calculate the osmotic pressure of a 4.0% aqueous NaCl solution at 25°C.
b. If the normal osmotic pressure inside a yeast cell is 7.3 atm, corresponding to a total concentration of dissolved particles of
0.30 M, what concentration of glycerol must the cells synthesize to exactly balance the external osmotic pressure at 25°C?
Given: concentration, density, and temperature of NaCl solution; internal osmotic pressure of cell
Asked for: osmotic pressure of NaCl solution and concentration of glycerol needed
Strategy:
A. Calculate the molarity of the NaCl solution using the formula mass of the solute and the density of the solution. Then
calculate the total concentration of dissolved particles.
B. Use Equation 4.3.8 to calculate the osmotic pressure of the solution.
C. Subtract the normal osmotic pressure of the cells from the osmotic pressure of the salt solution to obtain the additional
pressure needed to balance the two. Use Equation 4.3.8 to calculate the molarity of glycerol needed to create this osmotic
pressure.
Solution:
A The solution contains 4.0 g of NaCl per 100 g of solution. Using the formula mass of NaCl (58.44 g/mol) and the density of
the solution (1.02 g/mL), we can calculate the molarity:

4.3.11 https://chem.libretexts.org/@go/page/43416
 moles N aC l
MN aC l =
liter solution

4.0 g N aC l ⎛ 1 ⎞⎛ 1.02 g solution ⎞ 1000 mL

=( ) ( )
58.44 g /mol N aC l ⎝ 100 1 L
g solution ⎠ ⎝ 1.00 mL solution ⎠

= 0.70 M NaCl

Because 1 mol of NaCl produces 2 mol of particles in solution, the total concentration of dissolved particles in the solution is
(2)(0.70 M) = 1.4 M.
B Now we can use Equation 4.3.8 to calculate the osmotic pressure of the solution:
Π = M RT

= (1.4 mol/L) [0.0821 (L ⋅ atm)/(K ⋅ mol)] (298 K)

= 34 atm

C If the yeast cells are to exactly balance the external osmotic pressure, they must produce enough glycerol to give an
additional internal pressure of (34 atm − 7.3 atm) = 27 atm. Glycerol is a nonelectrolyte, so we can solve Equation 4.3.8 for the
molarity corresponding to this osmotic pressure:
Π
M =
RT

27 atm
=
[0.0821(L ⋅ atm )/( K ⋅ mol)](298 K )

= 1.1 M glycerol

In solving this problem, we could also have recognized that the only way the osmotic pressures can be the same inside the cells
and in the solution is if the concentrations of dissolved particles are the same. We are given that the normal concentration of
dissolved particles in the cells is 0.3 M, and we have calculated that the NaCl solution is effectively 1.4 M in dissolved
particles. The yeast cells must therefore synthesize enough glycerol to increase the internal concentration of dissolved particles
from 0.3 M to 1.4 M—that is, an additional 1.1 M concentration of glycerol.

 Exercise 4.3.7

Assume that the fluids inside a sausage are approximately 0.80 M in dissolved particles due to the salt and sodium nitrite used
to prepare them. Calculate the osmotic pressure inside the sausage at 100°C to learn why experienced cooks pierce the
semipermeable skin of sausages before boiling them.

Answer
24 atm

Because of the large magnitude of osmotic pressures, osmosis is extraordinarily important in biochemistry, biology, and medicine.
Virtually every barrier that separates an organism or cell from its environment acts like a semipermeable membrane, permitting the
flow of water but not solutes. The same is true of the compartments inside an organism or cell. Some specialized barriers, such as
those in your kidneys, are slightly more permeable and use a related process called dialysis, which permits both water and small
molecules to pass through but not large molecules such as proteins.
The same principle has long been used to preserve fruits and their essential vitamins over the long winter. High concentrations of
sugar are used in jams and jellies not for sweetness alone but because they greatly increase the osmotic pressure. Thus any bacteria
not killed in the cooking process are dehydrated, which keeps them from multiplying in an otherwise rich medium for bacterial
growth. A similar process using salt prevents bacteria from growing in ham, bacon, salt pork, salt cod, and other preserved meats.
The effect of osmotic pressure is dramatically illustrated in Figure 4.3.7, which shows what happens when red blood cells are
placed in a solution whose osmotic pressure is much lower or much higher than the internal pressure of the cells.

4.3.12 https://chem.libretexts.org/@go/page/43416
 Figure 4.3.7 : Effect on Red Blood Cells of the Surrounding Solution’s Osmotic Pressure. (a) When red blood cells are placed in a
dilute salt solution having the same osmotic pressure as the intracellular fluid, the rate of flow of water into and out of the cells is
the same and their shape does not change. (b) When cells are placed in distilled water whose osmotic pressure is less than that of
the intracellular fluid, the rate of flow of water into the cells is greater than the rate of flow out of the cells. The cells swell and
eventually burst. (c) When cells are placed in a concentrated salt solution with an osmotic pressure greater than that of the
intracellular fluid, the rate of flow of water out of the cells is greater than the rate of flow into the cells. The cells shrivel and
become so deformed that they cannot function. (CC BY-NC-SA; anonymous)

In addition to capillary action, trees use osmotic pressure to transport water and other nutrients from the roots to the upper
branches. Evaporation of water from the leaves results in a local increase in the salt concentration, which generates an osmotic
pressure that pulls water up the trunk of the tree to the leaves.
Finally, a process called reverse osmosis can be used to produce pure water from seawater. As shown schematically in Figure 4.3.8,
applying high pressure to seawater forces water molecules to flow through a semipermeable membrane that separates pure water
from the solution, leaving the dissolved salt behind. Large-scale desalinization plants that can produce hundreds of thousands of
gallons of freshwater per day are common in the desert lands of the Middle East, where they supply a large proportion of the
freshwater needed by the population. Similar facilities are now being used to supply freshwater in southern California. Small, hand-
operated reverse osmosis units can produce approximately 5 L of freshwater per hour, enough to keep 25 people alive, and are now
standard equipment on US Navy lifeboats.

Figure 4.3.8 : Desalinization of Seawater by Reverse Osmosis. (top) When the pressure applied to seawater equals its osmotic
pressure (Π ), there is no net flow of water across the semipermeable membrane. (bottom) The application of pressure greater
sol n

than the osmotic pressure of seawater forces water molecules to flow through the membrane, leaving behind a concentrated salt
solution. In desalinization plants, seawater is continuously introduced under pressure and pure water is collected, so the process
continues indefinitely. (CC BY-NC-SA; anonymous)

4.3.5: Colligative Properties of Electrolyte Solutions

Thus far we have assumed that we could simply multiply the molar concentration of a solute by the number of ions per formula
unit to obtain the actual concentration of dissolved particles in an electrolyte solution. We have used this simple model to predict
such properties as freezing points, melting points, vapor pressure, and osmotic pressure. If this model were perfectly correct, we
would expect the freezing point depression of a 0.10 m solution of sodium chloride, with 2 mol of ions per mole of NaCl in
solution, to be exactly twice that of a 0.10 m solution of glucose, with only 1 mol of molecules per mole of glucose in solution. In
reality, this is not always the case. Instead, the observed change in freezing points for 0.10 m aqueous solutions of NaCl and KCl
are significantly less than expected (−0.348°C and −0.344°C, respectively, rather than −0.372°C), which suggests that fewer
particles than we expected are present in solution.
The relationship between the actual number of moles of solute added to form a solution and the apparent number as determined by
colligative properties is called the van ’t Hoff factor (i) and is defined as follows:

4.3.13 https://chem.libretexts.org/@go/page/43416
 apparent number of particles in solution
i = (4.3.9)
number of moles of solute dissolved

Named for Jacobus Hendricus van ’t Hoff (1852–1911), a Dutch chemistry professor at the University of Amsterdam who won the
first Nobel Prize in Chemistry (1901) for his work on thermodynamics and solutions.

As the solute concentration increases, the van ’t Hoff factor decreases.

The van ’t Hoff factor is therefore a measure of a deviation from ideal behavior. The lower the van ’t Hoff factor, the greater the
deviation. As the data in Table 4.3.2 show, the van ’t Hoff factors for ionic compounds are somewhat lower than expected; that is,
their solutions apparently contain fewer particles than predicted by the number of ions per formula unit. As the concentration of the
solute increases, the van ’t Hoff factor decreases because ionic compounds generally do not totally dissociate in aqueous solution.
Table 4.3.2 : van ’t Hoff Factors for 0.0500 M Aqueous Solutions of Selected Compounds at 25°C
Compound i (measured) i (ideal)

glucose 1.0 1.0

sucrose 1.0 1.0

N aCl 1.9 2.0

HCl 1.9 2.0

M gCl2 2.7 3.0

F eCl3 3.4 4.0

Ca(N O3 )2 2.5 3.0

AlCl3 3.2 4.0

M gSO4 1.4 2.0

Instead, some of the ions exist as ion pairs, a cation and an anion that for a brief time are associated with each other without an
intervening shell of water molecules (Figure 4.3.9). Each of these temporary units behaves like a single dissolved particle until it
dissociates. Highly charged ions such as M g , Al , SO , and P O have a greater tendency to form ion pairs because of their
2+ 3+ 2−
4
3−
4

strong electrostatic interactions. The actual number of solvated ions present in a solution can be determined by measuring a
colligative property at several solute concentrations.

Figure 4.3.9 : Ion Pairs. In concentrated solutions of electrolytes like , some of the ions form neutral ion pairs that are not
N aC l

separated by solvent and diffuse as single particles.

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  Example 4.3.8: Iron Chloride in Water

A 0.0500 M aqueous solution of FeCl has an osmotic pressure of 4.15 atm at 25°C. Calculate the van ’t Hoff factor i for the
3

solution.
Given: solute concentration, osmotic pressure, and temperature
Asked for: van ’t Hoff factor
Strategy:
A. Use Equation 4.3.8 to calculate the expected osmotic pressure of the solution based on the effective concentration of
dissolved particles in the solvent.
B. Calculate the ratio of the observed osmotic pressure to the expected value. Multiply this number by the number of ions of
solute per formula unit, and then use Equation 4.3.9 to calculate the van ’t Hoff factor.
Solution:
A If FeCl dissociated completely in aqueous solution, it would produce four ions per formula unit (one Fe (aq) and three \
3
3 +

(\ce{Cl^{-}(aq)} ions) for an effective concentration of dissolved particles of 4 × 0.0500 M = 0.200 M. The osmotic pressure
would be
Π = M RT

= (0.200 mol/L) [0.0821 (L ⋅ atm)/(K ⋅ mol)] (298 K) = 4.89 atm

B The observed osmotic pressure is only 4.15 atm, presumably due to ion pair formation. The ratio of the observed osmotic
pressure to the calculated value is 4.15 atm/4.89 atm = 0.849, which indicates that the solution contains (0.849)(4) = 3.40
moles of particles per mole of FeCl dissolved. Alternatively, we can calculate the observed particle concentration from the
3

osmotic pressure of 4.15 atm:

0.0821 (L ⋅ atm)
4.15 atm = M ( ) (298 K)
(K ⋅ mol)

or after rearranging

M = 0.170mol

The ratio of this value to the expected value of 0.200 M is 0.170 M/0.200 M = 0.850, which again gives us (0.850)(4) = 3.40
mole of particles per mole of FeCl dissolved. From Equation 4.3.9, the van ’t Hoff factor for the solution is
3

3.40 particles observed

i = = 3.40
1 formula unit FeCl
3

 Exercise 4.3.8: Magnesium Chloride in Water

Calculate the van ’t Hoff factor for a 0.050 m aqueous solution of MgCl that has a measured freezing point of −0.25°C.
2

Answer
2.7 (versus an ideal value of 3).

4.3.6: Summary
The colligative properties of a solution depend on only the total number of dissolved particles in solution, not on their chemical
identity. Colligative properties include vapor pressure, boiling point, freezing point, and osmotic pressure. The addition of a
nonvolatile solute (one without a measurable vapor pressure) decreases the vapor pressure of the solvent. The vapor pressure of the
solution is proportional to the mole fraction of solvent in the solution, a relationship known as Raoult’s law. The boiling point
elevation (ΔT ) and freezing point depression (ΔT ) of a solution are defined as the differences between the boiling and freezing
b f

points, respectively, of the solution and the pure solvent. Both are proportional to the molality of the solute. When a solution and a
pure solvent are separated by a semipermeable membrane, a barrier that allows solvent molecules but not solute molecules to pass

4.3.15 https://chem.libretexts.org/@go/page/43416
through, the flow of solvent in opposing directions is unequal and produces an osmotic pressure, which is the difference in pressure
between the two sides of the membrane. Osmosis is the net flow of solvent through such a membrane due to different solute
concentrations. Dialysis uses a semipermeable membrane with pores that allow only small solute molecules and solvent molecules
to pass through. In more concentrated solutions, or in solutions of salts with highly charged ions, the cations and anions can
associate to form ion pairs, which decreases their effect on the colligative properties of the solution. The extent of ion pair
formation is given by the van ’t Hoff factor (i), the ratio of the apparent number of particles in solution to the number predicted by
the stoichiometry of the salt.
Henry’s law:

C = kP

Raoult’s law:
0
PA = χA P
A

vapor pressure lowering:

0 0
P − PA = ΔPA = χB P
A A

vapor pressure of a system containing two volatile components:

0 0
Ptot = χA P + (1 − χA )P
A B

boiling point elevation:

ΔTb = m Kb

freezing point depression:

ΔTf = m Kf

osmotic pressure:
n
Π = RT = M RT
V

van ’t Hoff factor:

apparent number of particles in solution
i =
number of moles of solute dissolved

4.3: Phase Equilibrium in Solutions - Nonvolatile Solutes is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.

4.3.16 https://chem.libretexts.org/@go/page/43416
4.4: Phase Equilibrium in Solutions - Volatile Solutes
 Learning Objectives
To understand the relationship among temperature, pressure, and solubility.
The understand that the solubility of a solid may increase or decrease with increasing temperature,
To understand that the solubility of a gas decreases with an increase in temperature and a decrease in pressure.
Describe the physical reasons that a binary liquid solution might exhibit non-ideal behavior

4.4.1: Vapor Pressure of Solutions and Raoult’s Law For Volatile Solutes
When a solute is volatile, meaning that it has a measurable vapor pressure, we can still use Raoult’s law. In this case, we calculate
the vapor pressure of each component separately. The total vapor pressure of the solution (P ) is the sum of the vapor pressures of
tot

the components:

Ptot = PA + PB (4.4.1)

0 0
= χA P + χB P (4.4.2)
A B

Because χ B = 1 − χA for a two-component system,

0 0
Ptot = χA P + (1 − χA )P (4.4.3)
A B

Thus we need to specify the mole fraction of only one of the components in a two-component system. Consider, for example, the
vapor pressure of solutions of benzene and toluene of various compositions. At 20°C, the vapor pressures of pure benzene and
toluene are 74.7 and 22.3 mmHg, respectively. The vapor pressure of benzene in a benzene–toluene solution is
0
PC H6 = χC H6 P (4.4.4)
6 6 C6 H6

and the vapor pressure of toluene in the solution is

0
P C6 H5 C H3 = χC6 H5 C H3 P (4.4.5)
C6 H5 C H 3

Equations 4.4.4 and 4.4.5 are both in the form of the equation for a straight line: y = mx + b , where b = 0 . Plots of the vapor
pressures of both components versus the mole fractions are therefore straight lines that pass through the origin, as shown in Figure
4.4.3. Furthermore, a plot of the total vapor pressure of the solution versus the mole fraction is a straight line that represents the

sum of the vapor pressures of the pure components. Thus the vapor pressure of the solution is always greater than the vapor
pressure of either component.

Figure : Vapor Pressures of Benzene–Toluene Solutions. Plots of the vapor pressures of benzene (C H ) and toluene (
4.4.1
6 6

C H CH
6 5
) versus the mole fractions at 20°C are straight lines. For a solution like this, which approximates an ideal solution, the
3

total vapor pressure of the solution (P ) is the sum of the vapor pressures of the components. (CC BY-NS-SA 4.0;
tot

Anonymous via LibreTexts).

4.4.1 https://chem.libretexts.org/@go/page/43417
A solution of two volatile components that behaves like the solution in Figure 4.4.3, which is defined as a solution that obeys
Raoult’s law. Like an ideal gas, an ideal solution is a hypothetical system whose properties can be described in terms of a simple
model. Mixtures of benzene and toluene approximate an ideal solution because the intermolecular forces in the two pure liquids are
almost identical in both kind and magnitude. Consequently, the change in enthalpy on solution formation is essentially zero (
ΔH soln≈ 0 ), which is one of the defining characteristics of an ideal solution.

Ideal solutions and ideal gases are both simple models that ignore intermolecular interactions.

 Example 4.4.1

For each system, compare the intermolecular interactions in the pure liquids and in the solution to decide whether the vapor
pressure will be greater than that predicted by Raoult’s law (positive deviation), approximately equal to that predicted by
Raoult’s law (an ideal solution), or less than the pressure predicted by Raoult’s law (negative deviation).
a. cyclohexane and ethanol
b. methanol and acetone
c. n-hexane and isooctane (2,2,4-trimethylpentane)
Given: identity of pure liquids
Asked for: predicted deviation from Raoult’s law (Equation 4.4.2)
Strategy:
Identify whether each liquid is polar or nonpolar, and then predict the type of intermolecular interactions that occur in solution.
Solution:
a. Liquid ethanol contains an extensive hydrogen bonding network, and cyclohexane is nonpolar. Because the cyclohexane
molecules cannot interact favorably with the polar ethanol molecules, they will disrupt the hydrogen bonding. Hence the
A–B interactions will be weaker than the A–A and B–B interactions, leading to a higher vapor pressure than predicted by
Raoult’s law (a positive deviation).
b. Methanol contains an extensive hydrogen bonding network, but in this case the polar acetone molecules create A–B
interactions that are stronger than the A–A or B–B interactions, leading to a negative enthalpy of solution and a lower vapor
pressure than predicted by Raoult’s law (a negative deviation).
c. Hexane and isooctane are both nonpolar molecules (isooctane actually has a very small dipole moment, but it is so small
that it can be ignored). Hence the predominant intermolecular forces in both liquids are London dispersion forces. We
expect the A–B interactions to be comparable in strength to the A–A and B–B interactions, leading to a vapor pressure in
good agreement with that predicted by Raoult’s law (an ideal solution).

 Exercise 4.4.1

For each system, compare the intermolecular interactions in the pure liquids with those in the solution to decide whether the
vapor pressure will be greater than that predicted by Raoult’s law (positive deviation), approximately equal to that predicted by
Raoult’s law (an ideal solution), or less than the pressure predicted by Raoult’s law (negative deviation):
a. benzene and n-hexane
b. ethylene glycol and CCl 4

c. acetic acid and n-propanol

Answer a
approximately equal
Answer b
positive deviation (vapor pressure greater than predicted)
Answer c
negative deviation (vapor pressure less than predicted)

4.4.2 https://chem.libretexts.org/@go/page/43417
4.4.2: Ideal vs. Real Solutions
Another solution whose components follow Raoult's law quite closely is a solution of hexane C H and heptane C H . The total
6 14 7 16

vapor pressure of this solution varies in a straight-line manner with the mole fraction composition of the mixture (Figure 4.4.2).
Note that the mole fraction scales at the top and bottom run in opposite directions, since by definition,

χhexane = 1– χheptane

If this solution behaves ideally, then is the sum of the Raoult's law plots for the two pure compounds (i.e., Equation 4.4.1):

Ptotal = Pheptane + Phexane

Figure 4.4.2 : Raoult's law plot for a mixture of hexane and heptane. (CC BY 4.0; Stephen Lower via Chem1).
An ideal solution is one whose vapor pressure follows Raoult's law throughout its range of compositions. Experience has shown
solutions that approximate ideal behavior are composed of molecules having very similar structures. Thus hexane and heptane are
both linear hydrocarbons that differ only by a single –CH2 group.

Most real solutions, however, do not obey Raoult’s law precisely, just as most real gases do not obey the ideal gas law exactly. Real
solutions generally deviate from Raoult’s law because the intermolecular interactions between the two components A and B differ.
We can distinguish between two general kinds of behavior, depending on whether the intermolecular interactions between
molecules A and B are stronger or weaker than the A–A and B–B interactions in the pure components.
If the A–B interactions are stronger than the A–A and B–B interactions, each component of the solution exhibits a lower vapor
pressure than expected for an ideal solution, as does the solution as a whole. The favorable A–B interactions effectively
stabilize the solution compared with the vapor. This kind of behavior is called a negative deviation from Raoult’s law. Systems
stabilized by hydrogen bonding between two molecules, such as acetone and ethanol, exhibit negative deviations from Raoult’s
law. The chloroform-acetone system (Figure 4.4.3) is a good example.
Conversely, if the A–B interactions are weaker than the A–A and B–B interactions yet the entropy increase is enough to allow
the solution to form, both A and B have an increased tendency to escape from the solution into the vapor phase. The result is a
higher vapor pressure than expected for an ideal solution, producing a positive deviation from Raoult’s law. In a solution of
CCl and methanol, for example, the nonpolar CCl molecules interrupt the extensive hydrogen bonding network in methanol,
4 4

and the lighter methanol molecules have weaker London dispersion forces than the heavier CCl molecules. Consequently,
4

solutions of CCl and methanol exhibit positive deviations from Raoult’s law. It should not be surprising molecules as
4

different as benzene and C S should interact more strongly with their own kind, hence the positive deviation in Figure 4.4.3).
2

4.4.3 https://chem.libretexts.org/@go/page/43417
 Figure 4.4.3 : Systems with negative deviation (left) and positive deviation (right) of Raoult's law. (CC BY 4.0; Stephen Lower via
Chem1)

 Ideal Solutions vs. Ideal Gases

The ideal solution differs in a fundamental way from the definition of an ideal gas, defined as a hypothetical substance that
follows the ideal gas law. The kinetic molecular theory that explains ideal gas behavior assumes that the molecules occupy no
space and that intermolecular attractions are totally absent.
The definition of an ideal gas is clearly inapplicable to liquids, whose volumes directly reflect the volumes of their component
molecules. And of course, the very ability of the molecules to form a condensed phase is due to the attractive forces between
the molecules. So the most we can say about an ideal solution is that the attractions between its all of its molecules are identical
— that is, A-type molecules are as strongly attracted to other A molecules as to B-type molecules. Ideal solutions are perfectly
democratic: there are no favorites.
You will recall that all gases approach ideal behavior as their pressures approach zero. In the same way, as the mole fraction of
either component approaches unity, the behavior of the solution approaches ideality. This is a simple consequence of the fact
that at these limits, each molecule is surrounded mainly by its own kind, and the few A-B interactions will have little effect.
Raoult's law is therefore a limiting law:
o
Pi = lim P χi (4.4.6)
xi →0

it gives the partial pressure of a substance in equilibrium with the solution more and more closely as the mole fraction of that
substance approaches unity.

4.4.3: Effect of Pressure on the Solubility of Gases - Henry’s Law

External pressure has very little effect on the solubility of liquids and solids. In contrast, the solubility of gases increases as the
partial pressure of the gas above a solution increases. This point is illustrated in Figure 4.4.4, which shows the effect of increased
pressure on the dynamic equilibrium that is established between the dissolved gas molecules in solution and the molecules in the
gas phase above the solution. Because the concentration of molecules in the gas phase increases with increasing pressure, the
concentration of dissolved gas molecules in the solution at equilibrium is also higher at higher pressures.

4.4.4 https://chem.libretexts.org/@go/page/43417
 Figure 4.4.4 : A Model Depicting Why the Solubility of a Gas Increases as the Partial Pressure Increases at Constant Temperature.
(a) When a gas comes in contact with a pure liquid, some of the gas molecules (purple spheres) collide with the surface of the
liquid and dissolve. When the concentration of dissolved gas molecules has increased so that the rate at which gas molecules
escape into the gas phase is the same as the rate at which they dissolve, a dynamic equilibrium has been established, as depicted
here. This equilibrium is entirely analogous to the one that maintains the vapor pressure of a liquid. (b) Increasing the pressure of
the gas increases the number of molecules of gas per unit volume, which increases the rate at which gas molecules collide with the
surface of the liquid and dissolve. (c) As additional gas molecules dissolve at the higher pressure, the concentration of dissolved
gas increases until a new dynamic equilibrium is established.
The relationship between pressure and the solubility of a gas is described quantitatively by Henry’s law, which is named for its
discoverer, the English physician and chemist, William Henry (1775–1836):

C = kH P (4.4.7)

where C is the concentration of dissolved gas at equilibrium, P is the partial pressure of the gas, and kH is the Henry’s law
constant, which must be determined experimentally for each combination of gas, solvent, and temperature.
Although the gas concentration may be expressed in any convenient units, we will use molarity exclusively. The units of the
Henry’s law constant are therefore mol/(L·atm) = M/atm. Values of the Henry’s law constants for solutions of several gases in
water at 20°C are listed in Table 4.4.1.
As the data in Table 4.4.1 demonstrate, the concentration of a dissolved gas in water at a given pressure depends strongly on its
physical properties. For a series of related substances, London dispersion forces increase as molecular mass increases. Thus among
the Group 18 elements, the Henry’s law constants increase smoothly from He to Ne to Ar.
Table 4.4.1 : Henry’s Law Constants for Selected Gases in Water at 20°C
Gas Henry’s Law Constant [mol/(L·atm)] × 10−4

He 3.9

Ne 4.7

Ar 15

H
2
8.1

N
2
7.1

O
2
14

CO
2
392

 Oxygen is Especially Soluble

Nitrogen and oxygen are the two most prominent gases in the Earth’s atmosphere and they share many similar physical
properties. However, as Table 4.4.1 shows, O is twice as soluble in water as N . Many factors contribute to solubility
2 2

including the nature of the intermolecular forces at play. For a details discussion, see "The O2/N2 Ratio Gas Solubility
Mystery" by Rubin Battino and Paul G. Seybold (J. Chem. Eng. Data 2011, 56, 5036–5044),

Gases that react chemically with water, such as HCl and the other hydrogen halides, H S , and NH , do not obey Henry’s law; all
2 3

of these gases are much more soluble than predicted by Henry’s law. For example, HCl reacts with water to give H (aq) and +

4.4.5 https://chem.libretexts.org/@go/page/43417
 (aq) , not dissolved HCl molecules, and its dissociation into ions results in a much higher solubility than expected for a neutral
−
Cl

molecule.

Gases that react with water do not obey Henry’s law.

Henry’s law has important applications. For example, bubbles of CO form as soon as a carbonated beverage is opened because
2

the drink was bottled under CO at a pressure greater than 1 atm. When the bottle is opened, the pressure of CO above the
2 2

solution drops rapidly, and some of the dissolved gas escapes from the solution as bubbles. Henry’s law also explains why scuba
divers have to be careful to ascend to the surface slowly after a dive if they are breathing compressed air. At the higher pressures
under water, more N2 from the air dissolves in the diver’s internal fluids. If the diver ascends too quickly, the rapid pressure change
causes small bubbles of N to form throughout the body, a condition known as “the bends.” These bubbles can block the flow of
2

blood through the small blood vessels, causing great pain and even proving fatal in some cases.
Due to the low Henry’s law constant for O in water, the levels of dissolved oxygen in water are too low to support the energy
2

needs of multicellular organisms, including humans. To increase the O concentration in internal fluids, organisms synthesize
2

highly soluble carrier molecules that bind O reversibly. For example, human red blood cells contain a protein called hemoglobin
2

that specifically binds O and facilitates its transport from the lungs to the tissues, where it is used to oxidize food molecules to
2

provide energy. The concentration of hemoglobin in normal blood is about 2.2 mM, and each hemoglobin molecule can bind four
O molecules. Although the concentration of dissolved O in blood serum at 37°C (normal body temperature) is only 0.010 mM,
2 2

the total dissolved O concentration is 8.8 mM, almost a thousand times greater than would be possible without hemoglobin.
2

Synthetic oxygen carriers based on fluorinated alkanes have been developed for use as an emergency replacement for whole blood.
Unlike donated blood, these “blood substitutes” do not require refrigeration and have a long shelf life. Their very high Henry’s law
constants for O result in dissolved oxygen concentrations comparable to those in normal blood.
2

 Example 4.4.2: Oxygen in Water

The Henry’s law constant for O in water at 25°C is 1.27 × 10 M /atm , and the mole fraction of
2
−3
O
2
in the atmosphere is
0.21. Calculate the solubility of O in water at 25°C at an atmospheric pressure of 1.00 atm.
2

Given: Henry’s law constant, mole fraction of O , and pressure 2

Asked for: solubility

Strategy:
A. Use Dalton’s law of partial pressures to calculate the partial pressure of oxygen.
B. Use Henry’s law (Equation 4.4.7) to calculate the solubility, expressed as the concentration of dissolved gas.
Solution:
A According to Dalton’s law, the partial pressure of O is proportional to the mole fraction of O :
2 2

PA = χA Pt = (0.21)(1.00 atm) = 0.21 atm

B From Henry’s law, the concentration of dissolved oxygen under these conditions is
−3 −4
[ CO ] = kH PO = (1.27 × 10 M / atm )(0.21 atm ) = 2.7 × 10 M
2 2

 Exercise 4.4.2: Carbon Dioxide in Water

To understand why soft drinks “fizz” and then go “flat” after being opened, calculate the concentration of dissolved C O in a 2

soft drink:
a. bottled under a pressure of 5.0 atm of C O 2

b. in equilibrium with the normal partial pressure of C O in the atmosphere (approximately 3 × 10

2
−4
atm ). The Henry’s law
constant for C O in water at 25°C is 3.4 × 10 M /atm .
2
−2

Answer a
0.17 M
Answer b

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 −5
1 × 10 M

4.4.4: Summary
The vapor pressure of the solution with volatile solute and solvent is proportional to the mole fraction of solute and solvent in the
solution, via a modified version of Raoult’s law discussed previously. Solutions that obey Raoult’s law are called ideal solutions.
Most real solutions exhibit positive or negative deviations from Raoult’s law. In an ideal solution, the interactions are there, but
they are all energetically identical. Thus in an ideal solution of molecules A and B, A—A and B—B attractions are the same as A
—B attractions. This is the case only when the two components are chemically and structurally very similar.
The solubility of most substances depends strongly on the temperature and, in the case of gases, on the pressure. The solubility of
most solid or liquid solutes increases with increasing temperature. The components of a mixture can often be separated using
fractional crystallization, which separates compounds according to their solubilities. The solubility of a gas decreases with
increasing temperature. Henry’s law describes the relationship between the pressure and the solubility of a gas.

4.4: Phase Equilibrium in Solutions - Volatile Solutes is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.
13.5: Colligative Properties by Anonymous is licensed CC BY-NC-SA 3.0.
8.8: Ideal vs. Real Solutions by Stephen Lower is licensed CC BY 3.0. Original source:
http://www.chem1.com/acad/webtext/virtualtextbook.html.

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4.5: Separating Volatile Solutions - Distillation
 Learning Objectives

Make sure you thoroughly understand the following essential ideas:

Sketch out a typical boiling point diagram for a binary liquid solution, and use this to show how a simple one-stage
distillation works.
Explain the role of the lever rule in fractional distillation
Describe the purpose and function of a fractionating column
Sketch out boiling point diagrams for high- and low-boiling azeotropes
Describe the role of distillation in crude oil refining, and explain, in a very general way, how further processing is used to
increase the yield of gasoline motor fuel.

Distillation is a process whereby a mixture of liquids having different vapor pressures is separated into its components. At first one
might think that this would be quite simple: if you have a solution consisting of liquid A that boils at 50°C and liquid B with a
boiling point of 90°C, all that would be necessary would be to heat the mixture to some temperature between these two values; this
would boil off all the A (whose vapor could then be condensed back into pure liquid A), leaving pure liquid B in the pot. But that
overlooks that fact that these liquids will have substantial vapor pressures at all temperatures, not only at their boiling points.

4.5.1: Vapor Pressure vs. Composition Phase Diagrams

To fully understand distillation, we will consider an ideal binary liquid mixture of A and B . If the mole fraction of A in the mixture
is χ , then by the definition of mole fraction, that of B is
A

χB = 1– χA (4.5.1)

Since distillation depends on the different vapor pressures of the components to be separated, let's first consider the vapor pressure
vs. composition plots (Figure 4.5.1) for a hypothetical mixture at some arbitrary temperature at which both liquid and gas phases
can exist, depending on the total pressure.

Figure 4.5.1 : Liquid-Vapor Equilibrium curve.

In Figure 4.5.2, all states of the system (i.e., combinations of pressure and composition) in which the solution exists solely as a
liquid are shaded in green. Since liquids are more stable at higher pressures, these states occupy the upper part of the diagram. At
any given total vapor pressure such as at , the composition of the vapor in equilibrium with the liquid (designated by x ) A

corresponds to the intercept with the diagonal equilibrium line at . The diagonal line is just an expression of the linearity
between vapor pressure and composition according to Raoult's law.

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 Figure 4.5.2 : Liquid-Vapor Equilibrium curve. of the pressure line with the equilibrium curve defines the mole fractions of
A and B present in the vapor. (Note that mole fractions of gases, which we are dealing with here, are conventionally represented by

y, hence yA and yB). The curvature of the equilibrium line arises from the need to combine Raoult's law with Dalton's law of partial
pressures which applies to gaseous mixtures. Figure 4.5.3 .

Figure 4.5.3
The two liquid-vapor equilibrium lines (one curved, the other straight) now enclose an area in which liquid and vapor can coexist;
outside of this region, the mixture will consist entirely of liquid or of vapor. At this particular pressure , the intercept with the
upper boundary of the two-phase region gives the mole fractions of A and B in the liquid phase, while the intercept with the
lower boundary gives the mole fractions of the two components in the vapor.

 Exercise 4.5.1
Take a moment to study Figure 4.5.5 and to confirm that
because both intercepts occur on equilibrium lines, they describe the compositions of the liquid and vapor that can
simultaneously exist;
the compositions of the vapor and liquid are not the same;
in the vapor, the mole fraction of B (the more volatile component of the solution) is greater than that in the liquid;
in the liquid, the mole fraction of A (the less volatile component) is smaller than that of the vapor.

The vapor in equilibrium with a solution of two or more liquids is always richer in the more volatile component.

4.5.2: Temperatures vs. Composition Phase Diagrams (Boiling Point Diagrams)

The lever rule discussed above suggests that if we heat a mixture sufficiently to bring its total vapor pressure into the two-phase
region, we will have a means of separating the mixture into two portions which will be enriched in the more volatile and less
volatile components respectively. This is the principle on which distillation is based. But what temperature is required to achieve
this? Again, we will spare you the mathematical details, but it is possible to construct a plot similar to the Figure 4.5.4 except that
the vertical axis represents temperature rather than pressure. This kind of plot is called a boiling point diagram.

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 Figure 4.5.4 : Boiling point diagram of a volatile two-component system.

 Important Properties of Boiling Point Diagrams

Some important things to understand about Figure 4.5.6:

The shape of the two-phase region is bi-convex, as opposed to the half-convex shape of the pressure-composition plot.
The slope of the two-phase region is opposite to what we saw in the previous plot, and the areas corresponding to the
single-phase regions are reversed. This simply reflects the fact that liquids having a higher vapor pressure boil at lower
temperatures, and vice versa.
The horizontal line that defines the temperature is called the tie line. Its intercepts with the two equilibrium curves specify
the composition of the liquid and vapor in equilibrium with the mixture at the given temperature.
The vapor composition line is also known as the dew point line — the temperature at which condensation begins on
cooling.
The liquid composition line is also called the bubble point line — the temperature at which boiling begins on heating.

The tie line shown in Figure 4.5.4 is for one particular temperature. But when we heat a liquid to its boiling point, the composition
will change as the more volatile component (B in these examples) is selectively removed as vapor. The remaining liquid will be
enriched in the less volatile component, and its boiling point will consequently rise. To understand this process more thoroughly, let
us consider the situation at several points during the distillation of an equimolar solution of A and B .

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 Figure 4.5.5A: We begin with the liquid at T1, below its boiling point. When the temperature rises to T2, boiling begins and the
first vapor (and thus the first drop of condensate) will have the composition y2.

Figure 4.5.5B : As the more volatile component B is boiled off, the liquid and vapor/condensate compositions shift to the left
(orange arrows).

Figure 4.5.5C : At T4, the last trace of liquid disappears. The system is now entirely vapor, of
composition y4.

Notice that the vertical green system composition line remains in the same location in the three plots because the "system" is
defined as consisting of both the liquid in the "pot" and that in the receiving container which was condensed from the vapor. The
principal ideas you should take away from this are that
distillation can never completely separate two volatile liquids;
the composition of the vapor and thus of the condensed distillate changes continually as each drop forms, starting at y2 and
ending at y4 in this example;
if the liquid is completely boiled away, the composition of the distillate will be the same as that of the original solution.

4.5.3: Laboratory Distillation Setup

The apparatus used for a simple laboratory batch distillation is shown here. The purpose of the thermometer is to follow the
progress of the distillation; as a rough rule of thumb, the distillation should be stopped when the temperature rises to about half-
way between the boiling points of the two pure liquids, which should be at least 20-30 C° apart (if they are closer, then fractional
distillation, described below, becomes necessary).

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 Figure 4.5.6 : Simple distillation apparatus. An round-bottom flask is used as a receiving flask. Here the distillation head and
fractionating column are combined in one piece. (CC BY-NC-ND; Lisa Nichols (Butte Community College)).
Condensers are available in a number of types. The simple Liebig condenser shown above is the cheapest and therefore most
commonly used in student laboratories. Several other classic designs increase the surface area separating the vapor/distillate and
cooling water, leading to greater heat exchange efficiency and allowing higher throughput.

4.5.4: Fractional Distillation

Although distillation can never achieve complete separation of volatile liquids, it can in principal be carried out in such a way that
any desired degree of separation can be achieved if the solution behaves ideally and one is willing to go to the trouble. The general
procedure is to distill only a fraction of the liquid, the smaller the better. The condensate, now enriched in the more volatile
component, is then collected and re-distilled (again, only a small fraction), thus obtaining a condensate even-more-enriched in the
more volatile component. If we repeat this sequence many times, we can eventually obtain almost-pure, if minute, samples of the
two components.
However, since this would hardly be practical, there is a better way. To understand it, you need to know about the lever rule, which
provides a simple way of determining the relative quantities (not just the compositions) of two phases in equilibrium. The lever
rule is easily derived from Raoult's and Dalton's laws, but we will simply illustrate it graphically (Figure 4.5.7). The plot shows
the boiling point diagram of a simple binary mixture of composition . At the temperature corresponding to the tie line, the
composition of the liquid corresponds to and that of the vapor to .

Figure 4.5.7 :
So now for the lever rule: the relative quantities of the liquid and the vapor we identified above are given by the lengths of the tie-
line segments labeled a and b. Thus in this particular example, in which b is about four times longer than a, we can say that the
mole ratio of vapor (of composition ) to liquid (composition ) is 4.
It is not practical to carry out an almost-infinite number of distillation steps to obtain nearly-infinitesimal quantities of the two pure
liquids we wish to separate. So instead of collecting each drop of condensate and re-distilling it, we will distil half of the mixture in

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each step. Suppose you want to separate a liquid mixture composed of 20 mole-% B and 80 mole-% A, with A being the more
volatile.

Figure 4.5.8 : Steps in Fractional Distillation

As we heat the mixture whose overall composition is indicated by , the first vapor is formed at T0 and has the
composition y0, found by extending the horizontal dashed line until it meets the vapor curve. This vapor is clearly enriched in
B; if it is condensed, the resulting liquid will have a mole fraction xB approaching that of A in the original liquid. But this is
only the first drop, we don't want to stop there!
As the liquid continues to boil, the boiling temperature rises. When it reaches T1, we will have boiled away half of the
liquid. At this point, the "system" composition (liquid plus vapor) is still the same ( ), but is now equally divided between
the liquid, which we call "residue" R1, and the condensed vapor, the distillate D1.
How do we know it is equally divided? We have picked T1 so that the tie line is centered on the system concentration,
so by the lever rule, R1 and D1 contain equal numbers of moles.
We now take the condensed liquid D1 having the composition , and distill half of it, obtaining distillate of composition
D2.
.. and then carry out yet another distillation, this time using D3 as our feedstock.
Our four-stage fractionation has enriched the more volatile solute from 20 to slightly over 80 mole-percent in D4. The less
volatile component A is most concentrated in R1. R2 through R4 are thrown away (but not down the sink, please!)

Figure 4.5.9 : Boiling point diagrams illustrating four fractional distillation steps.

4.5.5: Azeotropes: the Limits of Distillation (Non-Ideal Behavior)

The boiling point diagrams discussed above apply to solutions that behave in a reasonably ideal manner — that is, to solutions that
do not deviate too far from Raoult's law. As we explained above, mixtures of liquids whose intermolecular interactions are widely
different do not behave ideally, and may be impossible to separate by ordinary distillation. The reason for this is that under certain
conditions, the compositions of the liquid and of the vapor in equilibrium with it become identical, precluding any further
separation. These cross-over points appear as "kinks" in the boiling point diagrams (Figure 4.5.10).
Thus in this boiling point diagram for a mixture exhibiting a positive deviation from Raoult's law (Figure 4.5.10A), successive
fractionations of mixtures correspond to either or bring the distillation closer to the azeotropic composition indicated by the
dashed vertical line. Once this point is reached, further distillation simply yields more of the same "high-boiling" azeotrope.

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 Figure 4.5.10 : Maximum Boiling Azeotrope (left) and Maximum Bioling Azeotrope (right).
Distillation of a mixture having a negative deviation from Raoult's law leads to a similar stalemate, in this case yielding a "low-
boiling" azeotrope (Figure 4.5.10B). High- and low-boiling azeotropes are commonly referred to as constant-boiling mixtures, and
they are more common than most people think.
Table 4.5.8: Some constant-boiling mixtures
Mixture Azeotrope

Ethanol : water 98%, high, 78.1°C

Hydrochloric acid : water 20.2% high, 108.6°C

Hydrofluoric acid : water 35.6%, 111.3°C

Nitric acid : water 68%, 120.5°C

Sulfuric acid : water 98.3%, 338°C

 Distillation of Ethanol

Ethanol is one of the major industrial chemicals, and is of course the essential component of beverages that have been a part of
civilization throughout recorded history. Most ethanol is produced by fermentation of the starch present in food grains, or of
sugars formed by the enzymatic degradation of cellulose. Because ethanol is toxic to the organisms whose enzymes mediate
the fermentation process, the ethanol concentration in the fermented mixture is usually limited to about 15%. The liquid phase
of the mixture is then separated and distilled.

Figure 4.5.11 : The normal boiling point of ethanol is 78.4°C, but its formation of a low-boiling azeotrope with water limits the
maximum concentration that can be obtained by ordinary distillation to 95.6 volume-% (89.5 mole-%). This concentration is
adequate for many applications, for which the product is commonly sold as "95% ethanol".
For applications requiring anhydrous ethanol ("absolute ethanol "), the most common method is the use of zeolite-based
molecular sieves to absorb the remaining water. Addition of benzene can break the azeotrope, and this was the most common
production method in earlier years. For certain critical uses where the purest ethanol is required, it is synthesized directly from
ethylene.

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4.5.5.1: How to "Break" an Azeotrope
There are four general ways of dealing with azeotropes. The first two of these are known collectively as azeotropic distillation.
Addition of a third substance that alters the intermolecular attractions is the most common trick. The drawback is that another
procedure is usually needed to remove this other substance.
Pressure-swing distillation takes advantage of the fact that boiling point (T,X) diagrams are two-dimensional slices of a (T,X,P)
diagram in which the pressure is the third variable. This means that the azeotropic composition depends on the pressure, so
distillation at some pressure other than 1 atm may allow one to "jump" the azeotrope.
Use of a molecular sieve — a porous material that selectively absorbs one of the liquids, most commonly water when the latter
is present at a low concentration.
Give up. It often happens that the azeotropic composition is sufficiently useful that it's not ordinarily worth the trouble of
obtaining a more pure product. This accounts for the concentrations of many commercial chemicals such as mineral acids.

4.5.6: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook

This page titled 4.5: Separating Volatile Solutions - Distillation is shared under a CC BY license and was authored, remixed, and/or curated by
Stephen Lower via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon
request.

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4.6: Colloidal Suspensions
 Learning Objectives
To distinguish between true solutions and solutions with aggregate particles.

Suspensions and colloids are two common types of mixtures whose properties are in many ways intermediate between those of true
solutions and heterogeneous mixtures. A suspension is a heterogeneous mixture of particles with diameters of about 1 µm (1000
nm) that are distributed throughout a second phase. Common suspensions include paint, blood, and hot chocolate, which are solid
particles in a liquid, and aerosol sprays, which are liquid particles in a gas. If the suspension is allowed to stand, the two phases will
separate, which is why paints must be thoroughly stirred or shaken before use. A colloid is also a heterogeneous mixture, but the
particles of a colloid are typically smaller than those of a suspension, generally in the range of 2 to about 500 nm in diameter.
Colloids include fog and clouds (liquid particles in a gas), milk (solid particles in a liquid), and butter (solid particles in a solid).
Other colloids are used industrially as catalysts. Unlike in a suspension, the particles in a colloid do not separate into two phases on
standing. The only combination of substances that cannot produce a suspension or a colloid is a mixture of two gases because their
particles are so small that they always form true solutions. The properties of suspensions, colloids, and solutions are summarized in
Table 4.6.1.
Table 4.6.1 : Properties of Liquid Solutions, Colloids, and Suspensions
Approximate Size of Particles
Type of Mixture Characteristic Properties Examples
(nm)

not filterable; does not separate on

air, white wine, gasoline, salt
solution <2 standing; does not scatter visible
water
light

scatters visible light; translucent

smoke, fog, ink, milk, butter,
colloid 2–500 or opaque; not filterable; does not
cheese
separate on standing

cloudy or opaque; filterable; muddy water, hot cocoa, blood,

suspension 500–1000
separates on standing paint

4.6.1: Colloids and Suspensions

Colloids were first characterized in about 1860 by Thomas Graham, who also gave us Graham’s law of diffusion and effusion.
Although some substances, such as starch, gelatin, and glue, appear to dissolve in water to produce solutions, Graham found that
they diffuse very slowly or not at all compared with solutions of substances such as salt and sugar. Graham coined the word colloid
(from the Greek kólla, meaning “glue”) to describe these substances, as well as the words sol and gel to describe certain types of
colloids in which all of the solvent has been absorbed by the solid particles, thus preventing the mixture from flowing readily, as we
see in Jell-O. Two other important types of colloids are aerosols, which are dispersions of solid or liquid particles in a gas, and
emulsions, which are dispersions of one liquid in another liquid with which it is immiscible.
Colloids share many properties with solutions. For example, the particles in both are invisible without a powerful microscope, do
not settle on standing, and pass through most filters. However, the particles in a colloid scatter a beam of visible light, a
phenomenon known as the Tyndall effect,The effect is named after its discoverer, John Tyndall, an English physicist (1820–1893).
whereas the particles of a solution do not. The Tyndall effect is responsible for the way the beams from automobile headlights are
clearly visible from the side on a foggy night but cannot be seen from the side on a clear night. It is also responsible for the colored
rays of light seen in many sunsets, where the sun’s light is scattered by water droplets and dust particles high in the atmosphere. An
example of the Tyndall effect is shown in Figure 4.6.1.

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 Figure 4.6.1 : Tyndall Effect, the Scattering of Light by Colloids (CC BY; LibreTexts)
Although colloids and suspensions can have particles similar in size, the two differ in stability: the particles of a colloid remain
dispersed indefinitely unless the temperature or chemical composition of the dispersing medium is changed. The chemical
explanation for the stability of colloids depends on whether the colloidal particles are hydrophilic or hydrophobic.
Most proteins, including those responsible for the properties of gelatin and glue, are hydrophilic because their exterior surface is
largely covered with polar or charged groups. Starch, a long-branched polymer of glucose molecules, is also hydrophilic. A
hydrophilic colloid particle interacts strongly with water, resulting in a shell of tightly bound water molecules that prevents the
particles from aggregating when they collide. Heating such a colloid can cause aggregation because the particles collide with
greater energy and disrupt the protective shell of solvent. Moreover, heat causes protein structures to unfold, exposing previously
buried hydrophobic groups that can now interact with other hydrophobic groups and cause the particles to aggregate and precipitate
from solution. When an egg is boiled, for example, the egg white, which is primarily a colloidal suspension of a protein called
albumin, unfolds and exposes its hydrophobic groups, which aggregate and cause the albumin to precipitate as a white solid.

Figure 4.6.2 : Sickle-Cell Anemia The characteristic shape of sickled red blood cells is the result of fibrous aggregation of
hemoglobin molecules inside the cell.
A normal blood cell is circular in shape with a dimple in the middle, a sickled cell is banana shaped.
In some cases, a stable colloid can be transformed to an aggregated suspension by a minor chemical modification. Consider, for
example, the behavior of hemoglobin, a major component of red blood cells. Hemoglobin molecules normally form a colloidal
suspension inside red blood cells, which typically have a “donut” shape and are easily deformed, allowing them to squeeze through
the capillaries to deliver oxygen to tissues. In a common inherited disease called sickle-cell anemia, one of the amino acids in
hemoglobin that has a hydrophilic carboxylic acid side chain (glutamate) is replaced by another amino acid that has a hydrophobic
side chain (valine). Under some conditions, the abnormal hemoglobin molecules can aggregate to form long, rigid fibers that cause
the red blood cells to deform, adopting a characteristic sickle shape that prevents them from passing through the capillaries (Figure
4.6.2). The reduction in blood flow results in severe cramps, swollen joints, and liver damage. Until recently, many patients with

sickle-cell anemia died before the age of 30 from infection, blood clots, or heart or kidney failure, although individuals with the
sickle-cell genetic trait are more resistant to malaria than are those with “normal” hemoglobin.

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 Figure 4.6.3 : Formation of New Land by the Destabilization of a Colloid Suspension. This satellite photograph shows the
Mississippi River delta from New Orleans (top) to the Gulf of Mexico (bottom). Where seawater mixes with freshwater from the
Mississippi River, colloidal clay particles in the river water precipitate (tan area).
Aggregation and precipitation can also result when the outer, charged layer of a particle is neutralized by ions with the opposite
charge. In inland waterways, clay particles, which have a charged surface, form a colloidal suspension. High salt concentrations in
seawater neutralize the charge on the particles, causing them to precipitate and form land at the mouths of large rivers, as seen in
the satellite view in Figure 4.6.3. Charge neutralization is also an important strategy for precipitating solid particles from gaseous
colloids such as smoke, and it is widely used to reduce particulate emissions from power plants that burn fossil fuels.

4.6.2: Emulsions
Emulsions are colloids formed by the dispersion of a hydrophobic liquid in water, thereby bringing two mutually insoluble liquids,
such as oil and water, in close contact. Various agents have been developed to stabilize emulsions, the most successful being
molecules that combine a relatively long hydrophobic “tail” with a hydrophilic “head”:

Bond line drawing of soap, The hydrophobic tail is a long hydrocarbon chain. The hydrophilic heat is a carbon double bonded to an
oxygen and single bonded to a negatively charged oxygen.
Examples of such emulsifying agents include soaps, which are salts of long-chain carboxylic acids, such as sodium stearate
CO − Na ] , and detergents, such as sodium dodecyl sulfate [ CH (CH ) OSO − Na ] , whose structures are as
+ +
[ CH (CH )
3 2 16 2 3 2 11 3

follows:

When you wash your laundry, the hydrophobic tails of soaps and detergents interact with hydrophobic particles of dirt or grease
through dispersion forces, dissolving in the interior of the hydrophobic particle. The hydrophilic group is then exposed at the

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surface of the particle, which enables it to interact with water through ion–dipole forces and hydrogen bonding. This causes the
particles of dirt or grease to disperse in the wash water and allows them to be removed by rinsing. Similar agents are used in the
food industry to stabilize emulsions such as mayonnaise.
A related mechanism allows us to absorb and digest the fats in buttered popcorn and French fries. To solubilize the fats so that they
can be absorbed, the gall bladder secretes a fluid called bile into the small intestine. Bile contains a variety of bile salts, detergent-
like molecules that emulsify the fats.

4.6.3: Micelles
Detergents and soaps are surprisingly soluble in water in spite of their hydrophobic tails. The reason for their solubility is that they
do not, in fact, form simple solutions. Instead, above a certain concentration they spontaneously form micelles, which are spherical
or cylindrical aggregates that minimize contact between the hydrophobic tails and water. In a micelle, only the hydrophilic heads
are in direct contact with water, and the hydrophobic tails are in the interior of the aggregate (Figure 4.6.4a).

Figure 4.6.4 : Micelles and a Phospholipid Bilayer. (a) Soaps and detergents, which contain a single hydrophobic tail on each
molecule, form spherical micelles with the intertwined tails in the interior and the hydrophilic head groups on the exterior. (b)
Phospholipids, which have two hydrophobic tails, tend to form extended double layers in which the hydrophobic tails are
sandwiched between the hydrophilic head groups.
A large class of biological molecules called phospholipids consists of detergent-like molecules with a hydrophilic head and two
hydrophobic tails, as can be seen in the molecule of phosphatidylcholine. The additional tail results in a cylindrical shape that
prevents phospholipids from forming a spherical micelle. Consequently, phospholipids form bilayers, extended sheets consisting of
a double layer of molecules. As shown in Figure 4.6.4b, the hydrophobic tails are in the center of the bilayer, where they are not in
contact with water, and the hydrophilic heads are on the two surfaces, in contact with the surrounding aqueous solution.

A cell membrane is essentially a mixture of phospholipids that form a phospholipid bilayer. One definition of a cell is a collection
of molecules surrounded by a phospholipid bilayer that is capable of reproducing itself. The simplest cells are bacteria, which
consist of only a single compartment surrounded by a single membrane. Animal and plant cells are much more complex, however,
and contain many different kinds of compartments, each surrounded by a membrane and able to carry out specialized tasks.

4.6.4: Summary
A suspension is a heterogeneous mixture of particles of one substance distributed throughout a second phase; the dispersed
particles separate from the dispersing phase on standing. In contrast, the particles in a colloid are smaller and do not separate on
standing. A colloid can be classified as a sol, a dispersion of solid particles in a liquid or solid; a gel, a semisolid sol in which all of
the liquid phase has been absorbed by the solid particles; an aerosol, a dispersion of solid or liquid particles in a gas; or an
emulsion, a dispersion of one liquid phase in another. A colloid can be distinguished from a true solution by its ability to scatter a
beam of light, known as the Tyndall effect. Hydrophilic colloids contain an outer shell of groups that interact favorably with water,

4.6.4 https://chem.libretexts.org/@go/page/43418
whereas hydrophobic colloids have an outer surface with little affinity for water. Emulsions are prepared by dispersing a
hydrophobic liquid in water. In the absence of a dispersed hydrophobic liquid phase, solutions of detergents in water form
organized spherical aggregates called micelles. Phospholipids are a class of detergent-like molecules that have two hydrophobic
tails attached to a hydrophilic head. A bilayer is a two-dimensional sheet consisting of a double layer of phospholipid molecules
arranged tail to tail with a hydrophobic interior and a hydrophilic exterior. Cells are collections of molecules that are surrounded by
a phospholipid bilayer called a cell membrane and are able to reproduce themselves.

4.6: Colloidal Suspensions is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
13.6: Colloids is licensed CC BY-NC-SA 3.0.

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4.E: Solutions (Exercises)
These are homework exercises to accompany the Textmap created for "Principles of Modern Chemistry" by Oxtoby et al.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here.

4.E.1: Q.1
mg
A student goes to the hospital and has blood work done and the results state that he has a bromide count of 3.17 dL
.
a. What is the molar concentration of the students blood?
g
b. What is the molality of the student's blood if the density of his blood was found to be 1.06 mL
?
c. How much of the students blood would be require to get 3g of bromide?

4.E.2: Q.5
g
Given a 3.1416 M aqueous solution of sucrose, C H O 12 22 11
with a density of 1.5986
mL
. Calculate the molality of this solution,
g
remember that the molar mass of sucrose is 342.297 . mol

4.E.3: Q.9
A solution contains 75% of ethanol (C 2
H O
6
) by mass and the rest is water.
a. What is the density of the solution if there is 15 mol of ethanol per liter of solution?
b. To prepare a 3.5L of 2M ethanol, how many milliliters of the solution is needed?

4.E.4: Q.14
Rewrite the following balanced equations as net ionic equations.
a. H SO (aq) + 2 NaOH(aq) → 2 H O(l) + Na SO (aq)
2 4 2 2 4

b. 2 Na PO (aq) + 3 CaCl (aq) → 6 NaCl(aq) + Ca (PO )

3 4 2 3 4 2
(s)

c. BaCl (aq) + Na SO (aq) → BaSO (s) + 2 NaCl(aq)

2 2 4 4

d. 2 AgNO (aq) + ZnCl (aq) → 2 AgCl(s) + Zn(NO ) (aq)

3 2 3 2

4.E.5: Q.15
Write the balanced chemical equation for the titration of H SO
2 4
with KOH , then find the volume of a 5.49 M KOH solution
needed to neutralize 36.2 g of H SO . 2 4

4.E.6: Q.16
Phosphoric acid is made industrially as a by-product of the extraction of calcium phosphate

Ca (PO ) + 6 HNO + 12 H O ⟶ 2 H PO + 3 Ca (NO ) + 12 H O

3 4 2 3 2 3 4 3 2 2

What volume of 8.5 M phosphoric acid is generated by the reaction of 4.5 metric tons (4500 kg) of calcium phosphate?

4.E.7: Q.19
Write a balanced equation for the acid-base reaction that leads to the production of each of the following salts.
a. BaSO 4

b. MgSO 3

c. PbSO 4

d. AgCl

4.E.8: Q.21
Hydrogen selenide is classified as a binary acid that has similar properties as hydrogen sulfide. Write down the balanced equation
of hydrogen selenide reacting with the base potassium hydroxide and name the salt product of the reaction.

4.E.1 https://chem.libretexts.org/@go/page/69605
4.E.9: Q.25
A student working with an unknown solution of hydrochloric acid is assigned the task of finding its concentration. The student
places a 200.0 mL sample of the solution in a 350.0 mL Erlenmeyer flask and titrates the solution with a 0.1234 M solution of
sodium hydroxide, where a phenolphthalein indicator is used to find the endpoint. The endpoint is found to be 31.416 mL, what is
the concentration of the original hydrochloric acid solution sample?

4.E.10: Q.41
The vapor pressure of salicylic acid C H O at 200°C is 0.1598 atm. A 19.0 g sample of ethanol C
7 6 3 2
H O
6
is dissolved in 60.0 g of
salicylic acid. Calculate the vapor pressure of salicylic acid above the resulting solution.

4.E.11: Q.43
When 53 mol of an unknown compound was added to 100 g of water, the normal boiling point of water increased to 101.1oC. What
is the boiling point elevation constant of water? The compound does not dissociate in solution.

4.E.12: Q.45
When 5.82 g of uniformly dissociating unknown salt, YX, is dissolved in 100.0 g of water, the boiling point of the water is raised
by 0.20°C. When 7.09 g of uniformly dissociating unknown salt, ZX, is dissolved in 200.0 g of water, the boiling point of the water
is raised by 0.30°C. Assuming both have a van't hoff factor of 2, identify the elements that X, Y, and Z represent.

4.E.13: Q.47
Camphor is a useful agent for determining solute’s molar mass. Camphor’s melting point and Kf are given at 451.55 K and
K kg
37.7
mol
. Find the freezing point of the solution of 0.72 g of glucose is dissolved in the 30.0 g of camphor.

4.E.14: Q.48
It is observed that 2 grams of a non-electrolyte solute dissolved in 100 grams of benzene lowered the freezing point of the solution
by 0.40°C compared to pure benzene. Given that the freezing point depression constant of benzene is 5.12 K kg/mol, find the molar
mass of the solute. If it is given that the molecular formula of the solute is X where X is an element, what is the formula of the
8

solute?

4.E.15: Q.49
At what temperature does the first ice crystals begin to form in a 27% salt (by mass) aqueous solution of NaCl? As the
crystallization of water carries on, the remaining solution becomes more concentrated, so what happens to the freezing point of the
o
C kg
solution? Given that the freezing point depression constant (K f ) of water is 1.86 mol
.

4.E.16: Q.50
When homemade ice cream is being made, the temperature ranging downward from -3°C are needed. Ice cubes from a freezer have
a temperature of about -12°C, which is cold enough; however, when the ice cream mixture is mixed with the ice cubes, the liquid
balances out to 0°C, which is too warm. To obtain a liquid that is cold enough, salt NaCl is dissolved in water and ice is added to
the saltwater. The salt lowers the freezing point of the water enough so that it can freeze the liquid inside the ice cream maker. The
instruction for the ice cream maker say to add one part salt to 11 parts water (by mass). What is the freezing point of this solution in
°C? Assume the NaCl dissociates fully into ions, and that the solution is ideal.

4.E.17: Q.53
A sample of a purified unknown compound is dissolved in toluene, diluting the solvent to a volume of 1.05 mL. The resulting
solution has an osmotic pressure of 0.025 atm at 275 K. If the solute has a molar mass of 46.06 g/mol, how many grams of the
unknown compound were added?

4.E.18: Q.57
An amount of hydrogen gas (H ) with a partial pressure of 4.6 atm is dissolved in water and this solution is sealed. The Henry's
2

Law constant K for this solution at 25 C is 7.8 × 10

o
. −4 M

atm

4.E.2 https://chem.libretexts.org/@go/page/69605
 grams
a. How many moles of hydrogen gas will dissolve per liter of water? Assume the density of water is 1.0 cm3
and has not been
affected by the temperature.
b. What will the dissolved gas molecules do if the sealed solution is unsealed?

4.E.19: Q.59
Propene is a colorless organic compound with a weak but unpleasant smell. However, a company can take advantage of its
chemical properties to produce propanol:

C H + H O ⟶ CH (CH ) OH
3 6 2 3 2 2

The heat of formation of propene is 20.4 . kJ

mol

The heat of formation of H O is −241.8 .

2
kJ

mol

The heat of formation of CH (CH ) OH is −104.6

3 2 2
kJ

mol
.
What suggestions can you give to the company regarding the conditions of pressure and temperature that will have a maximum
yield of propanol at equilibrium without calculating the actual data?

4.E.20: Q.61
Suppose heptane and octane form an ideal solution. At 20.0°C, pure heptane has a vapor pressure of P °= 0.0562 atm while pure
1

octane has a vapor pressure of P °= 0.0145 atm. What is the mole fraction of heptane vapor over a solution of heptane and octane
2

if the solution contained 0.300 mol heptane and 0.700 mol octane?

4.E.21: Q.63
At 50oC, benzene (C H ) has a vapor pressure of 42.5 kPa and isobutene (C H ) has a vapor pressure of 0.83 torr. When 10.0 g of
6 6 3 8

benzene and 30 g of isobutene are mixed in a solution, they form a nearly ideal solution.
a. Calculate the mole fraction of benzene in the solution.
b. What is the total vapor pressure above the solution in kPa at 50oC ?
c. Calculate the mole fraction of isobutene that exists above the solution in the vapor phase.

4.E.22: Q.65
A solution is prepared by mixing 2g of CaCl (s) , 2g of MgCl (s), and 3g of MnO
2 2 2
(s) in enough water to make a total volume of
150 mL. Calculate the concentration of chlorine in the solution in grams per liter.

4.E.23: Q.69
Chromium ion, Cr , is a good reducing agent, often being itself turned into Cr
2 + 3 +
. Suppose that 10 mL of 0.1 M Cr(OH) was 2

needed to reduce completely an 0.05 grams of unknown substance X.

a. If each molecule of X accept just one electron, what is the molecular weight of X?
b. If each molecule of X accept five electrons, what is the molecular weight of X?

4.E.24: Q.71
A 0.200 g sample of chloride with unknown purity was dissolved in 200 mL of water was then titrated with AgNO solution with 3

a molarity of 0.1 M. After the titration it was determined that 28 mL of AgNO was required to fully titrate the sample of chloride.
3

What's the mass percent of chloride in the original dry sample?

4.E.25: Q.73
At 20°C, the vapor pressure of pure water is 17.5 mmHg. When 110 g of a substance X is dissolved in 500 g of water, the vapor
y

pressure of the solution is 15.0 mmHg. Given that this substance has a molecular mass of 12.011 g/mol, what is the molecular
formula of this substance X . (i.e. what is the number value of subscript y).
y

4.E.3 https://chem.libretexts.org/@go/page/69605
4.E.26: Q.81
The cell membrane of a plant cell is permeable to water. In a salt solution, the plant cells shrivel (lose water) when the
concentration is high, and swell (take up water) when the concentration is low. Scientists perform an experiment at 30°C, where an
aqueous solution of NaCl with a freezing point of -0.028°C is used to water the plant cells. This causes the plant cells to neither
swell nor shrink indicating that the osmotic pressure of the plant cell contents is equal to that of the NaCl solution. Assuming the
molarity and molality of the plant cell contents are equal, calculate the osmotic pressure of the solution inside the plant cells. The
K kg
Kf for the solution is 1.86 mol
.

4.E.27: Q.83
Jim loves the smell of grass. He loves it so much that he frequently sniffs the fumes from 1-Hexanol, which is a chemical
compound that is known to smell like grass trimmings. Because of his love, he decides to make his garage into a “gas den”, and
aimed to have 60% of the air in it as 1-Hexanol gas. He achieves this by filling a pool with a mixture of 1-Hexanol and Water.
Assume that the air in the “gas den” consists of only the fumes from this mixture. If the pool has 10000L of water in it, how many
litres of 1-Hexanol does he need? Use Henry’s Law to determine this amount.
Relevant Information:
1-Hexanol:
kg
Density: 814 3
m
g
Molar mass: 107.1748
mol
molal
Henry’s Law Constant: 64
bar

Water:
kg
Density: 1000 3
m

4.E.28: Q.87
A 3.5 gram sample is decomposed into a compound containing nitrogen, hydrogen, and oxygen, together creating 4.00 g of NO
2
g
and 7.00 g of H O . The molar mass of the sample is 78.5 . Find the molecular formula of this sample.
2 mol

4.E.29: Q.87
5 grams of a substance containing hydrogen, carbon and oxygen were fully combusted and produced 3.00 grams of H O and 7.33 2

grams of CO . When 10.64 grams of the substance was mixed with 0.5 kg of water, the freezing point was found to decrease by
2

0.0605°C. What is the substance?

4.E: Solutions (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

4.E.4 https://chem.libretexts.org/@go/page/69605
 SECTION OVERVIEW

Unit III: Chemical Equilibria

Chemical equilibrium is a state in which the rate of the forward reaction equals the rate of the backward reaction. In other words,
there is no net change in concentrations of reactants and products. This kind of equilibrium is also called dynamic equilibrium and
can be used in a wide range of processes including both chemical and physical changes. An equilibrium is a situation whereby the
quantity or quality of the sample does not change in time. Such a situation is intimately connected to "thermodynamics" as
discussed in previously. As you will learn in Chem 2CH, electrochemistry is the third member of this troika.

V: Chemical Equilibrium
5.1: The Nature of Chemical Equilibrium
5.2: The Empirical Law of Mass Action
5.3: Thermodynamic Description of the Equilibrium State
5.4: The Law of Mass Action for Related and Simultaneous Equilibria
5.5: Gas-Phase and Heterogeneous Reaction Equilibria
5.6: The Direction of Change in Chemical Reactions: Empirical Description
5.7: The Direction of Change in Chemical Reactions - Thermodynamic Explanation
5.8: Distribution between Immiscible Phases - Extraction and Separation Processes
5.E: Chemical Equilibrium (Exercises)

VI: Acid–Base Equilibria

6.1: Classifications of Acids and Bases
6.2: The Brønsted-Lowry Scheme
6.3: Acid and Base Strength
6.4: Equilibria Involving Weak Acids and Bases
6.5: Buffer Solutions
6.6: Acid-Base Titration Curves
6.7: Polyprotic Acids
6.8: A Deeper Look - Exact Treatment of Acid-Base Equilibria
6.9: Organic Acids and Bases - Structure and Reactivity
6.10: Lewis Bases as Nucleophilic Reactants in Organic Reactions

VII: Solubility and Precipitation Equilibria

7.1: The Nature of Solubility Equilibria
7.2: Ionic Equilibria between Solids and Solutions
7.3: Precipitation and the Solubility Product
7.4: The Effects of pH on Solubility
7.5: Complex Ions and Solubility
7.6: A Deeper Look - Selective Precipitation of Ions

Unit III: Chemical Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
 CHAPTER OVERVIEW

V: Chemical Equilibrium

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

Chemical equilibrium is the state in which both reactants and products are present in concentrations which have no further
tendency to change with time. This results when the forward reaction proceeds at the same rate as the reverse reaction. Thus, no net
changes in the concentrations of the reactant(s) and product(s) are observed. This is known as dynamic equilibrium
5.1: The Nature of Chemical Equilibrium
5.2: The Empirical Law of Mass Action
5.3: Thermodynamic Description of the Equilibrium State
5.4: The Law of Mass Action for Related and Simultaneous Equilibria
5.5: Gas-Phase and Heterogeneous Reaction Equilibria
5.6: The Direction of Change in Chemical Reactions: Empirical Description
5.7: The Direction of Change in Chemical Reactions - Thermodynamic Explanation
5.8: Distribution between Immiscible Phases - Extraction and Separation Processes
5.E: Chemical Equilibrium (Exercises)

V: Chemical Equilibrium is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
5.1: The Nature of Chemical Equilibrium
 Learning Objectives
To understand what is meant by chemical equilibrium.

In the last chapter, we discussed the principles of chemical kinetics, which deal with the rate of change, or how quickly a given
chemical reaction occurs. We now turn our attention to the extent to which a reaction occurs and how reaction conditions affect the
final concentrations of reactants and products. For most of the reactions that we have discussed so far, you may have assumed that
once reactants are converted to products, they are likely to remain that way. In fact, however, virtually all chemical reactions are
reversible to some extent. That is, an opposing reaction occurs in which the products react, to a greater or lesser degree, to re-form
the reactants. Eventually, the forward and reverse reaction rates become the same, and the system reaches chemical equilibrium,
the point at which the composition of the system no longer changes with time.

Figure 5.1.1 : Dinitrogen tetroxide is a powerful oxidizer that reacts spontaneously upon contact with various forms of hydrazine,
which makes the pair a popular propellant combination for rockets. Nitrogen dioxide at −196 °C, 0 °C, 23 °C, 35 °C, and 50 °C.
(NO2) converts to the colorless dinitrogen tetroxide (N2O4) at low temperatures, and reverts to NO2 at higher temperatures. (CC
BY-SA 3.0; Eframgoldberg).
Chemical equilibrium is a dynamic process that consists of a forward reaction, in which reactants are converted to products, and a
reverse reaction, in which products are converted to reactants. At equilibrium, the forward and reverse reactions proceed at equal
rates. Consider, for example, a simple system that contains only one reactant and one product, the reversible dissociation of
dinitrogen tetroxide (N O ) to nitrogen dioxide (NO ). You may recall that NO is responsible for the brown color we associate
2 4 2 2

with smog. When a sealed tube containing solid N O (mp = −9.3°C; bp = 21.2°C) is heated from −78.4°C to 25°C, the red-brown
2 4

color of NO appears (Figure 5.1.1). The reaction can be followed visually because the product (NO ) is colored, whereas the
2 2

reactant (N O ) is colorless:
2 4

kf

N O (g) ⇌ 2 NO (g) (5.1.1)

2 4 2
colorless kr red−brown

The double arrow indicates that both the forward reaction

kf

N O (g) −
→ 2 NO (g) (5.1.2)
2 4 2

and reverse reaction

kr

2 NO (g) −
→ N O (g) (5.1.3)
2 2 4

occurring simultaneously (i.e, the reaction is reversible). However, this does not necessarily mean the system is equilibrium as the
following chapter demonstrates.
Figure 5.1.2 shows how the composition of this system would vary as a function of time at a constant temperature. If the initial
concentration of NO were zero, then it increases as the concentration of N O decreases. Eventually the composition of the
2 2 4

system stops changing with time, and chemical equilibrium is achieved. Conversely, if we start with a sample that contains no
N O
2 4
but an initial NO concentration twice the initial concentration of N O (Figure 5.1.2a), in accordance with the
2 2 4

5.1.1 https://chem.libretexts.org/@go/page/43441
stoichiometry of the reaction, we reach exactly the same equilibrium composition (Figure 5.1.2b ). Thus equilibrium can be
approached from either direction in a chemical reaction.

Figure 5.1.2 : The Composition of N O /NO Mixtures as a Function of Time at Room Temperature. (a) Initially, this idealized
2 4 2

system contains 0.0500 M gaseous N O and no gaseous NO . The concentration of N O decreases with time as the
2 4 2 2 4

concentration of NO increases. (b) Initially, this system contains 0.1000 M NO and no N O . The concentration of NO
2 2 2 4 2

decreases with time as the concentration of N O increases. In both cases, the final concentrations of the substances are the same: [
2 4

N O ] = 0.0422 M and [NO ] = 0.0156 M at equilibrium. (CC BY-SA-NC; Anonymous by request)

2 4 2

Figure 5.1.3 shows the forward and reverse reaction rates for a sample that initially contains pure NO . Because the initial 2

concentration of N O is zero, the forward reaction rate (dissociation of N O ) is initially zero as well. In contrast, the reverse
2 4 2 4

reaction rate (dimerization of NO ) is initially very high (2.0 × 10 M /s ), but it decreases rapidly as the concentration of NO
2
6
2

decreases. As the concentration of N O increases, the rate of dissociation of N O increases—but more slowly than the
2 4 2 4

dimerization of NO —because the reaction is only first order in N O (rate = k [N O ], where k is the rate constant for the
2 2 4 f 2 4 f

forward reaction in Equations 5.1.1 and 5.1.2). Eventually, the forward and reverse reaction rates become identical, k = k , and f r

the system has reached chemical equilibrium. If the forward and reverse reactions occur at different rates, then the system is not at
equilibrium.

Figure 5.1.3 : The Forward and Reverse Reaction Rates as a Function of Time for the N 2 O4(g) ⇌2N O 2(g)
System Shown in Part (b)
in Figure 5.1.2 . (CC BY-SA-NC; Anonymous by request)
The rate of dimerization of NO (reverse reaction) decreases rapidly with time, as expected for a second-order reaction. Because
2

the initial concentration of N O is zero, the rate of the dissociation reaction (forward reaction) at t = 0 is also zero. As the
2 4

dimerization reaction proceeds, the N O concentration increases, and its rate of dissociation also increases. Eventually the rates of
2 4

the two reactions are equal: chemical equilibrium has been reached, and the concentrations of N O and NO no longer change.
2 4 2

At equilibrium, the forward reaction rate is equal to the reverse reaction rate.

5.1.2 https://chem.libretexts.org/@go/page/43441
 Example 5.1.1

The three reaction systems (1, 2, and 3) depicted in the accompanying illustration can all be described by the equation:

2A ⇌ B

where the blue circles are A and the purple ovals are B . Each set of panels shows the changing composition of one of the three
reaction mixtures as a function of time. Which system took the longest to reach chemical equilibrium?

In reaction system 1 theree are four purple ovals at t3. In reaction system 2 there are size purple ovals at t3. In reaction system
systems there are six ovals at t2 and t3.
Given: three reaction systems
Asked for: relative time to reach chemical equilibrium
Strategy:
Compare the concentrations of A and B at different times. The system whose composition takes the longest to stabilize took
the longest to reach chemical equilibrium.
Solution:
In systems 1 and 3, the concentration of A decreases from t through t but is the same at both t and t . Thus systems 1 and 3
0 2 2 3

are at equilibrium by t . In system 2, the concentrations of A and B are still changing between t and t , so system 2 may not
3 2 3

yet have reached equilibrium by t . Thus system 2 took the longest to reach chemical equilibrium.
3

 Exercise 5.1.1

In the following illustration, A is represented by blue circles, B by purple squares, and C by orange ovals; the equation for the
reaction is A + B ⇌ C. The sets of panels represent the compositions of three reaction mixtures as a function of time. Which, if
any, of the systems shown has reached equilibrium?

In reaction system 1 there are seven orange ovals at t3. In reaction system two there are four orange ovals at t3. In reaction
system three there are three orange ovals at t3.

Answer
system 2

5.1.3 https://chem.libretexts.org/@go/page/43441
 Introduction to Dynamic Equilibrium

A Video Introduction to Dynamic Equilibrium: Introduction to Dynamic Equilibrium(opens in new window) [youtu.be]

5.1.1: Summary
At equilibrium, the forward and reverse reactions of a system proceed at equal rates. Chemical equilibrium is a dynamic process
consisting of forward and reverse reactions that proceed at equal rates. At equilibrium, the composition of the system no longer
changes with time. The composition of an equilibrium mixture is independent of the direction from which equilibrium is
approached.

5.1: The Nature of Chemical Equilibrium is shared under a CC BY-NC-SA 3.0 license and was authored, remixed, and/or curated by LibreTexts.
15.1: The Concept of Equilibrium is licensed CC BY-NC-SA 3.0.

5.1.4 https://chem.libretexts.org/@go/page/43441
5.2: The Empirical Law of Mass Action
 Learning Objectives
To know the relationship between the equilibrium constant and the rate constants for the forward and reverse reactions.
To write an equilibrium constant expression for any reaction.
To understand how different phases affect equilibria.

Because an equilibrium state is achieved when the forward reaction rate equals the reverse reaction rate, under a given set of
conditions there must be a relationship between the composition of the system at equilibrium and the kinetics of a reaction
(represented by rate constants). We can show this relationship using the decomposition reaction of N O to NO . Both the forward 2 4 2

and reverse reactions for this system consist of a single elementary reaction, so the reaction rates are as follows:
forward rate = kf [ N O ] (5.2.2)
2 4

and
2
reverse rate = kr [ NO ] (5.2.3)
2

At equilibrium, the forward rate equals the reverse rate (definition of equilibrium):
2
kf [ N O ] = kr [ NO ] (5.2.4)
2 4 2

so
2
kf [NO ]
2
= (5.2.5)
kr [N O ]
2 4

The ratio of the rate constants gives us a new constant, the equilibrium constant (K ), which is defined as follows:
kf
K = (5.2.6)
kr

Hence there is a fundamental relationship between chemical kinetics and chemical equilibrium: under a given set of conditions, the
composition of the equilibrium mixture is determined by the magnitudes of the rate constants for the forward and the reverse
reactions.

The equilibrium constant is equal to the rate constant for the forward reaction divided by the rate constant for the reverse
reaction.

Table 5.2.1 lists the initial and equilibrium concentrations from five different experiments using the reaction system described by
Equation 5.2.2. At equilibrium the magnitude of the quantity [NO ] /[N O ] is essentially the same for all five experiments. In
2
2
2 4

fact, no matter what the initial concentrations of NO and N O are, at equilibrium the quantity [NO ] /[N O ] will always be
2 2 4 2
2
2 4

6.53 ± 0.03 × 10 at 25°C, which corresponds to the ratio of the rate constants for the forward and reverse reactions (Equation
−3

5.2.6). That is, at a given temperature, the equilibrium constant for a reaction always has the same value, even though the specific

concentrations of the reactants and products vary depending on their initial concentrations.
Table 5.2.1 : Initial and Equilibrium Concentrations for N O 2 : N2 O4 Mixtures at 25°C
Initial Concentrations Concentrations at Equilibrium

Experiment [N 2 O4 ] (M) [N O ] (M)

2 [N 2 O4 ] (M) [N O ] (M)
2
2
K = [N O2 ] /[N2 O4 ]

1 0.0500 0.0000 0.0417 0.0165 6.54 × 10

−3

2 0.0000 0.1000 0.0417 0.0165 6.54 × 10

−3

3 0.0750 0.0000 0.0647 0.0206 6.56 × 10

−3

4 0.0000 0.0750 0.0304 0.0141 6.54 × 10

−3

5 0.0250 0.0750 0.0532 0.0186 6.50 × 10

−3

5.2.1 https://chem.libretexts.org/@go/page/43442
5.2.1: Developing an Equilibrium Constant Expression
In 1864, the Norwegian chemists Cato Guldberg (1836–1902) and Peter Waage (1833–1900) carefully measured the compositions
of many reaction systems at equilibrium. They discovered that for any reversible reaction of the general form

aA + bB ⇌ cC + dD (5.2.7)

where A and B are reactants, C and D are products, and a , b , c , and d are the stoichiometric coefficients in the balanced chemical
equation for the reaction, the ratio of the product of the equilibrium concentrations of the products (raised to their coefficients in the
balanced chemical equation) to the product of the equilibrium concentrations of the reactants (raised to their coefficients in the
balanced chemical equation) is always a constant under a given set of conditions. This relationship is known as the law of mass
action and can be stated as follows:
c d
[C ] [D]
K = (5.2.8)
a b
[A] [B]

where K is the equilibrium constant for the reaction. Equation 5.2.7 is called the equilibrium equation, and the right side of
Equation 5.2.8 is called the equilibrium constant expression. The relationship shown in Equation 5.2.8 is true for any pair of
opposing reactions regardless of the mechanism of the reaction or the number of steps in the mechanism.
The equilibrium constant can vary over a wide range of values. The values of K shown in Table 5.2.2, for example, vary by 60
orders of magnitude. Because products are in the numerator of the equilibrium constant expression and reactants are in the
denominator, values of K greater than 10 indicate a strong tendency for reactants to form products. In this case, chemists say that
3

equilibrium lies to the right as written, favoring the formation of products. An example is the reaction between H and Cl to 2 2

produce HCl, which has an equilibrium constant of 1.6 × 10 at 300 K. Because H is a good reductant and Cl is a good
33
2 2

oxidant, the reaction proceeds essentially to completion. In contrast, values of K less than 10 indicate that the ratio of products
−3

to reactants at equilibrium is very small. That is, reactants do not tend to form products readily, and the equilibrium lies to the left
as written, favoring the formation of reactants.
Table 5.2.2 : Equilibrium Constants for Selected Reactions*
Reaction Temperature (K) Equilibrium Constant (K)

S(s) + O (g) ⇌ SO (g)

2 2
300 4.4 × 10
53

2 H (g) + O (g) ⇌ 2 H O(g)

2 2 2
500 2.4 × 10
47

H (g) + Cl (g) ⇌ 2 HCl(g)

2 2
300 1.6 × 10
33

H (g) + Br (g) ⇌ 2 HBr(g)

2 2
300 4.1 × 10
18

2 NO(g) + O (g) ⇌ 2 NO (g)

2 2
300 4.2 × 10
13

3 H (g) + N (g) ⇌ 2 NH (g)

2 2 3
300 2.7 × 10
8

H (g) + D (g) ⇌ 2 HD(g)

2 2
100 1.92

H (g) + I (g) ⇌ 2 HI(g)

2 2
300 2.9 × 10
−1

I (g) ⇌ 2 I(g)
2
800 4.6 × 10
−7

Br (g) ⇌ 2 Br(g)
2
1000 4.0 × 10
−7

Cl (g) ⇌ 2 Cl(g)
2
1000 1.8 × 10
−9

F (g) ⇌ 2 F(g)
2
500 7.4 × 10
−13

*Equilibrium constants vary with temperature. The K values shown are for systems at the indicated temperatures.

You will also notice in Table 5.2.2 that equilibrium constants have no units, even though Equation 5.2.8 suggests that the units of
concentration might not always cancel because the exponents may vary. In fact, equilibrium constants are calculated using
“effective concentrations,” or activities, of reactants and products, which are the ratios of the measured concentrations to a
standard state of 1 M. As shown in Equation 5.2.9, the units of concentration cancel, which makes K unitless as well:

5.2.2 https://chem.libretexts.org/@go/page/43442
 mol

[A]measured M L

= = (5.2.9)
[A]standard state M mol

Many reactions have equilibrium constants between 1000 and 0.001 (10 ≥ K ≥ 10 ), neither very large nor very small. At
3 −3

equilibrium, these systems tend to contain significant amounts of both products and reactants, indicating that there is not a strong
tendency to form either products from reactants or reactants from products. An example of this type of system is the reaction of
gaseous hydrogen and deuterium, a component of high-stability fiber-optic light sources used in ocean studies, to form HD:

H (g) + D (g) ⇌ 2 HD(g) (5.2.10)

2 2

The equilibrium constant expression for this reaction is

2
[H D]
K = (5.2.11)
[ H2 ][ D2 ]

with K varying between 1.9 and 4 over a wide temperature range (100–1000 K). Thus an equilibrium mixture of H , D , and HD 2 2

contains significant concentrations of both product and reactants.

Figure 5.2.1 summarizes the relationship between the magnitude of K and the relative concentrations of reactants and products at
equilibrium for a general reaction, written as reactants \rightleftharpoons products. Because there is a direct relationship between
the kinetics of a reaction and the equilibrium concentrations of products and reactants (Equations 5.2.9 and 5.2.8), when k ≫ k , f r

K is a large number, and the concentration of products at equilibrium predominate. This corresponds to an essentially irreversible

reaction. Conversely, when k ≪ k , K is a very small number, and the reaction produces almost no products as written. Systems
f r

for which k ≈ k have significant concentrations of both reactants and products at equilibrium.
f r

Magnitude of K increasing

Small Intermediate Large

(K < 10-3) (10-3 ≤ K ≤ 103) (K > 103)

Reactants Products Reactants Products Reactants Products

Mostly reactants Significant amounts of Mostly products

reactants and products

Composition of equilibrium mixture

Figure 5.2.1 : The Relationship between the Composition of the Mixture at Equilibrium and the Magnitude of the Equilibrium
Constant. The larger the K, the farther the reaction proceeds to the right before equilibrium is reached, and the greater the ratio of
products to reactants at equilibrium. (CC BY-NC; Ümit Kaya)

A large value of the equilibrium constant K means that products predominate at equilibrium; a small value means that
reactants predominate at equilibrium.

 Example 5.2.1

Write the equilibrium constant expression for each reaction.

N (g) + 3 H (g) ⇌ 2 NH (g)
2 2 3
1
CO(g) + O (g) ⇌ CO (g)
2 2 2
+
2 CO (g) ⇌ 2 CO(g) O (g)
2 2

Given: balanced chemical equations

5.2.3 https://chem.libretexts.org/@go/page/43442
Asked for: equilibrium constant expressions
Strategy:
Refer to Equation 5.2.8. Place the arithmetic product of the concentrations of the products (raised to their stoichiometric
coefficients) in the numerator and the product of the concentrations of the reactants (raised to their stoichiometric coefficients)
in the denominator.
Solution:
The only product is ammonia, which has a coefficient of 2. For the reactants, N has a coefficient of 1 and H has a coefficient
2 2

of 3. The equilibrium constant expression is as follows:

2
[N H3 ]

3
[ N2 ][ H2 ]

The only product is carbon dioxide, which has a coefficient of 1. The reactants are C O, with a coefficient of 1, and O , with a 2

coefficient of . Thus the equilibrium constant expression is as follows:

1

[C O2 ]

1/2
[C O][O2 ]

This reaction is the reverse of the reaction in part b, with all coefficients multiplied by 2 to remove the fractional coefficient for
O . The equilibrium constant expression is therefore the inverse of the expression in part b, with all exponents multiplied by 2:
2

2
[C O] [ O2 ]

2
[C O2 ]

 Exercise 5.2.1

Write the equilibrium constant expression for each reaction.

a. N O(g) ⇌ N (g) + O (g)
2 2
1

2 2

b. 2 C H (g) + 25 O (g) ⇌ 16 CO
8 18 2 2
(g) + 18 H O(g)
2

c. H (g) + I (g) ⇌ 2 HI(g)

2 2

Answer a
1/2
[ N2 ][ O2 ]
K =
[ N2 O]

Answer b
16 18
[C O2 ] [ H2 O]
K =
2 25
[ C8 H18 ] [ O2 ]

Answer c
2
[H I ]
K =
[ H2 ][ I2 ]

 Example 5.2.2

Predict which systems at equilibrium will (a) contain essentially only products, (b) contain essentially only reactants, and (c)
contain appreciable amounts of both products and reactants.
1. H 2(g)+I ⇌ 2H I 2(g) (g) K(700K) = 54

2. 2C O ⇌ 2C O
2(g) +O (g) 2(g) K(1200K) = 3.1 × 10
−18

3. P C l ⇌ P Cl
5(g)
+ Cl 3(g) 2(g)
K(613K) = 97

4. 2O ⇌ 3O
3(g)
K 2(g) (298K)
= 5.9 × 10
55

5.2.4 https://chem.libretexts.org/@go/page/43442
 Given: systems and values of K
Asked for: composition of systems at equilibrium
Strategy:
Use the value of the equilibrium constant to determine whether the equilibrium mixture will contain essentially only products,
essentially only reactants, or significant amounts of both.
Solution:
a. Only system 4 has K >> 10 , so at equilibrium it will consist of essentially only products.
3

b. System 2 has K << 10 , so the reactants have little tendency to form products under the conditions specified; thus, at
−3

equilibrium the system will contain essentially only reactants.

c. Both systems 1 and 3 have equilibrium constants in the range 10 ≥ K ≥ 10 , indicating that the equilibrium mixtures
3 −3

will contain appreciable amounts of both products and reactants.

 Exercise 5.2.2

Hydrogen and nitrogen react to form ammonia according to the following balanced chemical equation:

3 H2(g) + N2(g) ⇌ 2N H3(g)

Values of the equilibrium constant at various temperatures were reported as

K25°C = 3.3 × 10
8
,
K177°C = 2.6 × 10
3
, and
K327°C = 4.1 .
a. At which temperature would you expect to find the highest proportion of H and N in the equilibrium mixture?
2 2

b. Assuming that the reaction rates are fast enough so that equilibrium is reached quickly, at what temperature would you
design a commercial reactor to operate to maximize the yield of ammonia?

Answer a
327°C, where K is smallest
Answer b
25°C

5.2.2: Variations in the Form of the Equilibrium Constant Expression

Because equilibrium can be approached from either direction in a chemical reaction, the equilibrium constant expression and thus
the magnitude of the equilibrium constant depend on the form in which the chemical reaction is written. For example, if we write
the reaction described in Equation 5.2.7 in reverse, we obtain the following:

cC + dD ⇌ aA + bB (5.2.12)

The corresponding equilibrium constant K' is as follows:

a b
[A] [B]
′
K = (5.2.13)
c d
[C ] [D]

This expression is the inverse of the expression for the original equilibrium constant, so K' = 1/K . That is, when we write a
reaction in the reverse direction, the equilibrium constant expression is inverted. For instance, the equilibrium constant for the
reaction N O ⇌ 2N O is as follows:
2 4 2

2
[N O2 ]
K = (5.2.14)
[ N2 O4 ]

but for the opposite reaction, 2N O 2 ⇌ N2 O4 , the equilibrium constant K′ is given by the inverse expression:

5.2.5 https://chem.libretexts.org/@go/page/43442
 [ N2 O4 ]
′
K = (5.2.15)
2
[N O2 ]

Consider another example, the formation of water: 2H +O 2(g)

⇌ 2H O . Because H is a good reductant and O is a good
2(g) 2 (g) 2 2

oxidant, this reaction has a very large equilibrium constant (K = 2.4 × 10 at 500 K). Consequently, the equilibrium constant for
47

the reverse reaction, the decomposition of water to form O and H , is very small: K' = 1/K = 1/(2.4 × 10 ) = 4.2 × 10
2 2 . 47 −48

As suggested by the very small equilibrium constant, and fortunately for life as we know it, a substantial amount of energy is
indeed needed to dissociate water into H and O .
2 2

The equilibrium constant for a reaction written in reverse is the inverse of the equilibrium constant for the reaction as written
originally.

Writing an equation in different but chemically equivalent forms also causes both the equilibrium constant expression and the
magnitude of the equilibrium constant to be different. For example, we could write the equation for the reaction
2N O2 ⇌ N2 O4 (5.2.16)

as
1
N O2 ⇌ N2 O4 (5.2.17)
2

with the equilibrium constant K″ is as follows:

1/2
[N2 O4 ]
K'' = (5.2.18)
[N O2 ]

The values for K′ (Equation 5.2.15) and K″ are related as follows:

−
−−
′ 1/2 ′
K'' = (K ) = √K (5.2.19)

In general, if all the coefficients in a balanced chemical equation were subsequently multiplied by n , then the new equilibrium
constant is the original equilibrium constant raised to the n power. th

 Example 5.2.3: The Haber Process

At 745 K, K is 0.118 for the following reaction:

N (g) + 3 H (g) ⇌ 2 NH (g)

2 2 3

What is the equilibrium constant for each related reaction at 745 K?

a. 2 NH (g) ⇌ N (g) + 3 H
3 2 2
(g)

b. N (g) + H (g) ⇌ NH
1

2 2
3

2 2 3
(g)

Given: balanced equilibrium equation, K at a given temperature, and equations of related reactions
Asked for: values of K for related reactions
Strategy:
Write the equilibrium constant expression for the given reaction and for each related reaction. From these expressions,
calculate K for each reaction.
Solution:
The equilibrium constant expression for the given reaction of N 2
(g) with H 2
(g) to produce NH
3
(g) at 745 K is as follows:
2
[N H3 ]
K = = 0.118
3
[ N2 ][ H2 ]

This reaction is the reverse of the one given, so its equilibrium constant expression is as follows:

5.2.6 https://chem.libretexts.org/@go/page/43442
 3
1 [ N2 ][ H2 ] 1
′
K = = = = 8.47
2
K [N H3 ] 0.118

In this reaction, the stoichiometric coefficients of the given reaction are divided by 2, so the equilibrium constant is calculated
as follows:
[N H3 ] −
− −−−−
1/2
K'' = =K = √K = √0.118 = 0.344
1/2 3/2
[ N2 ] [ H2 ]

 Exercise

At 527°C, the equilibrium constant for the reaction

2 SO (g) + O (g) ⇌ 2 SO (g)

2 2 3

is 7.9 × 10 . Calculate the equilibrium constant for the following reaction at the same temperature:
4

1
SO (g) ⇌ SO (g) + O (g)
3 2 2 2

Answer
−3
3.6 × 10

5.2.3: Law of Mass Action for Gas-Phase Reactions

For reactions that involve species in solution, the concentrations used in equilibrium calculations are usually expressed in
moles/liter. For gases, however, the concentrations are usually expressed in terms of partial pressures rather than molarity, where
the standard state is 1 atm of pressure. The symbol K is used to denote equilibrium constants calculated from partial pressures.
p

For the general reaction

aA + bB −
↽⇀
− cC + dD

in which all the components are gases, the equilibrium constant expression can be written as the ratio of the partial pressures of the
products and reactants (each raised to its coefficient in the chemical equation):
c d
(PC ) (PD )
Kp = (5.2.20)
a b
(PA ) (PB )

Thus K for the decomposition of N

p 2 O4 (Equation 5.2.2) is as follows:
2
(PN O )
2
Kp = (5.2.21)
PN2 O4

Like K , K is a unitless quantity because the quantity that is actually used to calculate it is an “effective pressure,” the ratio of the
p

measured pressure to a standard state of 1 bar (approximately 1 atm), which produces a unitless quantity. The “effective pressure”
is called the fugacity, just as activity is the effective concentration.
Because partial pressures are usually expressed in atmospheres or mmHg, the molar concentration of a gas and its partial pressure
do not have the same numerical value. Consequently, the numerical values of K and K are usually different. They are, however, p

related by the ideal gas constant (R ) and the absolute temperature (T ):

Δn
Kp = K(RT ) (5.2.22)

where K is the equilibrium constant expressed in units of concentration and Δn is the difference between the numbers of moles of
gaseous products and gaseous reactants (n − n ). The temperature is expressed as the absolute temperature in Kelvin. According
p r

to Equation 5.2.22, K = K only if the moles of gaseous products and gaseous reactants are the same (i.e., Δn = 0 ). For the
p

decomposition of N O , there are 2 mol of gaseous product and 1 mol of gaseous reactant, so Δn = 1 . Thus, for this reaction,
2 4

1
Kp = K(RT ) = KRT (5.2.23)

5.2.7 https://chem.libretexts.org/@go/page/43442
  Example 5.2.4: The Haber Process (again)
The equilibrium constant for the reaction of nitrogen and hydrogen to give ammonia is 0.118 at 745 K. The balanced
equilibrium equation is as follows:

N2(g) + 3 H2(g) ⇌ 2N H3(g)

What is K for this reaction at the same temperature?

p

Given: equilibrium equation, equilibrium constant, and temperature

Asked for: K p

Strategy:
Use the coefficients in the balanced chemical equation to calculate Δn. Then use Equation 5.2.22 to calculate K from K . p

Solution:
This reaction has 2 mol of gaseous product and 4 mol of gaseous reactants, so Δn = (2 − 4) = −2 . We know K , and
T = 745 K . Thus, from Equation 5.2.19, we have the following:

−2
K 0.118 −5
Kp = K(RT ) = = = 3.16 × 10
2 2
(RT ) {[0.08206(L ⋅ atm)/(mol ⋅ K)][745 K]}

Because K is a unitless quantity, the answer is K

p p = 3.16 × 10
−5
.

 Exercise 5.2.4:

Calculate K for the reaction

p

2S O2(g) + O2(g) ⇌ 2S O3(g)

at 527°C, if K = 7.9 × 10 at this temperature.

4

Answer
3
Kp = 1.2 × 10

5.2.4: Law of Mass Action for Reactions Involving Pure Substances and Multiple Phases
When the products and reactants of a reaction at equilibrium in a single phase (e.g., liquid, gas or solids of different lattices), the
system is a homogeneous equilibrium. In such situations, the concentrations of the reactants and products can vary over a wide
range. In contrast, a system where the reactants and products are in two or more phase is called a heterogeneous equilibrium (e.g,
the reaction of a gas with a solid or liquid or two different solid lattices in co-existing).
Because the molar concentrations of pure liquids and solids normally do not vary greatly with temperature, their concentrations are
treated as constants, which allows us to simplify equilibrium constant expressions that involve pure solids or liquids.The reference
states for pure solids and liquids are those forms stable at 1 bar (approximately 1 atm), which are assigned an activity of 1. (Recall
that the density of water, and thus its volume, changes by only a few percentage points between 0 °C and 100 °C.)
Consider the following reaction, which is used in the final firing of some types of pottery to produce brilliant metallic glazes:

CO (g) + C(s) −
↽⇀
− 2 CO(g) (5.2.24)
2

The glaze is created when metal oxides are reduced to metals by the product, carbon monoxide. The equilibrium constant
expression for this reaction is as follows:
2
[C O]
K = (5.2.25)
[C O2 ][C ]

Because graphite is a solid, however, its molar concentration, determined from its density and molar mass, is essentially constant
and has the following value:

5.2.8 https://chem.libretexts.org/@go/page/43442
 3
2.26 g / cm
3
[C ] = × 1000 cm /L = 188 mol/L = 188 M (5.2.26)
12.01 g /mol

We can rearrange Equation 5.2.26 so that the constant terms are on one side:
2
[C O]
K[C ] = K(188) = (5.2.27)
[C O2 ]

Incorporating the constant value of [C ] into the equilibrium equation for the reaction in Equation 5.2.27,
2
[C O]
′
K = (5.2.28)
[C O2 ]

The equilibrium constant for this reaction can also be written in terms of the partial pressures of the gases:
2
(PC O )
Kp = (5.2.29)
PC O
2

Incorporating all the constant values into K' or K allows us to focus on the substances whose concentrations change during the
p

reaction.
Although the concentrations of pure liquids or solids are not written explicitly in the equilibrium constant expression, these
substances must be present in the reaction mixture for chemical equilibrium to occur. Whatever the concentrations of C O and
C O , the system described in Equation 5.2.24 will reach chemical equilibrium only if a stoichiometric amount of solid carbon or
2

excess solid carbon has been added so that some is still present once the system has reached equilibrium. As shown in Figure 5.2.2,
it does not matter whether 1 g or 100 g of solid carbon is present; in either case, the composition of the gaseous components of the
system will be the same at equilibrium.

Figure 5.2.2 : Effect of the Amount of Solid Present on Equilibrium in a Heterogeneous Solid–Gas System. In the system, the
equilibrium composition of the gas phase at a given temperature, 1000 K in this case, is the same whether a small amount of solid
carbon (left) or a large amount (right) is present.

 Example 5.2.1

Write each expression for K , incorporating all constants, and K for the following equilibrium reactions.
p

a. P C l 3(l)
+ C l2(g) ⇌ P C l5(s)

b. F e O
3 4(s) + 4 H2(g) ⇌ 3F e(s) + 4 H2 O(g)

5.2.9 https://chem.libretexts.org/@go/page/43442
 Given: balanced equilibrium equations
Asked for: expressions for K and K p

Strategy:
Find K by writing each equilibrium constant expression as the ratio of the concentrations of the products and reactants, each
raised to its coefficient in the chemical equation. Then express K as the ratio of the partial pressures of the products and
p

reactants, each also raised to its coefficient in the chemical equation.

Solution
This reaction contains a pure solid (P C l ) and a pure liquid (P C l ). Their concentrations do not appear in the equilibrium
5 3

constant expression because they do not change significantly. So

1
K =
[C l2 ]

and
1
Kp =
PC l
2

This reaction contains two pure solids (F e O and F e), which do not appear in the equilibrium constant expressions. The two
3 4

gases do, however, appear in the expressions:

4
[ H2 O]
K =
4
[H2 ]

and
4
(PH2 O )
Kp =
4
(PH )
2

 Exercise 5.2.1

Write the expressions for K and K for the following reactions.

p

a. C aC O 3(s)
⇌ C aO(s) + C O2(g)

b. C H O
6 12 6(s) + 6 O2(g) ⇌ 6C O2(g) + 6 H2 O(g)
glucose

Answer a
K = [C O2 ] and K p = PC O2

Answer b
6 6 6 6
[C O2 ] [ H2 O] (PC O ) (PH O)
and K
2 2
K = p =
6 6
[O2 ] (PO2 )

For reactions carried out in solution, the concentration of the solvent is omitted from the equilibrium constant expression even
when the solvent appears in the balanced chemical equation for the reaction. The concentration of the solvent is also typically much
greater than the concentration of the reactants or products (recall that pure water is about 55.5 M, and pure ethanol is about 17 M).
Consequently, the solvent concentration is essentially constant during chemical reactions, and the solvent is therefore treated as a
pure liquid. The equilibrium constant expression for a reaction contains only those species whose concentrations could change
significantly during the reaction.

The concentrations of pure solids, pure liquids, and solvents are omitted from equilibrium constant expressions because they
do not change significantly during reactions when enough is present to reach equilibrium.

5.2.10 https://chem.libretexts.org/@go/page/43442
5.2.5: Summary
The law of mass action describes a system at equilibrium in terms of the concentrations of the products and the reactants.
For a system involving one or more gases, either the molar concentrations of the gases or their partial pressures can be used.
Definition of equilibrium constant in terms of forward and reverse rate constants:
kf
K =
kr

Equilibrium constant expression (law of mass action):

c d
[C ] [D]
K =
a b
[A] [B]

Equilibrium constant expression for reactions involving gases using partial pressures:
c d
(PC ) (PD )
Kp =
a b
(PA ) (PB )

Relationship between K and K :

p

Δn
Kp = K(RT )

The ratio of the rate constants for the forward and reverse reactions at equilibrium is the equilibrium constant (K), a unitless
quantity. The composition of the equilibrium mixture is therefore determined by the magnitudes of the forward and reverse rate
constants at equilibrium. Under a given set of conditions, a reaction will always have the same K . For a system at equilibrium, the
law of mass action relates K to the ratio of the equilibrium concentrations of the products to the concentrations of the reactants
raised to their respective powers to match the coefficients in the equilibrium equation. The ratio is called the equilibrium constant
expression. When a reaction is written in the reverse direction, K and the equilibrium constant expression are inverted. For gases,
the equilibrium constant expression can be written as the ratio of the partial pressures of the products to the partial pressures of the
reactants, each raised to a power matching its coefficient in the chemical equation. An equilibrium constant calculated from partial
pressures (K ) is related to K by the ideal gas constant (R ), the temperature (T ), and the change in the number of moles of gas
p

during the reaction. An equilibrated system that contains products and reactants in a single phase is a homogeneous equilibrium; a
system whose reactants, products, or both are in more than one phase is a heterogeneous equilibrium.

5.2: The Empirical Law of Mass Action is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5.2.11 https://chem.libretexts.org/@go/page/43442
5.3: Thermodynamic Description of the Equilibrium State
 Learning Objectives
Gibbs Energy is a state function defined as G = H – T S .
The practical utility of the Gibbs function is that ΔG for any process is negative if it leads to an increase in the entropy of
the world. Thus spontaneous change at a given temperature and pressure can only occur when it would lead to a decrease in
G.

The sign of the standard free energy change ΔG of a chemical reaction determines whether the reaction will tend to
o

proceed in the forward or reverse direction.

Similarly, the relative signs of ΔH and ΔH determine whether the spontaneity of a chemical reaction will be affected
o o

by the temperature, and if so, in what way.

The existence of sharp melting and boiling points reflects the differing temperature dependancies of the free energies of the
solid, liquid, and vapor phases of a pure substance, which are in turn reflect their differing entropies.

Previously, we saw that it is the sum of the entropy changes of the system and surroundings that determines whether a process will
occur spontaneously. In chemical thermodynamics we prefer to focus our attention on the system rather than the surroundings, and
would like to avoid having to calculate the entropy change of the surroundings explicitly.
In this unit we introduce a new thermodynamic function, the free energy, which turns out to be the single most useful criterion for
predicting the direction of a chemical reaction and the composition of the system at equilibrium. However, the term "free energy",
although still widely used, is rather misleading, so we will often refer to it as "Gibbs energy." The free energy enables us to do this
for changes that occur at a constant temperature and pressure (the Gibbs energy) or constant temperature and volume (the
Helmholtz energy.)

5.3.1: Free energy: the Gibbs function

The Gibbs energy (also known as the Gibbs function or Gibbs Potential) is defined as
G = H– T S (5.3.1)

in which S refers to the entropy of the system. Since H , T and S are all state functions, so is G . Thus for any change in state
(under constant temperature), we can write the extremely important relation
ΔG = ΔH – T ΔS (5.3.2)

How does this simple equation encompass the entropy change of the world ΔS , which we already know is the sole criterion for
total

spontaneous change from the second law of thermodynamics? Starting with the definition

ΔStotal = ΔSsurr + ΔSsys (5.3.3)

we would first like to get rid of ΔS surr. How can a chemical reaction (a change in the system) affect the entropy of the
surroundings? Because most reactions are either exothermic or endothermic, they are accompanied by a flow of heat qp across the
system boundary. The enthalpy change of the reaction ΔH is defined as the flow of heat into the system from the surroundings
when the reaction is carried out at constant pressure, so the heat withdrawn from the surroundings will be – q which will cause the
p

entropy of the surroundings to change by – q /T =– ΔH /T . We can therefore rewrite Equation 5.3.3 as

p

−ΔH
ΔStotal = + ΔSsys (5.3.4)
T

Multiplying each side by −T , we obtain

−T ΔStotal = ΔH − T ΔSsys (5.3.5)

which expresses the entropy change of the world in terms of thermodynamic properties of the system exclusively. If −T ΔS total is
denoted by ΔG, then we have Equation 5.3.2 which defines the Gibbs energy change for the process.

5.3.1 https://chem.libretexts.org/@go/page/43443
From the foregoing, you should convince yourself that G will decrease in any process occurring at constant temperature and
pressure which is accompanied by an overall increase in the entropy. The constant temperature is a consequence of the temperature
and the enthalpy appearing in the preceding Equation 5.3.5. Since most chemical and phase changes of interest to chemists take
place under such conditions, the Gibbs energy is the most useful of all the thermodynamic properties of a substance, and (as we
shall see in the lesson that follows this one) it is closely linked to the equilibrium constant.
Some textbooks and teachers say that the free energy, and thus the spontaneity of a reaction, depends on both the enthalpy and
entropy changes of a reaction, and they sometimes even refer to reactions as "energy driven" or "entropy driven" depending on
whether ΔH or the T ΔS term dominates. This is technically correct, but misleading because it disguises the important fact that
ΔS , which this equation expresses in an indirect way, is the only criterion of spontaneous change.
total

 Helmholtz Energy is also a "Free Energy"

We will deal only with the Gibbs energy in this course. The Helmholtz free energy is of interest mainly to chemical engineers
(whose industrial-scale processes are often confined to tanks and reactors of fixed volume) and some geochemists whose
interest is centered on the chemistry that occurs deep within the earth's surface.

5.3.2: Gibbs Energy and Chemical Change

Remember that ΔG is meaningful only for changes in which the temperature and pressure remain constant. These are the
conditions under which most reactions are carried out in the laboratory; the system is usually open to the atmosphere (constant
pressure) and we begin and end the process at room temperature (after any heat we have added or which is liberated by the reaction
has dissipated.) The importance of the Gibbs function can hardly be over-stated: it serves as the single master variable that
determines whether a given chemical change is thermodynamically possible. Thus if the free energy of the reactants is greater than
that of the products, the entropy of the world will increase when the reaction takes place as written, and so the reaction will tend to
take place spontaneously. Conversely, if the free energy of the products exceeds that of the reactants, then the reaction will not take
place in the direction written, but it will tend to proceed in the reverse direction.

ΔG serves as the single master variable that determines whether a given chemical
change is thermodynamically possible. Moreover, it determines the direction and extent of
chemical change.
In a spontaneous change, Gibbs energy always decreases and never increases. This of course reflects the fact that the entropy of the
world behaves in the exact opposite way (owing to the negative sign in the T ΔS term).
H O(l) → H O(s) (5.3.6)
2 2

water below its freezing point undergoes a decrease in its entropy, but the heat released into the surroundings more than
compensates for this, so the entropy of the world increases, the free energy of the H2O diminishes, and the process proceeds
spontaneously.

In a spontaneous change, Gibbs energy always decreases and never increases.

An important consequence of the one-way downward path of the free energy is that once it reaches its minimum possible value, all
net change comes to a halt. This, of course, represents the state of chemical equilibrium. These relations are nicely summarized as
follows:
ΔG < 0 : reaction can spontaneously proceed to the right:

A → B

ΔG > 0 : reaction can spontaneously proceed to the left:

5.3.2 https://chem.libretexts.org/@go/page/43443
 A ← B

ΔG = 0 : the reaction is at equilibrium and both [A] and [B] will not change:

A ⇌ B.

5.3.3: No need to find the value of ΔG for a Specific Reaction!

This might seem strange, given the key importance ΔG in determining whether or not a reaction will take place in a given
direction. It turns out, however, that it is almost never necessary to explicitly evaluate ΔG. As we will show in the lesson that
follows this one, it is far more convenient to work with the equilibrium constant of a reaction, within which ΔG is "hidden". This
is just as well, because for most reactions (those that take place in solutions or gas mixtures) the value of ΔG depends on the
proportions of the various reaction components in the mixture; it is not a simple sum of the "products minus reactants" type, as is
the case with ΔH .
Recalling the condition for spontaneous change
ΔG = ΔH – T ΔS < 0 (5.3.7)

it is apparent that the temperature dependence of ΔG depends almost entirely on the entropy change associated with the process.
(We say "almost" because the values of ΔH and ΔS are themselves slightly temperature dependent; both gradually increase with
temperature). In particular, notice that in the above equation the sign of the entropy change determines whether the reaction
becomes more or less spontaneous as the temperature is raised. For any given reaction, the sign of ΔH can also be positive or
negative. This means that there are four possibilities for the influence that temperature can have on the spontaneity of a process:

5.3.3.1: Case 1: ΔH < 0 and ΔS > 0

Both enthalpic ΔH and entropic −T ΔS terms will be negative, so ΔG will be negative regardless of the temperature. An
exothermic reaction whose entropy increases will be spontaneous at all temperatures.

A B A B
kJ
TΔS

0
ΔG
ΔH ΔH
ΔH
ΔG < 0
low T T high T
0

Figure 5.3.1 : A hypothetical A ⟶ B reaction that is favored enthalpically and entropically (spontaneous at all temperatures). (CC
BY 4.0; Ümit Kaya via LibreTexts)

5.3.3.2: Case 2: ΔH < 0 and ΔS < 0

If the reaction is sufficiently exothermic it can force ΔG negative only at temperatures below which |T ΔS| < |ΔH | . This means
that there is a temperature T = ΔH /ΔS at which the reaction is at equilibrium; the reaction will only proceed spontaneously
below this temperature. The freezing of a liquid or the condensation of a gas are the most common examples of this condition.

5.3.3 https://chem.libretexts.org/@go/page/43443
 A B A B
kJ

0
TΔS

ΔH ΔH ΔH

low T ΔG < 0 ΔG high T

0 T

Figure 5.3.2 : A hypothetical A ⟶ B reaction that is favored enthalpically and is not favored entropically (spontaneous at low
temperatures). (CC BY 4.0; Ümit Kaya via LibreTexts)

5.3.3.3: Case 3: ΔH > 0 and ΔS > 0

This is the reverse of the previous case; the entropy increase must overcome the handicap of an endothermic process so that
T ΔS > ΔH . Since the effect of the temperature is to "magnify" the influence of a positive ΔS , the process will be spontaneous at

temperatures above T = ΔH /ΔS . (Think of melting and boiling.)

A B A B
kJ

TΔS ΔG
ΔH
ΔG

ΔH ΔH
0
ΔG > 0 ΔG < 0
low T T high T
0

Figure 5.3.3 : A hypothetical A ⟶ B reaction that is not favored enthalpically and is favored entropically (spontaneous at high
temperatures). (CC BY 4.0; Ümit Kaya via LibreTexts)

5.3.3.4: Case 4: ΔH > 0 and ΔS < 0

With both ΔH and ΔS working against it, this kind of process will not proceed spontaneously at any temperature. Substance A
always has a greater number of accessible energy states, and is therefore always the preferred form.

A B kJ A B
ΔH

ΔG
0

ΔH TΔS ΔH
ΔG > 0
low T T high T
0

Figure 5.3.4 : A hypothetical A ⟶ B reaction that is not favored enthalpically and is not is favored entropically (not spontaneous
at temperatures). (CC BY 4.0; Ümit Kaya via LibreTexts)
The plots above are the important ones; do not try to memorize them, but make sure you understand and can explain or reproduce
them for a given set of ΔH and ΔS.
Their most important differentiating features are the position of the ΔH line (above or below the is TΔS line), and the slope of
the latter, which of course depends on the sign of ΔS.
The reaction A → B will occur spontaneously only when ΔG is negative (blue arrows pointing down.)
TΔS plots are not quite straight lines as shown here. Similarly, the lines representing ΔH are even more curved.

5.3.4 https://chem.libretexts.org/@go/page/43443
The other two plots on each diagram are only for the chemistry-committed.
Each pair of energy-level diagrams depicts the relative spacing of the microscopic energy levels in the reactants and products as
reflected by the value of ΔS°. (The greater the entropy, the more closely-spaced are the quantized microstates.)
The red shading indicates the range of energy levels that are accessible to the system at each temperature. The spontaneous
direction of the reaction will always be in the direction in which the red shading overlaps the greater number of energy levels,
resulting in the maximum dispersal of thermal energy.
Note that the vertical offsets correspond to ΔH° for the reaction.
Never forget that it is the ability of thermal energy to spread into as many of these states as possible that determines the
tendency of the process to take place. None of this is to scale, of course!

5.3.4: The Standard Gibbs Energy

You have already been introduced to the terms such as ΔU and ΔH in which the sign indicates that all components (reactants
o o o

and products) are in their standard states. This concept of standard states is especially important in the case of the free energy, so
let's take a few moments to review it. More exact definitions of the conventional standard states can be found in most physical
chemistry textbooks. In specialized fields such as biochemistry and oceanography, alternative definitions may apply. For example,
the "standard pH" of zero (corresponding to [H ] = 1 M ) is impractical in biochemistry, so pH = 7 is commonly employed. For
+

most practical purposes, the following definitions are good enough:

gases: 1 atmosphere partial pressure
pure liquids: the liquid under a total (hydrostatic) pressure of 1 atm.
solutes: an effective concentration of 1 mol L–1 (1 mol dm–3). ("Effective" concentrations approach real concentrations as the
latter approach zero; for practical purposes, these can be considered identical at real concentrations smaller than about 10–4
molar.)
solids: the pure solid under 1 atm pressure

 Reminder on Standard States

There is actually no "standard temperature", but because most thermodynamics tables list values for 298.15 K (25° C), this
temperature is usually implied.
These same definitions apply to standard enthalpies and internal energies.
Do not confuse these thermodynamic standard states with the "standard temperature and pressure" (STP) widely employed
in gas law calculations.

To make use of Gibbs energies to predict chemical changes, we need to know the free energies of the individual components of the
reaction. For this purpose we can combine the standard enthalpy of formation and the standard entropy of a substance to get its
standard free energy of formation
o o o
ΔG = ΔH – T ΔS (5.3.8)
f f f

Recall that the symbol ° refers to the standard state of a substance measured under the conditions of 1 atm pressure or an effective
concentration of 1 mol L–1 and a temperature of 298 K. Then determine the standard Gibbs energy of the reaction according to
o o o
ΔG = ∑ ΔG (products)– ∑ ΔG (reactants) (5.3.9)
f f

As with standard heats of formation, the standard free energy of a substance represents the free energy change associated with the
formation of the substance from the elements in their most stable forms as they exist under the standard conditions of 1 atm
pressure and 298 K. Standard Gibbs free energies of formation are normally found directly from tables. Once the values for all the
reactants and products are known, the standard Gibbs energy change for the reaction is found by Equation 5.3.8. Most tables of
thermodynamic values list ΔG values for common substances (e.g., Table T2), which can, of course, always be found from values
o
f

of ΔHf° and ΔSf°.

5.3.5 https://chem.libretexts.org/@go/page/43443
  Example 5.3.1

Find the standard Gibbs energy change for the reaction

CaCO (s) → CaO(s) + CO (g)

3 2

The ΔG ° values for the three components of this reaction system are CaCO
o
f 3
(s) : –1128 kJ mol–1, CaO(s): –603.5 kJ mol–1,
CO2(g): –137.2 kJ mol–1.

Solution
Substituting into Equation 5.3.8, we have
o –1 –1
ΔG = (– 603.5– 137.2)– (– 1128)kJ mol = +130.9 kJ mol

This indicates that the process is not spontaneous under standard conditions (i.e., solid calcium carbone will not form solid
calcium oxide and CO2 at 1 atm partial pressure at 25° C).
Comment: This reaction is carried out on a huge scale to manufacture cement, so it is obvious that the process can be
spontaneous under different conditions.

The practical importance of the Gibbs energy is that it allows us to make predictions based on the properties (ΔG° values) of the
reactants and products themselves, eliminating the need to experiment. But bear in mind that while thermodynamics always
correctly predicts whether a given process can take place (is spontaneous in the thermodynamic sense), it is unable to tell us if it
will take place at an observable rate.

When thermodynamics says "no", it means exactly that. When it says "yes", it means
"maybe".

 Example 5.3.2

The reaction
1
O (g) + H (g) → H O(l)
2 2 2 2

is used in fuel cells to produce an electrical current. The reaction can also be carried out by direct combustion.
Thermodynamic data: molar entropies in J mol–1 K–1: O2(g) 205.0; H2(g)130.6; H2O(l) 70.0; H2O(l) ΔH°f = –285.9 kJ mol–1.
Use this information to find
a. The amount of heat released when the reaction takes place by direct combustion;
b. The amount of electrical work the same reaction can perform when carried out in a fuel cell at 298 K under reversible
conditions;
c. The amount of heat released under the same conditions.

Solution
First, we need to find ΔH and ΔS for the process. Recalling that the standard enthalpy of formation of the elements is zero,
o o

o p
∘
ΔH = ΔH (products)– ΔH (reactants)
f f

–1
=– 285.9 kJ mol –0 .

–1
=– 285.9 kJ mol

Similarly,

5.3.6 https://chem.libretexts.org/@go/page/43443
 o o o
ΔS =S (products)– S (reactants)
f f

= (70.0)– ( ½ × 205.0 + 130.6)

–1 –1
=– 163 J K mol

a. When the hydrogen and oxygen are combined directly, the heat released will be ΔH o
=– 285.9 kJ mol
–1
.
b. The maximum electrical work the fuel cell can perform is given by
o o o
ΔG = ΔH – T ΔS

–1 –1 –1
=– 285.9 kJ mol – (298 K)(– 163 J K mol ).

–1
=– 237.2 kJ mol .

c. The heat released in the fuel cell reaction is the difference between the enthalpy change (the total energy available) and the
reversible work that was expended:
o o o
ΔH – ΔG = T ΔS

–1 –1
= (298 K)(– 163 J K mol )
.
–1
=– 48, 800 J mol

–1
=– 48.8 kJ mol .

The foregoing example illustrates an important advantage of fuel cells. Although direct combustion of a mole of hydrogen gas
yields more energy than is produced by the same net reaction within the fuel cell, the latter, in the form of electrical energy, can be
utilized at nearly 100-percent energy efficiency by a motor or some other electrical device. If the thermal energy released by direct
combustion were supplied to a heat engine, second-law considerations would require that at least half of this energy be "wasted" to
the surroundings.

 ΔG vs. ΔG°: what's the difference?

ΔG° refer to single, specific chemical changes in which all components (reactants and products) are in their standard states.

The ΔG of a substance, like ΔH , refers to the reaction in which that substance is formed from the elements as they exist in their
o
f f
o

most stable forms at 1 atm pressure and (usually) 298 K. Both of these terms are by definition zero for the elements in their
standard states. There are only a few common cases in which this might create some ambiguity:
Table 5.3.1 : Standard Gibbs Energies of Select Substances
Stable Form ΔG
o
f
(kJ mol–1) Unstable Form ΔG
o
f
(kJ mol–1)

O (g)
2
0 O (g)
3
163.2

C(graphite) 0 C(diamond) 2.9

S(rhombic) 0 S(monoclinic) 0.1

P(white) 0 P (g)
4
24.4

Ions in aqueous solution are a special case; their standard free energies are relative to the hydrated hydrogen ion H +
(aq) which is
assigned ΔG = 0 .
o
f

ΔG is very different from ΔG°. The distinction is nicely illustrated in Figure 5.3.5 in which ΔG is plotted on a vertical axis for two
hypothetical reactions having opposite signs of ΔG°. The horizontal axis schematically expresses the relative concentrations of
reactants and products at any point of the process. Note that the origin corresponds to the composition at which half of the reactants
have been converted into products.

5.3.7 https://chem.libretexts.org/@go/page/43443
 ΔG

plot for ΔG° > 0

ΔG°
ΔG ΔG
1 3
more reactants ΔG=0 more products

ΔG° plot for ΔG° < 0

G°products G°reactants
2 1

Gibbs function G
Gibbs function G

ΔG° > 0 ΔG° < 0

G°products
G°reactants 2
1

reverse reaction forward reaction

3 3
0 extent of reaction 1 0 extent of reaction 1

Figure 5.3.5 : (CC BY 4.0; Ümit Kaya via LibreTexts)

Take careful note of the following:
for the ΔG° > 0 reaction. Notice that there are an infinite number of these values, depending on the progress of the reaction. In
contrast there is only a single value of ΔG°, corresponding to the composition at which ΔG = 0 ( ).
At this point, some products have been formed, but the composition is still dominated by reactants.
If we begin at a composition to the left of , ΔG will be negative and the composition will move to the right. Similarly if we
begin with a composition to the right of , ΔG will be positive and the composition will move to the left.
The plot on the right is for the ΔG° < 0 reaction, for which ΔG° is shown at . At its equilibrium point , there are more
products than reactants. If we start at a composition to the right of , the composition will tend to move to the left. If the initial
composition is to the left of , the reaction will tend to proceed to the right.
What would happen if ΔG° were 0? The equilibrium point of such a reaction would be at the origin, corresponding to half the
reactants being converted to products.
The important principle you should understand from this is that a negative ΔG° does not mean that the reactants will be completely
transformed into products. By the same token, a positive ΔG° does not mean that no products are formed at all.
It should now be clear from the discussion above that a given reaction carried out under standard conditions is characterized by a
single value of ΔG°.
The reason for the Gibbs energy minimum at equilibrium relates to the increase in entropy when products and reactants coexist in
the same phase. As seen in the plot, even a minute amount of "contamination" of products by reactants reduces the free energy
below that of the pure products. In contrast, composition of a chemical reaction system undergoes continual change until the
equilibrium state is reached. So the a single reaction can have an infinite number of ΔG values, reflecting the infinite possible
compositions between the extremes of pure reactants (zero extent of reaction) and pure products (unity extent of reaction).
In the example of a reaction A → B, depicted in the above diagram, the standard free energy of the products is smaller than that
of the reactants , so the reaction will take place spontaneously. This does not mean that each mole of pure A will be converted
into one mole of pure B. For reactions in which products and reactants occupy a single phase (gas or solution), the meaning of
"spontaneous" is that the equilibrium composition will correspond to an extent of reaction greater than 0.5 but smaller than
unity.Note, however, that for ΔG° values in excess of about ±50 kJ mol–1, the equilibrium composition will be negligibly different

5.3.8 https://chem.libretexts.org/@go/page/43443
from zero or unity extent-of-reaction. The physical meaning of ΔG is that it tells us how far the free energy of the system has
changed from G° of the pure reactants . As the reaction proceeds to the right, the composition changes, and ΔG begins to fall.
When the composition reaches , ΔG reaches its minimum value and further reaction would cause it to rise. But because free
energy can only decrease but never increase, this does not happen. The composition of the system remains permanently at its
equilibrium value.
A G vs. extent-of-reaction diagram for a non-spontaneous reaction can be interpreted in a similar way; the equilibrium composition
will correspond to an extent of reaction greater than zero but less than 0.5. In this case, the minimum at reflects the increase
in entropy when the reactants are "contaminated" by a small quantity of products.
If all this detail about ΔG seems a bit overwhelming, do not worry: it all gets hidden in the equilibrium constant and reaction
quotient that we discuss in the next lesson!

5.3.5: Interpretation of Standard Gibbs energy changes

Although it is ΔG rather than ΔG that serves as a criterion for spontaneous change at constant temperature and pressure, ΔG
o o

values are so readily available that they are often used to get a rough idea of whether a given chemical change is possible. This is
practical to do in some cases, but not in others:

 Example

It generally works for reactions such as

4 NH (g) + 5 O (g) → 4 NO(g) + 6 H O(g)

3 2 2

with ΔG o
=– 1, 010 kJ .
(industrially important for the manufacture of nitric acid) because ΔG is so negative that the reaction will be spontaneous and
o

virtually complete under just about any reasonable set of conditions.

 Example

The following reaction expresses the fact that the water molecule is thermodynamically stable:
1
2 H (g) + O (g) → H O(l)
2 2 2 2

with ΔG o
=– 237.2 kJ .
Note that this refers to liquid water (the standard state of H2O at 25°). If you think about it, a negative standard Gibbs energy of
formation (of which this is an example) can in fact be considered a definition of molecular stability.

 Example

Similarly, dissociation of dihydrogen into its atoms is highly unlikely under standard conditions:

H O(g) → 2 H(g) + O(g)

2

with ΔG o
= +406.6 kJ .
Again, an analogous situation would apply to any stable molecule.

 Example

Now consider the dissociation of dinitrogen tetroxide

N O (g) → 2 NO (g)
2 4 2

with ΔG o
= +2.8kJ .
in which the positive value of ΔG° tells us that N2O4 at 1 atm pressure will not change into two moles of NO2 at the same
pressure, but owing to the small absolute value of ΔG°, we can expect the spontaneity of the process to be quite sensitive to

5.3.9 https://chem.libretexts.org/@go/page/43443
 both the temperature (as shown in the table below) and to the pressure in exactly the way the Le Chatelier principle predicts.

 Example

For reactions involving dissolved ions, one has to be quite careful. Thus for the dissociation of the weak hydrofluoric acid
+
HF(aq) → H (aq) + F– (aq)

with ΔG o
=– 317 kJ .
it is clear that a 1 mol/L solution of HF will not dissociate into 1M ions, but this fact is not very useful because if the HF is
added to water, the initial concentration of the fluoride ion will be zero (and that of H+ very close to zero), and the Le Chatelier
principle again predicts that some dissociation will be spontaneous.

 Example
It is common knowledge that dissociation of water into hydrogen- and hydroxyl ions occurs only very sparingly:
+
H O(l) → H (aq) + OH– (aq)
2

with ΔG o
= 79.9 kJ .
which correctly predicts that the water will not form 1M (effective concentration) of the ions, but this is hardly news if you
already know that the product of these ion concentrations can never exceed 10–14 at 298K.

 Example

Finally, consider this most familiar of all phase change processes, the vaporization of liquid water:

H O(l) → H O(g)
2 2

with ΔG o
= 8.58 kJ .
Conversion of liquid water to its vapor at 1 atm partial pressure does not take place at 25° C, at which temperature the
equilibrium partial pressure of the vapor (the "vapor pressure") is only 0.031 atm (23.8 torr.) Gaseous H2O at a pressure of 1
atm can only exist at 100° C. Of course, water left in an open container at room temperature will spontaneously evaporate if
the partial pressure of water vapor in the air is less than 0.031 atm, corresponding to a relative humidity of under 100%

5.3.6: Finding the Equilibrium Temperature

A reaction is in its equilibrium state when
ΔG = ΔH – T ΔS = 0 (5.3.10)

The temperature at which this occurs is given by

ΔH
T = (5.3.11)
T ΔS

If we approximate ΔH by ΔH and ΔS by ΔS , so Equation 5.3.10 would be

o o

o o
ΔG ≈ ΔH – T ΔS =0 (5.3.12)

We can then estimate the normal boiling point of a liquid. From the following thermodynamic data for water:

5.3.10 https://chem.libretexts.org/@go/page/43443
  Caution!

Because ΔH° values are normally expressed in kilojoules while ΔS° is given in joules, a very common student error is to
overlook the need to express both in the same units.

We find that liquid water is in equilibrium with water vapor at a partial pressure of 1 atm when the temperature is
44, 100 J
T = = 371.5 K (5.3.13)
–1
118.7 J K

But "the normal boiling point of water is 373 K", you say? Very true. The reason we are off here is that both ΔH ° and ΔS ° have
their own temperature dependencies; we are using the "standard" 25° values without correcting them to 100° C. Nevertheless, if
you think about it, the fact that we can estimate the boiling point of a liquid from a table of thermodynamic data should be rather
impressive! Of course, the farther one gets from 298 K, the more unreliable will be the result. Thus for the dissociation of
dihydrogen into its atoms,

436, 000 J
T = = 4, 420 K (5.3.14)
–1
98.6 J K

All one can say here is that H2 will break down at something over 3000 K or so. (You may already know that all molecules will
dissociate into their atoms at high temperatures.) We tend to think of high temperatures as somehow "forcing" molecules to
dissociate into their atoms, but this is wrong. In order to get the H–H bond to vibrate so violently through purely thermal excitation
that the atoms would fly apart, a temperature more like 30,000 K would be required. The proper interpretation is at the temperature
corresponding to ΔH/TΔS, the molecule spontaneously absorbs energy from the surroundings sufficient to overcome the H-H bond
strength.

5.3.7: Predicting the Effects of Temperature

The T ΔS term interacts with the ΔH term in ΔG to determine whether the reaction can take place at a given temperature. This
can be more clearly understood by examining plots of T ΔS and ΔH as functions of the temperature for some actual reactions.
o o

Of course these parameters refer to standard states that generally do not correspond to the temperatures, pressures, or
concentrations that might be of interest in an actual case. Nevertheless, these quantities are easily found and they can usefully
predict the way that temperature affects these systems.

5.3.7.1: Case 1: Exothermic reaction, ΔS° > 0

C(graphite) + O (g) → CO (g)
2 2

o
ΔH =– 393 kJ

ΔG
o
=– 394 kJ at 298 K

kJ
TΔS

0
ΔG

ΔH
ΔG < 0
T
0

Figure 5.3.6 : (CC BY 4.0; Ümit Kaya via LibreTexts)

This combustion reaction, like most such reactions, is spontaneous at all temperatures. The positive entropy change is due
mainly to the greater mass of CO molecules compared to those of O .
2 2

5.3.11 https://chem.libretexts.org/@go/page/43443
5.3.7.2: Case 2: Exothermic reaction, ΔS° < 0
3H +N → 2 NH (g)
2 2 3

o
ΔH =– 46.2 kJ

ΔG
o
=– 16.4 kJ at 298 K

kJ

0
TΔS

ΔH

ΔG < 0 ΔG
0 T

Figure 5.3.7 : (CC BY 4.0; Ümit Kaya via LibreTexts)

The decrease in moles of gas in the Haber ammonia synthesis drives the entropy change negative, making the reaction
spontaneous only at low temperatures. Thus higher T, which speeds up the reaction, also reduces its extent.

5.3.7.3: Case 3: Endothermic reaction, ΔS° > 0

N O (g) → 2 NO (g)
2 4 2

o
ΔH = 55.3 kJ

ΔG
o
= +2.8 kJ at 298 K

kJ

TΔS ΔG
ΔH
ΔG

0
ΔG > 0 ΔG < 0
0 T

Figure 5.3.8 : (CC BY 4.0; Ümit Kaya via LibreTexts)

Dissociation reactions are typically endothermic with positive entropy change, and are therefore spontaneous at high
temperatures. Ultimately, all molecules decompose to their atoms at sufficiently high temperatures.

5.3.7.4: Case 4: Endothermic Reaction, ΔS° < 0

1
N (g) + O (g) → NO (g)
2 2 2 2

∘
ΔH = 33.2 kJ
o –1
ΔS =– 249 J K

ΔG
o
= +51.3 kJ at 298 K

5.3.12 https://chem.libretexts.org/@go/page/43443
 kJ ΔH

ΔG
0

TΔS
ΔG > 0
0 T

Figure 5.3.9 : (CC BY 4.0; Ümit Kaya via LibreTexts)

This reaction is not spontaneous at any temperature, meaning that its reverse is always spontaneous. But because the reverse
reaction is kinetically inhibited, NO2 can exist indefinitely at ordinary temperatures even though it is thermodynamically unstable.

5.3.8: Concluding remarks on Gibbs Energy

The appellation “free energy” for G has led to so much confusion that many scientists now refer to it simply as the Gibbs energy.
The “free” part of the older name reflects the steam-engine origins of thermodynamics with its interest in converting heat into
work: ΔG is the maximum amount of energy, which can be “freed” from the system to perform useful work. By "useful", we mean
work other than that which is associated with the expansion of the system. This is most commonly in the form of electrical work
(moving electric charge through a potential difference), but other forms of work (osmotic work, increase in surface area) are also
possible.
A much more serious difficulty with the Gibbs function, particularly in the context of chemistry, is that although G has the units of
energy (joules, or in its intensive form, J mol–1), it lacks one of the most important attributes of energy in that it is not conserved.
Thus, although the free energy always falls when a gas expands or a chemical reaction takes place spontaneously, there need be no
compensating increase in energy anywhere else. Referring to G as an energy also reinforces the false but widespread notion that a
fall in energy must accompany any change. But if we accept that energy is conserved, it is apparent that the only necessary
condition for change (whether the dropping of a weight, expansion of a gas, or a chemical reaction) is the redistribution of energy.
The quantity \(–ΔG\) associated with a process represents the quantity of energy that is “shared and spread”, which as we have
already explained is the meaning of the increase in the entropy. The quotient – ΔG/T is in fact identical with ΔS , the entropy
total

change of the world, whose increase is the primary criterion for any kind of change.
G differs from the thermodynamic quantities H and S in another significant way: it has no physical reality as a property of matter,
whereas H and S can be related to the quantity and distribution of energy in a collection of molecules. The free energy is simply a
useful construct that serves as a criterion for change and makes calculations easier.

 What Gibbs Energy is not...

Gibbs Energy is not free energy
Gibbs Energy is not energy
Gibbs Energy is not even "real"

5.3: Thermodynamic Description of the Equilibrium State is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.
15.4: Free Energy and the Gibbs Function by Stephen Lower is licensed CC BY 3.0. Original source:
http://www.chem1.com/acad/webtext/virtualtextbook.html.

5.3.13 https://chem.libretexts.org/@go/page/43443
5.4: The Law of Mass Action for Related and Simultaneous Equilibria
 Learning Objectives
To know the relationship between the equilibrium constant and the rate constants for the forward and reverse reactions.
To write an equilibrium constant expression for any reaction.

5.4.1: Relationship among Equilibrium Expressions

Chemists frequently need to know the equilibrium constant for a reaction that has not been previously studied. In such cases, the
desired reaction can often be written as the sum of other reactions for which the equilibrium constants are known. The equilibrium
constant for the unknown reaction can then be calculated from the tabulated values for the other reactions.
To illustrate this procedure, let’s consider the reaction of N with O to give N O . This reaction is an important source of the
2 2 2

N O that gives urban smog its typical brown color. The reaction normally occurs in two distinct steps. In the first reaction (1), N
2 2

reacts with O at the high temperatures inside an internal combustion engine to give N O . The released N O then reacts with
2

additional O to give N O (2). The equilibrium constant for each reaction at 100°C is also given.
2 2

1. N +O
2(g) 2(g)
⇌ 2N O(g) K1 = 2.0 × 10
−25

2. 2N O + O (g) 2(g) ⇌ 2N O2(g) K2 = 6.4 × 10

9

Summing reactions (1) and (2) gives the overall reaction of N with O : 2 2

3. N 2(g)
+ 2 O2(g) ⇌ 2N O2(g) K3 =?

The equilibrium constant expressions for the reactions are as follows:

2 2 2
[N O] [N O2 ] [N O2 ]
K1 = K2 = K3 = (5.4.1)
2 2
[ N2 ][ O2 ] [N O] [ O2 ] [ N2 ][ O2 ]

What is the relationship between K , K , and K , all at 100°C? The expression for K has [N O] in the numerator, the expression
1 2 3 1
2

for K has [N O] in the denominator, and [N O] does not appear in the expression for K . Multiplying K by K and canceling
2
2 2
3 1 2

the [N O] terms,
2

2
[N O] 2 2
[N O2 ] [N O2 ]
K1 K2 = × = = K3 (5.4.2)
2
[ N2 ][ O2 ] 2 [ N2 ][ O2 ]
[N O] [ O2 ]

Thus the product of the equilibrium constant expressions for K and K is the same as the equilibrium constant expression for K :
1 2 3

−25 9 −15
K3 = K1 K2 = (2.0 × 10 )(6.4 × 10 ) = 1.3 × 10 (5.4.3)

The equilibrium constant for a reaction that is the sum of two or more reactions is equal to the product of the equilibrium constants
for the individual reactions. In contrast, recall that according to Hess’s Law, ΔH for the sum of two or more reactions is the sum of
the ΔH values for the individual reactions.

 Note
To determine K for a reaction that is the sum of two or more reactions, add the reactions but multiply the equilibrium
constants.

 Example 5.4.6
The following reactions occur at 1200°C:
1. C O (g)
+ 3 H2(g) ⇌ C H4(g) + H2 O(g) K1 = 9.17 × 10
−2

2. C H 4(g) + 2 H2 S(g) ⇌ C S2(g) + 4 H2(g ) K2 = 3.3 × 10

4

Calculate the equilibrium constant for the following reaction at the same temperature.
3. C O (g)
+ 2 H2 S(g) ⇌ C S2(g) + H2 O(g) + H2(g) K3 =?

5.4.1 https://chem.libretexts.org/@go/page/43444
 Given: two balanced equilibrium equations, values of K , and an equilibrium equation for the overall reaction
Asked for: equilibrium constant for the overall reaction
Strategy:
Arrange the equations so that their sum produces the overall equation. If an equation had to be reversed, invert the value of K
for that equation. Calculate K for the overall equation by multiplying the equilibrium constants for the individual equations.
Solution:
The key to solving this problem is to recognize that reaction 3 is the sum of reactions 1 and 2:

C O(g) + 3H2(g) ⇌ C H4(g) + H2 O(g) (5.4.4)

C H4(g) + 2 H2 S(g) ⇌ C S2(g) + 3H2(g) + H2(g) (5.4.5)

C O(g) + 3 H2(g) ⇌ C S2(g) + H2 O(g) + H2(g) (5.4.6)

The values for K and K are given, so it is straightforward to calculate K :

1 2 3

−2 4 3
K3 = K1 K2 = (9.17 × 10 )(3.3 × 10 ) = 3.03 × 10 (5.4.7)

 Exercise 5.4.6

In the first of two steps in the industrial synthesis of sulfuric acid, elemental sulfur reacts with oxygen to produce sulfur
dioxide. In the second step, sulfur dioxide reacts with additional oxygen to form sulfur trioxide. The reaction for each step is
shown, as is the value of the corresponding equilibrium constant at 25°C. Calculate the equilibrium constant for the overall
reaction at this same temperature.
1. S
1

8 8(s)
+ O2(g) ⇌ S O2(g) K1 = 4.4 × 10
53

2. SO 2(g) +
1

2
O2(g) ⇌ S O3(g) K2 = 2.6 × 10
12

3. S
1

8 8(s)
+
3

2
O2(g) ⇌ S O3(g) K3 =?

Answer
66
K3 = 1.1 × 10

5.4.2: Summary
An equilibrium system that contains products and reactants in a single phase is a homogeneous equilibrium; a system whose
reactants, products, or both are in more than one phase is a heterogeneous equilibrium. When a reaction can be expressed as the
sum of two or more reactions, its equilibrium constant is equal to the product of the equilibrium constants for the individual
reactions.

5.4: The Law of Mass Action for Related and Simultaneous Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by LibreTexts.

5.4.2 https://chem.libretexts.org/@go/page/43444
5.5: Gas-Phase and Heterogeneous Reaction Equilibria
 Learning Objectives
To solve quantitative problems involving chemical equilibriums.

There are two fundamental kinds of equilibrium problems:

1. those in which we are given the concentrations of the reactants and the products at equilibrium (or, more often, information that
allows us to calculate these concentrations), and we are asked to calculate the equilibrium constant for the reaction; and
2. those in which we are given the equilibrium constant and the initial concentrations of reactants, and we are asked to calculate
the concentration of one or more substances at equilibrium. In this section, we describe methods for solving both kinds of
problems.

5.5.1: Calculating an Equilibrium Constant from Equilibrium Concentrations

The equilibrium constant for the decomposition of C aC O 3(s) to C aO and C O
(s) is K = [C O ] . At 800°C, the concentration
2(g) 2

of C O in equilibrium with solid C aC O and C aO is 2.5 × 10 M . Thus K at 800°C is 2.5 × 10

2 3
−3
(remember that
−3

equilibrium constants are unitless). A more complex example of this type of problem is the conversion of n-butane, an additive
used to increase the volatility of gasoline, into isobutane (2-methylpropane).

This reaction can be written as follows:

n−butane ⇌ isobutane (5.5.1)

(g) (g)

and the equilibrium constant K = [isobutane]/[n-butane] . At equilibrium, a mixture of n-butane and isobutane at room
temperature was found to contain 0.041 M isobutane and 0.016 M n-butane. Substituting these concentrations into the equilibrium
constant expression,
[isobutane]
K =
[\texTn − butane]

0.041 M
=
0.016 M

= 2.6

Thus the equilibrium constant for the reaction as written is 2.6.

 Example 5.5.1

The reaction between gaseous sulfur dioxide and oxygen is a key step in the industrial synthesis of sulfuric acid:
2 SO (g) + O (g) ⇌ 2 SO (g)
2 2 3

A mixture of SO and O was maintained at 800 K until the system reached equilibrium. The equilibrium mixture contained
2 2

5.0 × 10
−2
M S O3 ,

5.5.1 https://chem.libretexts.org/@go/page/43445
 3.5 × 10
−3
M O2 , and
3.0 × 10
−3
M S O2 .
Calculate K and K at this temperature.
p

Given: balanced equilibrium equation and composition of equilibrium mixture

Asked for: equilibrium constant
Strategy
Write the equilibrium constant expression for the reaction. Then substitute the appropriate equilibrium concentrations into this
equation to obtain K .

Solution
Substituting the appropriate equilibrium concentrations into the equilibrium constant expression,
2 −2 2
[SO3 ] (5.0 × 10 )
4
K = = = 7.9 × 10
2 −3 −3
[S O2 ] [ O2 ] (3.0 × 10 )2 (3.5 × 10 )

To solve for K , we need to identify Δn where Δn = 2 − 3 = −1 and then

p

Δn
Kp = K(RT )

4 −1
Kp = 7.9 × 10 [(0.08206 L ⋅ atm/mol ⋅ K)(800K)]

3
Kp = 1.2 × 10

 Exercise 5.5.1

Hydrogen gas and iodine react to form hydrogen iodide via the reaction
H (g) + I (g) ⇌ 2 HI(g)
2 2

A mixture of H and I was maintained at 740 K until the system reached equilibrium. The equilibrium mixture contained
2 2

1.37 × 10
−2
M HI ,
6.47 × 10
−3
M H2 , and
5.94 × 10
−4
M I2 .
Calculate K and K for this reaction.
p

Answer (K )
K = 48.8

Answer (K ) p

Kp = 48.8

Chemists are not often given the concentrations of all the substances, and they are not likely to measure the equilibrium
concentrations of all the relevant substances for a particular system. In such cases, we can obtain the equilibrium concentrations
from the initial concentrations of the reactants and the balanced chemical equation for the reaction, as long as the equilibrium
concentration of one of the substances is known. Example 5.5.2 shows one way to do this.

 Example 5.5.2

A 1.00 mol sample of N OC l was placed in a 2.00 L reactor and heated to 227°C until the system reached equilibrium. The
contents of the reactor were then analyzed and found to contain 0.056 mol of C l . Calculate K at this temperature. The
2

equation for the decomposition of N OC l to N O and C l is as follows: 2

2 NOCl(g) ⇌ 2 NO(g) + Cl (g)

2

5.5.2 https://chem.libretexts.org/@go/page/43445
Given: balanced equilibrium equation, amount of reactant, volume, and amount of one product at equilibrium
Asked for: K
Strategy:
A. Write the equilibrium constant expression for the reaction. Construct a table showing the initial concentrations, the changes
in concentrations, and the final concentrations (as initial concentrations plus changes in concentrations).
B. Calculate all possible initial concentrations from the data given and insert them in the table.
C. Use the coefficients in the balanced chemical equation to obtain the changes in concentration of all other substances in the
reaction. Insert those concentration changes in the table.
D. Obtain the final concentrations by summing the columns. Calculate the equilibrium constant for the reaction.

Solution
A The first step in any such problem is to balance the chemical equation for the reaction (if it is not already balanced) and use
it to derive the equilibrium constant expression. In this case, the equation is already balanced, and the equilibrium constant
expression is as follows:
2
[N O] [C l2 ]
K =
[N OC l]2

To obtain the concentrations of N OC l, N O , and C l at equilibrium, we construct a table showing what is known and what
2

needs to be calculated. We begin by writing the balanced chemical equation at the top of the table, followed by three lines
corresponding to the initial concentrations, the changes in concentrations required to get from the initial to the final state, and
the final concentrations.

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [Cl2 ]

Initial

Change

Final

B Initially, the system contains 1.00 mol of N OC l in a 2.00 L container. Thus [N OC l] = 1.00 mol/2.00 L = 0.500 M. The
i

initial concentrations of N O and C l are 0 M because initially no products are present. Moreover, we are told that at
2

equilibrium the system contains 0.056 mol of C l in a 2.00 L container, so [C l ] = 0.056 mol/2.00 L = 0.028 M. We
2 2 f

insert these values into the following table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [Cl2 ]

Initial 0.500 0 0

Change

Final 0.028

C We use the stoichiometric relationships given in the balanced chemical equation to find the change in the concentration of
C l , the substance for which initial and final concentrations are known:
2

Δ[C l2 ] = 0.028 M(f inal) − 0.00 M(initial) ] = +0.028 M

According to the coefficients in the balanced chemical equation, 2 mol of NO are produced for every 1 mol of C l2 , so the
change in the N O concentration is as follows:

5.5.3 https://chem.libretexts.org/@go/page/43445
 0.028 mol C l2 2 mol N O
Δ[N O] = ( )( ) = 0.056 M
L 1 mol C l2

Similarly, 2 mol of N OC l are consumed for every 1 mol of C l2 produced, so the change in the N OC l concentration is as
follows:

0.028 mol C l2 −2 mol N OC l

Δ[N OC l] = ( )( ) = −0.056 M
L 1 mol C l2

We insert these values into our table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [Cl2 ]

Initial 0.500 0 0

Change −0.056 +0.056 +0.028

Final 0.028

D We sum the numbers in the [N OC l] and [N O] columns to obtain the final concentrations of N O and N OC l:

[N O]f = 0.000 M + 0.056 M = 0.056 M

[N OC l]f = 0.500 M + (−0.056 M ) = 0.444M

We can now complete the table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [Cl2 ]

initial 0.500 0 0

change −0.056 +0.056 +0.028

final 0.444 0.056 0.028

We can now calculate the equilibrium constant for the reaction:

2 2
[N O] [C l2 ] (0.056 ) (0.028)
−4
K = = = 4.5 × 10
2 2
[N OC l] (0.444)

 Exercise 5.5.2
The German chemist Fritz Haber (1868–1934; Nobel Prize in Chemistry 1918) was able to synthesize ammonia (N H ) by 3

reacting 0.1248 M H and 0.0416 M N at about 500°C. At equilibrium, the mixture contained 0.00272 M N H . What is K
2 2 3

for the reaction

N2 + 3 H2 ⇌ 2N H3

at this temperature? What is K ? p

Answer (K )
K = 0.105

Answer (K ) p

−5
Kp = 2.61 × 10

5.5.4 https://chem.libretexts.org/@go/page/43445
5.5.2: Calculating Equilibrium Concentrations from the Equilibrium Constant
To describe how to calculate equilibrium concentrations from an equilibrium constant, we first consider a system that contains only
a single product and a single reactant, the conversion of n-butane to isobutane (Equation 5.5.1), for which K = 2.6 at 25°C. If we
begin with a 1.00 M sample of n-butane, we can determine the concentration of n-butane and isobutane at equilibrium by
constructing a table showing what is known and what needs to be calculated, just as we did in Example 5.5.2.

n-butane(g) ⇌ isobutane(g) (5.5.2)

ICE [ n-butane ( g) ] [ isobutane ( g) ]

Initial

Change

Final

The initial concentrations of the reactant and product are both known: [n-butane]i = 1.00 M and [isobutane]i = 0 M. We need to
calculate the equilibrium concentrations of both n-butane and isobutane. Because it is generally difficult to calculate final
concentrations directly, we focus on the change in the concentrations of the substances between the initial and the final
(equilibrium) conditions. If, for example, we define the change in the concentration of isobutane (Δ[isobutane]) as +x, then the
change in the concentration of n-butane is Δ[n-butane] = −x. This is because the balanced chemical equation for the reaction tells
us that 1 mol of n-butane is consumed for every 1 mol of isobutane produced. We can then express the final concentrations in terms
of the initial concentrations and the changes they have undergone.
n-butane (g) ⇌ isobutane (g) (5.5.3)

ICE [ n-butane ( g) ] [ isobutane ( g) ]

Initial 1.00 0

Change −x +x

Final (1.00 − x) (0 + x) = x

Substituting the expressions for the final concentrations of n-butane and isobutane from the table into the equilibrium equation,
[isobutane] x
K = = = 2.6 (5.5.4)
[n-butane] 1.00 − x

Rearranging and solving for x,

x = 2.6(1.00 − x) = 2.6 − 2.6x

x + 2.6x = 2.6

x = 0.72

We obtain the final concentrations by substituting this x value into the expressions for the final concentrations of n-butane and
isobutane listed in the table:
[n-butane]f = (1.00 − x)M = (1.00 − 0.72)M = 0.28 M (5.5.5)

[isobutane]f = (0.00 + x)M = (0.00 + 0.72)M = 0.72 M (5.5.6)

We can check the results by substituting them back into the equilibrium constant expression to see whether they give the same K
that we used in the calculation:

[isobutane] 0.72 M
K = =( ) = 2.6 (5.5.7)
[n-butane] 0.28 M

This is the same K we were given, so we can be confident of our results.

Example 5.5.3 illustrates a common type of equilibrium problem that you are likely to encounter.

5.5.5 https://chem.libretexts.org/@go/page/43445
 Example 5.5.3

The water–gas shift reaction is important in several chemical processes, such as the production of H2 for fuel cells.
Thisreaction can be written as follows:

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

K = 0.106 at 700 K. If a mixture of gases that initially contains 0.0150 M H and 0.0150 M C O is allowed to equilibrate at
2 2

700 K, what are the final concentrations of all substances present?

Given: balanced equilibrium equation, K , and initial concentrations
Asked for: final concentrations
Strategy:
A. Construct a table showing what is known and what needs to be calculated. Define x as the change in the concentration of
one substance. Then use the reaction stoichiometry to express the changes in the concentrations of the other substances in
terms of x. From the values in the table, calculate the final concentrations.
B. Write the equilibrium equation for the reaction. Substitute appropriate values from the ICE table to obtain x.
C. Calculate the final concentrations of all species present. Check your answers by substituting these values into the
equilibrium constant expression to obtain K.

Solution
A The initial concentrations of the reactants are [H ] = [C O ] = 0.0150 M . Just as before, we will focus on the change in
2 i 2 i

the concentrations of the various substances between the initial and final states. If we define the change in the concentration of
H O as x, then Δ[ H O] = +x . We can use the stoichiometry of the reaction to express the changes in the concentrations of
2 2

the other substances in terms of x. For example, 1 mol of C O is produced for every 1 mol of H O, so the change in the C O2

concentration can be expressed as Δ[C O] = +x. Similarly, for every 1 mol of H O produced, 1 mol each of H and C O are
2 2 2

consumed, so the change in the concentration of the reactants is Δ[H ] = Δ[C O ] = −x . We enter the values in the following
2 2

table and calculate the final concentrations.

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

ICE [ H2 ] [CO2 ] [ H2 O] [CO]

Initial 0.0150 0.0150 0 0

Change −x −x +x +x

Final (0.0150 − x) (0.0150 − x) x x

B We can now use the equilibrium equation and the given K to solve for x:
2
[ H2 O][C O] (x)(x) x
K = = = = 0.106
2
[ H2 ][C O2 ] (0.0150 − x)(0.0150 − x) (0.0150 − x)

We could solve this equation with the quadratic formula, but it is far easier to solve for x by recognizing that the left side of the
equation is a perfect square; that is,
2 2
x x
=( ) = 0.106
(0.0150 − x)2 0.0150 − x

Taking the square root of the middle and right terms,

2
x
1/2
= (0.106 ) = 0.326
2
(0.0150 − x)

x = (0.326)(0.0150) − 0.326x

5.5.6 https://chem.libretexts.org/@go/page/43445
 1.326x = 0.00489

−3
x = 0.00369 = 3.69 × 10

C The final concentrations of all species in the reaction mixture are as follows:
[ H2 ]f = [ H2 ]i + Δ[ H2 ] = (0.0150 − 0.00369) M = 0.0113 M

[C O2 ]f = [C O2 ]i + Δ[C O2 ] = (0.0150 − 0.00369) M = 0.0113 M

[ H2 O]f = [ H2 O]i + Δ[ H2 O] = (0 + 0.00369) M = 0.00369 M

[C O]f = [C O]i + Δ[C O] = (0 + 0.00369) M = 0.00369 M

We can check our work by inserting the calculated values back into the equilibrium constant expression:
2
[ H2 O][C O] (0.00369)
K = = = 0.107
[ H2 ][C O2 ] (0.0113)2

To two significant figures, this K is the same as the value given in the problem, so our answer is confirmed.

 Exercise 5.5.3
Hydrogen gas reacts with iodine vapor to give hydrogen iodide according to the following chemical equation:
H2(g) + I2(g) ⇌ 2H I(g)

K = 54 at 425°C. If 0.172 M H and I are injected into a reactor and maintained at 425°C until the system equilibrates, what is
2 2

the final concentration of each substance in the reaction mixture?

Answer
[H I ]f = 0.270 M [ H2 ]f = [ I2 ]f = 0.037 M

In Example 5.5.3, the initial concentrations of the reactants were the same, which gave us an equation that was a perfect square and
simplified our calculations. Often, however, the initial concentrations of the reactants are not the same, and/or one or more of the
products may be present when the reaction starts. Under these conditions, there is usually no way to simplify the problem, and we
must determine the equilibrium concentrations with other means. Such a case is described in Example 5.5.4.

 Example 5.5.4
In the water–gas shift reaction shown in Example 5.5.3, a sample containing 0.632 M CO and 0.570 M H is allowed to
2 2

equilibrate at 700 K. At this temperature, K = 0.106 . What is the composition of the reaction mixture at equilibrium?
Given: balanced equilibrium equation, concentrations of reactants, and K
Asked for: composition of reaction mixture at equilibrium
Strategy:
A. Write the equilibrium equation. Construct a table showing the initial concentrations of all substances in the mixture.
Complete the table showing the changes in the concentrations (x) and the final concentrations.
B. Write the equilibrium constant expression for the reaction. Substitute the known K value and the final concentrations to
solve for x.
C. Calculate the final concentration of each substance in the reaction mixture. Check your answers by substituting these values
into the equilibrium constant expression to obtain K.

Solution
A [C O ] = 0.632 M and [H ] = 0.570 M . Again, x is defined as the change in the concentration of H O: Δ[H O] = +x .
2 i 2 i 2 2

Because 1 mol of C O is produced for every 1 mol of H O, the change in the concentration of C O is the same as the change in
2

the concentration of H2O, so Δ[CO] = +x. Similarly, because 1 mol each of H and C O are consumed for every 1 mol of
2 2

5.5.7 https://chem.libretexts.org/@go/page/43445
H2 O produced, Δ[H ] = Δ[C O
2 2] = −x . The final concentrations are the sums of the initial concentrations and the changes
in concentrations at equilibrium.

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

ICE H
2( g)
CO
2( g)
H2 O
( g)
CO
( g)

Initial 0.570 0.632 0 0

Change −x −x +x +x

Final (0.570 − x) (0.632 − x) x x

B We can now use the equilibrium equation and the known K value to solve for x:
2
[ H2 O][C O] x
K = = = 0.106
[ H2 ][C O2 ] (0.570 − x)(0.632 − x)

In contrast to Example 5.5.3, however, there is no obvious way to simplify this expression. Thus we must expand the
expression and multiply both sides by the denominator:
2 2
x = 0.106(0.360 − 1.20x + x )

Collecting terms on one side of the equation,

2
0.894 x + 0.127x − 0.0382 = 0

This equation can be solved using the quadratic formula:

− − −−−−− − −−−−−−−−−−−−−−−−−−−−− −
2 2
−b ± √ b − 4ac −0.127 ± √ (0.127 ) − 4(0.894)(−0.0382)
x = =
2a 2(0.894)

x = 0.148 and − 0.290

Only the answer with the positive value has any physical significance, so Δ[ H2 O] = Δ[C O] = +0.148M , and
Δ[ H ] = Δ[C O ] = −0.148 M .
2 2

C The final concentrations of all species in the reaction mixture are as follows:
[ H2 ]f [= [ H2 ]i + Δ[ H2 ] = 0.570 M − 0.148 M = 0.422M

[C O2 ]f = [C O2 ]i + Δ[C O2 ] = 0.632 M − 0.148 M = 0.484M

[ H2 O]f = [ H2 O]i + Δ[ H2 O] = 0 M + 0.148 M = 0.148 M

[C O]f = [C O]i + Δ[C O] = 0M + 0.148 M = 0.148M

We can check our work by substituting these values into the equilibrium constant expression:
2
[ H2 O][C O] (0.148)
K = = = 0.107
[ H2 ][C O2 ] (0.422)(0.484)

Because K is essentially the same as the value given in the problem, our calculations are confirmed.

 Exercise 5.5.4
The exercise in Example 5.5.1 showed the reaction of hydrogen and iodine vapor to form hydrogen iodide, for which K = 54
at 425°C. If a sample containing 0.200 M H and 0.0450 M I is allowed to equilibrate at 425°C, what is the final
2 2

concentration of each substance in the reaction mixture?

Answer
[ HI ]f = 0.0882 M

[ H2 ]f = 0.156 M

−4
[ I2 ]f = 9.2 × 10 M

5.5.8 https://chem.libretexts.org/@go/page/43445
In many situations it is not necessary to solve a quadratic (or higher-order) equation. Most of these cases involve reactions for
which the equilibrium constant is either very small (K ≤ 10 ) or very large (K ≥ 10 ), which means that the change in the
−3 3

concentration (defined as x) is essentially negligible compared with the initial concentration of a substance. Knowing this
simplifies the calculations dramatically, as illustrated in Example 5.5.5.

 Example 5.5.5

Atmospheric nitrogen and oxygen react to form nitric oxide:

N (g) + O (g) ⇌ 2 NO(g) (5.5.8)
2 2

with K p = 2.0 × 10
−31
at 25°C.
What is the partial pressure of NO in equilibrium with N2 and O2 in the atmosphere (at 1 atm) PN
2
= 0.78 atm and
PO2= 0.21 atm ?

Given: balanced equilibrium equation and values of K , P , and P p O2 N2

Asked for: partial pressure of NO

Strategy:
A. Construct a table and enter the initial partial pressures, the changes in the partial pressures that occur during the course of the
reaction, and the final partial pressures of all substances.
B. Write the equilibrium equation for the reaction. Then substitute values from the table to solve for the change in concentration
(x).
C. Calculate the partial pressure of N O . Check your answer by substituting values into the equilibrium equation and solving for
K.

Solution
A Because we are given Kp and partial pressures are reported in atmospheres, we will use partial pressures. The initial partial
pressure of O is 0.21 atm and that of N is 0.78 atm. If we define the change in the partial pressure of N O as 2x, then the change
2 2

in the partial pressure of O and of N is −x because 1 mol each of N and of O is consumed for every 2 mol of NO produced.
2 2 2 2

Each substance has a final partial pressure equal to the sum of the initial pressure and the change in that pressure at equilibrium.
N (g) + O (g) ⇌ 2 NO(g) (5.5.9)
2 2

ICE PN
2
PO
2
PN O

Initial 0.78 0.21 0

Change −x −x +2x

Final (0.78 − x) (0.21 − x) 2x

B Substituting these values into the equation for the equilibrium constant,
2 2
(PN O ) (2x)
−31
Kp = = = 2.0 × 10
(PN )(PO ) (0.78 − x)(0.21 − x)
2 2

In principle, we could multiply out the terms in the denominator, rearrange, and solve the resulting quadratic equation. In practice,
it is far easier to recognize that an equilibrium constant of this magnitude means that the extent of the reaction will be very small;
therefore, the x value will be negligible compared with the initial concentrations. If this assumption is correct, then to two
significant figures, (0.78 − x) = 0.78 and (0.21 − x) = 0.21. Substituting these expressions into our original equation,
2
(2x)
−31
= 2.0 × 10
(0.78)(0.21)

5.5.9 https://chem.libretexts.org/@go/page/43445
 2
4x −31
= 2.0 × 10
0.16

−31
0.33 × 10
2
x =
4

= −17
x 9.1 × 10

C Substituting this value of x into our expressions for the final partial pressures of the substances,
−16
PN O = 2x atm = 1.8 × 10 atm

PN = (0.78 − x) atm = 0.78 atm

2

PO = (0.21 − x) atm = 0.21 atm

2

From these calculations, we see that our initial assumption regarding x was correct: given two significant figures, 2.0 × 10 is −16

certainly negligible compared with 0.78 and 0.21. When can we make such an assumption? As a general rule, if x is less than about
5% of the total, or 10 > K > 10 , then the assumption is justified. Otherwise, we must use the quadratic formula or some other
−3 3

approach. The results we have obtained agree with the general observation that toxic N O , an ingredient of smog, does not form
from atmospheric concentrations of N and O to a substantial degree at 25°C. We can verify our results by substituting them into
2 2

the original equilibrium equation:

2 −16 2
(PN O ) (1.8 × 10 )
−31
Kp = = = 2.0 × 10
(PN )(PO ) (0.78)(0.21)
2 2

The final K agrees with the value given at the beginning of this example.
p

 Exercise 5.5.5

Under certain conditions, oxygen will react to form ozone, as shown in the following equation:

3 O2(g) ⇌ 2 O3(g)

with Kp = 2.5 × 10
−59
at 25°C. What ozone partial pressure is in equilibrium with oxygen in the atmosphere (
PO2 = 0.21 atm )?

Answer
−31
4.8 × 10 atm

Another type of problem that can be simplified by assuming that changes in concentration are negligible is one in which the
equilibrium constant is very large (K ≥ 10^3). A large equilibrium constant implies that the reactants are converted almost entirely
to products, so we can assume that the reaction proceeds 100% to completion. When we solve this type of problem, we view the
system as equilibrating from the products side of the reaction rather than the reactants side. This approach is illustrated in Example
5.5.6.

 Example 5.5.6

The chemical equation for the reaction of hydrogen with ethylene (C 2 H4 ) to give ethane (C 2 H6 ) is as follows:
Ni
H2(g) + C2 H4(g) ⇌ C2 H6(g)

with K = 9.6 × 10 at 25°C. If a mixture of 0.200 M H and 0.155 M C H is maintained at 25°C in the presence of a
18
2 2 4

powdered nickel catalyst, what is the equilibrium concentration of each substance in the mixture?
Given: balanced chemical equation, K , and initial concentrations of reactants
Asked for: equilibrium concentrations
Strategy:
A. Construct a table showing initial concentrations, concentrations that would be present if the reaction were to go to
completion, changes in concentrations, and final concentrations.

5.5.10 https://chem.libretexts.org/@go/page/43445
 B. Write the equilibrium constant expression for the reaction. Then substitute values from the table into the expression to solve
for x (the change in concentration).
C. Calculate the equilibrium concentrations. Check your answers by substituting these values into the equilibrium equation.
Solution:
A From the magnitude of the equilibrium constant, we see that the reaction goes essentially to completion. Because the initial
concentration of ethylene (0.155 M) is less than the concentration of hydrogen (0.200 M), ethylene is the limiting reactant; that
is, no more than 0.155 M ethane can be formed from 0.155 M ethylene. If the reaction were to go to completion, the
concentration of ethane would be 0.155 M and the concentration of ethylene would be 0 M. Because the concentration of
hydrogen is greater than what is needed for complete reaction, the concentration of unreacted hydrogen in the reaction mixture
would be 0.200 M − 0.155 M = 0.045 M. The equilibrium constant for the forward reaction is very large, so the equilibrium
constant for the reverse reaction must be very small. The problem then is identical to that in Example 5.5.5. If we define −x as
the change in the ethane concentration for the reverse reaction, then the change in the ethylene and hydrogen concentrations is
+x. The final equilibrium concentrations are the sums of the concentrations for the forward and reverse reactions.
Ni

H2(g) + C2 H4(g) ⇌ C2 H6(g)

IACE [ H2( g) ] [ C2 H4( g) ] [ C2 H6( g) ]

Initial 0.200 0.155 0

Assuming 100% reaction 0.045 0 0.155

Change +x +x −x

Final (0.045 + x) (0 + x) (0.155 − x)

B Substituting values into the equilibrium constant expression,

[ C2 H6 ] 0.155 − x
18
K = = = 9.6 × 10
[ H2 ][ C2 H4 ] (0.045 + x)x

Once again, the magnitude of the equilibrium constant tells us that the equilibrium will lie far to the right as written, so the
reverse reaction is negligible. Thus x is likely to be very small compared with either 0.155 M or 0.045 M, and the equation can
be simplified [(0.045 + x) = 0.045 and (0.155 − x) = 0.155] as follows:
0.155
18
K = = 9.6 × 10
0.045x

−19
x = 3.6 × 10

C The small x value indicates that our assumption concerning the reverse reaction is correct, and we can therefore calculate the
final concentrations by evaluating the expressions from the last line of the table:
[ C2 H6 ]f = (0.155 − x) M = 0.155 M
−19
[ C2 H4 ]f = x M = 3.6 × 10 M

[ H2 ]f = (0.045 + x) M = 0.045 M

We can verify our calculations by substituting the final concentrations into the equilibrium constant expression:
[ C2 H6 ] 0.155
18
K = = = 9.6 × 10
−19
[ H2 ][ C2 H4 ] (0.045)(3.6 × 10 )

This K value agrees with our initial value at the beginning of the example.

 Exercise 5.5.6
Hydrogen reacts with chlorine gas to form hydrogen chloride:

H2(g) + C l2(g) ⇌ 2H C l(g)

5.5.11 https://chem.libretexts.org/@go/page/43445
 with K = 4.0 × 10 at 47°C. If a mixture of 0.257 M
p
31
H2 and 0.392 M C l2 is allowed to equilibrate at 47°C, what is the
equilibrium composition of the mixture?

Answer
−32
[ H2 ]f = 4.8 × 10 M

[C l2 ]f = 0.135 M

[H C l]f = 0.514 M

5.5.3: Summary
Various methods can be used to solve the two fundamental types of equilibrium problems:
1. those in which we calculate the concentrations of reactants and products at equilibrium and
2. those in which we use the equilibrium constant and the initial concentrations of reactants to determine the composition of the
equilibrium mixture.
When an equilibrium constant is calculated from equilibrium concentrations, molar concentrations or partial pressures are
substituted into the equilibrium constant expression for the reaction. Equilibrium constants can be used to calculate the equilibrium
concentrations of reactants and products by using the quantities or concentrations of the reactants, the stoichiometry of the balanced
chemical equation for the reaction, and a tabular format to obtain the final concentrations of all species at equilibrium.

5.5: Gas-Phase and Heterogeneous Reaction Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

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5.6: The Direction of Change in Chemical Reactions: Empirical Description
 Learning Objectives
To predict in which direction a reaction will proceed.
Describe the ways in which an equilibrium system can be stressed
Predict the response of a stressed equilibrium using Le Chatelier’s principle

We previously saw that knowing the magnitude of the equilibrium constant under a given set of conditions allows chemists to
predict the extent of a reaction. Often, however, chemists must decide whether a system has reached equilibrium or if the
composition of the mixture will continue to change with time. In this section, we describe how to quantitatively analyze the
composition of a reaction mixture to make this determination.

5.6.1: The Reaction Quotient

To determine whether a system has reached equilibrium, chemists use a quantity called the Reaction Quotient (Q). The expression
for the Reaction Quotient has precisely the same form as the equilibrium constant expression from the Law of Mass Action, except
that Q may be derived from a set of values measured at any time during the reaction of any mixture of the reactants and the
products, regardless of whether the system is at equilibrium. Therefore, for the following general reaction:

aA + bB → cC + dD (5.6.1)

the Reaction Quotient is defined as follows:

c d
[C ] [D]
Q = (5.6.2)
a b
[A] [B]

To understand how information is obtained using a Reaction Quotient, consider the dissociation of dinitrogen tetroxide to nitrogen
dioxide,
N O (g) ⇌ 2 NO (g). (5.6.3)
2 4 2

For this reaction, K = 4.65 × 10 −3

at 298 K. We can write Q for this reaction as follows:
2
[N O2 ]
Q = (5.6.4)
[ N2 O4 ]

The following table lists data from three experiments in which samples of the reaction mixture were obtained and analyzed at
equivalent time intervals, and the corresponding values of Q were calculated for each. Each experiment begins with different
proportions of product and reactant:
Table 5.6.1 : Three Conditions of the dissociation of dinitrogen tetroxide to nitrogen dioxide (Equation 5.6.1 )
2 2
[N O ]
Experiment [N O2 ] (M ) [ N2 O4 ] (M ) Q =
2 4
[N O ]

2
0
1 0 0.0400 = 0
0.0400

2
(0.0600)
2 0.0600 0 = undefined
0

2
(0.0200)
3 0.0200 0.0600 = 6.67 × 10
−3

0.0600

As these calculations demonstrate, Q can have any numerical value between 0 and infinity (undefined); that is, Q can be greater
than, less than, or equal to K.
Comparing the magnitudes of Q and K enables us to determine whether a reaction mixture is already at equilibrium and, if it is not,
predict how its composition will change with time to reach equilibrium (i.e., whether the reaction will proceed to the right or to the
left as written). All you need to remember is that the composition of a system not at equilibrium will change in a way that makes Q
approach K. If Q = K , for example, then the system is already at equilibrium, and no further change in the composition of the

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system will occur unless the conditions are changed. If Q < K , then the ratio of the concentrations of products to the
concentrations of reactants is less than the ratio at equilibrium. Therefore, the reaction will proceed to the right as written, forming
products at the expense of reactants. Conversely, if Q > K , then the ratio of the concentrations of products to the concentrations of
reactants is greater than at equilibrium, so the reaction will proceed to the left as written, forming reactants at the expense of
products. These points are illustrated graphically in Figure 5.6.1.

Figure 5.6.1 : Two Different Ways of Illustrating How the Composition of a System Will Change Depending on the Relative Values
of Q and K.(a) Both Q and K are plotted as points along a number line: the system will always react in the way that causes Q to
approach K. (b) The change in the composition of a system with time is illustrated for systems with initial values of Q > K ,
Q < K , and Q = K .

If Q <K , the reaction will proceed to the right as written. If Q >K , the reaction will proceed to the left as written. If
Q =K , then the system is at equilibrium.

 Example 5.6.1: steam-reforming

At elevated temperatures, methane (C H ) reacts with water to produce hydrogen and carbon monoxide in what is known as a
4

steam-reforming reaction:

CH (g) + H O(g) ⇌ CO(g) + 3 H (g)

4 2 2

K = 2.4 × 10
−4
at 900 K. Huge amounts of hydrogen are produced from natural gas in this way and are then used for the
industrial synthesis of ammonia. If 1.2 × 10 mol of C H , 8.0 × 10
−2
4 mol of H O, 1.6 × 10
−3
2mol of C O, and
−2

6.0 × 10
−3
mol of H are placed in a 2.0 L steel reactor and heated to 900 K, will the reaction be at equilibrium or will it
2

proceed to the right to produce C O and H or to the left to form C H and H O?

2 4 2

Given: balanced chemical equation, K , amounts of reactants and products, and volume
Asked for: direction of reaction
Strategy:
A. Calculate the molar concentrations of the reactants and the products.
B. Use Equation 5.6.2 to determine Q. Compare Q and K to determine in which direction the reaction will proceed.
Solution:
A: We must first find the initial concentrations of the substances present. For example, we have 1.2 × 10
−2
mol of C H in a
4

2.0 L container, so
−2
1.2 × 10 mol
[C H4 ] =
2.0 L

−3
= 6.0 × 10 M

We can calculate the other concentrations in a similar way:

[ H2 O] = 4.0 × 10
−3
M ,

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 [C O] = 8.0 × 10
−3
M , and
[ H2 ] = 3.0 × 10
−3
M .
B: We now compute Q and compare it with K :
3
[C O][H2 ]
Q =
[C H4 ][ H2 O]

−3 −3 3
(8.0 × 10 )(3.0 × 10 )
=
−3 −3
(6.0 × 10 )(4.0 × 10 )

−6
= 9.0 × 10

Because K = 2.4 × 10 , we see that Q < K . Thus the ratio of the concentrations of products to the concentrations of
−4

reactants is less than the ratio for an equilibrium mixture. The reaction will therefore proceed to the right as written, forming
H and CO at the expense of H O and C H . 2 4
2

 Exercise 5.6.1

In the water–gas shift reaction introduced in Example 5.6.1, carbon monoxide produced by steam-reforming reaction of
methane reacts with steam at elevated temperatures to produce more hydrogen:

CO(g) + H O(g) ⇌ CO (g) + H (g)

2 2 2

K = 0.64 at 900 K. If 0.010 mol of both CO and H O , 0.0080 mol of CO , and 0.012 mol of
2 2
H
2
are injected into a 4.0 L
reactor and heated to 900 K, will the reaction proceed to the left or to the right as written?

Answer
Q = 0.96 (Q > K), so the reaction will proceed to the left, and C O and H 2O will form.

5.6.2: Predicting the Direction of a Reaction with a Graph

By graphing a few equilibrium concentrations for a system at a given temperature and pressure, we can readily see the range of
reactant and product concentrations that correspond to equilibrium conditions, for which Q = K . Such a graph allows us to predict
what will happen to a reaction when conditions change so that Q no longer equals K , such as when a reactant concentration or a
product concentration is increased or decreased.
Lead carbonate decomposes to lead oxide and carbon dioxide according to the following equation:
PbCO (s) ⇌ PbO(s) + CO (g) (5.6.5)
3 2

Because P bC O and P bO are solids, the equilibrium constant is simply K = [C O ] . At a given temperature, therefore, any
3 2

system that contains solid P bC O and solid P bO will have exactly the same concentration of C O at equilibrium, regardless of
3 2

the ratio or the amounts of the solids present. This situation is represented in Figure 5.6.2, which shows a plot of [C O ] versus the 2

amount of P bC O added. Initially, the added P bC O decomposes completely to C O because the amount of P bC O is not
3 3 2 3

sufficient to give a C O concentration equal to K . Thus the left portion of the graph represents a system that is not at equilibrium
2

because it contains only CO2(g) and PbO(s). In contrast, when just enough P bC O has been added to give [C O ] = K , the 3 2

system has reached equilibrium, and adding more P bC O has no effect on the C O concentration: the graph is a horizontal line.
3 2

Thus any C O concentration that is not on the horizontal line represents a nonequilibrium state, and the system will adjust its
2

composition to achieve equilibrium, provided enough P bC O and P bO are present. For example, the point labeled A in Figure
3

5.6.2 lies above the horizontal line, so it corresponds to a [C O ] that is greater than the equilibrium concentration of C O (Q > K).
2 2

To reach equilibrium, the system must decrease [C O ], which it can do only by reacting C O with solid P bO to form solid
2 2

P bC O . Thus the reaction in Equation 5.6.5 will proceed to the left as written, until [C O ] = K . Conversely, the point labeled B
3 2

in Figure 5.6.2 lies below the horizontal line, so it corresponds to a [C O ] that is less than the equilibrium concentration of C O
2 2

(Q < K). To reach equilibrium, the system must increase [C O ], which it can do only by decomposing solid P bC O to form C O
2 3 2

and solid P bO. The reaction in Equation 5.6.5 will therefore proceed to the right as written, until [C O ] = K . 2

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 Figure 5.6.2 : The Concentration of Gaseous C O in a Closed System at Equilibrium as a Function of the Amount of Solid P bC O
2 3

Added. Initially the concentration of CO2(g) increases linearly with the amount of solid P bC O added, as P bC O decomposes to
3 3

CO2(g) and solid PbO. Once the C O concentration reaches the value that corresponds to the equilibrium concentration, however,
2

adding more solid P bC O has no effect on [C O ] , as long as the temperature remains constant.
3 2

In contrast, the reduction of cadmium oxide by hydrogen gives metallic cadmium and water vapor:
CdO(s) + H (g) ⇌ Cd(s) + H O(g) (5.6.6)
2 2

and the equilibrium constant K is [H O]/[H ]. If [H O] is doubled at equilibrium, then [H2] must also be doubled for the system
2 2 2

to remain at equilibrium. A plot of [H O] versus [H ] at equilibrium is a straight line with a slope of K (Figure 5.6.3). Again, only
2 2

those pairs of concentrations of H O and H that lie on the line correspond to equilibrium states. Any point representing a pair of
2 2

concentrations that does not lie on the line corresponds to a nonequilibrium state. In such cases, the reaction in Equation 5.6.6 will
proceed in whichever direction causes the composition of the system to move toward the equilibrium line. For example, point A in
Figure 5.6.3 lies below the line, indicating that the [H O]/[H ] ratio is less than the ratio of an equilibrium mixture (Q < K). Thus
2 2

the reaction in Equation 5.6.6 will proceed to the right as written, consuming H and producing H O, which causes the
2 2

concentration ratio to move up and to the left toward the equilibrium line. Conversely, point B in Figure 5.6.3 lies above the line,
indicating that the [H O]/[H ] ratio is greater than the ratio of an equilibrium mixture (Q > K). Thus the reaction in Equation
2 2

5.6.6 will proceed to the left as written, consuming H O and producing H , which causes the concentration ratio to move down
2 2

and to the right toward the equilibrium line.

Figure 5.6.3 : The

Concentration of Water Vapor versus the Concentration of Hydrogen for the
C dO(s) + H2(g) ⇌ C d(s) + H2 O(g) System at Equilibrium. For any equilibrium concentration of H O , there is only one
2 (g)

equilibrium concentration of H2(g). Because the magnitudes of the two concentrations are directly proportional, a large [H O] at
2

equilibrium requires a large [H ] and vice versa. In this case, the slope of the line is equal to K.
2

In another example, solid ammonium iodide dissociates to gaseous ammonia and hydrogen iodide at elevated temperatures:
N H4 I(s) ⇌ N H3(g) + H I(g) (5.6.7)

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For this system, K is equal to the product of the concentrations of the two products: [N H ][H I ]. If we double the concentration of
3

NH3, the concentration of HI must decrease by approximately a factor of 2 to maintain equilibrium, as shown in Figure 5.6.4. As a
result, for a given concentration of either H I or N H , only a single equilibrium composition that contains equal concentrations of
3

both N H and HI is possible, for which [N H ] = [H I ] = K . Any point that lies below and to the left of the equilibrium curve
3 3
1/2

(such as point A in Figure 5.6.4) corresponds to Q < K , and the reaction in Equation 5.6.7 will therefore proceed to the right as
written, causing the composition of the system to move toward the equilibrium line. Conversely, any point that lies above and to the
right of the equilibrium curve (such as point B in Figure 5.6.4) corresponds to Q > K , and the reaction in Equation 5.6.7 will
therefore proceed to the left as written, again causing the composition of the system to move toward the equilibrium line. By
graphing equilibrium concentrations for a given system at a given temperature and pressure, we can predict the direction of reaction
of that mixture when the system is not at equilibrium.

Figure 5.6.4 : The Concentration of N H 3(g)versus the Concentration of H I for the N H I ⇌ N H

(g) 4 (s) + HI
3(g) System at
(g)

Equilibrium. Only one equilibrium concentration of N H 3(g) is possible for any given equilibrium concentration of HI(g). In this
case, the two are inversely proportional. Thus a large [H I] at equilibrium requires a small [N H ] at equilibrium and vice versa.
3

5.6.3: Effect of Change in Pressure on Equilibrium

Sometimes we can change the position of equilibrium by changing the pressure of a system. However, changes in pressure have a
measurable effect only in systems in which gases are involved, and then only when the chemical reaction produces a change in the
total number of gas molecules in the system. An easy way to recognize such a system is to look for different numbers of moles of
gas on the reactant and product sides of the equilibrium. While evaluating pressure (as well as related factors like volume), it is
important to remember that equilibrium constants are defined with regard to concentration (for K ) or partial pressure (for K ).
c p

Some changes to total pressure, like adding an inert gas that is not part of the equilibrium, will change the total pressure but not the
partial pressures of the gases in the equilibrium constant expression. Thus, addition of a gas not involved in the equilibrium will not
perturb the equilibrium.

Volume Effect on Equilibrium - LeChateli…

LeChateli…

Video 5.6.1 : See www.youtube.com/watch?v=pnU7ogsgUW8 to see a dramatic visual demonstration of how equilibrium changes
with pressure changes.

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As we increase the pressure of a gaseous system at equilibrium, either by decreasing the volume of the system or by adding more of
one of the components of the equilibrium mixture, we introduce a stress by increasing the partial pressures of one or more of the
components. In accordance with Le Chatelier's principle, a shift in the equilibrium that reduces the total number of molecules per
unit of volume will be favored because this relieves the stress. The reverse reaction would be favored by a decrease in pressure.
Consider what happens when we increase the pressure on a system in which NO, O , and NO are at equilibrium:
2 2

2 NO(g) + O2(g) ⇌ 2 NO2(g) (5.6.8)

The formation of additional amounts of NO decreases the total number of molecules in the system because each time two
2

molecules of NO form, a total of three molecules of NO and O are consumed. This reduces the total pressure exerted by the
2 2

system and reduces, but does not completely relieve, the stress of the increased pressure. On the other hand, a decrease in the
pressure on the system favors decomposition of NO into NO and O , which tends to restore the pressure.
2 2

Now consider this reaction:

N (g) + O (g) ⇌ 2 NO(g) (5.6.9)
2 2

Because there is no change in the total number of molecules in the system during reaction, a change in pressure does not favor
either formation or decomposition of gaseous nitrogen monoxide.

5.6.4: Effect of Change in Temperature on Equilibrium

Changing concentration or pressure perturbs an equilibrium because the Reaction Quotient is shifted away from the equilibrium
value. Changing the temperature of a system at equilibrium has a different effect: A change in temperature actually changes the
value of the equilibrium constant. However, we can qualitatively predict the effect of the temperature change by treating it as a
stress on the system and applying Le Chatelier's principle.
When hydrogen reacts with gaseous iodine, heat is evolved.

H (g) + I (g) ⇌ 2 HI(g) ΔH = −9.4 kJ (exothermic) (5.6.10)

2 2

Because this reaction is exothermic, we can write it with heat as a product.

H (g) + I (g) ⇌ 2 HI(g) + heat (5.6.11)

2 2

Increasing the temperature of the reaction increases the internal energy of the system. Thus, increasing the temperature has the
effect of increasing the amount of one of the products of this reaction. The reaction shifts to the left to relieve the stress, and there
is an increase in the concentration of H and I and a reduction in the concentration of HI . Lowering the temperature of this
2 2

system reduces the amount of energy present, favors the production of heat, and favors the formation of hydrogen iodide.
When we change the temperature of a system at equilibrium, the equilibrium constant for the reaction changes. Lowering the
temperature in the HI system increases the equilibrium constant: At the new equilibrium the concentration of HI has increased and
the concentrations of H and I decreased. Raising the temperature decreases the value of the equilibrium constant, from 67.5 at
2 2

357 °C to 50.0 at 400 °C.

Temperature affects the equilibrium between NO and N 2 2
O
4
in this reaction
N O4(g) ⇌ 2 NO2(g) ΔH = 57.20 kJ (5.6.12)
2

The positive ΔH value tells us that the reaction is endothermic and could be written
heat + N O4(g) ⇌ 2 NO2(g) (5.6.13)
2

At higher temperatures, the gas mixture has a deep brown color, indicative of a significant amount of brown NO molecules. If, 2

however, we put a stress on the system by cooling the mixture (withdrawing energy), the equilibrium shifts to the left to supply
some of the energy lost by cooling. The concentration of colorless N O increases, and the concentration of brown NO
2 4 2

decreases, causing the brown color to fade.

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  Temperature is Neither a Reactant nor Product
It is not uncommon that textbooks and instructors to consider heat as a independent "species" in a reaction. While this is
rigorously incorrect because one cannot "add or remove heat" to a reaction as with species, it serves as a convenient
mechanism to predict the shift of reactions with changing temperature. For example, if heat is a "reactant" (ΔH > 0 ), then the
reaction favors the formation of products at elevated temperature. Similarly, if heat is a "product" (ΔH < 0 ), then the reaction
favors the formation of reactants. A more accurate, and hence preferred, description is discussed below.

 Example 5.6.2: Steam Reforming of Methane

The commercial production of hydrogen is carried out by treating natural gas with steam at high temperatures and in the
presence of a catalyst (“steam reforming of methane”):

CH +H O −
↽⇀
− CH OH + H
4 2 3 2

Given the following boiling points: CH4 (methane) = –161°C, H2O = 100°C, CH3OH = 65°, H2 = –253°C, predict the effects
of an increase in the total pressure on this equilibrium at 50°, 75° and 120°C.
Solution
To identify the influence of changing pressure on the three reaction conditions, we need to identify the correct reaction
including the phase of each reactant and product. Calculate the change in the moles of gas for each process:

Temperature

Equation
Δng

shift
50° [CH 4
(g) + H O(l) → CH OH(l) + H (g)
2 3 2
0 none 75° CH (g) + H 4 2
O(l) → CH OH(g) + H (g)
3 2
+1 to left 120°
CH (g) + H O(g) → CH OH(g) + H (g)
4 2 3 2
0 none

 Exercise 5.6.2
What will happen to the equilibrium when the volume of the system is decreased?

2 SO (g) + O (g) ⇌ 2 SO (g)

2 2 3

Answer
Decreasing the volume leads to an increase in pressure which will cause the equilibrium to shift towards the side with fewer
moles. In this reaciton, there are three moles on the reactant side and two moles on the product side, so the new equilibrium
will shift towards the products (to the right).

5.6.5: Summary
The Reaction Quotient (Q) is used to determine whether a system is at equilibrium and if it is not, to predict the direction of
reaction. Reaction Quotient:
c d
[C ] [D]
Q =
a b
[A] [B]

The Reaction Quotient (Q or Q ) has the same form as the equilibrium constant expression, but it is derived from concentrations
p

obtained at any time. When a reaction system is at equilibrium, Q = K . Graphs derived by plotting a few equilibrium
concentrations for a system at a given temperature and pressure can be used to predict the direction in which a reaction will
proceed. Points that do not lie on the line or curve represent nonequilibrium states, and the system will adjust, if it can, to achieve
equilibrium.
Systems at equilibrium can be disturbed by changes to temperature, concentration, and, in some cases, volume and pressure;
volume and pressure changes will disturb equilibrium if the number of moles of gas is different on the reactant and product sides of

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the reaction. The system's response to these disturbances is described by Le Chatelier's principle: The system will respond in a way
that counteracts the disturbance. Not all changes to the system result in a disturbance of the equilibrium. Adding a catalyst affects
the rates of the reactions but does not alter the equilibrium, and changing pressure or volume will not significantly disturb systems
with no gases or with equal numbers of moles of gas on the reactant and product side.
Effects of Disturbances of Equilibrium and K
Observed Change as
Disturbance Direction of Shift Effect on K
Equilibrium is Restored

added reactant is partially

reactant added toward products none
consumed

added product is partially

product added toward reactants none
consumed

decrease in volume/increase in gas toward side with fewer moles of

pressure decreases none
pressure gas

increase in volume/decrease in gas toward side with more moles of

pressure increases none
pressure gas

toward products for endothermic,

temperature increase heat is absorbed changes
toward reactants for exothermic

toward reactants for endothermic,

temperature decrease heat is given off changes
toward products for exothermic

5.6.6: Footnotes
1. 1 Herrlich, P. “The Responsibility of the Scientist: What Can History Teach Us About How Scientists Should Handle Research
That Has the Potential to Create Harm?” EMBO Reports 14 (2013): 759–764.

5.6.7: Glossary
Le Chatelier's principle
when a chemical system at equilibrium is disturbed, it returns to equilibrium by counteracting the disturbance

position of equilibrium
concentrations or partial pressures of components of a reaction at equilibrium (commonly used to describe conditions before a
disturbance)

stress
change to a reaction's conditions that may cause a shift in the equilibrium

5.6.8: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

This page titled 5.6: The Direction of Change in Chemical Reactions: Empirical Description is shared under a CC BY license and was authored,
remixed, and/or curated by OpenStax.

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5.7: The Direction of Change in Chemical Reactions - Thermodynamic Explanation
 Learning Objectives
To know the relationship between free energy and the equilibrium constant.

We have identified three criteria for whether a given reaction will occur spontaneously:
ΔSuniv > 0 (2nd law of thermodynamics),
ΔGsys < 0 (Gibbs Energy version), and
the relative magnitude of the reaction quotient Q versus the equilibrium constant K .
Recall that if Q < K , then the reaction proceeds spontaneously to the right as written, resulting in the net conversion of reactants
to products. Conversely, if Q > K , then the reaction proceeds spontaneously to the left as written, resulting in the net conversion
of products to reactants. If Q = K , then the system is at equilibrium, and no net reaction occurs. Table 5.7.1 summarizes these
criteria and their relative values for spontaneous, nonspontaneous, and equilibrium processes.
Table 5.7.1 : Criteria for the Spontaneity of a Process as Written
Spontaneous Equilibrium Nonspontaneous*

ΔSuniv > 0 ΔSuniv = 0 ΔSuniv < 0

ΔGsys < 0 ΔGsys = 0 ΔGsys > 0

Q<K Q=K Q>K

*Spontaneous in the reverse direction.

Because all three criteria assess the same thing—the spontaneity of the process—it would be most surprising indeed if they were
not related. In this section, we explore the relationship between the standard free energy of reaction (ΔG°) and the equilibrium
constant (K ).

5.7.1: Free Energy and the Equilibrium Constant

Because ΔH° and ΔS° determine the magnitude of ΔG° and because K is a measure of the ratio of the concentrations of products to
the concentrations of reactants, we should be able to express K in terms of ΔG° and vice versa. "Free Energy", ΔG is equal to the
maximum amount of work a system can perform on its surroundings while undergoing a spontaneous change. For a reversible
process that does not involve external work, we can express the change in free energy in terms of volume, pressure, entropy, and
temperature, thereby eliminating ΔH from the equation for ΔG. The general relationship can be shown as follow (derivation not
shown):
ΔG = V ΔP − SΔT (5.7.1)

If a reaction is carried out at constant temperature (ΔT =0 ), then Equation 5.7.1 simplifies to
ΔG = V ΔP (5.7.2)

Under normal conditions, the pressure dependence of free energy is not important for solids and liquids because of their small
molar volumes. For reactions that involve gases, however, the effect of pressure on free energy is very important.
Assuming ideal gas behavior, we can replace the V in Equation 5.7.2 by nRT/P (where n is the number of moles of gas and R is the
ideal gas constant) and express ΔG in terms of the initial and final pressures (P and P , respectively):
i f

nRT
ΔG = ( ) ΔP (5.7.3)
P

ΔP Pf
= nRT = nRT ln( ) (5.7.4)
P Pi

If the initial state is the standard state with Pi = 1 atm, then the change in free energy of a substance when going from the standard
state to any other state with a pressure P can be written as follows:

5.7.1 https://chem.libretexts.org/@go/page/43447
 ∘
G−G = nRT ln P (5.7.5)

This can be rearranged as follows:

∘
G=G + nRT ln P (5.7.6)

As you will soon discover, Equation 5.7.6 allows us to relate ΔG and K . Any relationship that is true for K must also be true
o
p p

for K because K and K are simply different ways of expressing the equilibrium constant using different units.
p

Let’s consider the following hypothetical reaction, in which all the reactants and the products are ideal gases and the lowercase
letters correspond to the stoichiometric coefficients for the various species:

aA + bB ⇌ cC + dD (5.7.7)

Because the free-energy change for a reaction is the difference between the sum of the free energies of the products and the
reactants, we can write the following expression for ΔG:

ΔG = ∑ Gproducts − ∑ Greactants (5.7.8)

m n

= (c GC + dGD ) − (aGA + b GB ) (5.7.9)

Substituting Equation 5.7.6 for each term into Equation 5.7.9,

o o o o
ΔG = [(c G + cRT ln PC ) + (dG + dRT ln PD )] − [(aG + aRT ln PA ) + (b G + bRT ln PB )] (5.7.10)
C D A B

Combining terms gives the following relationship between ΔG and the reaction quotient Q:
c d
P P
∘ C D
ΔG = ΔG + RT ln( ) (5.7.11)
a b
P P
A B

∘
= ΔG + RT ln Q (5.7.12)

where ΔG° indicates that all reactants and products are in their standard states. For gases at equilibrium (Q = K ,), and as you’ve p

learned in this chapter, ΔG = 0 for a system at equilibrium. Therefore, we can describe the relationship between ΔG and K for o
p

gases as follows:
0 = ΔG° + RT ln Kp (5.7.13)

ΔG° = −RT ln Kp (5.7.14)

If the products and reactants are in their standard states and ΔG° < 0, then Kp > 1, and products are favored over reactants.
Conversely, if ΔG° > 0, then Kp < 1, and reactants are favored over products. If ΔG° = 0, then K = 1 , and neither reactants nor
p

products are favored: the system is at equilibrium.

For a spontaneous process under standard conditions, K eq

and K are greater than 1.
p

To further illustrate the relation between these two essential thermodynamic concepts, consider the observation that reactions
spontaneously proceed in a direction that ultimately establishes equilibrium. As may be shown by plotting the free energy change
versus the extent of the reaction (for example, as reflected in the value of Q), equilibrium is established when the system’s free
energy is minimized (Figure 5.7.3). If a system is present with reactants and products present in nonequilibrium amounts (Q ≠ K),
the reaction will proceed spontaneously in the direction necessary to establish equilibrium.

5.7.2 https://chem.libretexts.org/@go/page/43447
 Figure 5.7.1 : These plots show the free energy versus reaction progress for systems whose standard free changes are (a) negative,
(b) positive, and (c) zero. Nonequilibrium systems will proceed spontaneously in whatever direction is necessary to minimize free
energy and establish equilibrium. (CC BY 4.0; OpenStax).

 Example 5.7.2

ΔG
o
is −32.7 kJ/mol of N2 for the reaction

N (g) + 3 H (g) ⇌ 2 NH (g)

2 2 3

This calculation was for the reaction under standard conditions—that is, with all gases present at a partial pressure of 1 atm and
a temperature of 25°C. Calculate ΔG for the same reaction under the following nonstandard conditions:
PN = 2.00 atm,
2

P = 7.00 atm,
H2

P = 0.021 atm,
NH3

and T = 100°C.
Does the reaction favor products or reactants?
Given: balanced chemical equation, partial pressure of each species, temperature, and ΔG°
Asked for: whether products or reactants are favored
Strategy:
A. Using the values given and Equation 5.7.12, calculate Q.
B. Substitute the values of ΔG° and Q into Equation 5.7.12 to obtain ΔG for the reaction under nonstandard conditions.
Solution:
A The relationship between ΔG° and ΔG under nonstandard conditions is given in Equation 5.7.12. Substituting the partial
pressures given, we can calculate Q:
2 2
P (0.021)
NH3 −7
Q = = = 6.4 × 10
3 3
PN2 P (2.00)(7.00)
H2

B Substituting the values of ΔG° and Q into Equation 5.7.12,

∘
ΔG = ΔG + RT ln Q

1 kJ
−7
= −32.7 kJ + [(8.314 J/K)(373 K) ( ) ln(6.4 × 10 )]
1000 J

= −32.7 kJ + (−44 kJ)

= −77 kJ/mol of N
2

Because ΔG < 0 and Q < 1.0, the reaction is spontaneous to the right as written, so products are favored over reactants.

5.7.3 https://chem.libretexts.org/@go/page/43447
  Exercise 5.7.2
Calculate ΔG for the reaction of nitric oxide with oxygen to give nitrogen dioxide under these conditions: T = 50°C, PNO =
0.0100 atm, P = 0.200 atm, and P
O2 NO2 = 1.00 × 10−4 atm. The value of ΔG° for this reaction is −72.5 kJ/mol of O2. Are
products or reactants favored?

Answer
−92.9 kJ/mol of O2; the reaction is spontaneous to the right as written, so products are favored.

 Example 5.7.3

Calculate Kp for the reaction of H2 with N2 to give NH3 at 25°C. ΔG for this reaction is −32.7 kJ/mol of N2.
o

Given: balanced chemical equation from Example 5.7.2, ΔG°, and temperature
Asked for: Kp
Strategy:
Substitute values for ΔG° and T (in kelvin) into Equation 5.7.14 to calculate K , the equilibrium constant for the formation of
p

ammonia.

Solution
In Example 10, we used tabulated values of ΔG∘f to calculate ΔG° for this reaction (−32.7 kJ/mol of N2). For equilibrium
conditions, rearranging Equation 5.7.14,
∘
ΔG = −RT ln Kp

∘
−ΔG
= ln Kp
RT

Inserting the value of ΔG° and the temperature (25°C = 298 K) into this equation,
(−32.7 kJ)(1000 J/kJ)
ln Kp = − = 13.2
(8.314 J/K)(298 K)

5
Kp = 5.4 × 10

Thus the equilibrium constant for the formation of ammonia at room temperature is favorable. However, the rate at which the
reaction occurs at room temperature is too slow to be useful.

 Exercise 5.7.3

Calculate Kp for the reaction of NO with O2 to give NO2 at 25°C. ΔG° for this reaction is −70.5 kJ/mol of O2.

Answer
2.2 × 1012

Although K is defined in terms of the partial pressures of the reactants and the products, the equilibrium constant K is defined in
p

terms of the concentrations of the reactants and the products. We described the relationship between the numerical magnitude of \
(K_p\) and K previously and showed that they are related:
Δn
Kp = K(RT ) (5.7.15)

where Δn is the number of moles of gaseous product minus the number of moles of gaseous reactant. For reactions that involve
only solutions, liquids, and solids, Δn = 0 , so K = K . For all reactions that do not involve a change in the number of moles of
p

gas present, the relationship in Equation 5.7.14 can be written in a more general form:

5.7.4 https://chem.libretexts.org/@go/page/43447
 ΔG° = −RT ln K (5.7.16)

Only when a reaction results in a net production or consumption of gases is it necessary to correct Equation 5.7.16 for the
difference between K and K . Although we typically use concentrations or pressures in our equilibrium calculations, recall that
p

equilibrium constants are generally expressed as unitless numbers because of the use of activities or fugacities in precise
thermodynamic work. Systems that contain gases at high pressures or concentrated solutions that deviate substantially from ideal
behavior require the use of fugacities or activities, respectively.
Combining Equations 5.7.16 with ΔG o
= ΔH
o
− T ΔS
o
provides insight into how the components of ΔG° influence the
magnitude of the equilibrium constant:
ΔG° = ΔH ° − T ΔS° = −RT ln K (5.7.17)

Notice that K becomes larger as ΔS° becomes more positive, indicating that the magnitude of the equilibrium constant is directly
influenced by the tendency of a system to move toward maximum disorder. Moreover, K increases as ΔH° decreases. Thus the
magnitude of the equilibrium constant is also directly influenced by the tendency of a system to seek the lowest energy state
possible.

The magnitude of the equilibrium constant is directly influenced by the tendency of a

system to move toward maximum disorder and seek the lowest energy state possible.

5.7.2: Temperature Dependence of the Equilibrium Constant

The fact that ΔG° and K are related provides us with another explanation of why equilibrium constants are temperature dependent.
This relationship is shown explicitly in Equation 5.7.17, which can be rearranged as follows:
∘ ∘
ΔH ΔS
ln K = − + (5.7.18)
RT R

Assuming ΔH° and ΔS° are temperature independent, for an exothermic reaction (ΔH° < 0), the magnitude of K decreases with
increasing temperature, whereas for an endothermic reaction (ΔH° > 0), the magnitude of K increases with increasing temperature.
The quantitative relationship expressed in Equation 5.7.18 agrees with the qualitative predictions made by applying Le Chatelier’s
principle. Because heat is produced in an exothermic reaction, adding heat (by increasing the temperature) will shift the equilibrium
to the left, favoring the reactants and decreasing the magnitude of K. Conversely, because heat is consumed in an endothermic
reaction, adding heat will shift the equilibrium to the right, favoring the products and increasing the magnitude of K. Equation
5.7.18 also shows that the magnitude of ΔH° dictates how rapidly K changes as a function of temperature. In contrast, the

magnitude and sign of ΔS° affect the magnitude of K but not its temperature dependence.
If we know the value of K at a given temperature and the value of ΔH° for a reaction, we can estimate the value of K at any other
temperature, even in the absence of information on ΔS°. Suppose, for example, that K1 and K2 are the equilibrium constants for a
reaction at temperatures T1 and T2, respectively. Applying Equation 5.7.18 gives the following relationship at each temperature:
∘ ∘
−ΔH ΔS
ln K1 = + (5.7.19)
RT1 R

∘ ∘
−ΔH ΔS
ln K2 = + (5.7.20)
RT2 R

Subtracting ln K from ln K ,
1 2

∘
K2 ΔH 1 1
ln K2 − ln K1 = ln = ( − ) (5.7.21)
K1 R T1 T2

Thus calculating ΔH° from tabulated enthalpies of formation and measuring the equilibrium constant at one temperature (K1) allow
us to calculate the value of the equilibrium constant at any other temperature (K2), assuming that ΔH° and ΔS° are independent of
temperature. Equation 5.7.21 is often referred to as the van 't Hoff equation after Dutch chemist Jacobus Henricus van 't Hoff in
1884 in his book Études de Dynamique chimique (Studies in dynamic chemistry).

5.7.5 https://chem.libretexts.org/@go/page/43447
  Example 5.7.4

The equilibrium constant for the formation of NH3 from H2 and N2 at 25°C was calculated to be Kp = 5.4 × 105 in Example
5.7.2. What is Kp at 500°C? (Use the data from Example 5.7.1)

Given: balanced chemical equation, ΔH°, initial and final T, and Kp at 25°C
Asked for: Kp at 500°C
Strategy:
Convert the initial and final temperatures to kelvin. Then substitute appropriate values into Equation 5.7.21 to obtain K2 , the
equilibrium constant at the final temperature.
Solution:
The value of ΔH° for the reaction obtained using Hess’s law is −91.8 kJ/mol of N2. If we set T1 = 25°C = 298 K and T2 =
500°C = 773 K, then from Equation 5.7.21 we obtain the following:
∘
K2 ΔH 1 1
ln = ( − )
K1 R T1 T2

(−91.8 kJ)(1000 J/kJ) 1 1

= ( − ) = −22.8
8.314 J/K 298 K 773 K

K2 −10
= 1.3 × 10
K1

5 −10 −5
K2 = (5.4 × 10 )(1.3 × 10 ) = 7.0 × 10

Thus at 500°C, the equilibrium strongly favors the reactants over the products.

 Exercise 5.7.4

The equilibrium constant for the reaction of NO with O to give NO at 25°C is

2 2
Kp = 2.2 × 1012 . Use the ΔH
f
o
values in
the exercise in Example 5.7.4 to calculate K for this reaction at 1000°C.
p

Answer
5.6 × 10−4

5.7.3: Summary
For a reversible process that does not involve external work, we can express the change in free energy in terms of volume, pressure,
entropy, and temperature. If we assume ideal gas behavior, the ideal gas law allows us to express ΔG in terms of the partial
pressures of the reactants and products, which gives us a relationship between ΔG and Kp, the equilibrium constant of a reaction
involving gases, or K, the equilibrium constant expressed in terms of concentrations. If ΔG° < 0, then K or Kp > 1, and products are
favored over reactants. If ΔG° > 0, then K or Kp < 1, and reactants are favored over products. If ΔG° = 0, then K or Kp = 1, and the
system is at equilibrium. We can use the measured equilibrium constant K at one temperature and ΔH° to estimate the equilibrium
constant for a reaction at any other temperature.

5.7.4: Contributors and Attributions

Mike Blaber (Florida State University)
Anonymous

This page titled 5.7: The Direction of Change in Chemical Reactions - Thermodynamic Explanation is shared under a CC BY-NC-SA 3.0 license
and was authored, remixed, and/or curated by Anonymous.

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5.8: Distribution between Immiscible Phases - Extraction and Separation Processes
A partitioning of a compound exist between a mixture of two immiscible phases at equilibrium, which is a measure of the
difference in solubility of the compound in these two phases. If one of the solvents is a gas and the other a liquid, the "gas/liquid
partition coefficient" is the same as the dimensionless form of the Henry's law constant. A solute can partition when one or both
solvents is a solid (e.g., solid solution).

5.8.1: Liquid-Liquid Extractions

We call the process of moving a species from one phase to another phase an extraction. Simple extractions are particularly useful
for separations where only one component has a favorable partition coefficient. Several important separation techniques are based
on a simple extraction, including liquid–liquid, liquid–solid, solid–liquid, and gas–solid extractions. The most important group of
separation techniques uses a selective partitioning of the solute between two immiscible phases. If we bring a phase containing a
solute, S, into contact with a second phase, the solute partitions itself between the two phases, as shown by the following
equilibrium reaction.
Sphase 1 ⇌ Sphase 2 (5.8.1)

The equilibrium constant for this equilbrium is

[ Sphase 2]
KD = (5.8.2)
[ Sphase 1]

is called the distribution constant or partition coefficient. If K is sufficiently large, then the solute moves from phase 1 to phase
D

2. The solute remains in phase 1 if the partition coefficient is sufficiently small. When we bring a phase containing two solutes into
contact with a second phase, if KD is favorable for only one of the solutes a separation of the solutes is possible. The physical states
of the phases are identified when describing the separation process, with the phase containing the sample listed first. For example,
if the sample is in a liquid phase and the second phase is a solid, then the separation involves liquid–solid partitioning.
It often happens that two immiscible liquid phases are in contact, one of which contains a solute. How will the solute tend to
distribute itself between the two phases? One’s first thought might be that some of the solute will migrate from one phase into the
other until it is distributed equally between the two phases, since this would correspond to the maximum dispersion (randomness)
of the solute. This, however, does not take into the account the differing solubilities the solute might have in the two liquids; if such
a difference does exist, the solute will preferentially migrate into the phase in which it is more soluble (Figure 5.8.1 ).

Figure 5.8.1: Scheme for a simple liquid–liquid extraction in which the solute’s partitioning depends only on the KD equilibrium.

 Biomagnification

The transport of substances between different phases is of immense importance in such diverse fields as pharmacology and
environmental science. For example, if a drug is to pass from the aqueous phase with the stomach into the bloodstream, it must
pass through the lipid (oil-like) phase of the epithelial cells that line the digestive tract. Similarly, a pollutant such as a pesticide
residue that is more soluble in oil than in water will be preferentially taken up and retained by marine organism, especially fish,
whose bodies contain more oil-like substances; this is basically the mechanism whereby such residues as DDT can undergo
biomagnification as they become more concentrated at higher levels within the food chain. For this reason, environmental
regulations now require that oil-water distribution ratios be established for any new chemical likely to find its way into natural
waters. The standard “oil” phase that is almost universally used is octanol, C8H17OH.

5.8.1 https://chem.libretexts.org/@go/page/43448
In preparative chemistry it is frequently necessary to recover a desired product present in a reaction mixture by extracting it into
another liquid in which it is more soluble than the unwanted substances. On the laboratory scale this operation is carried out in a
separatory funnel as shown below. The two immiscible liquids are poured into the funnel through the opening at the top. The
funnel is then shaken to bring the two phases into intimate contact, and then set aside to allow the two liquids to separate into
layers, which are then separated by allowing the more dense liquid to exit through the stopcock at the bottom.

Figure 5.8.2 : A separatory funnel with two solvents.

If the distribution ratio is too low to achieve efficient separation in a single step, it can be repeated; there are automated devices that
can carry out hundreds of successive extractions, each yielding a product of higher purity. In these applications our goal is to
exploit the Le Chatelier principle by repeatedly upsetting the phase distribution equilibrium that would result if two phases were to
remain in permanent contact.

Liquid-liquid extraction (or separation)

Video 5.8.1 : How to perform a liquid-liquid extraction using a separating funnel.

 Example 5.8.1

The distribution ratio for iodine between water and carbon disulfide is 650. Calculate the concentration of I2 remaining in the
aqueous phase after 50.0 mL of 0.10M I2 in water is shaken with 10.0 mL of CS2.

Solution
The equilibrium constant is
CC S
2
Kd = = 650
CH O
2

5.8.2 https://chem.libretexts.org/@go/page/43448
Let m1 and m2 represent the numbers of millimoles of solute in the water and CS2 layers, respectively. Kd can then be written as
(m2/10 mL) ÷ (m1/50 mL) = 650. The number of moles of solute is (50 mL) × (0.10 mmol mL–1) = 5.00 mmol, and mass
conservation requires that m1 + m2 = 5.00 mmol, so m2 = (5.00 – m1) mmol and we now have only the single unknown m1. The
equilibrium constant then becomes
(5.00– m1 ) mmol/10 mL
= 650
m1 mmol/50 mL

Simplifying and solving for m yields

1

(0.50– 0.1)m1
= 650
0.02 m1

with m1 = 0.0382 mmol.

The concentration of solute in the water layer is (0.0382 mmol) / (50 mL) = 0.000763 M, showing that almost all of the iodine has
moved into the CS2 layer.

5.8.2: Chromatographic Separations

In an extraction, the sample is one phase and we extract the analyte or the interferent into a second phase. We also can separate the
analyte and interferents by continuously passing one sample-free phase, called the mobile phase, over a second sample-free phase
that remains fixed or stationary. The sample is injected into the mobile phase and the sample’s components partition themselves
between the mobile phase and the stationary phase. Those components with larger partition coefficients are more likely to move
into the stationary phase, taking a longer time to pass through the system. This is the basis of all chromatographic separations.
Chromatography provides both a separation of analytes and interferents, and a means for performing a qualitative or quantitative
analysis for the analyte.

Figure 5.8.3 : Progress of a column chromatographic separation of a two-component mixture. In (a) the sample is layered on top of
the stationary phase. As mobile phase passes through the column, the sample separates into two solute bands (b–d). In (e) and (f),
we collect each solute as it elutes from the column.
Of the two methods for bringing the stationary phase and the mobile phases into contact, the most important is column
chromatography. In this section we develop a general theory that we may apply to any form of column chromatography. Figure
5.8.3 provides a simple view of a liquid–solid column chromatography experiment. The sample is introduced at the top of the

column as a narrow band. Ideally, the solute’s initial concentration profile is rectangular (Figure 5.8.1a). As the sample moves
down the column the solutes begin to separate (Figures 5.8.1b, c), and the individual solute bands begin to broaden and develop a
Gaussian profile. If the strength of each solute’s interaction with the stationary phase is sufficiently different, then the solutes
separate into individual bands (Figure 5.8.1d).

5.8.3 https://chem.libretexts.org/@go/page/43448
 Figure 5.8.4 : An alternative view of the separation in Figure 5.8.3 showing the concentration of each solute as a function of
distance down the column.
We can follow the progress of the separation either by collecting fractions as they elute from the column (Figure 5.8.4), or by
placing a suitable detector at the end of the column. A plot of the detector’s response as a function of elution time, or as a function
of the volume of mobile phase, is known as a chromatogram (Figure 5.8.5), and consists of a peak for each solute.

Figure 5.8.5 : Chromatogram for the separation shown in Figure 5.8.3 showing the detector’s response as a function of the elution
time.

5.8.3: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
David Harvey (DePauw University)

5.8: Distribution between Immiscible Phases - Extraction and Separation Processes is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

5.8.4 https://chem.libretexts.org/@go/page/43448
5.E: Chemical Equilibrium (Exercises)
These are homework exercises to accompany the Textmap created for "Principles of Modern Chemistry" by Oxtoby et al.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here.

5.E.1: Q1
Write an expression for the equilibrium constant K for each reaction below.
c

a. 2 NO(g) + O (g) −
↽
2
⇀
− 2 NO (g)
2

b. N 2
H (g) + 3 O (g) −
4 2
↽⇀
− 2 NO (g) + H O(g)
2 2

c. O 3
(g) + H O(l) −
2
↽⇀
− H (g) + 2 O (g)
2 2

5.E.2: Q3
Gaseous chlorine reacts with water vapor to form hydrogen chloride and oxygen gas. Write down the equilibrium expression (K ) p

for the reaction.

5.E.3: Q11
For each thermodynamics equilibrium expressions outlined below, determine one possible chemical reaction related to each.
2
a{CO}
a. K =
a{ CO }
2

2
a{ H O}
2
b. K =
2
a{ H } a{ O }
2 2

2
a{ Cl O}
2
c. K =
2
a{ Cl } a{ O }
2 2

a{ COCl }
d. K =
2

a{CO} ⋅ a{ Cl }
2

5.E.4: Q15A
Based on the following data, calculate the equilibrium constant and the value of ΔG at 273 K.
a. CO 2
(g) + H (g) −
2
↽⇀
− CO(g) + H O(g)
2
with
[ CO ]eq = 0.0954 M
2

[ H ]eq = 0.0454 M
2

[CO]eq = 0.0046 M

[ H O]eq = 0.0046 M
2

b. 2 NO(g) + 2 H 2
(g) −
↽⇀
− N (g) + 2 H O(g)
2 2
with
[NO]eq = 0.45 M

[ H ]eq = 0.63 M
2

[ N ]eq = 0.95 M
2

[ H O]eq = 1.3 M
2

5.E.5: Q15B
Calculate the appropriate K value for the following reactions using the information provided. Assume that they are preformed
under standard conditions (and 298.15 K).

a. 2 NO (g) −
2
↽⇀
− 2 NO(g) + O (g)
2

b. NH
+

4
(aq) + H O(l) −
2
↽⇀ +
− H O (aq) + NH (aq)
3 3

5.E.1 https://chem.libretexts.org/@go/page/69601
 c. Jim’s brother, Txeltoqlztop, goes to the bathroom only to find out that his sibling did not refill the toilet paper roll! To get
revenge, Txeltoqlztop decides to fill his brother’s room with carbon monoxide, via the following reaction:

2 CH (g) + 3 O (g) −
↽⇀
− 2 CO(g) + 4 H O(g)
4 2 2

Calculate the K value for this equation under standard conditions, interpret what it means in regards to the direction this
equation will go, and compare it to the other two.

5.E.6: Q15C
Use the thermodynamic data in Tables T1 and T2 to calculate the equilibrium constants for the following equations at 25°C.
a. H (g) + 2 F(g) −
2
↽⇀
− 2 HF(g)

b. FeCl (s) −
↽
3
⇀
− FeCl (s) + Cl (g)
2 2

c. CaSO (s) −↽⇀

− Ca
4
2 +
(aq) + SO
2 −

4
(aq)

5.E.7: Q17
To ignite this house on fire, you dowsed the house in some ethanol and used a combustion reaction:

C H OH(l) + O (g) −
↽⇀
− H O(l) + CO (g)
2 5 2 2 2

This reaction has an equilibrium constant of K1. If you multiply this equation by 5, will the equilibrium constant change? If so,
write this new equilibrium constant, K2, in terms of K1.

5.E.8: Q21
An unknown gas B5D10 reacts at room temperature and becomes B10D20, the reaction is illustrated with the equation

2B D (g) −
↽⇀
− B D (g)
5 10 10 20

At room temperature the equilibrium partial pressure of B5D10 is 1.23 × 10 −4

atm and that of B10D20 is 3.14 × 10−16
atm . Given
these constants, what is K of this reaction at room temperature.
p

5.E.9: Q23A
Suppose there exists a compound that can be found in two forms, red and blue, such that

X −
↽⇀
− X
red blue

During equilibrium at 25.0°C, 17% of the substance is determined to be in blue form. What is the equilibrium constant for this
reaction?

5.E.10: Q23B
1,2-dimethylcyclohexane can exist in both boat and chair conformation. There is equilibrium between the two forms. What is the
equilibrium constant for the reaction of boat conformation to chair conformation if the molecules in the boat form are 68.7%?

5.E.11: Q28
The K for the following reaction is 3.0 at 1000 K.
p

CO (g) + C(s) −
↽⇀
− 2 CO(g)
2

a. If the pressure in the container where the reaction occurs was initially 0.48 bar, calculate the partial pressures of CO and CO 2

at equilibrium.
b. Calculate the percentage of CO that has been dissociated.
2

5.E.12: Q29
A 100.0 mL glass bulb was filled which a weighed sample of solid XO , where X is an unknown element. The bulb was then
3

attached to a pressure gauge and heated to 325 K, at which, the pressure was read to be 0.891 atm. Given that all of the XO in the 3

bulb at 325 K was in the gas phase, and it also partially dissociated into O (g) and XO(g): 2

5.E.2 https://chem.libretexts.org/@go/page/69601
 XO (g) −
↽⇀
− O (g) + XO(g)
3 2

At 325 K, Kp = 3.14 for this reaction. Calculate the partial pressures of all three species in the bulb at equilibrium.

5.E.13: Q31
The equilibrium constant K for the reaction
c

F (g) + H (g) −
↽⇀
− 2 HF(g)
2 2

at 298 K is 5.07 × 10 . Hydrogen with a partial pressure of 0.03500 atm is mixed with fluorine with a partial pressure of 0.06800
4

atm, and allowed to reach the equilibrium. What is the partial pressure of each of the gasses at the equilibrium?

5.E.14: Q33
At 25 °C, the equilibrium constant for the reaction below has the value of 1.7 × 10 −13
:
1
N O(g) + O (g) −
↽⇀
− 2 NO(g)
2 2 2

In a container where N O has an initial partial pressure of 0.62 atm, O has a pressure of 0.24 atm, and NO has an initial pressure
2 2

of 0.08 atm, what will the partial pressure of the three gases be after reaching equilibrium at the same temperature?

5.E.15: Q35
The reaction:

2 HI(g) −
↽⇀
− H (g) + I (g)
2 2

has an equilibrium constant K = 1.82 × 10

c
−2
at 698 K. If the reaction took place in a tank at 698 K and started off with HI
having a partial pressure of 1 atm, what would the partial pressures of all the gases be at equilibrium?

5.E.16: Q37
What is the concentration of a XY that will be found in equilibrium at room temperature, given that X has a concentration of
2

M , Y has a concentration of 1.23 × 10 M , and the K of the reaction is 2.22 × 10 M.

−15 −4 −7
3.14 × 10 c
2

5.E.17: Q41
Hydrogen and oxygen gas react with each other to form gaseous water with an equilibrium constant for the reaction is
K = 1.33 × 10
c at 1000 K.
20

a. Consider a system at 1000.0 K in which 4.00 atm of oxygen is mixed with 0.500 atm of hydrogen and no water is initially
present. What is the concentration of hydrogen gas after equilibration.
b. Consider a system, also at 1000.0 K, where 0.250 atm of oxygen is mixed with 0.500 atm of hydrogen and 2.000 atm of water.
What is the concentration of hydrogen and oxygen gas after equilibration.

5.E.18: Q43
If you decompose ammonium nitrate into water and nitrous oxide, which further decomposes into oxygen and nitrogen gas, making
the final reaction:

2 NH NO (s) −
↽⇀
− 2 N (g) + O (g) + 4 H O(g)
4 3 2 2 2

This reaction takes place only in the molten salt, above its melting point of 169.6°C (for the anhydrous product). So, you get your
170°C blow torch and begin decomposing the ammonium nitrate under a sealed hood. Upon decomposition, all of the ammonium
nitrate is gone, i.e. the reaction goes to completion.
a. What can be said of the equilibrium constant of this reaction at 170°C?
b. Now, in another universe, the partial pressure of N2(g) is 0.3 atm initially. Will the reaction still go to, essentially, completion?

5.E.19: Q45
Al2Cl6 at a partial pressure of 0.600 atm is placed in a closed container at 454 K. Al3Cl9 (partial pressure 1.98 × 10 −3
atm) is also
placed in it as well. Argon is added to raise the total pressure up to 1.00 atm.

5.E.3 https://chem.libretexts.org/@go/page/69601
Find whether if there is going to be net production or consumption of Al3Cl9 given Kp = 1.04 × 10
−4
. Then find the final
pressure of Al3Cl9.

5.E.20: Q46
The thermal decomposition of NH4Cl solid proceeds as follows:

NH Cl(s) −
↽⇀
− NH (g) + HCl(g)
4 3

the equilibrium constant at 275°C is 1.04 × 10 . If the partial pressures of NH (g) and HCl(g) are equal, and the total partial
−2
3

pressure of the system is 0.200 atm, in what direction does the reaction proceed? What will be formed?

5.E.21: Q47
A tube contains a mixture of NO2 and N2O4 gas is set at 298K, in which the initial partial pressure NO2 is 0.38 atm, and the initial
partial pressure of N2O4 is 0.59 atm. NO2 is a brownish gas, while N2O4 is a colorless gas.

2 NO (g) ⇌ N O (g)
2 2 4

a. What is the reaction quotient at the start of this reaction?

b. As the reaction shown above reaches equilibrium, the mixture becomes more brown. With this in mind, is the equilibrium
constant, Kp, greater than or less than the Q calculated in part a?

5.E.22: Q49
At 500 K the equilibrium constant for the reaction:

PCl (g) + Cl (g) −

↽⇀
− PCl (g)
3 2 5

is K = 2.1 . Suppose the equilibrium is disturbed and shifts, while temperature remains constant. Calculate the reaction quotient
eq

for each one of the possible changes in equilibrium concentration given below and evaluate in what direction the reaction will shift
to reestablish equilibrium.
a. [PCl3]= 0.0563, [Cl2]= 0.0784, [PCl5]= 0.8934.
b. [PCl3]=0.4390 , [Cl2]= 0.3547, [PCl5]= 0.1048.
c. [PCl3]= 0.4018, [Cl2]= 0.8690, [PCl5]= 0.7205.

5.E.23: Q48
NO2 has a brownish color. At elevated temperatures, NO2 reacts with CO

NO (g) + CO(g) −
↽⇀
− NO(g) + CO (g)
2 2

The other gases in this equation are colorless. When a gas mixture is prepared at 600K, in which 9.6 atm is the initial partial
pressure of both NO2 and CO, and 5.4 atm is the partial pressure of both NO and CO2, the brown color of the mixture observed
begins to get stronger as the reaction progresses toward equilibrium. Give a condition that must be satisfied by the equilibrium
constant K.

5.E.24: Q51
The equilibrium constant (K ) for the reaction
p

As (g) −
↽⇀
− 2 As (g)
4 2

is 5.5837 × 10 −4
at 1090 K.
a. The initial molarity of [As ] is 2.3 M and the initial molarity of [As ] is 0.001 M. Calculate the reaction quotient Q and
4 2

determine which way the reaction proceeds.

b. Calculate the molarity of each compound at the equilibrium.
c. Which direction will the reaction proceed if the pressure on the reaction decreases? Explain your answer.

5.E.4 https://chem.libretexts.org/@go/page/69601
5.E.25: Q55
Consider a reaction involving only gaseous compounds. The product yield at equilibrium decreases when the temperature and
volume increase.
a. Is this reaction endothermic or exothermic?
b. Does the number of gas molecules in this reaction increase or decrease?

5.E.26: Q57
the Haber process, also called the Haber–Bosch process, is an artificial nitrogen fixation process and is the main industrial
procedure for the production of ammonia today.

N +3 H −
↽⇀
− 2 NH (ΔH = −92.4 kJ/mol)
3 2 3

Determine the best condition of temperature and pressure to yield the most ammonia.

5.E.27: Q59
At room temperature, a vessel is filled with gaseous carbon dioxide. Some water is added at 2.00 atm. It is well-shaken, integrating
carbon dioxide gas into the water. 0.5 kg of the solution is taken out and boiled to extract 2.50 L of carbon dioxide. The system is at
10 degree Celsius and 1.00 atm. What is the Henry’s Law constant for carbon dioxide in water?

5.E.28: Q61
The equilibrium constant for a reaction increases from K=4 ⋅ 5 × 10 to K=4 ⋅ 5 as the temperature increases from 0.00°C to
−2

300.0°C. Assuming the change in enthalpy (ΔH) and change in entropy (ΔS) are constant over this range of temperatures, what is

ΔS for this reaction? Is this reaction endothermic or exothermic?

5.E.29: Q63A
The equilibrium constant for the reaction N O (g) −
2 4
↽⇀
− 2 NO (g)
2
is measured to be −3
5.9 × 10 at 298\;K and 1.3 × 10
−6
at
398 K

a. Calculate ΔG at 298 K for the reaction.

∘

b. Calculate ΔH and ΔS , assuming the enthalpy and entropy changes are independent of temperature between 298 K and 398
∘

K.

5.E.30: Q63B
For the reaction: Br 2
(g) −
↽⇀
− 2 Br(g) , the equilibrium constant is 4.64 × 10 −29
at 25oC and 1.1 × 10 −3
at 1280 K.
a. What is ∆G of the reaction at 298 K?
b. Assuming that ΔH and ΔS are independent of temperature, what are the values of enthalpy and entropy when the
o o

temperature changes to 1280 K?

5.E.31: Q65
Calculate the equilibrium constant for the reaction,
2 NO2 (g) ⇌ N2O4 (g) at 500 K,
given the equilibrium constant K = 4.65 x 10 at 298 K, and ΔH° = -57.2 kJ mol-1. Assume that ΔH° does not change between 298
-3

K and 500 K

5.E.32: Q69
The equilibrium constant for the following reaction was experientially calculated at different temperatures.

N (g) + 3 H (g) ⇌ 2 NH (g)

2 2 3

Temperature (°C) 300 400 450 500 550 600

5.E.5 https://chem.libretexts.org/@go/page/69601
 Equilibrium
4.34 x 10-3 1.64 x 10-4 4.51 x 10-5 1.45 x 10-5 5.38 x 10-6 2.25 x 10-6
Constant (Keq)

a. Plot ln K as a function of 1/T (K-1)

b. What is ΔH º of the equilibrium reaction with ammonia? HINT: use the slope to find the ΔH º

5.E.33: Q71
At a certain temperature, 0.5 mol I
2 (aq)
is dissolved in 2 L H O
2
and shaken vigorously in a container with 2 L of CCl
4 , an
immiscible liquid. The container is then left to equilibrate during which time the iodine redistributes itself between the layers of
H O and CCl as indicated by the following reaction:
2 4

I ⇌ I (CCl )
2 (aq) 2 4

The final concentration of I2 (aq)

is determined to be 0.0710 M. What is the partition coefficient (K) for this process?

5.E.34: Q73
At 25°C, 0.130 g/L of chloroacetic acid (C2H3ClO2) dissolve in of water, and at the same temperature 0.2834 g/L of chloroacetic
acid dissolve in 1-octanol.
a. Calculate the following equilibrium constants

C H ClO H(s) ⇌ C H ClO H(aq)

2 2 2 2 2 2

C H ClO H(s) ⇌ C H ClO H(octanol)

2 2 2 2 2 2

b. Calculate the participation coefficient, K , of the combined reactions.

C H ClO H(aq) ⇌ C H ClO H(octanol)

2 2 2 2 2 2

5.E.35: Q75
At 298 K, the two gases NOBr and Br2 have the number of moles of 1.25 and 8.5 x 10-5 at equilibrium with a sufficient amount of
solid NO. Determine the equilibrium constant of the reaction:

2N OBr(g) ⇌ 2N O(s) + Br2(g)

5.E.36: Q79
At 300 K and 1 atm, N2O4 is partly dissociated into NO2. The density of the equilibrium mixture was 2.076 g/L. What is the degree
of dissociation of N2O4 under these circumstances?

5.E.37: Q85
The decompressions of calcium carbonate (CaCO ) occurs according to the following reaction:
3

CaCO (s) ⇌ CaO(s) + CO (g)

3 2

100 g of solid calcium carbonate (CaCO ) and 50 g of calcium oxide (CaO) are placed in an evacuated round bottom flask that is
3

heated up to 35°C. At this temperature the pressure in the round bottom flask is found to be 0.5 atm.
a. What is the equilibrium constant of the decompressions of calcium carbonate (CaCO ) at 35°C? 3

b. If 100 g of calcium oxide (CaO) at 35°C was added to the flask what would be the new total pressure of the flask and why?
c. If the pressure in the round bottom flask would to increase to 1.0 atm, then what would would be the new equilibrium constant?

5.E.38: Q87
Let's say you have the reaction:

A(s) + B(g) ⇋ C (s) + D(g)

5.E.6 https://chem.libretexts.org/@go/page/69601
At 25°C, this reaction has an equilibrium constant of 157.2. Find the partial pressures of B(g) and D(g) when the total pressure of
the system is equal to 4.3 atm.

5.E.39: Q91
Given the reaction

C3 H5 N (g) + 3 H2 (g) ⇋ C5 H11 N (g)

whose equilibrium constant is solved by this equation

10.56 K
log10 (K) = −20.28 +
T

a. Solve for K when T = 200 K

b. What is partial pressure of C H N (g) when T
3 5 = 200 K and the partial pressure of hydrogen is 1.0 atm and the partial
pressure of C H N (g) is 2.0 × 10 atm.
5 11
−5

5.E.40: Q93
Two equal volume solutions of 2M HCOO- and 2M HCOOH are mixed together. Assume that the volumes are additive. The value
of the equilibrium constant Ka for HCOOH is 1.77 x 10-4. What is the ratio between the amounts of HCOOH and HCOO- in the
solution at equilibrium?

5.E.41: Q101
The \(∆G_f^o\) of PbO(s) is -188.95 kJ mol-1. Calculate the equilibrium pressure of O2(g) over a sample of pure PbO(s) in contact
with pure Pb(s) at 25°C. PbO(s) decomposes according to the equation
1
PbO −
↽⇀
− Pb(s) + O (g)
(s) 2 2

5.E.42: Q105
If that weren’t enough, Jim’s sister, ., knocked his grass juice (a mixture of 1-Hexanol, C l , C aC l , and cyclohexane) into the
2 2

family’s benzene-ethanol vat! Assume that the two solvents in the vat are immiscible with each other but are miscible with the
grass juice components. Jim separates the benzene and ethanol, and drinks the one with the greater amount of 1-Hexanol. Which
one does he drink? Which of the two solvents have the highest concentration of the other components of the grass juice?

5.E.43: Q107
Calculate the pH of a 0.5 M H 3P O4 acid solution given that K a1 = 7.1 × 10
−3
,K
a2 = 6.3 × 10
−8
and K a3 = 4.2 × 10
−13
.

5.E.44: Q107
The Haber-Bosch process is a method invented in the 20th century as a method for hydrogen fixation. It is widely used in industry
today, and involves reacting nitrogen and hydrogen in the following manner:

N (g) + 3 H (g) ⇌ 2 NH (g)

2 2 3

Calculate ∘
ΔGrxn . If the pressure of the products and reaction are all kept constant at the same value, in which direction will the
reaction go?
Relevant information:
kJ
∘
ΔG N H2 (g)
= 199.83
f
mol

5.E.45: Q109
At 273 K, the equation: H2(g) + I2(g) → 2HI(g) has an equilibrium constant of 60.2
a. Solve for ΔGº at 273 K
b. How does G change when the pressure of HI is 2 atm, I2 is 4 atm and H2 is 6 atm?
c. Is this reaction spontaneous?

5.E.7 https://chem.libretexts.org/@go/page/69601
5.E.46: Q109
At 773 K the equilibrium constant for the Haber-Bosch process is 1.45x10-5. The chemical reaction involved in the Haber-Bosch
process is:

N2 (g)
+ 3 H2 (g)
⇌ 2N H3 (g)

a. What is ΔG°(773) for this reaction?

b. What is ΔG at 773 K for transforming 1 mole of N2 and 3 moles H2 held at 30 atm to 2 moles of NH3 held at 1 atm?
c. In which direction would the previous reaction run spontaneously?

5.E.47: Q111
The following reaction is exothermic

SnO (s) + 2 H (g) → Sn(g) + 2 H O(l)

2 2 2

a. What is the equilibrium expression based on this chemical equation?

b. What happens to the reaction if more H2 is added? SnO2 is added into the system?
c. What effect would an increase in temperature have on the system?
d. What affect would an increase in pressure have on the system?

5.E.48: Q112
Given the chemical reaction
SnO (s) ⇌ Sn(s) + O (g)
2 2

a. Formulate the equilibrium expression using activities

b. State the effect on pO at equilibrium if more SnCl (l) is added to the system
2 4

c. State the effect on pO at equilibrium if more O (g) is added to the system

2 2

5.E.49: Q113
Arrange the following solutions in order of most acidic to basic: NaOH, NaCN, H2SO4, NH4NO3, NaCl

5.E.50: Q115
Given that the K values for NH and NH
b 3 2
NH
2
are 1.8 × 10 −5
and 8.5 × 10 −7
, respectively. Which is the stronger acid?

5.E.51: Q119
Calculate the pH of the following solutions.
a. 0.5 M NaCN (K of HCN = 6.2 × 10
a
−10
)
b. 0.01 M NH Cl (K of NH = 1.8 × 10
4 b 3
−5
)

5.E.52: Q131
Identify the stronger acid in each of the following combination. Explain.
a. HF and HBr
b. H2SO4 and H2SO3
c. HOCl and HOBr

5.E.53: Q137
Identify the Lewis acid and Lewis base for each of the following reaction.
a. H (aq) + NH (aq) −
+
↽⇀− NH (aq)
3
+

b. Al (aq) + 6 H O(l) −
3 +
↽⇀
− Al (H O)
2 2
3 +

6
(aq)

c. CO (g) + H O(l) −
2 2
↽⇀
− H CO (aq)
2 3

5.E.8 https://chem.libretexts.org/@go/page/69601
5.E.54: Q139
Beryllium hydroxide is an amphoteric compound. It can react as an acid as well as a base. Please write the reactions of Be(OH)2
and describe its role base on Brønsted-Lowry and Lewis theories.

5.E: Chemical Equilibrium (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5.E.9 https://chem.libretexts.org/@go/page/69601
 CHAPTER OVERVIEW

VI: Acid–Base Equilibria

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

Acids and bases have been defined differently by three sets of theories. One is the Arrhenius definition, which revolves around the
idea that acids are substances that ionize (break off) in an aqueous solution to produce hydrogen (H+) ions while bases produce
hydroxide (OH-) ions in solution. On the other hand, the Bronsted-Lowry definition defines acids as substances that donate protons
(H+) whereas bases are substances that accept protons. Also, the Lewis theory of acids and bases states that acids are electron pair
acceptors while bases are electron pair donors. Acids and bases can be defined by their physical and chemical observations.
6.1: Classifications of Acids and Bases
6.2: The Brønsted-Lowry Scheme
6.3: Acid and Base Strength
6.4: Equilibria Involving Weak Acids and Bases
6.5: Buffer Solutions
6.6: Acid-Base Titration Curves
6.7: Polyprotic Acids
6.8: A Deeper Look - Exact Treatment of Acid-Base Equilibria
6.9: Organic Acids and Bases - Structure and Reactivity
6.10: Lewis Bases as Nucleophilic Reactants in Organic Reactions

VI: Acid–Base Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
6.1: Classifications of Acids and Bases
 Learning Objectives
To understand the differences between the three definitions of Acids and Bases
Identify acids, bases, and conjugate acid-base pairs according to the three definitions of Acids and Bases
To understand the concept of conjugate acid–base pairs in acid/base reactions
Write the equation for the proton transfer reaction involving a Brønsted-Lowry acid or base, and show how it can be
interpreted as an electron-pair transfer reaction, clearly identifying the donor and acceptor.
Give an example of a Lewis acid-base reaction that does not involve protons.

Acids and bases have been known for a long time. When Robert Boyle characterized them in 1680, he noted that acids dissolve
many substances, change the color of certain natural dyes (for example, they change litmus from blue to red), and lose these
characteristic properties after coming into contact with alkalis (bases). In the eighteenth century, it was recognized that acids have a
sour taste, react with limestone to liberate a gaseous substance (now known to be CO2), and interact with alkalis to form neutral
substances. In 1815, Humphry Davy contributed greatly to the development of the modern acid-base concept by demonstrating that
hydrogen is the essential constituent of acids. Around that same time, Joseph Louis Gay-Lussac concluded that acids are substances
that can neutralize bases and that these two classes of substances can be defined only in terms of each other. The significance of
hydrogen was reemphasized in 1884 when Carl Axel Arrhenius defined an acid as a compound that dissolves in water to yield
hydrogen cations (now recognized to be hydronium ions) and a base as a compound that dissolves in water to yield hydroxide
anions.
Acids and bases are common solutions that exist everywhere. Almost every liquid that we encounter in our daily lives consists of
acidic and basic properties, with the exception of water. They have completely different properties and are able to neutralize to
form H2O, which will be discussed later in a subsection. Acids and bases can be defined by their physical and chemical
observations (Table 6.1.1).
Table 6.1.1 : General Properties of Acids and Bases
ACIDS BASES

produce a piercing pain in a wound. give a slippery feel.

taste sour. taste bitter.

are colorless when placed in phenolphthalein (an indicator). are pink when placed in phenolphthalein (an indicator).

are red on blue litmus paper (a pH indicator). are blue on red litmus paper (a pH indicator).

have a pH<7. have a pH>7.

produce hydrogen gas when reacted with metals.

produce carbon dioxide when reacted with carbonates.

Common examples: Lemons, oranges, vinegar, urine, sulfuric acid, Common Examples: Soap, toothpaste, bleach, cleaning agents,
hydrochloric acid limewater, ammonia water, sodium hydroxide.

Acids and bases in aqueous solutions will conduct electricity because they contain dissolved ions. Therefore, acids and bases are
electrolytes. Strong acids and bases will be strong electrolytes. Weak acids and bases will be weak electrolytes. This affects the
amount of conductivity.
In chemistry, acids and bases have been defined differently by three sets of theories: One is the Arrhenius definition defined
above, which revolves around the idea that acids are substances that ionize (break off) in an aqueous solution to produce hydrogen
(H+) ions while bases produce hydroxide (OH-) ions in solution. The other two definitions are discussed in detail include the
Brønsted-Lowry definition the defines acids as substances that donate protons (H+) whereas bases are substances that accept
protons and the Lewis theory of acids and bases states that acids are electron pair acceptors while bases are electron pair donors.

6.1.1 https://chem.libretexts.org/@go/page/43430
6.1.1: Arrhenius Acids and Bases
In 1884, the Swedish chemist Svante Arrhenius proposed two specific classifications of compounds, termed acids and bases. When
dissolved in an aqueous solution, certain ions were released into the solution. The Arrhenius definition of acid-base reactions is a
development of the "hydrogen theory of acids". It was used to provide a modern definition of acids and bases, and followed from
Arrhenius's work with Friedrich Wilhelm Ostwald in establishing the presence of ions in aqueous solution in 1884. This led to
Arrhenius receiving the Nobel Prize in Chemistry in 1903.
An Arrhenius acid is a compound that increases the concentration of H ions that are present when added to water.
+

+ −
HCl(g) → H (aq) + Cl (aq) (6.1.1)

In this reaction, hydrochloric acid (HCl) gas dissociates into hydrogen (H ) and chloride (Cl ) ions when dissolved in water,
+ −

thereby releasing H ions into solution. These H ions form the hydronium ion (H O ) when they combine with water molecules.
+ +

3
+

Both processes can be represented in a chemical equation by adding H O to the reactants side of Equation 6.1.1 and switching
2

hydronium ions for free protons.

+ −
HCl(g) + H O(l) → H O (aq) + Cl (aq) (6.1.2)
2 3

An Arrhenius base is a compound that dissociates to yield hydroxide ions (OH ) in aqueous solution. Common examples of −

Arrhenus bases include Sodium hydroxide (NaOH), Potassium hydroxide (KOH ), Magnesium hydroxide Mg(OH) , and 2

Calcium hydroxide (Ca(OH) . All of these bases are solids at room temperature and when dissolved in water, will generate a
2

metal cation and the hydroxide ion ((OH ), for example, Sodium hydroxide
−

+ −
NaOH(s) ⟶ Na (aq) + OH (aq) (6.1.3)

All Arrhenius acids have easily detachable hydrogen that leave to form hydronium ions in solution and all Arrhenius bases
have easily detachable OH groups that form hydroxide ions in solution.

 Limitation of the Arrhenius Definition of Acids and Bases

The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the concentration of the
solvated ions. Under this definition, pure H SO or HCl dissolved in toluene are not acidic, despite the fact that both of these
2 4

acids will donate a proton to toluene. In addition, under the Arrhenius definition, a solution of sodium amide (NaNH ) in 2

liquid ammonia is not alkaline, despite the fact that the amide ion (NH ) will readily deprotonate ammonia. Thus, the
−
2

Arrhenius definition can only describe acids and bases in an aqueous environment. The Arrhenius definition can only describe
acids and bases in protic solvents and environments (e.g., water, alcohols, within proteins etc.).

6.1.2: Brønsted-Lowry Acids and Bases

The Arrhenius definitions identified an acid as a compound that dissolves in water to yield hydronium ions (Equation 6.1.2\) and a
base as a compound that dissolves in water to yield hydroxide ions (Equation 6.1.3). As mentioned above, this definition limited.
We extended the definition of an acid or a base using the more general definition proposed in 1923 by the Danish chemist Johannes
Brønsted and the English chemist Thomas Lowry. Their definition centers on the proton, H . A proton is what remains when a +

normal hydrogen atom, H , loses an electron. A compound that donates a proton to another compound is called a Brønsted-Lowry
1
1

acid, and a compound that accepts a proton is called a Brønsted-Lowry base. An acid-base reaction is the transfer of a proton
from a proton donor (acid) to a proton acceptor (base).
Acids may be compounds such as HCl or H SO , organic acids like acetic acid (CH COOH ) or ascorbic acid (vitamin C), or
2 4 3

H O . Anions (such as HSO , H PO , HS , and HCO ) and cations (such as H O , NH , and [Al (H O) ] ) may also act
− − − − + + 3 +

2 4 2 4 3 3 4 2 6

as acids.
Bases fall into the same three categories and may be neutral molecules (such as H O , NH , and CH NH ), anions (such as OH ,
2 3 3 2
−

2 +
HS , HCO , CO , F , and PO ), or cations (such as [Al(H O) OH] ). The most familiar bases are ionic compounds
− − 2 − − 3 −
3 3 4 2 5

such as NaOH and Ca(OH) , which contain the hydroxide ion, OH . The hydroxide ion in these compounds accepts a proton
2
−

from acids to form water:

+ −
H + OH → H O (6.1.4)
2

6.1.2 https://chem.libretexts.org/@go/page/43430
We call the product that remains after an acid donates a proton the conjugate base of the acid. This species is a base because it can
accept a proton (to re-form the acid):
acid ⇌ proton + conjugate base

+ −
HF ⇌ H +F

+ −
H SO ⇌ H + HSO 4
2 4

+ −
H O ⇌ H + OH
2

− + 2 −
HSO ⇌ H + SO
4 4

+ +
NH ⇌ H + NH
4 3

We call the product that results when a base accepts a proton the base’s conjugate acid. This species is an acid because it can give
up a proton (and thus re-form the base):
base+ proton ⇌ conjugate acid

− +
OH +H ⇌ H O
2

+ +
H O+H ⇌ H O
2 3

+ +
NH +H ⇌ NH
3 4

2 − + −
S +H ⇌ HS

2 − + −
CO +H ⇌ HCO
3 3

− +
F +H ⇌ HF

In these two sets of equations, the behaviors of acids as proton donors and bases as proton acceptors are represented in isolation. In
reality, all acid-base reactions involve the transfer of protons between acids and bases. For example, consider the acid-base reaction
that takes place when ammonia is dissolved in water. A water molecule (functioning as an acid) transfers a proton to an ammonia
molecule (functioning as a base), yielding the conjugate base of water, OH , and the conjugate acid of ammonia, NH :
− +

The reaction between a Brønsted-Lowry acid and water is called acid ionization. For example, when hydrogen fluoride dissolves in
water and ionizes, protons are transferred from hydrogen fluoride molecules to water molecules, yielding hydronium ions and
fluoride ions:

with
+ −
[H O ][ F ]
3
K =
[HF]

When we add a base to water, a base ionization reaction occurs in which protons are transferred from water molecules to base
molecules. For example, adding ammonia to water yields hydroxide ions and ammonium ions:

6.1.3 https://chem.libretexts.org/@go/page/43430
with
+ −
[ C NH ][ OH ]
5 6
K =
[ C NH ]
5 5

Notice that both these ionization reactions are represented as equilibrium processes. The relative extent to which these acid and
base ionization reactions proceed is an important topic treated in a later section of this chapter. In the preceding paragraphs we saw
that water can function as either an acid or a base, depending on the nature of the solute dissolved in it. In fact, in pure water or in
any aqueous solution, water acts both as an acid and a base. A very small fraction of water molecules donate protons to other water
molecules to form hydronium ions and hydroxide ions:

This type of reaction, in which a substance ionizes when one molecule of the substance reacts with another molecule of the same
substance, is referred to as autoionization. Pure water undergoes autoionization to a very slight extent. Only about two out of
every 10 molecules in a sample of pure water are ionized at 25 °C. The equilibrium constant for the ionization of water is called
9

the ion-product constant for water (K ):

w

+ −
H O(l) + H O(l) −
↽⇀
− H O (aq) + OH (aq) (6.1.5)
2 2 3

with
+ −
Kw = [ H O ][ OH ] (6.1.6)
3

The slight ionization of pure water is reflected in the small value of the equilibrium constant; at 25 °C, K has a value of
w

1.0 × 10 . The process is endothermic, and so the extent of ionization and the resulting concentrations of hydronium ion and
−14

hydroxide ion increase with temperature. For example, at 100 °C, the value for K is approximately 5.1 × 10 , roughly 100-
w
−13

times larger than the value at 25 °C.

 Example 6.1.1: Ion Concentrations in Pure Water

What are the hydronium ion concentration and the hydroxide ion concentration in pure water at 25 °C?
Solution
The autoionization of water yields the same number of hydronium and hydroxide ions. Therefore, in pure water,
[ H O ] = [ OH ] . At 25 °C:
+ −
3

+ −
Kw = [ H O ][ OH ]
3

+ 2
= [H O ]
3

− 2
= [OH ]

−14
= 1.0 × 10

So

6.1.4 https://chem.libretexts.org/@go/page/43430
 − −−−−−−− −
+ − −14 −7
[H O ] = [ OH ] = √ 1.0 × 10 = 1.0 × 10 M
3

The hydronium ion concentration and the hydroxide ion concentration are the same, and we find that both equal
M .
−7
1.0 × 10

 Exercise 6.1.1

The ion product of water at 80 °C is 2.4 × 10 −13

. What are the concentrations of hydronium and hydroxide ions in pure water
at 80 °C?
Answer
+ − −7
[H O ] = [ OH ] = 4.9 × 10 M
3

It is important to realize that the autoionization equilibrium for water is established in all aqueous solutions. Adding an acid or base
to water will not change the position of the equilibrium. Example 6.1.2 demonstrates the quantitative aspects of this relation
between hydronium and hydroxide ion concentrations.

 Example 6.1.2: The Inverse Proportionality of [H 3

O
+
] and [OH −
]

The Inverse Proportionality of [H3O+] and [OH-] A solution of carbon dioxide in water has a hydronium ion concentration of
M . What is the concentration of hydroxide ion at 25 °C?
−6
2.0 × 10

Solution
We know the value of the ion-product constant for water at 25 °C:
+ −
2 H O(l) ⇌ H O + OH
2 3 (aq) (aq)

+ − −14
Kw = [ H O ][ OH ] = 1.0 × 10
3

Thus, we can calculate the missing equilibrium concentration.

Rearrangement of the Kw expression yields that [OH −
] is directly proportional to the inverse of [H3O+]:
−14
Kw 1.0 × 10
− −9
[ OH ] = = = 5.0 × 10
+ −6
[H O ] 2.0 × 10
3

The hydroxide ion concentration in water is reduced to 5.0 × 10 M as the hydrogen ion concentration increases to
−9

M . This is expected from Le Chatelier’s principle; the autoionization reaction shifts to the left to reduce the stress
−6
2.0 × 10

of the increased hydronium ion concentration and the [OH ] is reduced relative to that in pure water.
−

A check of these concentrations confirms that our arithmetic is correct:

+ − −6 −9 −14
Kw = [ H O ][ OH ] = (2.0 × 10 )(5.0 × 10 ) = 1.0 × 10
3

 Exercise 6.1.2

What is the hydronium ion concentration in an aqueous solution with a hydroxide ion concentration of 0.001 M at 25 °C?

Answer
+ −11
[H O ] = 1 × 10 M
3

6.1.3: Amphoteric Species

Like water, many molecules and ions may either gain or lose a proton under the appropriate conditions. Such species are said to be
amphiprotic. Another term used to describe such species is amphoteric, which is a more general term for a species that may act
either as an acid or a base by any definition (not just the Brønsted-Lowry one). Consider for example the bicarbonate ion, which
may either donate or accept a proton as shown here:

6.1.5 https://chem.libretexts.org/@go/page/43430
 2 − +
HCO−3 (aq) + H O(l) −
↽⇀
− CO3 (aq) + H O (aq)
2 3

− −
HCO (aq) + H O(l) −
↽⇀
− H CO (aq) + OH (aq)
3 2 2 3

 Example 6.1.3: The Acid-Base Behavior of an Amphoteric Substance

Write separate equations representing the reaction of HSO −

3

a. as an acid with OH −

b. as a base with HI
Solution
a. HSO −
3
(aq) + OH
−
(aq) ⇌ SO 3
2−
(aq) + H O(l)
2

b. HSO −
3
(aq) + HI(aq) ⇌ H SO (aq) + I
2 3
−
(aq)

 Exercise 6.1.3

Write separate equations representing the reaction of H 2

PO
−
4

a. as a base with HBr

b. as an acid with OH −

Answer a
− −
H PO (aq) + HBr(aq) ⇌ H PO (aq) + Br (aq)
2 4 3 4

Answer b
− − 2−
H PO (aq) + OH (aq) ⇌ HPO (aq) + H O(l)
2 4 4 2

6.1.4: Lewis Acids and Bases

The Brønsted-Lowry proton donor-acceptor concept has been one of the most successful theories of Chemistry. But as with any
such theory, it is fair to ask if this is not just a special case of a more general theory that could encompass an even broader range of
chemical science. In 1916, G.N. Lewis of the University of California proposed that the electron pair is the dominant actor in acid-
base chemistry. The Lewis theory did not become very well known until about 1923 (the same year that Brønsted and Lowry
published their work), but since then it has been recognized as a very powerful tool for describing chemical reactions of widely
different kinds and is widely used in organic and inorganic chemistry. The Brønsted–Lowry concept of acids and bases defines a
base as any species that can accept a proton, and an acid as any substance that can donate a proton. Lewis proposed an alternative
definition that focuses on pairs of electrons instead. According to Lewis:
An acid is a substance that accepts a pair of electrons, and in doing so, forms a covalent bond with the entity that supplies the
electrons.
A base is a substance that donates an unshared pair of electrons to a recipient species with which the electrons can be shared.

In modern chemistry, electron donors are often referred to as nucleophiles, while

acceptors are electrophiles.
6.1.4.1: Lewis Acid-Base Neutralization Involving Electron-Pair Transfer
Just as any Arrhenius acid is also a Brønsted acid, any Brønsted acid is also a Lewis acid, so the various acid-base concepts are all
"upward compatible". Although we do not really need to think about electron-pair transfers when we deal with ordinary aqueous-
solution acid-base reactions, it is important to understand that it is the opportunity for electron-pair sharing that enables proton
transfer to take place.

6.1.6 https://chem.libretexts.org/@go/page/43430
This equation for a simple acid-base neutralization shows how the Brønsted and Lewis definitions are really just different views of
the same process. Take special note of the following points:
The arrow shows the movement of a proton from the hydronium ion to the hydroxide ion.
Note that the electron-pairs themselves do not move; they remain attached to their central atoms. The electron pair on the base
is "donated" to the acceptor (the proton) only in the sense that it ends up being shared with the acceptor, rather than being the
exclusive property of the oxygen atom in the hydroxide ion.
Although the hydronium ion is the nominal Lewis acid here, it does not itself accept an electron pair, but acts merely as the
source of the proton that coordinates with the Lewis base.

 Note
The point about the electron-pair remaining on the donor species is especially important to bear in mind. For one thing, it
distinguishes a Lewis acid-base reaction from an oxidation-reduction reaction, in which a physical transfer of one or more
electrons from donor to acceptor does occur.

The product of a Lewis acid-base reaction is known formally as an "adduct" or "complex", although we do not ordinarily use these
terms for simple proton-transfer reactions such as the one in the above example. Here, the proton combines with the hydroxide ion
to form the "adduct" H O . The following examples illustrate these points for some other proton-transfer reactions that you should
2

already be familiar with.

Another example, showing the autoprotolysis of water. Note that the conjugate acid is also the adduct.

Ammonia is both a Brønsted and a Lewis base, owing to the unshared electron pair on the nitrogen. The reverse of this reaction
represents the hydrolysis of the ammonium ion.

Because HF is a weak acid, fluoride salts behave as bases in aqueous solution. As a Lewis base, F
–
accepts a proton from water,
which is transformed into a hydroxide ion.

The bisulfite ion is amphiprotic and can act as an electron donor or acceptor.

All Brønsted–Lowry bases (proton acceptors), such as OH , H O , and NH , are also electron-pair donors. Thus the Lewis
−

2 3

definition of acids and bases does not contradict the Brønsted–Lowry definition. Rather, it expands the definition of acids to
include substances other than the H ion.
+

6.1.7 https://chem.libretexts.org/@go/page/43430
6.1.4.2: Lewis Acid-Base Neutralization without Transferring Protons
Electron-deficient molecules, such as BCl3, contain less than an octet of electrons around one atom and have a strong tendency to
gain an additional pair of electrons by reacting with substances that possess a lone pair of electrons. Lewis’s definition, which is
less restrictive than either the Brønsted–Lowry or the Arrhenius definition, grew out of his observation of this tendency. A general
Brønsted–Lowry acid–base reaction can be depicted in Lewis electron symbols as follows:

The proton (H+), which has no valence electrons, is a Lewis acid because it accepts a lone pair of electrons on the base to form a
bond. The proton, however, is just one of many electron-deficient species that are known to react with bases. For example, neutral
compounds of boron, aluminum, and the other Group 13 elements, which possess only six valence electrons, have a very strong
tendency to gain an additional electron pair. Such compounds are therefore potent Lewis acids that react with an electron-pair
donor such as ammonia to form an acid–base adduct, a new covalent bond, as shown here for boron trifluoride (BF3):

The bond formed between a Lewis acid and a Lewis base is a coordinate covalent bond because both electrons are provided by
only one of the atoms (N, in the case of F3B:NH3). After it is formed, however, a coordinate covalent bond behaves like any other
covalent single bond.

Species that are very weak Brønsted–Lowry bases can be relatively strong Lewis bases. For example, many of the group 13
trihalides are highly soluble in ethers (R–O–R′) because the oxygen atom in the ether contains two lone pairs of electrons, just as in
H2O. Hence the predominant species in solutions of electron-deficient trihalides in ether solvents is a Lewis acid–base adduct. A
reaction of this type is shown in Figure 6.1.1 for boron trichloride and diethyl ether:

Figure 6.1.1: Lewis Acid/Base reaction of boron trichloride and diethyl ether reaction

 Note
Electron-deficient molecules (those with less than an octet of electrons) are Lewis acids.
The acid-base behavior of many compounds can be explained by their Lewis electron structures.

Many molecules with multiple bonds can act as Lewis acids. In these cases, the Lewis base typically donates a pair of electrons to
form a bond to the central atom of the molecule, while a pair of electrons displaced from the multiple bond becomes a lone pair on
a terminal atom.

6.1.8 https://chem.libretexts.org/@go/page/43430
 Figure 6.1.2 : The highly electronegative oxygen atoms pull electron density away from carbon, so the carbon atom acts as a Lewis
acid. Arrows indicate the direction of electron flow.

Figure 6.1.2: Lewis Acid/Base reaction of the hydroxide ion with carbon dioxide

 Example 6.1.4

Identify the acid and the base in each Lewis acid–base reaction.
a. BH3 + (CH3)2S → H3B:S(CH3)2
b. CaO + CO2 → CaCO3
c. BeCl2 + 2 Cl− → BeCl42−
Given: reactants and products
Asked for: identity of Lewis acid and Lewis base
Strategy:
In each equation, identify the reactant that is electron deficient and the reactant that is an electron-pair donor. The electron-
deficient compound is the Lewis acid, whereas the other is the Lewis base.
Solution:
a. In BH3, boron has only six valence electrons. It is therefore electron deficient and can accept a lone pair. Like oxygen, the
sulfur atom in (CH3)2S has two lone pairs. Thus (CH3)2S donates an electron pair on sulfur to the boron atom of BH3. The
Lewis base is (CH3)2S, and the Lewis acid is BH3.
b. As in the reaction shown in Equation 8.21, CO2 accepts a pair of electrons from the O2− ion in CaO to form the carbonate
ion. The oxygen in CaO is an electron-pair donor, so CaO is the Lewis base. Carbon accepts a pair of electrons, so CO2 is
the Lewis acid.
c. The chloride ion contains four lone pairs. In this reaction, each chloride ion donates one lone pair to BeCl2, which has only
four electrons around Be. Thus the chloride ions are Lewis bases, and BeCl2 is the Lewis acid.

 Exercise 6.1.4A
Identify the acid and the base in each Lewis acid–base reaction.
a. (CH3)2O + BF3 → (CH3)2O:BF3
b. H2O + SO3 → H2SO4

Answer a
Lewis base: (CH3)2O; Lewis acid: BF3

6.1.9 https://chem.libretexts.org/@go/page/43430
 Answer b
Lewis base: H2O; Lewis acid: SO3

 Exercise 6.1.4B

Here are several more examples of Lewis acid-base reactions that cannot be accommodated within the Brønsted or Arrhenius
models. Identify the Lewis acid and Lewis base in each reaction.
a. Al(OH ) + OH → Al(OH )
3
–
–
4

b. SnS + S → SnS
2
2– 2–
3

c. C d(C N ) + 2C N → C d(C N )
2
– 2+

d. AgC l + 2N H → Ag(N H ) + C l
3 3
+

2
–

e. F e + N O → F e(N O)
2+ 2+

f. [N i + 6N H → N i(N H )
2+
3 3
2+
5

Lewis Acids & Lewis Bases: Introduction

Video 6.1.1 : Overview of Lewis Acids and Bases

6.1.5: Summary
A compound that can donate a proton (a hydrogen ion) to another compound is called a Brønsted-Lowry acid. The compound that
accepts the proton is called a Brønsted-Lowry base. The species remaining after a Brønsted-Lowry acid has lost a proton is the
conjugate base of the acid. The species formed when a Brønsted-Lowry base gains a proton is the conjugate acid of the base. Thus,
an acid-base reaction occurs when a proton is transferred from an acid to a base, with formation of the conjugate base of the
reactant acid and formation of the conjugate acid of the reactant base. Amphiprotic species can act as both proton donors and
proton acceptors. Water is the most important amphiprotic species. It can form both the hydronium ion, H3O+, and the hydroxide
ion, OH when it undergoes autoionization:
−

+ −
2 H O(l) ⇌ H O (aq) + OH (aq)
2 3

The ion product of water, Kw is the equilibrium constant for the autoionization reaction:
+ − −14
Kw = [ H3 O ][OH ] = 1.0 × 10 at 25°C

6.1.6: Glossary
acid ionization
reaction involving the transfer of a proton from an acid to water, yielding hydronium ions and the conjugate base of the acid

amphiprotic
species that may either gain or lose a proton in a reaction

amphoteric

6.1.10 https://chem.libretexts.org/@go/page/43430
 species that can act as either an acid or a base

autoionization
reaction between identical species yielding ionic products; for water, this reaction involves transfer of protons to yield
hydronium and hydroxide ions

base ionization
reaction involving the transfer of a proton from water to a base, yielding hydroxide ions and the conjugate acid of the base

Brønsted-Lowry acid
proton donor

Brønsted-Lowry base
proton acceptor

conjugate acid
substance formed when a base gains a proton

conjugate base
substance formed when an acid loses a proton

ion-product constant for water (Kw)

equilibrium constant for the autoionization of water

6.1.7: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

6.1: Classifications of Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
15.1: Classifications of Acids and Bases is licensed CC BY-NC-SA 4.0.

6.1.11 https://chem.libretexts.org/@go/page/43430
6.2: The Brønsted-Lowry Scheme
 Learning Objectives
Explain the characterization of aqueous solutions as acidic, basic, or neutral
To know the relationship between acid or base strength and the magnitude of K , K , pK , and pK .
a b a b

Express hydronium and hydroxide ion concentrations on the pH and pOH scales
Perform calculations relating pH and pOH

We now turn our attention to acid–base reactions to see how the concepts of chemical equilibrium and equilibrium constants can
deepen our understanding of this kind of chemical behavior. We begin with a qualitative description of acid–base equilibria in
terms of the Brønsted–Lowry model and then proceed to a quantitative description the following sections.

6.2.1: Free Hydrogen Ions do not Exist in Water

Owing to the overwhelming excess of H O molecules in aqueous solutions, a bare hydrogen ion has no chance of surviving in
2

water. The hydrogen ion in aqueous solution is no more than a proton, a bare nucleus. Although it carries only a single unit of
positive charge, this charge is concentrated into a volume of space that is only about a hundred-millionth as large as the volume
occupied by the smallest atom. (Think of a pebble sitting in the middle of a sports stadium!) The resulting extraordinarily high
charge density of the proton strongly attracts it to any part of a nearby atom or molecule in which there is an excess of negative
charge. In the case of water, this will be the lone pair (unshared) electrons of the oxygen atom; the tiny proton will be buried within
the lone pair and will form a shared-electron (coordinate) bond with it, creating a hydronium ion, H O . In a sense, H O is acting
3
+
2

as a base here, and the product H O is the conjugate acid of water:

3
+

Although other kinds of dissolved ions have water molecules bound to them more or less tightly, the interaction between H+ and
+
H O is so strong that writing “H (aq)” hardly does it justice, although it is formally correct. The formula H O more adequately
+
2 3

conveys the sense that it is both a molecule in its own right, and is also the conjugate acid of water. However, the equation
+ –
HA → H +A

is so much easier to write that chemists still use it to represent acid-base reactions in contexts in which the proton donor-acceptor
mechanism does not need to be emphasized. Thus it is permissible to talk about “hydrogen ions” and use the formula H+ in writing
chemical equations as long as you remember that they are not to be taken literally in the context of aqueous solutions.
Interestingly, experiments indicate that the proton does not stick to a single H O molecule, but changes partners many times per
2

second. This molecular promiscuity, a consequence of the uniquely small size and mass the proton, allows it to move through the
solution by rapidly hopping from one H O molecule to the next, creating a new H O ion as it goes. The overall effect is the
2 3
+

same as if the H O ion itself were moving. Similarly, a hydroxide ion, which can be considered to be a “proton hole” in the
3
+

water, serves as a landing point for a proton from another H O molecule, so that the OH– ion hops about in the same way.
2

The hydronium ion is an important factor when dealing with chemical reactions that occur in aqueous solutions. Because
hydronium and hydroxide ions can “move without actually moving” and thus without having to plow their way through the
solution by shoving aside water molecules as do other ions, solutions which are acidic or alkaline have extraordinarily high
electrical conductivities. The hydronium ion has a trigonal pyramidal geometry and is composed of three hydrogen atoms and one
oxygen atom. There is a lone pair of electrons on the oxygen giving it this shape. The bond angle between the atoms is 113 degrees.

6.2.1 https://chem.libretexts.org/@go/page/43431
 Figure 6.2.1 . The picture above illustrates the electron density of hydronium. The red area represents oxygen; this is the area where
the electrostatic potential is the highest and the electrons are most dense.
As H+ ions are formed, they bond with H O molecules in the solution to form H O (the hydronium ion). This is because
2 3
+

hydrogen ions do not exist in aqueous solutions, but take the form the hydronium ion, H O . A reversible reaction is one in which
3
+

the reaction goes both ways. In other words, the water molecules dissociate while the OH- ions combine with the H+ ions to form
water. Water has the ability to attract H+ ions because it is a polar molecule. This means that it has a partial charge, in this case the
charge is negative. The partial charge is caused by the fact that oxygen is more electronegative than hydrogen. This means that in
the bond between hydrogen and oxygen, oxygen "pulls" harder on the shared electrons thus causing a partial negative charge on the
molecule and causing it to be attracted to the positive charge of H+ to form hydronium. Another way to describe why the water
molecule is considered polar is through the concept of dipole moment. The electron geometry of water is tetrahedral and the
molecular geometry is bent. This bent geometry is asymmetrical, which causes the molecule to be polar and have a dipole moment,
resulting in a partial charge.

6.2.2: The pH Scale

As discussed earlier, hydronium and hydroxide ions are present both in pure water and in all aqueous solutions, and their
concentrations are inversely proportional as determined by the ion product of water (Kw). The concentrations of these ions in a
solution are often critical determinants of the solution’s properties and the chemical behaviors of its other solutes, and specific
vocabulary has been developed to describe these concentrations in relative terms. A solution is neutral if it contains equal
concentrations of hydronium and hydroxide ions; acidic if it contains a greater concentration of hydronium ions than hydroxide
ions; and basic if it contains a lesser concentration of hydronium ions than hydroxide ions.
A common means of expressing quantities, the values of which may span many orders of magnitude, is to use a logarithmic scale.
One such scale that is very popular for chemical concentrations and equilibrium constants is based on the p-function, defined as
shown where “X” is the quantity of interest and “log” is the base-10 logarithm:
pX = − log X (6.2.1)

The pH of a solution is therefore defined as shown here, where [H3O+] is the molar concentration of hydronium ion in the solution:
+
pH = − log[ H3 O ] (6.2.2)

Rearranging this equation to isolate the hydronium ion molarity yields the equivalent expression:
+ −pH
[ H3 O ] = 10 (6.2.3)

Likewise, the hydroxide ion molarity may be expressed as a p-function, or pOH:

−
pOH = − log[OH ] (6.2.4)

or
− −pOH
[OH ] = 10 (6.2.5)

Finally, the relation between these two ion concentration expressed as p-functions is easily derived from the K expression: w

+ −
Kw = [ H O ][ OH ]
3

+ −
− log Kw = − log([ H3 O ][OH ])

+ −
= − log[ H3 O ] + − log[OH ]

pKw = pH + pOH

At 25 °C, the value of K is 1.0 × 10

w
−14
and so:

6.2.2 https://chem.libretexts.org/@go/page/43431
 14.00 = pH + pOH (6.2.6)

The hydronium ion molarity in pure water (or any neutral solution) is 1.0 × 10
−7
M at 25 °C. The pH and pOH of a neutral
solution at this temperature are therefore:
+ −7
pH = − log[ H3 O ] = − log(1.0 × 10 ) = 7.00 (6.2.7)

− −7
pOH = − log[OH ] = − log(1.0 × 10 ) = 7.00 (6.2.8)

And so, at this temperature, acidic solutions are those with hydronium ion molarities greater than 1.0 × 10 M and hydroxide ion −7

molarities less than 1.0 × 10 M (corresponding to pH values less than 7.00 and pOH values greater than 7.00). Basic solutions
−7

are those with hydronium ion molarities less than 1.0 × 10 M and hydroxide ion molarities greater than 1.0 × 10 M
−7 −7

(corresponding to pH values greater than 7.00 and pOH values less than 7.00).
Since the autoionization constant K is temperature dependent, these correlations between pH values and the acidic/neutral/basic
w

adjectives will be different at temperatures other than 25 °C. For example, the hydronium molarity of pure water at 80 °C is 4.9 ×
10−7 M, which corresponds to pH and pOH values of:
+
pH = − log[ H3 O ]

−7
= − log(4.9 × 10 )

= 6.31

−
pOH = − log[OH ]

−7
= − log(4.9 × 10 )

= 6.31

At this temperature, then, neutral solutions exhibit pH = pOH = 6.31, acidic solutions exhibit pH less than 6.31 and pOH greater
than 6.31, whereas basic solutions exhibit pH greater than 6.31 and pOH less than 6.31. This distinction can be important when
studying certain processes that occur at nonstandard temperatures, such as enzyme reactions in warm-blooded organisms. Unless
otherwise noted, references to pH values are presumed to be those at standard temperature (25 °C) (Table 6.2.1).
Table 6.2.1 : Summary of Relations for Acidic, Basic and Neutral Solutions
Classification Relative Ion Concentrations pH at 25 °C pH at 80 °C

acidic [H3O+] > [OH−] pH < 7 pH < 6.31

neutral [H3O+] = [OH−] pH = 7 pH = 6.31

basic [H3O+] < [OH−] pH > 7 pH > 6.31

Figure 6.2.2 shows the relationships between [H3O+], [OH−], pH, and pOH, and gives values for these properties at standard
temperatures for some common substances.

6.2.3 https://chem.libretexts.org/@go/page/43431
 Figure 6.2.2 : The pH and pOH scales represent concentrations of [H3O+] and OH−, respectively. The pH and pOH values of some
common substances at standard temperature (25 °C) are shown in this chart.

 Example 6.2.1: Calculation of pH from [H 3

O
+
]

What is the pH of stomach acid, a solution of HCl with a hydronium ion concentration of 1.2 × 10 −3
M ?

Solution
+
pH = − log[ H3 O ]

−3
= − log(1.2 × 10 )

= −(−2.92) = 2.92

 Exercise 6.2.1
Water exposed to air contains carbonic acid, H2CO3, due to the reaction between carbon dioxide and water:

CO2(aq) + H O(l) ⇌ H CO3(aq)

2 2

Air-saturated water has a hydronium ion concentration caused by the dissolved CO of 2.0 × 10 2
−6
M , about 20-times larger
than that of pure water. Calculate the pH of the solution at 25 °C.

Answer
5.70

 Example 6.2.2: Calculation of Hydronium Ion Concentration from pH

Calculate the hydronium ion concentration of blood, the pH of which is 7.3.

6.2.4 https://chem.libretexts.org/@go/page/43431
 Solution
+
pH = − log[ H O ] = 7.3
3

+ −7.3
[H O ] = 10
3

+ −8
[H O ] = 5 × 10 M
3

(On a calculator take the antilog, or the “inverse” log, of −7.3, or calculate 10−7.3.)

 Exercise 6.2.2A

Calculate the hydronium ion concentration of a solution with a pH of −1.07.

Answer
12 M
This uses the definition of pH that we commonly use:
+
pH = − log[ H3 O ]

So for this solution:

+
pH = − log[ H O ] = −1.07
3

+ +1.07
[H O ] = 10
3

= 12 (with significant figure)

However, at this high concentration, the solution will be non-ideal and we have to use the proper definition in terms of
hydronium activities
+
pH = − log a{ H3 O }

See this module for more details.

 Exercise 6.2.2B

The ionization constant of water Kw at 37 °C is 2.42 × 10 −14

. What is the pH for a neutral solution at this human
physiological temperature? Is the water acidic, basic or neutral?

Answer
+ − −14
Kw = [ H O ][ OH ] = 2.42 × 10
3

and
− −−−−−−−− −
+ − −14
[H O ] = [ OH ] = √ 2.42 × 10
3

−7
= 1.55 × 10

+ −7
pH = − log[ H3 O ] = − log 1.55 × 10 = 6.81 (6.2.9)

If we use the definition of acidic systems like in Figure 6.2.2, then we would (incorrectly) argue the solution is acidic.
However, since [OH ] = [H O ] , the solution is still neutral. This is only a strange idea, if one ignores the temperature
−

3
+

dependence of Kw .

6.2.3: Environmental Science

Normal rainwater has a pH between 5 and 6 due to the presence of dissolved CO2 which forms carbonic acid:

H O(l) + CO2(g) ⟶ H CO3(aq) (6.2.10)

2 2

6.2.5 https://chem.libretexts.org/@go/page/43431
 + −
H CO3(aq) ⇌ H + HCO (6.2.11)
2 (aq) 3(aq)

Acid rain is rainwater that has a pH of less than 5, due to a variety of nonmetal oxides, including CO2, SO2, SO3, NO, and NO2
being dissolved in the water and reacting with it to form not only carbonic acid, but sulfuric acid and nitric acid. The formation and
subsequent ionization of sulfuric acid are shown here:
H O(l) + SO 3(g) ⟶ H SO 4(aq) (6.2.12)
2 2

+ −
H SO 4(aq) ⟶ H + HSO (6.2.13)
2 (aq) 4(aq)

Carbon dioxide is naturally present in the atmosphere because we and most other organisms produce it as a waste product of
metabolism. Carbon dioxide is also formed when fires release carbon stored in vegetation or when we burn wood or fossil fuels.
Sulfur trioxide in the atmosphere is naturally produced by volcanic activity, but it also stems from burning fossil fuels, which have
traces of sulfur, and from the process of “roasting” ores of metal sulfides in metal-refining processes. Oxides of nitrogen are
formed in internal combustion engines where the high temperatures make it possible for the nitrogen and oxygen in air to
chemically combine.

Figure 6.2.3: (a) Acid rain makes trees more susceptible to drought and insect infestation, and depletes nutrients in the soil. (b) It
also is corrodes statues that are carved from marble or limestone. (credit a: modification of work by Chris M Morris; credit b:
modification of work by “Eden, Janine and Jim”/Flickr)
Acid rain is a particular problem in industrial areas where the products of combustion and smelting are released into the air without
being stripped of sulfur and nitrogen oxides. In North America and Europe until the 1980s, it was responsible for the destruction of
forests and freshwater lakes, when the acidity of the rain actually killed trees, damaged soil, and made lakes uninhabitable for all
but the most acid-tolerant species. Acid rain also corrodes statuary and building facades that are made of marble and limestone
(Figure 6.2.3). Regulations limiting the amount of sulfur and nitrogen oxides that can be released into the atmosphere by industry
and automobiles have reduced the severity of acid damage to both natural and manmade environments in North America and
Europe. It is now a growing problem in industrial areas of China and India.
The acidity of a solution is typically assessed experimentally by measurement of its pH. The pOH of a solution is not usually
measured, as it is easily calculated from an experimentally determined pH value. The pH of a solution can be directly measured
using a pH meter (Figure 6.2.4).

Figure 6.2.4: (a) A research-grade pH meter used in a laboratory can have a resolution of 0.001 pH units, an accuracy of ± 0.002
pH units, and may cost in excess of $1000. (b) A portable pH meter has lower resolution (0.01 pH units), lower accuracy (± 0.2 pH
units), and a far lower price tag. (credit b: modification of work by Jacopo Werther).

6.2.6 https://chem.libretexts.org/@go/page/43431
  Example 6.2.3: Calculation of pOH
What are the pOH and the pH of a 0.0125-M solution of potassium hydroxide, KOH at 25 °C?

Solution
Potassium hydroxide is a highly soluble ionic compound and completely dissociates when dissolved in dilute solution, yielding
[OH−] = 0.0125 M:
−
pOH = − log[OH ] = − log 0.0125 (6.2.14)

= −(−1.903) = 1.903 (6.2.15)

The pH can be found from the pOH :

pH + pOH = 14.00 (6.2.16)

pH = 14.00 − pOH = 14.00 − 1.903 = 12.10 (6.2.17)

 Exercise 6.2.3

The hydronium ion concentration of vinegar is approximately 4 × 10

−3
M at 25 °C. What are the corresponding values of
pOH and pH?

Answer
pOH = 11.6, pH = 2.4

The pH of a solution may also be visually estimated using colored indicators (Figure 6.2.5).

Figure 6.2.5: (a) A universal indicator assumes a different color in solutions of different pH values. Thus, it can be added to a
solution to determine the pH of the solution. The eight vials each contain a universal indicator and 0.1-M solutions of progressively
weaker acids: HCl (pH = l), CH3CO2H (pH = 3), and NH4Cl (pH = 5), deionized water, a neutral substance (pH = 7); and 0.1-M
solutions of the progressively stronger bases: KCl (pH = 7), aniline, C6H5NH2 (pH = 9), NH3 (pH = 11), and NaOH (pH = 13). (b)
pH paper contains a mixture of indicators that give different colors in solutions of differing pH values. (credit: modification of
work by Sahar Atwa).

6.2.4: Summary
The concentration of hydronium ion in a solution of an acid in water is greater than 1.0 × 10 M at 25 °C. The concentration of
−7

hydroxide ion in a solution of a base in water is greater than 1.0 × 10 M at 25 °C. The concentration of H3O+ in a solution can
−7

be expressed as the pH of the solution; pH = − log H O . The concentration of OH− can be expressed as the pOH of the solution:
3
+

pOH = − log[ OH ] . In pure water, pH = 7.00 and pOH = 7.00

−

6.2.5: Key Equations

+
pH = − log[ H O ]
3
−
pOH = − log[ OH ]

[H3O+] = 10−pH
[OH−] = 10−pOH
pH + pOH = pKw = 14.00 at 25 °C

6.2.7 https://chem.libretexts.org/@go/page/43431
6.2.6: Glossary
acidic
describes a solution in which [H3O+] > [OH−]

basic
describes a solution in which [H3O+] < [OH−]

neutral
describes a solution in which [H3O+] = [OH−]

pH
logarithmic measure of the concentration of hydronium ions in a solution

pOH
logarithmic measure of the concentration of hydroxide ions in a solution

6.2.7: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

6.2: The Brønsted-Lowry Scheme is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
15.2: Properties of Acids and Bases in Aqueous Solutions is licensed CC BY-NC-SA 4.0.

6.2.8 https://chem.libretexts.org/@go/page/43431
6.3: Acid and Base Strength
 Learning Objectives
Assess the relative strengths of acids and bases according to their ionization constants
Rationalize trends in acid–base strength in relation to molecular structure
Carry out equilibrium calculations for weak acid–base systems

We can rank the strengths of acids by the extent to which they ionize in aqueous solution. The reaction of an acid with water is
given by the general expression:
+ −
HA(aq) + H O(l) ⇌ H O (aq) + A (aq) (6.3.1)
2 3

Water is the base that reacts with the acid HA, A is the conjugate base of the acid HA, and the hydronium ion is the conjugate
−

acid of water. A strong acid yields 100% (or very nearly so) of H O and A when the acid ionizes in water; Figure 6.3.1 lists
3
+ −

several strong acids. A weak acid gives small amounts of H O and A . 3

+ −

Figure 6.3.1 : Some of the common strong acids and bases are listed here.
Six Strong Acids Six Strong Bases

HClO
4
perchloric acid LiOH lithium hydroxide

HCl hydrochloric acid NaOH sodium hydroxide

HBr hydrobromic acid KOH potassium hydroxide

HI hydroiodic acid Ca(OH)

2
calcium hydroxide

HNO
3
nitric acid Sr(OH)
2
strontium hydroxide

H SO
2 4
sulfuric acid Ba(OH)
2
barium hydroxide

The relative strengths of acids may be determined by measuring their equilibrium constants in aqueous solutions. In solutions of the
same concentration, stronger acids ionize to a greater extent, and so yield higher concentrations of hydronium ions than do weaker
acids. The equilibrium constant for an acid is called the acid-ionization constant, Ka. For the reaction of an acid HA:
+ −
HA(aq) + H O(l) ⇌ H O (aq) + A (aq) (6.3.2)
2 3

we write the equation for the ionization constant as:

+ −
[H O ][ A ]
3
Ka = (6.3.3)
[HA]

where the concentrations are those at equilibrium. Although water is a reactant in the reaction, it is also the solvent. If the solution
is assumed to be dilute, the activity of the water is approximated by the activity of pure water, which is defined as having a value of
1. The larger the K of an acid, the larger the concentration of H O and A relative to the concentration of the nonionized acid,
a 3
+ −

HA . Thus a stronger acid has a larger ionization constant than does a weaker acid. The ionization constants increase as the

strengths of the acids increase.

The following data on acid-ionization constants indicate the order of acid strength: CH 3
CO H < HNO
2 2
< HSO
−
4

+ − −5
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO2 (aq) Ka = 1.8 × 10
3 2 2 3 3

+ − −4
HNO (aq) + H O(l) ⇌ H O (aq) + NO (aq) Ka = 4.6 × 10
2 2 3 2

− + 2− −2
HSO (aq) + H O(aq) ⇌ H O (aq) + SO (aq) Ka = 1.2 × 10
4 2 3 4

Another measure of the strength of an acid is its percent ionization. The percent ionization of a weak acid is the ratio of the
concentration of the ionized acid to the initial acid concentration, times 100:
+
[H O ]
3 eq
% ionization = × 100% (6.3.4)
[HA]
0

Access for free at OpenStax 6.3.1 https://chem.libretexts.org/@go/page/43432

Because the ratio includes the initial concentration, the percent ionization for a solution of a given weak acid varies depending on
the original concentration of the acid, and actually decreases with increasing acid concentration.

 Example 6.3.1: Calculation of Percent Ionization from pH

Calculate the percent ionization of a 0.125-M solution of nitrous acid (a weak acid), with a pH of 2.09.
Solution
The percent ionization for an acid is:
+
[H O ]
3 eq
× 100
[ HNO ]
2 0

The chemical equation for the dissociation of the nitrous acid is:
− +
HNO (aq) + H O(l) ⇌ NO (aq) + H O (aq).
2 2 2 3

Since 10 −pH
= [H O
3
+
] , we find that 10
−2.09
= 8.1 × 10
−3
M , so that percent ionization (Equation 6.3.4) is:
−3
8.1 × 10
× 100 = 6.5%
0.125

Remember, the logarithm 2.09 indicates a hydronium ion concentration with only two significant figures.

 Exercise 6.3.1

Calculate the percent ionization of a 0.10 M solution of acetic acid with a pH of 2.89.

Answer
1.3% ionized

We can rank the strengths of bases by their tendency to form hydroxide ions in aqueous solution. The reaction of a Brønsted-Lowry
base with water is given by:
+ −
B(aq) + H O(l) ⇌ HB (aq) + OH (aq) (6.3.5)
2

Water is the acid that reacts with the base, HB is the conjugate acid of the base B , and the hydroxide ion is the conjugate base of
+

water. A strong base yields 100% (or very nearly so) of OH− and HB+ when it reacts with water; Figure 6.3.1 lists several strong
bases. A weak base yields a small proportion of hydroxide ions. Soluble ionic hydroxides such as NaOH are considered strong
bases because they dissociate completely when dissolved in water.
As we did with acids, we can measure the relative strengths of bases by measuring their base-ionization constant (Kb) in aqueous
solutions. In solutions of the same concentration, stronger bases ionize to a greater extent, and so yield higher hydroxide ion
concentrations than do weaker bases. A stronger base has a larger ionization constant than does a weaker base. For the reaction of a
base, B :
+ −
B(aq) + H O(l) ⇌ HB (aq) + OH (aq), (6.3.6)
2

we write the equation for the ionization constant as:

+ −
[ HB ][ OH ]
Kb = (6.3.7)
[B]

where the concentrations are those at equilibrium. Again, we do not include [H2O] in the equation because water is the solvent. The
chemical reactions and ionization constants of the three bases shown are:

Access for free at OpenStax 6.3.2 https://chem.libretexts.org/@go/page/43432

 − − −11
NO (aq) + H O(l) ⇌ HNO (aq) + OH (aq) Kb = 2.17 × 10
2 2 2

− − −10
CH CO2 (aq) + H O(l) ⇌ CH CO H(aq) + OH (aq) Kb = 5.6 × 10
3 2 3 2

+ − −5
NH (aq) + H O(l) ⇌ NH (aq) + OH (aq) Kb = 1.8 × 10
3 2 4

A table of ionization constants of weak bases appears in Table E2. As with acids, percent ionization can be measured for basic
solutions, but will vary depending on the base ionization constant and the initial concentration of the solution.
Consider the ionization reactions for a conjugate acid-base pair, HA − A : −

+ −
HA(aq) + H O(l) ⇌ H O (aq) + A (aq) (6.3.8)
2 3

+ −
[H O ][ A ]
with K a =
3
.
[HA]

− −
A (aq) + H O(l) ⇌ OH (aq) + HA(aq) (6.3.9)
2

[HA][OH]
with K b =
−
.
[A ]

Adding these two chemical equations yields the equation for the autoionization for water:
− + − −
HA(aq) + H O(l) + A (aq) + H O(l) ⇌ H O (aq) + A (aq) + OH (aq) + HA(aq)
2 2 3

+ −
2 H O(l) ⇌ H O (aq) + OH (aq)
2 3

As shown in the previous chapter on equilibrium, the K expression for a chemical equation derived from adding two or more other
equations is the mathematical product of the other equations’ K expressions. Multiplying the mass-action expressions together and
cancelling common terms, we see that:
+ − −
[H O ][ A ] [HA][ OH ]
3 + −
Ka × Kb = × = [H O ][ OH ] = Kw (6.3.10)
− 3
[HA] [A ]

For example, the acid ionization constant of acetic acid (CH3COOH) is 1.8 × 10−5, and the base ionization constant of its conjugate
base, acetate ion (CH COO ), is 5.6 × 10−10. The product of these two constants is indeed equal to K :
3
−
w

−5 −10 −14
Ka × Kb = (1.8 × 10 ) × (5.6 × 10 ) = 1.0 × 10 = Kw (6.3.11)

The extent to which an acid, HA, donates protons to water molecules depends on the strength of the conjugate base, A , of the −

acid. If A is a strong base, any protons that are donated to water molecules are recaptured by A . Thus there is relatively little
− −

A
−
and H O in solution, and the acid, HA, is weak. If A is a weak base, water binds the protons more strongly, and the
3
+ −

solution contains primarily A and H O —the acid is strong. Strong acids form very weak conjugate bases, and weak acids form
−

3
+

stronger conjugate bases (Figure 6.3.2).

Figure 6.3.2 : This diagram shows the relative strengths of conjugate acid-base pairs, as indicated by their ionization constants in
aqueous solution.
Figure 6.3.3 lists a series of acids and bases in order of the decreasing strengths of the acids and the corresponding increasing
strengths of the bases. The acid and base in a given row are conjugate to each other.

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The first six acids in Figure 6.3.3 are the most common strong acids. These acids are completely dissociated in aqueous solution.
The conjugate bases of these acids are weaker bases than water. When one of these acids dissolves in water, their protons are
completely transferred to water, the stronger base.
Those acids that lie between the hydronium ion and water in Figure 6.3.3 form conjugate bases that can compete with water for
possession of a proton. Both hydronium ions and nonionized acid molecules are present in equilibrium in a solution of one of these
acids. Compounds that are weaker acids than water (those found below water in the column of acids) in Figure 6.3.3 exhibit no
observable acidic behavior when dissolved in water. Their conjugate bases are stronger than the hydroxide ion, and if any conjugate
base were formed, it would react with water to re-form the acid.

Figure 6.3.3 : The chart shows the relative strengths of conjugate acid-base pairs.
The extent to which a base forms hydroxide ion in aqueous solution depends on the strength of the base relative to that of the
hydroxide ion, as shown in the last column in Figure 6.3.3. A strong base, such as one of those lying below hydroxide ion, accepts
protons from water to yield 100% of the conjugate acid and hydroxide ion. Those bases lying between water and hydroxide ion
accept protons from water, but a mixture of the hydroxide ion and the base results. Bases that are weaker than water (those that lie
above water in the column of bases) show no observable basic behavior in aqueous solution.

 Example 6.3.2: The Product Ka × Kb = Kw

Use the K for the nitrite ion, NO , to calculate the K for its conjugate acid.
b
−
2 a

Solution
Kb for NO is given in this section as 2.17 × 10−11. The conjugate acid of
−

2
NO
−

2
is HNO2; Ka for HNO2 can be calculated
using the relationship:
−14
Ka × Kb = 1.0 × 10 = Kw

Solving for Ka, we get:

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 Kw
Ka =
Kb

−14
1.0 × 10
=
−11
2.17 × 10

−4
= 4.6 × 10

This answer can be verified by finding the Ka for HNO2 in Table E1

 Exercise 6.3.2

We can determine the relative acid strengths of NH and HCN by comparing their ionization constants. The ionization
+
4

constant of HCN is given in Table E1 as 4.9 × 10−10. The ionization constant of NH is not listed, but the ionization constant
+
4

of its conjugate base, NH , is listed as 1.8 × 10−5. Determine the ionization constant of NH , and decide which is the stronger
3
+
4

acid, HCN or NH . +
4

Answer
NH
+
4
is the slightly stronger acid (Ka for NH = 5.6 × 10−10).
+
4

6.3.1: Summary
The strengths of Brønsted-Lowry acids and bases in aqueous solutions can be determined by their acid or base ionization constants.
Stronger acids form weaker conjugate bases, and weaker acids form stronger conjugate bases. Thus strong acids are completely
ionized in aqueous solution because their conjugate bases are weaker bases than water. Weak acids are only partially ionized
because their conjugate bases are strong enough to compete successfully with water for possession of protons. Strong bases react
with water to quantitatively form hydroxide ions. Weak bases give only small amounts of hydroxide ion.

6.3.2: Key Equations

+ −
[H O ][ A ]
3
Ka =
[HA]
+ −
[ HB ][ OH ]
Kb =
[B]
−14
Ka × Kb = 1.0 × 10 = Kw (at room temperature)

6.3.3: Glossary
acid ionization constant (Ka)
equilibrium constant for the ionization of a weak acid

base ionization constant (Kb)

equilibrium constant for the ionization of a weak base

leveling effect of water

any acid stronger than H O , or any base stronger than OH− will react with water to form H O , or OH−, respectively; water
3
+
3
+

acts as a base to make all strong acids appear equally strong, and it acts as an acid to make all strong bases appear equally
strong

percent ionization
ratio of the concentration of the ionized acid to the initial acid concentration, times 100

6.3.4: Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed

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 under a Creative Commons Attribution License 4.0 license. Download for free at http://cnx.org/contents/85abf193-
2bd...a7ac8df6@9.110).

This page titled 6.3: Acid and Base Strength is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
OpenStax.
14.3: Relative Strengths of Acids and Bases by OpenStax is licensed CC BY 4.0. Original source:
https://openstax.org/details/books/chemistry-2e.

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6.4: Equilibria Involving Weak Acids and Bases
 Learning Objectives
Rationalize trends in acid–base strength in relation to molecular structure
Carry out equilibrium calculations for weak acid–base systems

Many acids and bases are weak; that is, they do not ionize fully in aqueous solution. A solution of a weak acid in water is a mixture
of the nonionized acid, hydronium ion, and the conjugate base of the acid, with the nonionized acid present in the greatest
concentration. Thus, a weak acid increases the hydronium ion concentration in an aqueous solution (but not as much as the same
amount of a strong acid).
Acetic acid (CH 3
CO H
2
) is a weak acid. When we add acetic acid to water, it ionizes to a small extent according to the equation:
+ −
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO (aq)
3 2 2 3 3 2

giving an equilibrium mixture with most of the acid present in the nonionized (molecular) form. This equilibrium, like other
equilibria, is dynamic; acetic acid molecules donate hydrogen ions to water molecules and form hydronium ions and acetate ions at
the same rate that hydronium ions donate hydrogen ions to acetate ions to reform acetic acid molecules and water molecules. We
can tell by measuring the pH of an aqueous solution of known concentration that only a fraction of the weak acid is ionized at any
moment (Figure 6.4.1). The remaining weak acid is present in the nonionized form.
For acetic acid, at equilibrium:
+ −
[H O ][ CH CO ]
3 3 2 −5
Ka = = 1.8 × 10
[ CH CO H]
3 2

Figure 6.4.1 : pH paper indicates that a 0.l-M solution of HCl (beaker on left) has a pH of 1. The acid is fully ionized and [H O ] 3
+

= 0.1 M. A 0.1-M solution of CH3CO2H (beaker on right) has a pH of 3 ( [H O ] = 0.001 M) because the weak acid CH3CO2H is
3
+

only partially ionized. In this solution, [H O ] < [CH CO H] . (credit: modification of work by Sahar Atwa)
3
+

3 2

Table 6.4.1 : Ionization Constants of Some Weak Acids

Ionization Reaction Ka at 25 °C

HSO
−

4
+H O ⇌ H O
2 3
+
+ SO
2−

4
1.2 × 10−2

HF + H O ⇌ H O
2 3
+
+F
−
3.5 × 10−4

HNO
2
+H O ⇌ H O
2 3
+
+ NO
−

2
4.6 × 10−4

HNCO + H O ⇌ H O
2 3
+
+ NCO
−
2 × 10−4

HCO H + H O ⇌ H O
2 2 3
+
+ HCO
−

2
1.8 × 10−4

CH CO H + H O ⇌ H O
3 2 2 3
+
+ CH CO
3
−

2
1.8 × 10−5

HCIO + H O ⇌ H O
2 3
+
+ CIO
−
2.9 × 10−8

HBrO + H O ⇌ H O
2 3
+
+ BrO
−
2.8 × 10−9

HCN + H O ⇌ H O
2 3
+
+ CN
−
4.9 × 10−10

6.4.1 https://chem.libretexts.org/@go/page/43433
Table 6.4.1 gives the ionization constants for several weak acids; additional ionization constants can be found in Table E1.
At equilibrium, a solution of a weak base in water is a mixture of the nonionized base, the conjugate acid of the weak base, and
hydroxide ion with the nonionized base present in the greatest concentration. Thus, a weak base increases the hydroxide ion
concentration in an aqueous solution (but not as much as the same amount of a strong base).
For example, a solution of the weak base trimethylamine, (CH3)3N, in water reacts according to the equation:
+ −
(CH ) N(aq) + H O(l) ⇌ (CH ) NH (aq) + OH (aq)
3 3 2 3 3

This gives an equilibrium mixture with most of the base present as the nonionized amine. This equilibrium is analogous to that
described for weak acids.
We can confirm by measuring the pH of an aqueous solution of a weak base of known concentration that only a fraction of the base
reacts with water (Figure 6.4.2). The remaining weak base is present as the unreacted form. The equilibrium constant for the
ionization of a weak base, K , is called the ionization constant of the weak base, and is equal to the reaction quotient when the
b

reaction is at equilibrium. For trimethylamine, at equilibrium:

+ −
[ (CH ) NH ][ OH ]
3 3
Kb =
[ (CH ) N]
3 3

Figure 6.4.2 : pH paper indicates that a 0.1-M solution of NH3 (left) is weakly basic. The solution has a pOH of 3 ([OH−] = 0.001
M) because the weak base NH3 only partially reacts with water. A 0.1-M solution of NaOH (right) has a pOH of 1 because NaOH
is a strong base (credit: modification of work by Sahar Atwa).
The ionization constants of several weak bases are given in Table 6.4.2 and Table E2.
Table 6.4.2 : Ionization Constants of Some Weak Bases
Ionization Reaction Kb at 25 °C

(CH ) NH + H O ⇌ (CH ) NH
3 2 2 3 2
+
2
+ OH
−
5.9 × 10−4

CH NH
3 2
+ H O ⇌ CH NH
2 3
+
3
+ OH
−
4.4 × 10−4

(CH ) N + H O ⇌ (CH ) NH
3 3 2 3 3
+
+ OH
−
6.3 × 10−5

NH
3
+ H O ⇌ NH
2
+
4
+ OH
−
1.8 × 10−5

C H NH
6 5 2
+ H O ⇌ C N NH
2 6 5
+
3
+ OH
−
4.3 × 10−10

 Example 6.4.3: Determination of Ka from Equilibrium Concentrations

Acetic acid is the principal ingredient in vinegar; that's why it tastes sour. At equilibrium, a solution contains [CH3CO2H] =
0.0787 M and [H O ] = [CH CO ] = 0.00118 M. What is the value of K for acetic acid?
3
+

3
−

2 a

6.4.2 https://chem.libretexts.org/@go/page/43433
 Vinegar is a solution of acetic acid, a weak acid. (credit: modification of work by “HomeSpot HQ”/Flickr)
Solution
We are asked to calculate an equilibrium constant from equilibrium concentrations. At equilibrium, the value of the equilibrium
constant is equal to the reaction quotient for the reaction:
+ −
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO (aq)
3 2 2 3 3 2

+ −
[H O ][ CH CO ]
3 3 2
Ka =
[ CH CO H]
3 2

(0.00118)(0.00118)
=
0.0787

−5
= 1.77 × 10

 Exercise 6.4.3

What is the equilibrium constant for the ionization of the HSO ion, the weak acid used in some household cleansers:
−

− + 2−
HSO (aq) + H O(l) ⇌ H O (aq) + SO (aq)
4 2 3 4

In one mixture of NaHSO4 and Na2SO4 at equilibrium, [H 3

O
+
] = 0.027 M; [HSO −
4
] = 0.29 M ; and [SO 2−
4
] = 0.13 M .

Answer
Ka for HSO −

4
= 1.2 × ×10
−2

 Example 6.4.4: Determination of Kb from Equilibrium Concentrations

Caffeine, C8H10N4O2 is a weak base. What is the value of Kb for caffeine if a solution at equilibrium has [C8H10N4O2] = 0.050
M, [C H N O H ] = 5.0 × 10−3 M, and [OH−] = 2.5 × 10−3 M?
8 10 4 2
+

Solution
At equilibrium, the value of the equilibrium constant is equal to the reaction quotient for the reaction:
+ −
C H N O (aq) + H O(l) ⇌ C H N O H (aq) + OH (aq)
8 10 4 2 2 8 10 4 2

so
+ − −3 −3
[C H N O H ][ OH ] (5.0 × 10 )(2.5 × 10 )
8 10 4 2 −4
Kb = = = 2.5 × 10
[C H N O ] 0.050
8 10 4 2

 Exercise 6.4.4

What is the equilibrium constant for the ionization of the HPO 2−

4
ion, a weak base:
2− − −
HPO (aq) + H O(l) ⇌ H PO (aq) + OH (aq)
4 2 2 4

6.4.3 https://chem.libretexts.org/@go/page/43433
In a solution containing a mixture of NaH 2
PO
4
and Na 2
HPO
4
at equilibrium with:
− −6
[ OH ] = 1.3 × 10 M
−
[ H PO4 ]=0 ⋅ 042 M
2
and
[ HPO
2 −
4
]=0 ⋅ 341 M .

Answer
Kb for HPO 2−
4
= 1.6 × 10
−7

 Example 6.4.5: Determination of Ka or Kb from pH

The pH of a 0.0516-M solution of nitrous acid, HNO , is 2.34. What is its K ? 2 a

+ −
HNO (aq) + H O(l) ⇌ H O (aq) + NO (aq)
2 2 3 2

Solution
We determine an equilibrium constant starting with the initial concentrations of HNO2, H O , and NO as well as one of the 3
+ −

final concentrations, the concentration of hydronium ion at equilibrium. (Remember that pH is simply another way to express
the concentration of hydronium ion.)
We can solve this problem with the following steps in which x is a change in concentration of a species in the reaction:

We can summarize the various concentrations and changes as shown here (the concentration of water does not appear in the
expression for the equilibrium constant, so we do not need to consider its concentration):

To get the various values in the ICE (Initial, Change, Equilibrium) table, we first calculate [H O
3
+
, the equilibrium
]

concentration of H O , from the pH:

3
+

+ −2.34
[H O ] = 10 = 0.0046 M
3

The change in concentration of H O

3
+
, x
[H O
+
]
, is the difference between the equilibrium concentration of H3O+, which we
3

determined from the pH, and the initial concentration, [H O ] . The initial concentration of H
3
+
i 3
O
+
is its concentration in pure
water, which is so much less than the final concentration that we approximate it as zero (~0).

6.4.4 https://chem.libretexts.org/@go/page/43433
The change in concentration of NO is equal to the change in concentration of [H O ]. For each 1 mol of H O that forms,
−

2 3
+

3
+

1 mol of NO forms. The equilibrium concentration of HNO2 is equal to its initial concentration plus the change in its
−

concentration.
Now we can fill in the ICE table with the concentrations at equilibrium, as shown here:

Finally, we calculate the value of the equilibrium constant using the data in the table:
+ −
[H O ][ NO2 ] (0.0046)(0.0046)
3 −4
Ka = = = 4.5 × 10
[ HNO ] (0.0470)
2

 Exercise 6.4.5

The pH of a solution of household ammonia, a 0.950-M solution of NH3, is 11.612. What is Kb for NH3.

Answer
−5
Kb = 1.8 × 10

 Example 6.4.6: Equilibrium Concentrations in a Solution of a Weak Acid

Formic acid, HCO2H, is the irritant that causes the body’s reaction to ant stings.

The pain of an ant’s sting is caused by formic acid. (credit: John Tann)
What is the concentration of hydronium ion and the pH in a 0.534-M solution of formic acid?
+ − −4
HCO H(aq) + H O(l) ⇌ H O (aq) + HCO (aq) Ka = 1.8 × 10
2 2 3 2

Solution
1. Determine x and equilibrium concentrations. The equilibrium expression is:
+ −
HCO H(aq) + H O(l) ⇌ H O (aq) + HCO (aq)
2 2 3 2

The concentration of water does not appear in the expression for the equilibrium constant, so we do not need to consider its
change in concentration when setting up the ICE table.
The table shows initial concentrations (concentrations before the acid ionizes), changes in concentration, and equilibrium
concentrations follows (the data given in the problem appear in color):

6.4.5 https://chem.libretexts.org/@go/page/43433
 2. Solve for x and the equilibrium concentrations. At equilibrium:
+ −
[H O ][ HCO ]
−4 3 2
Ka = 1.8 × 10 =
[ HCO H]
2

(x)(x)
−4
= = 1.8 × 10
0.534 − x

Now solve for x. Because the initial concentration of acid is reasonably large and K is very small, we assume that a

x << 0.534, which permits us to simplify the denominator term as (0.534 − x) = 0.534. This gives:

2
x
−4
Ka = 1.8 × 10 =
0.534

Solve for x as follows:

2 −4
x = 0.534 × (1.8 × 10 )

−5
= 9.6 × 10

−−−−−−− −
−5
x = √ 9.6 × 10

−3
= 9.8 × 10

To check the assumption that x is small compared to 0.534, we calculate:

−3
x 9.8 × 10
=
0.534 0.534

−2
= 1.8 × 10 (1.8% of 0.534)

x is less than 5% of the initial concentration; the assumption is valid.

We find the equilibrium concentration of hydronium ion in this formic acid solution from its initial concentration and the change in
that concentration as indicated in the last line of the table:
+ −3
[H O ] = 0 + x = 0 + 9.8 × 10 M.
3

−3
= 9.8 × 10 M

The pH of the solution can be found by taking the negative log of the [H 3
O
+
], so:
−3
pH = − log(9.8 × 10 ) = 2.01

 Exercise 6.4.6: acetic acid

Only a small fraction of a weak acid ionizes in aqueous solution. What is the percent ionization of acetic acid in a 0.100-M
solution of acetic acid, CH3CO2H?
+ − −5
CH CO H(aq) + H O(l) ⇌ H O (aq) + CH CO (aq) Ka = 1.8 × 10
3 2 2 3 3 2

Hint
Determine [CH 3
−
CO
2
] at equilibrium.) Recall that the percent ionization is the fraction of acetic acid that is ionized × 100,
−
[ CH CO2 ]
3
or × 100 .
[ CH CO H]
3 2 initial

6.4.6 https://chem.libretexts.org/@go/page/43433
 Answer
percent ionization = 1.3%

The following example shows that the concentration of products produced by the ionization of a weak base can be determined by
the same series of steps used with a weak acid.

 Example 6.4.7: Equilibrium Concentrations in a Solution of a Weak Base

Find the concentration of hydroxide ion in a 0.25-M solution of trimethylamine, a weak base:
+ − −5
(CH ) N(aq) + H O(l) ⇌ (CH ) NH (aq) + OH (aq) Kb = 6.3 × 10
3 3 2 3 3

Solution This problem requires that we calculate an equilibrium concentration by determining concentration changes as the
ionization of a base goes to equilibrium. The solution is approached in the same way as that for the ionization of formic acid in
Example 6.4.6. The reactants and products will be different and the numbers will be different, but the logic will be the same:

1. Determine x and equilibrium concentrations. The table shows the changes and concentrations:

2. Solve for x and the equilibrium concentrations. At equilibrium:

+ −
[ (CH ) NH ][ OH ] (x)(x)
3 3 −5
Kb = = 6.3 × 10
[ (CH ) N] 0.25 − x =
3 3

If we assume that x is small relative to 0.25, then we can replace (0.25 − x) in the preceding equation with 0.25. Solving the
simplified equation gives:
−3
x = 4.0 × 10

This change is less than 5% of the initial concentration (0.25), so the assumption is justified.
Recall that, for this computation, x is equal to the equilibrium concentration of hydroxide ion in the solution (see earlier
tabulation):
− −3
([ OH ] = 0 + x = x = 4.0 × 10 M

−3
= 4.0 × 10 M

Then calculate pOH as follows:

−3
pOH = − log(4.3 × 10 ) = 2.40

Using the relation introduced in the previous section of this chapter:

pH + pOH = pKw = 14.00

permits the computation of pH:

pH = 14.00 − pOH = 14.00 − 2.37 = 11.60

6.4.7 https://chem.libretexts.org/@go/page/43433
 Check the work. A check of our arithmetic shows that K b = 6.3 × 10
−5
.

 Exercise 6.4.7
a. Show that the calculation in Step 2 of this example gives an x of 4.3 × 10−3 and the calculation in Step 3 shows Kb = 6.3 ×
10−5.
b. Find the concentration of hydroxide ion in a 0.0325-M solution of ammonia, a weak base with a Kb of 1.76 × 10−5.
+
[ NH ]
4
Calculate the percent ionization of ammonia, the fraction ionized × 100, or × 100%
[ NH ]
3

Answer a
7.56 × 10
−4
M , 2.33%
Answer b
2.33%

Some weak acids and weak bases ionize to such an extent that the simplifying assumption that x is small relative to the initial
concentration of the acid or base is inappropriate. As we solve for the equilibrium concentrations in such cases, we will see that we
cannot neglect the change in the initial concentration of the acid or base, and we must solve the equilibrium equations by using the
quadratic equation.

 Example 6.4.8: Equilibrium Concentrations in a Solution of a Weak Acid

Sodium bisulfate, NaHSO4, is used in some household cleansers because it contains the −
HSO 4 ion, a weak acid. What is the
pH of a 0.50-M solution of HSO ? −
4

− + 2− −2
HSO (aq) + H O(l) ⇌ H O (aq) + SO (aq) Ka = 1.2 × 10
4 2 3 4

Solution
We need to determine the equilibrium concentration of the hydronium ion that results from the ionization of HSO so that we −
4

can use [H O ] to determine the pH. As in the previous examples, we can approach the solution by the following steps:
3
+

1. Determine x and equilibrium concentrations. This table shows the changes and concentrations:

2. Solve for x and the concentrations.

As we begin solving for x, we will find this is more complicated than in previous examples. As we discuss these complications
we should not lose track of the fact that it is still the purpose of this step to determine the value of x.
At equilibrium:

6.4.8 https://chem.libretexts.org/@go/page/43433
 + 2−
[H O ][ SO ] (x)(x)
−2 3 4
Ka = 1.2 × 10 = =
−
[ HSO ] 0.50 − x
4

If we assume that x is small and approximate (0.50 − x) as 0.50, we find:

−2
x = 7.7 × 10

When we check the assumption, we confirm:

x ?

≤ 0.05
−
[HSO ]i
4

which for this system is

−2
x 7.7 × 10
= = 0.15(15%)
0.50 0.50

The value of x is not less than 5% of 0.50, so the assumption is not valid. We need the quadratic formula to find x.
The equation:
(x)(x)
−2
Ka = 1.2 × 10 =
0.50 − x

gives
−3 −2 2+
6.0 × 10 − 1.2 × 10 x =x

or
2+ −2 −3
x + 1.2 × 10 x − 6.0 × 10 =0

This equation can be solved using the quadratic formula. For an equation of the form
2+
ax + bx + c = 0,

x is given by the quadratic equation:

− −−−−− −−
−b ± √ b2+ − 4ac
x =
2a

In this problem, a = 1 , b = 1.2 × 10 −3

, and c = −6.0 × 10 −3
.
Solving for x gives a negative root (which cannot be correct since concentration cannot be negative) and a positive root:
−2
x = 7.2 × 10

Now determine the hydronium ion concentration and the pH:

+ −2
[H O ] = 0 + x = 0 + 7.2 × 10 M
3

−2
= 7.2 × 10 M

The pH of this solution is:

+ −2
pH = −log[ H3 O ] = −log7.2 × 10 = 1.14

 Exercise 6.4.8
a. Show that the quadratic formula gives x = 7.2 × 10 . −2

b. Calculate the pH in a 0.010-M solution of caffeine, a weak base:

+ − −4
C H N O (aq) + H O(l) ⇌ C H N O H (aq) + OH (aq) Kb = 2.5 × 10
8 10 4 2 2 8 10 4 2

Hint

6.4.9 https://chem.libretexts.org/@go/page/43433
 It will be necessary to convert [OH−] to [H 3
+
O ] or pOH to pH toward the end of the calculation.

Answer
pH 11.16

6.4.1: The Relative Strengths of Strong Acids and Bases

Strong acids, such as HCl, HBr , and HI , all exhibit the same strength in water. The water molecule is such a strong base compared
to the conjugate bases Cl−, Br−, and I− that ionization of these strong acids is essentially complete in aqueous solutions. In solvents
less basic than water, we find HCl, HBr , and HI differ markedly in their tendency to give up a proton to the solvent. For example,
when dissolved in ethanol (a weaker base than water), the extent of ionization increases in the order HCl < HBr < HI , and so HI
is demonstrated to be the strongest of these acids. The inability to discern differences in strength among strong acids dissolved in
water is known as the leveling effect of water.
Water also exerts a leveling effect on the strengths of strong bases. For example, the oxide ion, O2−, and the amide ion, NH , are −
2

such strong bases that they react completely with water:

2− − −
O (aq) + H O(l) ⟶ OH (aq) + OH (aq) (6.4.1)
2

− −
NH (aq) + H O(l) ⟶ NH (aq) + OH (aq) (6.4.2)
2 2 3

Thus, O2− and NH appear to have the same base strength in water; they both give a 100% yield of hydroxide ion.
−

In the absence of any leveling effect, the acid strength of binary compounds of hydrogen with nonmetals (A) increases as the H-A
bond strength decreases down a group in the periodic table. For group 17, the order of increasing acidity is
HF < HCl < HBr < HI . Likewise, for group 16, the order of increasing acid strength is H2O < H2S < H2Se < H2Te. Across a

row in the periodic table, the acid strength of binary hydrogen compounds increases with increasing electronegativity of the
nonmetal atom because the polarity of the H-A bond increases. Thus, the order of increasing acidity (for removal of one proton)
across the second row is CH < NH < H O < HF ; across the third row, it is SiH < PH < H S < HCl (see Figure 6.4.3).
4 3 2 4 3 2

Figure 6.4.3 : As you move from left to right and down the periodic table, the acid strength increases. As you move from right to
left and up, the base strength increases.
Compounds containing oxygen and one or more hydroxyl (OH) groups can be acidic, basic, or amphoteric, depending on the
position in the periodic table of the central atom E, the atom bonded to the hydroxyl group. Such compounds have the general
formula OnE(OH)m, and include sulfuric acid, O S(OH) , sulfurous acid, OS(OH) , nitric acid, O NOH , perchloric acid,
2 2 2 2

O ClOH, aluminum hydroxide, Al(OH) , calcium hydroxide, Ca(OH) , and potassium hydroxide, KOH :
3 3 2

6.4.10 https://chem.libretexts.org/@go/page/43433
If the central atom, E, has a low electronegativity, its attraction for electrons is low. Little tendency exists for the central atom to
form a strong covalent bond with the oxygen atom, and bond a between the element and oxygen is more readily broken than bond b
between oxygen and hydrogen. Hence bond a is ionic, hydroxide ions are released to the solution, and the material behaves as a
base—this is the case with Ca(OH)2 and KOH. Lower electronegativity is characteristic of the more metallic elements; hence, the
metallic elements form ionic hydroxides that are by definition basic compounds.
If, on the other hand, the atom E has a relatively high electronegativity, it strongly attracts the electrons it shares with the oxygen
atom, making bond a relatively strongly covalent. The oxygen-hydrogen bond, bond b, is thereby weakened because electrons are
displaced toward E. Bond b is polar and readily releases hydrogen ions to the solution, so the material behaves as an acid. High
electronegativities are characteristic of the more nonmetallic elements. Thus, nonmetallic elements form covalent compounds
containing acidic −OH groups that are called oxyacids.
Increasing the oxidation number of the central atom E also increases the acidity of an oxyacid because this increases the attraction
of E for the electrons it shares with oxygen and thereby weakens the O-H bond. Sulfuric acid, H2SO4, or O2S(OH)2 (with a sulfur
oxidation number of +6), is more acidic than sulfurous acid, H2SO3, or OS(OH)2 (with a sulfur oxidation number of +4). Likewise
nitric acid, HNO3, or O2NOH (N oxidation number = +5), is more acidic than nitrous acid, HNO2, or ONOH (N oxidation number
= +3). In each of these pairs, the oxidation number of the central atom is larger for the stronger acid (Figure 6.4.4).

Figure 6.4.4 : As the oxidation number of the central atom E increases, the acidity also increases.
Hydroxy compounds of elements with intermediate electronegativities and relatively high oxidation numbers (for example,
elements near the diagonal line separating the metals from the nonmetals in the periodic table) are usually amphoteric. This means
that the hydroxy compounds act as acids when they react with strong bases and as bases when they react with strong acids. The
amphoterism of aluminum hydroxide, which commonly exists as the hydrate Al(H O) (OH) , is reflected in its solubility in both
2 3 3

strong acids and strong bases. In strong bases, the relatively insoluble hydrated aluminum hydroxide, Al(H O) (OH) , is 2 3 3

converted into the soluble ion, [Al(H O) (OH) ] , by reaction with hydroxide ion:
2 2 4
−

− −
[Al (H O) (OH) ](aq) + OH (aq) ⇌ H O(l) + [Al (H O) (OH) ] (aq)
2 3 3 2 2 2 4

In this reaction, a proton is transferred from one of the aluminum-bound H2O molecules to a hydroxide ion in solution. The
Al(H O) (OH)
2 3 3
compound thus acts as an acid under these conditions. On the other hand, when dissolved in strong acids, it is
3+
converted to the soluble ion [Al(H O) ] by reaction with hydronium ion:
2 6

+ 3+
3H O (aq) + Al (H O) (OH) (aq) ⇌ Al (H O) (aq) + 3 H O(l)
3 2 3 3 2 6 2

In this case, protons are transferred from hydronium ions in solution to Al(H 2
O) (OH)
3 3
, and the compound functions as a base.

6.4.2: Summary
The strengths of Brønsted-Lowry acids and bases in aqueous solutions can be determined by their acid or base ionization constants.
Stronger acids form weaker conjugate bases, and weaker acids form stronger conjugate bases. Thus strong acids are completely
ionized in aqueous solution because their conjugate bases are weaker bases than water. Weak acids are only partially ionized
because their conjugate bases are strong enough to compete successfully with water for possession of protons. Strong bases react
with water to quantitatively form hydroxide ions. Weak bases give only small amounts of hydroxide ion. The strengths of the
binary acids increase from left to right across a period of the periodic table (CH4 < NH3 < H2O < HF), and they increase down a

6.4.11 https://chem.libretexts.org/@go/page/43433
group (HF < HCl < HBr < HI). The strengths of oxyacids that contain the same central element increase as the oxidation number of
the element increases (H2SO3 < H2SO4). The strengths of oxyacids also increase as the electronegativity of the central element
increases [H2SeO4 < H2SO4].

6.4.3: Key Equations

+ −
[H O ][ A ]
3
Ka =
[HA]
+ −
[ HB ][ OH ]
Kb =
[B]
−14
Ka × Kb = 1.0 × 10 = Kw (at room temperature)
+
[H O ]
3 eq
Percent ionization = × 100
[HA]
0

6.4.4: Glossary
acid ionization constant (Ka)
equilibrium constant for the ionization of a weak acid

base ionization constant (Kb)

equilibrium constant for the ionization of a weak base

leveling effect of water

any acid stronger than H O , or any base stronger than OH− will react with water to form H O , or OH−, respectively; water
3
+

3
+

acts as a base to make all strong acids appear equally strong, and it acts as an acid to make all strong bases appear equally
strong

oxyacid
compound containing a nonmetal and one or more hydroxyl groups

percent ionization
ratio of the concentration of the ionized acid to the initial acid concentration, times 100

6.4: Equilibria Involving Weak Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.
14.3: Relative Strengths of Acids and Bases by OpenStax is licensed CC BY 4.0. Original source:
https://openstax.org/details/books/chemistry-2e.

6.4.12 https://chem.libretexts.org/@go/page/43433
6.5: Buffer Solutions
 Learning Objectives
To understand how adding a common ion affects the position of an acid–base equilibrium.
To know how to use the Henderson-Hasselbalch approximation to calculate the pH of a buffer.

Buffers are solutions that maintain a relatively constant pH when an acid or a base is added. They therefore protect, or “buffer,”
other molecules in solution from the effects of the added acid or base. Buffers contain either a weak acid (H A) and its conjugate
base (A ) or a weak base (B ) and its conjugate acid (BH ), and they are critically important for the proper functioning of
− +

biological systems. In fact, every biological fluid is buffered to maintain its physiological pH.

6.5.1: The Common Ion Effect: Weak Acids Combined with Conjugate Bases
To understand how buffers work, let’s look first at how the ionization equilibrium of a weak acid is affected by adding either the
conjugate base of the acid or a strong acid (a source of H ). Le Chatelier’s principle can be used to predict the effect on the
+

equilibrium position of the solution. A typical buffer used in biochemistry laboratories contains acetic acid and a salt such as
sodium acetate. The dissociation reaction of acetic acid is as follows:
− +
CH COOH(aq) −
↽⇀
− CH COO (aq) + H (aq) (6.5.1)
3 3

and the equilibrium constant expression is as follows:

+ −
[H ][ CH COO ]
3
Ka = (6.5.2)
[ CH CO H]
3 2

Sodium acetate (CH CO Na) is a strong electrolyte that ionizes completely in aqueous solution to produce Na and CH CO
3 2
+
3
−

ions. If sodium acetate is added to a solution of acetic acid, Le Chatelier’s principle predicts that the equilibrium in Equation 6.5.1
will shift to the left, consuming some of the added CH COO and some of the H ions originally present in solution.
3
− +

Because Na is a spectator ion, it has no effect on the position of the equilibrium and can be ignored. The addition of sodium
+

acetate produces a new equilibrium composition, in which [H ] is less than the initial value. Because [H ] has decreased, the pH
+ +

will be higher. Thus adding a salt of the conjugate base to a solution of a weak acid increases the pH. This makes sense because
sodium acetate is a base, and adding any base to a solution of a weak acid should increase the pH.
If we instead add a strong acid such as HCl to the system, [H ] increases. Once again the equilibrium is temporarily disturbed, but
+

the excess H ions react with the conjugate base (CH CO ), whether from the parent acid or sodium acetate, to drive the
+

3
−

equilibrium to the left. The net result is a new equilibrium composition that has a lower [CH CO ] than before. In both cases,
3
−

only the equilibrium composition has changed; the ionization constant K for acetic acid remains the same. Adding a strong
a

electrolyte that contains one ion in common with a reaction system that is at equilibrium, in this case CH CO , will therefore shift
3
−

the equilibrium in the direction that reduces the concentration of the common ion. The shift in equilibrium is via the common ion
effect.

Adding a common ion to a system at equilibrium affects the equilibrium composition, but
not the ionization constant.

 Example 6.5.1
A 0.150 M solution of formic acid at 25°C (pKa = 3.75) has a pH of 2.28 and is 3.5% ionized.
a. Is there a change to the pH of the solution if enough solid sodium formate is added to make the final formate concentration
0.100 M (assume that the formic acid concentration does not change)?
b. What percentage of the formic acid is ionized if 0.200 M HCl is added to the system?
Given: solution concentration and pH, pK , and percent ionization of acid; final concentration of conjugate base or strong acid
a

added
Asked for: pH and percent ionization of formic acid

6.5.1 https://chem.libretexts.org/@go/page/43434
Strategy:
A. Write a balanced equilibrium equation for the ionization equilibrium of formic acid. Tabulate the initial concentrations, the
changes, and the final concentrations.
B. Substitute the expressions for the final concentrations into the expression for Ka. Calculate [H ] and the pH of the solution.
+

C. Construct a table of concentrations for the dissociation of formic acid. To determine the percent ionization, determine the
anion concentration, divide it by the initial concentration of formic acid, and multiply the result by 100.
Solution:
A Because sodium formate is a strong electrolyte, it ionizes completely in solution to give formate and sodium ions. The Na +

ions are spectator ions, so they can be ignored in the equilibrium equation. Because water is both a much weaker acid than
formic acid and a much weaker base than formate, the acid–base properties of the solution are determined solely by the formic
acid ionization equilibrium:
− +
HCO H(aq) −
↽⇀
− HCO2 (aq) + H (aq)
2

The initial concentrations, the changes in concentration that occur as equilibrium is reached, and the final concentrations can be
tabulated.
Final Concentration
ICE [HCO2 H(aq)] [H
+
(aq)] [HCO− (aq)]
2

Initial 0.150 1.00 × 10

−7
0.100

Change −x +x +x

Equilibrium (0.150 − x) x (0.100 + x)

B We substitute the expressions for the final concentrations into the equilibrium constant expression and make our usual
simplifying assumptions, so
+ −
[H ][H C O ] (x)(0.100 + x)
2
Ka = =
[H C O2 H ] 0.150 − x

x(0.100)
≈
0.150

−3.75
≈ 10

−4
≈ 1.8 × 10

Rearranging and solving for x,

−4
0.150 M
x = (1.8 × 10 )×
0.100 M

−4
= 2.7 × 10

+
= [H ]

The value of x is small compared with 0.150 or 0.100 M, so our assumption about the extent of ionization is justified.
Moreover,
−4 −5
Ka CH A = (1.8 × 10 )(0.150) = 2.7 × 10

which is greater than 1.0 × 10 −6

, so again, our assumption is justified. The final pH is:
−4
pH = − log(2.7 × 10 ) = 3.57

compared with the initial value of 2.29. Thus adding a salt containing the conjugate base of the acid has increased the pH of the
solution, as we expect based on Le Chatelier’s principle; the stress on the system has been relieved by the consumption of H +

ions, driving the equilibrium to the left.

6.5.2 https://chem.libretexts.org/@go/page/43434
C Because H C l is a strong acid, it ionizes completely, and chloride is a spectator ion that can be neglected. Thus the only
relevant acid–base equilibrium is again the dissociation of formic acid, and initially the concentration of formate is zero. We
can construct a table of initial concentrations, changes in concentration, and final concentrations.
+ −
H C O2 H (aq) ⇋ H (aq) + H C O (aq)
2

initial concentrations, changes in concentration, and final concentrations

+ −
[HC O2 H(aq)] [H (aq)] [HC O (aq)]
2

initial 0.150 0.200 0

change −x +x +x

final (0.150 − x) (0.200 + x) x

To calculate the percentage of formic acid that is ionized under these conditions, we have to determine the final [HCO ]. We −
2

substitute final concentrations into the equilibrium constant expression and make the usual simplifying assumptions, so
+ −
[H ][H C O ] (0.200 + x)(x) x(0.200)
2 −4
Ka = = ≈ = 1.80 × 10
[H C O2 H ] 0.150 − x 0.150

Rearranging and solving for x,

−4
0.150 M
x = (1.80 × 10 )×
0.200 M

−4 −
= 1.35 × 10 = [H C O ]
2

Once again, our simplifying assumptions are justified. The percent ionization of formic acid is as follows:
−4
1.35 × 10 M
percent ionization = × 100% = 0.0900%
0.150 M

Adding the strong acid to the solution, as shown in the table, decreased the percent ionization of formic acid by a factor of
approximately 38 (3.45%/0.0900%). Again, this is consistent with Le Chatelier’s principle: adding H ions drives the +

dissociation equilibrium to the left.

 Exercise 6.5.1

A 0.225 M solution of ethylamine (CH 3

CH NH
2 2
with p Kb = 3.19 ) has a pH of 12.08 and a percent ionization of 5.4% at
20°C. Calculate the following:
a. the pH of the solution if enough solid ethylamine hydrochloride (EtNH 3
Cl ) is added to make the solution 0.100 M in
+
EtNH
3

b. the percentage of ethylamine that is ionized if enough solid NaOH is added to the original solution to give a final
concentration of 0.050 M NaOH

Answer a
11.16
Answer b
1.3%

6.5.3 https://chem.libretexts.org/@go/page/43434
 The Common Ion Effect

A Video Discussing the Common Ion Effect: The Common Ion Effecr(opens in new window) [youtu.be]

6.5.2: The Common Ion Effect: Weak Bases Combined with Conjugate Acids
Now let’s suppose we have a buffer solution that contains equimolar concentrations of a weak base (B ) and its conjugate acid (
BH
+
). The general equation for the ionization of a weak base is as follows:
+ −
B(aq) + H2 O(l) ⇋ BH (aq) + OH (aq) (6.5.3)

If the equilibrium constant for the reaction as written in Equation 6.5.3 is small, for example Kb = 10
−5
, then the equilibrium
1
constant for the reverse reaction is very large: K =
5
= 10 . Adding a strong base such as OH
−
to the solution therefore
Kb

causes the equilibrium in Equation 6.5.3 to shift to the left, consuming the added OH . As a result, the OH ion concentration in
− −

solution remains relatively constant, and the pH of the solution changes very little. Le Chatelier’s principle predicts the same
outcome: when the system is stressed by an increase in the OH ion concentration, the reaction will proceed to the left to
−

counteract the stress.

If the pK of the base is 5.0, the pK of its conjugate acid is
b a

p Ka = p Kw − p Kb = 14.0– 5.0 = 9.0.

Thus the equilibrium constant for ionization of the conjugate acid is even smaller than that for ionization of the base. The ionization
reaction for the conjugate acid of a weak base is written as follows:
+ +
BH (aq) + H2 O(l) ⇋ B(aq) + H3 O (aq) (6.5.4)

Again, the equilibrium constant for the reverse of this reaction is very large: K = 1/Ka = 109. If a strong acid is added, it is
neutralized by reaction with the base as the reaction in Equation 6.5.4 shifts to the left. As a result, the H ion concentration does
+

not increase very much, and the pH changes only slightly. In effect, a buffer solution behaves somewhat like a sponge that can
absorb H and OH ions, thereby preventing large changes in pH when appreciable amounts of strong acid or base are added to a
+ −

solution.
Buffers are characterized by the pH range over which they can maintain a more or less constant pH and by their buffer capacity, the
amount of strong acid or base that can be absorbed before the pH changes significantly. Although the useful pH range of a buffer
depends strongly on the chemical properties of the weak acid and weak base used to prepare the buffer (i.e., on K ), its buffer
capacity depends solely on the concentrations of the species in the buffered solution. The more concentrated the buffer solution, the
greater its buffer capacity. As illustrated in Figure 6.5.1, when N aOH is added to solutions that contain different concentrations of
an acetic acid/sodium acetate buffer, the observed change in the pH of the buffer is inversely proportional to the concentration of
the buffer. If the buffer capacity is 10 times larger, then the buffer solution can absorb 10 times more strong acid or base before
undergoing a significant change in pH.

6.5.4 https://chem.libretexts.org/@go/page/43434
 Figure 6.5.1 : Effect of Buffer Concentration on the Capacity of a Buffer. (CC BY-SA-NC; Anonymous by request)
Graph of pH of solution against volume of NaOH added. Six different buffer concentrations are plotted.
A buffer maintains a relatively constant pH when acid or base is added to a solution. The addition of even tiny volumes of 0.10 M
N aOH to 100.0 mL of distilled water results in a very large change in pH. As the concentration of a 50:50 mixture of sodium

acetate/acetic acid buffer in the solution is increased from 0.010 M to 1.00 M, the change in the pH produced by the addition of the
same volume of N aOH solution decreases steadily. For buffer concentrations of at least 0.500 M, the addition of even 25 mL of
the N aOH solution results in only a relatively small change in pH.

6.5.3: Calculating the pH of a Buffer

The pH of a buffer can be calculated from the concentrations of the weak acid and the weak base used to prepare it, the
concentration of the conjugate base and conjugate acid, and the pK or pK of the weak acid or weak base. The procedure is
a b

analogous to that used in Example 6.5.1 to calculate the pH of a solution containing known concentrations of formic acid and
formate.
An alternative method frequently used to calculate the pH of a buffer solution is based on a rearrangement of the equilibrium
equation for the dissociation of a weak acid. The simplified ionization reaction is H A ⇋ H + A , for which the equilibrium
+ −

constant expression is as follows:

+ −
[H ][ A ]
Ka = (6.5.5)
[H A]

This equation can be rearranged as follows:

[H A]
+
[H ] = Ka (6.5.6)
−
[A ]

Taking the logarithm of both sides and multiplying both sides by −1,
[H A]
+
− log[ H ] = − log Ka − log( ) (6.5.7)
−
[A ]

−
[A ]
= − log Ka + log( ) (6.5.8)
[H A]

Replacing the negative logarithms in Equation 6.5.8,

−
[A ]
pH = p Ka + log( ) (6.5.9)
[H A]

or, more generally,

6.5.5 https://chem.libretexts.org/@go/page/43434
 [base]
pH = p Ka + log( ) (6.5.10)
[acid]

Equation 6.5.9 and Equation 6.5.10 are both forms of the Henderson-Hasselbalch approximation, named after the two early 20th-
century chemists who first noticed that this rearranged version of the equilibrium constant expression provides an easy way to
calculate the pH of a buffer solution. In general, the validity of the Henderson-Hasselbalch approximation may be limited to
solutions whose concentrations are at least 100 times greater than their K values. a

There are three special cases where the Henderson-Hasselbalch approximation is easily interpreted without the need for
calculations:
[base] = [acid] : Under these conditions,
[base]
=1
[acid]

in Equation 6.5.10. Because log 1 = 0,

pH = pKa

regardless of the actual concentrations of the acid and base. Recall that this corresponds to the midpoint in the titration of a
weak acid or a weak base.
[base]/[acid] = 10: In Equation 6.5.10, because log 10 = 1,

pH = p Ka + 1.

[base]/[acid] = 100 : In Equation 6.5.10, because log 100 = 2,

pH = p Ka + 2.

Each time we increase the [base]/[acid] ratio by 10, the pH of the solution increases by 1 pH unit. Conversely, if the [base]/[acid]
ratio is 0.1, then pH = pK − 1. Each additional factor-of-10 decrease in the [base]/[acid] ratio causes the pH to decrease by 1 pH
a

unit.

If [base] = [acid] for a buffer, then pH = pK . Changing this ratio by a factor of 10 either way changes the pH by ±1 unit.
a

 Example 6.5.2

What is the pH of a solution that contains

a. 0.135 M HCO H and 0.215 M HCO Na? (The pK of formic acid is 3.75.)
2 2 a

b. 0.0135 M HCO H and 0.0215 M HCO Na?

2 2

c. 0.119 M pyridine and 0.234 M pyridine hydrochloride? (The pK of pyridine is 8.77.)

b

Given: concentration of acid, conjugate base, and pK ; concentration of base, conjugate acid, and pK
a b

Asked for: pH
Strategy:
Substitute values into either form of the Henderson-Hasselbalch approximation (Equations 6.5.9 or 6.5.10) to calculate the pH.
Solution:
According to the Henderson-Hasselbalch approximation (Equation 6.5.9), the pH of a solution that contains both a weak acid
and its conjugate base is

pH = p Ka + log([A−]/[H A]).

A
Inserting the given values into the equation,

6.5.6 https://chem.libretexts.org/@go/page/43434
 0.215
pH = 3.75 + log( )
0.135

= 3.75 + log 1.593

= 3.95

This result makes sense because the [A −

]/[H A] ratio is between 1 and 10, so the pH of the buffer must be between the pKa

(3.75) and pK + 1 , or 4.75.

a

B
This is identical to part (a), except for the concentrations of the acid and the conjugate base, which are 10 times lower.
Inserting the concentrations into the Henderson-Hasselbalch approximation,
0.0215
pH = 3.75 + log( )
0.0135

= 3.75 + log 1.593

= 3.95

This result is identical to the result in part (a), which emphasizes the point that the pH of a buffer depends only on the ratio of
the concentrations of the conjugate base and the acid, not on the magnitude of the concentrations. Because the [A−]/[HA] ratio
is the same as in part (a), the pH of the buffer must also be the same (3.95).

C
In this case, we have a weak base, pyridine (Py), and its conjugate acid, the pyridinium ion (H P y ). We will therefore use
+

Equation 6.5.10, the more general form of the Henderson-Hasselbalch approximation, in which “base” and “acid” refer to the
appropriate species of the conjugate acid–base pair. We are given [base] = [Py] = 0.119 M and [acid] = [H P y ] = 0.234 M. +

We also are given pK = 8.77 for pyridine, but we need pK for the pyridinium ion. Recall from Equation 16.23 that the pK
b a b

of a weak base and the pK of its conjugate acid are related:

a

p Ka + p Kb = p Kw .

Thus pK for the pyridinium ion is

a p Kw − p Kb = 14.00 − 8.77 = 5.23 . Substituting this pKa value into the Henderson-
Hasselbalch approximation,
[base]
pH = p Ka + log( )
[acid]

0.119
= 5.23 + log( )
0.234

= 5.23 −0.294

= 4.94

Once again, this result makes sense: the [B]/[BH +

] ratio is about 1/2, which is between 1 and 0.1, so the final pH must be
between the pK (5.23) and pK − 1 , or 4.23.
a a

 Exercise 6.5.2

What is the pH of a solution that contains

a. 0.333 M benzoic acid and 0.252 M sodium benzoate?
b. 0.050 M trimethylamine and 0.066 M trimethylamine hydrochloride?
The pK of benzoic acid is 4.20, and the pK of trimethylamine is also 4.20.
a b

6.5.7 https://chem.libretexts.org/@go/page/43434
 Answer a
4.08
Answer b
9.68

Using the Henderson Hasselbalch Equa…

Equa…

A Video Discussing Using the Henderson Hasselbalch Equation: Using the Henderson Hasselbalch Equation(opens in new
window) [youtu.be] (opens in new window)
The Henderson-Hasselbalch approximation ((Equation 6.5.9) can also be used to calculate the pH of a buffer solution after adding
a given amount of strong acid or strong base, as demonstrated in Example 6.5.3.

 Example 6.5.3
The buffer solution in Example 6.5.2 contained 0.135 M HCO 2
H and 0.215 M HCO 2
Na and had a pH of 3.95.
a. What is the final pH if 5.00 mL of 1.00 M H C l are added to 100 mL of this solution?
b. What is the final pH if 5.00 mL of 1.00 M N aOH are added?
Given: composition and pH of buffer; concentration and volume of added acid or base
Asked for: final pH

Strategy:
A. Calculate the amounts of formic acid and formate present in the buffer solution using the procedure from Example 6.5.1.
Then calculate the amount of acid or base added.
B. Construct a table showing the amounts of all species after the neutralization reaction. Use the final volume of the solution
to calculate the concentrations of all species. Finally, substitute the appropriate values into the Henderson-Hasselbalch
approximation (Equation 6.5.10) to obtain the pH.
Solution:
The added HCl (a strong acid) or NaOH (a strong base) will react completely with formate (a weak base) or formic acid (a
weak acid), respectively, to give formic acid or formate and water. We must therefore calculate the amounts of formic acid and
formate present after the neutralization reaction.
A We begin by calculating the millimoles of formic acid and formate present in 100 mL of the initial pH 3.95 buffer:

0.135 mmol HCO H

2
100 mL ( ) = 13.5 mmol HCO H
2
mL

6.5.8 https://chem.libretexts.org/@go/page/43434
 −
0.215 mmol HCO
2 −
100 mL ( ) = 21.5 mmol HCO
2
mL

The millimoles of H in 5.00 mL of 1.00 M HCl is as follows:

+

+
1.00 mmol H
+
5.00 mL ( ) = 5 mmol H
mL

B Next, we construct a table of initial amounts, changes in amounts, and final amounts:
2 − +
HCO (aq) + H (aq) −
↽⇀
− HCO H(aq)
2

initial amounts, changes in amounts, and final amounts:

2− +
HC O (aq) H (aq) HC O2 H(aq)

Initial 21.5 mmol 5.00 mmol 13.5 mmol

Change −5.00 mmol −5.00 mmol +5.00 mmol

Final 16.5 mmol ∼0 mmol 18.5 mmol

The final amount of H in solution is given as “∼0 mmol.” For the purposes of the stoichiometry calculation, this is
+

essentially true, but remember that the point of the problem is to calculate the final [H ] and thus the pH. We now have all the
+

information we need to calculate the pH. We can use either the lengthy procedure of Example 6.5.1 or the Henderson–
Hasselbach approximation. Because we have performed many equilibrium calculations in this chapter, we’ll take the latter
approach. The Henderson-Hasselbalch approximation requires the concentrations of H C O and H C O H , which can be −

2 2

calculated using the number of millimoles (n ) of each and the total volume (V T ). Substituting these values into the
Henderson-Hasselbalch approximation (Equation 6.5.10):
−
[H C O ]
2
pH = p Ka + log( )
[H C O2 H ]

nH C O− / Vf
2
= p Ka + log( )
nH C O2 H / Vf

nH C O−
2
= p Ka + log( )
nH C O H
2

Because the total volume appears in both the numerator and denominator, it cancels. We therefore need to use only the ratio of
the number of millimoles of the conjugate base to the number of millimoles of the weak acid. So
n −
H C O2
pH = p Ka + log( )
nH C O2 H

16.5 mmol
= 3.75 + log( )
18.5 mmol

= 3.75 −0.050 = 3.70

Once again, this result makes sense on two levels. First, the addition of H C lhas decreased the pH from 3.95, as expected.
Second, the ratio of H C O to H C O H is slightly less than 1, so the pH should be between the pK and pK − 1.
−

2 2 a a

A The procedure for solving this part of the problem is exactly the same as that used in part (a). We have already calculated the
numbers of millimoles of formic acid and formate in 100 mL of the initial pH 3.95 buffer: 13.5 mmol of H C O H and 21.5 2

mmol of H C O . The number of millimoles of OH in 5.00 mL of 1.00 M N aOH is as follows:

−
2
−

B With this information, we can construct a table of initial amounts, changes in amounts, and final amounts.
− −
HCO H(aq) + OH (aq) −
↽⇀
− HCO (aq) + H O(l)
2 2 2

initial amounts, changes in amounts, and final amounts

6.5.9 https://chem.libretexts.org/@go/page/43434
 −
− −
−
HC O2 H(aq) OH HC O (aq)
2 22

Initial 13.5 mmol 5.00 mmol 21.5 mmol

Change −5.00 mmol −5.00 mmol +5.00 mmol

Final 8.5 mmol ∼0 mmol 26.5 mmol

The final amount of OH in solution is not actually zero; this is only approximately true based on the stoichiometric
−

calculation. We can calculate the final pH by inserting the numbers of millimoles of both H C O and H C O H into the
−
2 2

simplified Henderson-Hasselbalch expression used in part (a) because the volume cancels:
nH C O−
2
pH = p Ka + log( )
nH C O
2H

26.5 mmol
= 3.75 + log( )
8.5 mmol

= 3.75 + 0.494 = 4.24

Once again, this result makes chemical sense: the pH has increased, as would be expected after adding a strong base, and the
final pH is between the pK and pK + 1, as expected for a solution with a H C O /H C O H ratio between 1 and 10.
a a
−

2 2

 Exercise 6.5.3

The buffer solution from Example 6.5.2 contained 0.119 M pyridine and 0.234 M pyridine hydrochloride and had a pH of
4.94.
a. What is the final pH if 12.0 mL of 1.5 M NaOH are added to 250 mL of this solution?
b. What is the final pH if 12.0 mL of 1.5 M HCl are added?

Answer a
5.30
Answer b
4.42

Only the amounts (in moles or millimoles) of the acidic and basic components of the buffer are needed to use the Henderson-
Hasselbalch approximation, not their concentrations.

The Change in pH with the Addition of a…

a…

A Video Discussing the Change in pH with the Addition of a Strong Acid to a Buffer: The Change in pH with the Addition of a
Strong Acid to a Buffer(opens in new window) [youtu.be]

6.5.10 https://chem.libretexts.org/@go/page/43434
 The Change in pH with the Addition of a…
a…

The Change in pH with the Addition of a Strong Base to a Buffer:

The Change in pH with the Addition of a Strong Base to a Buffer (opens in new window) [youtu.be]
The results obtained in Example 6.5.3 and its corresponding exercise demonstrate how little the pH of a well-chosen buffer
solution changes despite the addition of a significant quantity of strong acid or strong base. Suppose we had added the same
amount of H C l or N aOH solution to 100 mL of an unbuffered solution at pH 3.95 (corresponding to 1.1 × 10 M HCl). In this −4

case, adding 5.00 mL of 1.00 M H C l would lower the final pH to 1.32 instead of 3.70, whereas adding 5.00 mL of 1.00 M N aOH
would raise the final pH to 12.68 rather than 4.24. (Try verifying these values by doing the calculations yourself.) Thus the
presence of a buffer significantly increases the ability of a solution to maintain an almost constant pH.

The most effective buffers contain equal concentrations of an acid and its conjugate base.
A buffer that contains approximately equal amounts of a weak acid and its conjugate base in solution is equally effective at
neutralizing either added base or added acid. This is shown in Figure 6.5.2 for an acetic acid/sodium acetate buffer. Adding a given
amount of strong acid shifts the system along the horizontal axis to the left, whereas adding the same amount of strong base shifts
the system the same distance to the right. In either case, the change in the ratio of C H C O to C H C O H from 1:1 reduces the
3
−

2 3 2

buffer capacity of the solution.

Figure 6.5.2 : Distribution Curve Showing the Fraction of Acetic Acid Molecules and Acetate Ions as a Function of pH in a
Solution of Acetic Acid. The pH range over which the acetic acid/sodium acetate system is an effective buffer (the darker shaded
region) corresponds to the region in which appreciable concentrations of both species are present (pH 3.76–5.76, corresponding to
pH = pK ± 1 ). (CC BY-SA-NC; Anonymous by request)
a

Graph of mole fraction against pH of solution. The green line is acetic acid and the purple line is the acetate ion.

6.5.11 https://chem.libretexts.org/@go/page/43434
 The Buffer Region

A Video Discussing The Buffer Region: The Buffer Region (opens in new window) [youtu.be]

6.5.4: The Relationship between Titrations and Buffers

There is a strong correlation between the effectiveness of a buffer solution and the titration curves discussed in Section 16.5.
Consider the schematic titration curve of a weak acid with a strong base shown in Figure 6.5.3. As indicated by the labels, the
region around pK corresponds to the midpoint of the titration, when approximately half the weak acid has been neutralized. This
a

portion of the titration curve corresponds to a buffer: it exhibits the smallest change in pH per increment of added strong base, as
shown by the nearly horizontal nature of the curve in this region. The nearly flat portion of the curve extends only from
approximately a pH value of 1 unit less than the pK to approximately a pH value of 1 unit greater than the pK , which is why
a a

buffer solutions usually have a pH that is within ±1 pH units of the pK of the acid component of the buffer.
a

Figure 6.5.3 : The Relationship between Titration Curves and Buffers. (CC BY-SA-NC; Anonymous by request)
Titration curves graph pH of solution against volume of strong base added. On the curve we look for the midpoints and equivalence
points.
This schematic plot of pH for the titration of a weak acid with a strong base shows the nearly flat region of the titration curve
around the midpoint, which corresponds to the formation of a buffer. At the lower left, the pH of the solution is determined by the
equilibrium for dissociation of the weak acid; at the upper right, the pH is determined by the equilibrium for reaction of the
conjugate base with water.
In the region of the titration curve at the lower left, before the midpoint, the acid–base properties of the solution are dominated by
the equilibrium for dissociation of the weak acid, corresponding to K . In the region of the titration curve at the upper right, after
a

the midpoint, the acid–base properties of the solution are dominated by the equilibrium for reaction of the conjugate base of the

6.5.12 https://chem.libretexts.org/@go/page/43434
weak acid with water, corresponding to K . However, we can calculate either K or K from the other because they are related by
b a b

K .
w

 Blood: A Most Important Buffer

Metabolic processes produce large amounts of acids and bases, yet organisms are able to maintain an almost constant internal
pH because their fluids contain buffers. This is not to say that the pH is uniform throughout all cells and tissues of a mammal.
The internal pH of a red blood cell is about 7.2, but the pH of most other kinds of cells is lower, around 7.0. Even within a
single cell, different compartments can have very different pH values. For example, one intracellular compartment in white
blood cells has a pH of around 5.0.
Because no single buffer system can effectively maintain a constant pH value over the entire physiological range of
approximately pH 5.0 to 7.4, biochemical systems use a set of buffers with overlapping ranges. The most important of these is
the CO /HCO system, which dominates the buffering action of blood plasma.
2
−

The acid–base equilibrium in the CO 2

/ HCO
−
3
buffer system is usually written as follows:
+ −
H CO (aq) −
↽⇀
− H (aq) + HCO (aq) (6.5.11)
2 3 3

with Ka = 4.5 × 10and pK = 6.35 at 25°C. In fact, Equation 6.5.11 is a grossly oversimplified version of the
−7
a

CO / HCO3
2
system because a solution of CO in water contains only rather small amounts of H C O . Thus Equation
−

2 2 3

6.5.11 does not allow us to understand how blood is actually buffered, particularly at a physiological temperature of 37°C.

As shown in Equation 6.5.12, CO is in equilibrium with

2
H CO
2 3
, but the equilibrium lies far to the left, with an
H CO / CO ratio less than 0.01 under most conditions:
2 3 2

CO (aq) + H O(l) −
↽⇀
− H CO (aq) (6.5.12)
2 2 2 3

with K' = 4.0 × 10 at 37°C. The true pK of carbonic acid at 37°C is therefore 3.70, not 6.35, corresponding to a K of
−3
a a

2.0 × 10 , which makes it a much stronger acid than Equation 6.5.11 suggests. Adding Equation 6.5.11 and Equation 6.5.12
−4

and canceling H CO from both sides give the following overall equation for the reaction of CO with water to give a proton
2 3 2

and the bicarbonate ion:

CO (aq) + H O(l) −
↽⇀
− H CO (aq) (6.5.13)
2 2 2 3

with K ′
= 4.0 × 10
−3
(37°C )

+ −
H CO (aq) −
↽⇀
− H (aq) + HCO (aq) (6.5.14)
2 3 3

with K a = 2.0 × 10
−4
(37°C )

+ −
CO (aq) + H O(l) −
↽⇀
− H (aq) + HCO (aq) (6.5.15)
2 2 3

with K = 8.0 × 10 −7
(37°C )

The K value for the reaction in Equation 6.5.15 is the product of the true ionization constant for carbonic acid (K ) and the a

equilibrium constant (K) for the reaction of CO (aq) with water to give carbonic acid. The equilibrium equation for the
2

reaction of CO with water to give bicarbonate and a proton is therefore

2

+ −
[H ][ HCO ]
3 −7
K = = 8.0 × 10 (6.5.16)
[ CO ]
2

The presence of a gas in the equilibrium constant expression for a buffer is unusual. According to Henry’s law,

[ CO ] = kPCO
2 2

where k is the Henry’s law constant for CO , which is 3.0 × 102

−5
M /mmH g at 37°C. Substituting this expression for [CO 2
]

in Equation 6.5.16,
+ −
[H ][ HCO ]
3
K =
−5
(3.0 × 10 M /mmH g)(PCO )
2

6.5.13 https://chem.libretexts.org/@go/page/43434
where P CO
2
is in mmHg. Taking the negative logarithm of both sides and rearranging,
−
[ HCO ]
3
pH = 6.10 + log( ) (6.5.17)
−5
(3.0 × 10 M /mm H g) (PCO )
2

Thus the pH of the solution depends on both the CO pressure over the solution and [HCO ]. Figure 6.5.4 plots the
2
−
3

relationship between pH and [HCO ] under physiological conditions for several different values of P
−
3
, with normal pH and CO
2

[ HCO ] values indicated by the dashed lines.

−

Figure 6.5.4 : Buffering in Blood: pH versus [HCO ] Curves for Buffers with Different Values of P
−
3
. Only those CO
2

combinations of pH and [HCO ] that lie on a given line are allowed for the particular value of P
−
3
indicated. Normal values
CO
2

of blood plasma pH and [HCO ] are indicated by dashed lines. (CC BY-SA-NC; Anonymous by request)
−
3

According to Equation 6.5.17, adding a strong acid to the CO /HCO system causes [HCO ] to decrease as HCO is
2
−
3
−
3
−
3

converted to CO . Excess CO is released in the lungs and exhaled into the atmosphere, however, so there is essentially no
2 2

change in P . Because the change in [HCO ]/P

CO
2
−
3
is small, Equation 6.5.17 predicts that the change in pH will also be
C O2

rather small. Conversely, if a strong base is added, the OH reacts with CO to form HCO , but CO is replenished by the
−
2
−
3 2

body, again limiting the change in both [HCO ]/P −

3 CO
2
and pH. The CO /HCO buffer system is an example of an open
2
−
3

system, in which the total concentration of the components of the buffer change to keep the pH at a nearly constant value.
If a passenger steps out of an airplane in Denver, Colorado, for example, the lower P at higher elevations (typically 31
CO
2

mmHg at an elevation of 2000 m versus 40 mmHg at sea level) causes a shift to a new pH and [HCO ]. The increase in pH −

and decrease in [HCO ] in response to the decrease in P

−

3
are responsible for the general malaise that many people
CO
2

experience at high altitudes. If their blood pH does not adjust rapidly, the condition can develop into the life-threatening
phenomenon known as altitude sickness.

6.5.14 https://chem.libretexts.org/@go/page/43434
 Summary of the pH Curve for a Strong …

A Video Summary of the pH Curve for a Strong Acid/Strong Base Titration:

Summary of the pH Curve for a Strong Acid/Strong Base Titration(opens in new window) [youtu.be]

6.5.5: Summary
Buffers are solutions that resist a change in pH after adding an acid or a base. Buffers contain a weak acid (H A) and its conjugate
weak base (A ). Adding a strong electrolyte that contains one ion in common with a reaction system that is at equilibrium shifts
−

the equilibrium in such a way as to reduce the concentration of the common ion. The shift in equilibrium is called the common ion
effect. Buffers are characterized by their pH range and buffer capacity. The useful pH range of a buffer depends strongly on the
chemical properties of the conjugate weak acid–base pair used to prepare the buffer (the K or K ), whereas its buffer capacity
a b

depends solely on the concentrations of the species in the solution. The pH of a buffer can be calculated using the Henderson-
Hasselbalch approximation, which is valid for solutions whose concentrations are at least 100 times greater than their K values. a

Because no single buffer system can effectively maintain a constant pH value over the physiological range of approximately 5 to
7.4, biochemical systems use a set of buffers with overlapping ranges. The most important of these is the C O /H C O system,
2
−
3

which dominates the buffering action of blood plasma.

6.5: Buffer Solutions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
17.2: Buffered Solutions by Anonymous is licensed CC BY-NC-SA 3.0.

6.5.15 https://chem.libretexts.org/@go/page/43434
6.6: Acid-Base Titration Curves
 Learning Objectives
To calculate the pH at any point in an acid–base titration.

In an acid–base titration, a buret is used to deliver measured volumes of an acid or a base solution of known concentration (the
titrant) to a flask that contains a solution of a base or an acid, respectively, of unknown concentration (the unknown). If the
concentration of the titrant is known, then the concentration of the unknown can be determined. The following discussion focuses
on the pH changes that occur during an acid–base titration. Plotting the pH of the solution in the flask against the amount of acid or
base added produces a titration curve. The shape of the curve provides important information about what is occurring in solution
during the titration.

6.6.1: Titrations of Strong Acids and Bases

Figure 6.6.1a shows a plot of the pH as 0.20 M HCl is gradually added to 50.00 mL of pure water. The pH of the sample in the
flask is initially 7.00 (as expected for pure water), but it drops very rapidly as HCl is added. Eventually the pH becomes constant at
0.70—a point well beyond its value of 1.00 with the addition of 50.0 mL of HCl (0.70 is the pH of 0.20 M HCl). In contrast, when
0.20 M NaOH is added to 50.00 mL of distilled water, the pH (initially 7.00) climbs very rapidly at first but then more gradually,
eventually approaching a limit of 13.30 (the pH of 0.20 M NaOH), again well beyond its value of 13.00 with the addition of 50.0
mL of NaOH as shown in Figure 6.6.1b. As you can see from these plots, the titration curve for adding a base is the mirror image
of the curve for adding an acid.

Figure 6.6.1 : Solution pH as a Function of the Volume of a Strong Acid or a Strong Base Added to Distilled Water. (a) When 0.20
M HCl is added to 50.0 mL of distilled water, the pH rapidly decreases until it reaches a minimum at the pH of 0.20 M HCl. (b)
Conversely, when 0.20 M NaOH is added to 50.0 mL of distilled water, the pH rapidly increases until it reaches a maximum at the
pH of 0.20 M N aOH . (CC BY-SA-NC; Anonymous by request)
The graphs of water with strong acid added and water with strong base added are inverses of each other.
Suppose that we now add 0.20 M NaOH to 50.0 mL of a 0.10 M solution of HCl. Because HCl is a strong acid that is completely
ionized in water, the initial [H ] is 0.10 M, and the initial pH is 1.00. Adding NaOH decreases the concentration of H+ because of
+

the neutralization reaction (Figure 6.6.2a):

− +
OH +H −
↽⇀
− H O.
2

Thus the pH of the solution increases gradually. Near the equivalence point, however, the point at which the number of moles of
base (or acid) added equals the number of moles of acid (or base) originally present in the solution, the pH increases much more
rapidly because most of the H ions originally present have been consumed. For the titration of a monoprotic strong acid (HCl)
+

with a monobasic strong base (NaOH), we can calculate the volume of base needed to reach the equivalence point from the
following relationship:

moles of base = (volume)b (molarity )b Vb Mb = moles of acid = (volume)a (molarity )a = Va Ma (6.6.1)

If 0.20 M NaOH is added to 50.0 mL of a 0.10 M solution of HCl, we solve for V : b

6.6.1 https://chem.libretexts.org/@go/page/43435
 Vb (0.20M e) = 0.025L = 25mL

Figure 6.6.2 : The Titration of (a) a Strong Acid with a Strong Base and (b) a Strong Base with a Strong Acid(a) As 0.20 M NaOH
is slowly added to 50.0 mL of 0.10 M HCl, the pH increases slowly at first, then increases very rapidly as the equivalence point is
approached, and finally increases slowly once more. (b) Conversely, as 0.20 M HCl is slowly added to 50.0 mL of 0.10 M N aOH ,
the pH decreases slowly at first, then decreases very rapidly as the equivalence point is approached, and finally decreases slowly
once more. (CC BY-SA-NC; Anonymous by request)
The titration curves of strong acid titrated with strong base and strong base titrated with strong acid are inverses of each other.
At the equivalence point (when 25.0 mL of NaOH solution has been added), the neutralization is complete: only a salt remains in
solution (NaCl), and the pH of the solution is 7.00. Adding more NaOH produces a rapid increase in pH, but eventually the pH
levels off at a value of about 13.30, the pH of 0.20 M N aOH .
As shown in Figure 6.6.2b, the titration of 50.0 mL of a 0.10 M solution of NaOH with 0.20 M HCl produces a titration curve that
is nearly the mirror image of the titration curve in Figure 6.6.2a. The pH is initially 13.00, and it slowly decreases as HCl is added.
As the equivalence point is approached, the pH drops rapidly before leveling off at a value of about 0.70, the pH of 0.20 M HCl.
The titration of either a strong acid with a strong base or a strong base with a strong acid produces an S-shaped curve. The curve is
somewhat asymmetrical because the steady increase in the volume of the solution during the titration causes the solution to become
more dilute. Due to the leveling effect, the shape of the curve for a titration involving a strong acid and a strong base depends on
only the concentrations of the acid and base, not their identities.

The shape of the titration curve involving a strong acid and a strong base depends only on their concentrations, not their
identities.

 Example 6.6.1: Hydrochloric Acid

Calculate the pH of the solution after 24.90 mL of 0.200 M NaOH has been added to 50.00 mL of 0.100 M HCl.
Given: volumes and concentrations of strong base and acid
Asked for: pH
Strategy:
A. Calculate the number of millimoles of H and OH to determine which, if either, is in excess after the neutralization
+ −

reaction has occurred. If one species is in excess, calculate the amount that remains after the neutralization reaction.
B. Determine the final volume of the solution. Calculate the concentration of the species in excess and convert this value to
pH.

Solution
A Because 0.100 mol/L is equivalent to 0.100 mmol/mL, the number of millimoles of H in 50.00 mL of 0.100 M HCl can be
+

calculated as follows:

6.6.2 https://chem.libretexts.org/@go/page/43435
 0.100 mmol H C l
+
50.00 mL ( ) = 5.00 mmol H C l = 5.00 mmol H
mL

The number of millimoles of NaOH added is as follows:

0.200 mmol N aOH

−
24.90 mL ( ) = 4.98 mmol N aOH = 4.98 mmol OH
mL

Thus H is in excess. To completely neutralize the acid requires the addition of 5.00 mmol of OH to the HCl solution.
+ −

Because only 4.98 mmol of OH has been added, the amount of excess H is 5.00 mmol − 4.98 mmol = 0.02 mmol of H .
− + +

B The final volume of the solution is 50.00 mL + 24.90 mL = 74.90 mL, so the final concentration of H is as follows: +

+
0.02 mmol H
+ −4
[H ] = = 3 × 10 M
74.90 mL

Hence,
+ −4
pH ≈ − log[ H ] = − log(3 × 10 ) = 3.5

This is significantly less than the pH of 7.00 for a neutral solution.

 Exercise 6.6.1

Calculate the pH of a solution prepared by adding 40.00 mL of 0.237 M H C l to 75.00 mL of a 0.133M solution of
N aOH .

Answer
11.6

pH after the addition of 10 ml of Strong …

pH after the addition of 10 ml of Strong Base to a Strong Acid:

https://youtu.be/_cM1_-kdJ20 (opens in new window)

6.6.3 https://chem.libretexts.org/@go/page/43435
 pH at the Equivalence point of a Strong …

pH at the Equivalence Point in a Strong Acid/Strong Base Titration:

https://youtu.be/7POGDA5Ql2M

6.6.2: Titrations of Weak Acids and Bases

In contrast to strong acids and bases, the shape of the titration curve for a weak acid or a weak base depends dramatically on the
identity of the acid or the base and the corresponding K or K . As we shall see, the pH also changes much more gradually around
a b

the equivalence point in the titration of a weak acid or a weak base. As you learned previously, [H ] of a solution of a weak acid
+

(HA) is not equal to the concentration of the acid but depends on both its pK and its concentration. Because only a fraction of a
a

weak acid dissociates, [\(H ] is less than [HA]. Thus the pH of a solution of a weak acid is greater than the pH of a solution of a
+

strong acid of the same concentration.

Figure 6.6.3a shows the titration curve for 50.0 mL of a 0.100 M solution of acetic acid with 0.200 M NaOH superimposed on the
curve for the titration of 0.100 M HCl shown in part (a) in Figure 6.6.2. Below the equivalence point, the two curves are very
different. Before any base is added, the pH of the acetic acid solution is greater than the pH of the HCl solution, and the pH
changes more rapidly during the first part of the titration. Note also that the pH of the acetic acid solution at the equivalence point
is greater than 7.00. That is, at the equivalence point, the solution is basic. In addition, the change in pH around the equivalence
point is only about half as large as for the HCl titration; the magnitude of the pH change at the equivalence point depends on the
pK a of the acid being titrated. Above the equivalence point, however, the two curves are identical. Once the acid has been
neutralized, the pH of the solution is controlled only by the amount of excess NaOH present, regardless of whether the acid is
weak or strong.

6.6.4 https://chem.libretexts.org/@go/page/43435
 Figure 6.6.3 : The Titration of (a) a Weak Acid with a Strong Base and (b) a Weak Base with a Strong Acid. (a) As 0.200 M NaOH
is slowly added to 50.0 mL of 0.100 M acetic acid, the pH increases slowly at first, then increases rapidly as the equivalence point
is approached, and then again increases more slowly. The corresponding curve for the titration of 50.0 mL of 0.100 M HCl with
0.200 M NaOH is shown as a dashed line. (b) As 0.200 M HCl is slowly added to 50.0 mL of 0.100 M NH3, the pH decreases
slowly at first, then decreases rapidly as the equivalence point is approached, and then again decreases more slowly. The
corresponding curve for the titration of 50.0 mL of 0.100 M NaOH with 0.200 M HCl is shown as a dashed line. (CC BY-SA-NC;
Anonymous by request)
The titration curves of weak acid titrated with strong base and weak base titrated with strong acid are inverse of each other. These
curves are shorter than the titration curves with strong acid and strong base.

The shape of the titration curve of a weak acid or weak base depends heavily on their identities and the K or K . a b

The titration curve in Figure 6.6.3a was created by calculating the starting pH of the acetic acid solution before any NaOH is
added and then calculating the pH of the solution after adding increasing volumes of N aOH . The procedure is illustrated in the
following subsection and Example 6.6.2 for three points on the titration curve, using the pK of acetic acid (4.76 at 25°C;
a

K = 1.7 × 10
a
−5
.

6.6.3: Calculating the pH of a Solution of a Weak Acid or a Weak Base

As explained discussed, if we know K or K and the initial concentration of a weak acid or a weak base, we can calculate the pH
a b

of a solution of a weak acid or a weak base by setting up a ICE table (i.e, initial concentrations, changes in concentrations, and final
concentrations). In this situation, the initial concentration of acetic acid is 0.100 M. If we define x as [H ] due to the dissociation
+

of the acid, then the table of concentrations for the ionization of 0.100 M acetic acid is as follows:
+ −
CH CO H(aq) −
↽⇀
− H (aq) + CH CO
3 2 3 2

table of concentrations for the ionization of 0.100 M acetic acid

ICE [C H3 C O2 H] [H
+
] [C H3 C O
−
2
]

initial 0.100 1.00 × 10

−7
0

change −x +x +x

final 0.100 − x x x

In this and all subsequent examples, we will ignore [H ] and [OH ] due to the autoionization of water when calculating the final
+ −

concentration. However, you should use Equation 16.45 and Equation 16.46 to check that this assumption is justified.
Inserting the expressions for the final concentrations into the equilibrium equation (and using approximations),

6.6.5 https://chem.libretexts.org/@go/page/43435
 + −
[H ][C H3 C O ]
2
Ka =
[C H3 C O2 H ]

(x)(x)
=
0.100 − x

2
x
≈
0.100

−5
≈ 1.74 × 10

Solving this equation gives x = [H +

] = 1.32 × 10
−3
M . Thus the pH of a 0.100 M solution of acetic acid is as follows:
−3
pH = − log(1.32 × 10 ) = 2.879

pH at the Start of a Weak Acid/Strong B…

B…

pH at the Start of a Weak Acid/Strong Base Titration: https://youtu.be/AtdBKfrfJNg

6.6.4: Calculating the pH during the Titration of a Weak Acid or a Weak Base
Now consider what happens when we add 5.00 mL of 0.200 M NaOH to 50.00 mL of 0.100 M C H C O H (part (a) in Figure 3 2

6.6.3). Because the neutralization reaction proceeds to completion, all of the OH ions added will react with the acetic acid to
−

generate acetate ion and water:

− −
C H3 C O2 H(aq) + OH → C H3 C O + H2 O(l) (6.6.2)
(aq) 2 (aq)

All problems of this type must be solved in two steps: a stoichiometric calculation followed by an equilibrium calculation. In the
first step, we use the stoichiometry of the neutralization reaction to calculate the amounts of acid and conjugate base present in
solution after the neutralization reaction has occurred. In the second step, we use the equilibrium equation to determine [H ] of the +

resulting solution.

6.6.4.1: Step 1
To determine the amount of acid and conjugate base in solution after the neutralization reaction, we calculate the amount of
CH CO H in the original solution and the amount of OH in the NaOH solution that was added. The acetic acid solution
−
3 2

contained

50.00 mL (0.100 mmol(CH CO H)/ mL ) = 5.00 mmol(CH CO H)

3 2 3 2

The NaOH solution contained

5.00 mL=1.00 mmol N aOH
Comparing the amounts shows that C H C O 3 2H is in excess. Because OH
−
reacts with C H3 C O2 H in a 1:1 stoichiometry, the
amount of excess C H C O H is as follows:
3 2

5.00 mmol C H 3 C O2 H − 1.00 mmol OH −

= 4.00 mmol C H 3 C O2 H

Each 1 mmol of OH −
reacts to produce 1 mmol of acetate ion, so the final amount of C H −
3 C O2 is 1.00 mmol.

6.6.6 https://chem.libretexts.org/@go/page/43435
The stoichiometry of the reaction is summarized in the following ICE table, which shows the numbers of moles of the various
species, not their concentrations.
− −
CH CO H(aq) + OH (aq) −
↽⇀
− CH CO (aq) + H O(l)
3 2 3 2 2

ICE table
ICE [CH CO H]
3 2
[OH
−
] [CH CO
3
−

2
]

initial 5.00 mmol 1.00 mmol 0 mmol

change −1.00 mmol −1.00 mmol +1.00 mmol

final 4.00 mmol 0 mmol 1.00 mmol

This ICE table gives the initial amount of acetate and the final amount of OH ions as 0. Because an aqueous solution of acetic
−

acid always contains at least a small amount of acetate ion in equilibrium with acetic acid, however, the initial acetate concentration
is not actually 0. The value can be ignored in this calculation because the amount of C H C O in equilibrium is insignificant 3
−
2

compared to the amount of OH added. Moreover, due to the autoionization of water, no aqueous solution can contain 0 mmol of
−

OH
−
, but the amount of OH due to the autoionization of water is insignificant compared to the amount of OH added. We use
− −

the initial amounts of the reactants to determine the stoichiometry of the reaction and defer a consideration of the equilibrium until
the second half of the problem.

6.6.4.2: Step 2
To calculate [H ] at equilibrium following the addition of N aOH , we must first calculate [CH
+

3
CO H
2
] and [CH 3
CO2 ]
−
using the
number of millimoles of each and the total volume of the solution at this point in the titration:

f inal volume = 50.00 mL + 5.00 mL = 55.00 mL

4.00 mmol C H3 C O2 H −2
[C H3 C O2 H ] = = 7.27 × 10 M
55.00 mL

−
1.00 mmol C H3 C O
− 2 −2
[C H3 C O ] = = 1.82 × 10 M
2
55.00 mL

Knowing the concentrations of acetic acid and acetate ion at equilibrium and Ka for acetic acid (1.74 × 10 −5
), we can calculate
[ H ] at equilibrium:
+

− +
[C H3 C O ] [H ]
2
Ka =
[C H3 C O2 H ]

−5 −2
Ka [C H3 C O2 H ] (1.72 × 10 ) (7.27 × 10 M)
+ −5
[H ] = = = 6.95 × 10 M
− −2
[C H3 C O ] (1.82 × 10 )
2

Calculating − log[H +
] gives
−5
pH = − log(6.95 × 10 ) = 4.158.

Comparing the titration curves for HCl and acetic acid in Figure 6.6.3a, we see that adding the same amount (5.00 mL) of 0.200 M
NaOH to 50 mL of a 0.100 M solution of both acids causes a much smaller pH change for HCl (from 1.00 to 1.14) than for acetic

acid (2.88 to 4.16). This is consistent with the qualitative description of the shapes of the titration curves at the beginning of this
section. In Example 6.6.2, we calculate another point for constructing the titration curve of acetic acid.

6.6.7 https://chem.libretexts.org/@go/page/43435
 pH Before the Equivalence Point of a W…
W…

pH Before the Equivalence Point of a Weak Acid/Strong Base Titration:

https://youtu.be/znpwGCsefXc

 Example 6.6.2
What is the pH of the solution after 25.00 mL of 0.200 M NaOH is added to 50.00 mL of 0.100 M acetic acid?
Given: volume and molarity of base and acid
Asked for: pH

Strategy:
A. Write the balanced chemical equation for the reaction. Then calculate the initial numbers of millimoles of OH and −

C H C O H. Determine which species, if either, is present in excess.

3 2

B. Tabulate the results showing initial numbers, changes, and final numbers of millimoles.
C. If excess acetate is present after the reaction with OH , write the equation for the reaction of acetate with water. Use a
−

tabular format to obtain the concentrations of all the species present.

D. Calculate K using the relationship K = K K . Calculate [OH−] and use this to calculate the pH of the solution.
b w a b

Solution
A Ignoring the spectator ion (N a ), the equation for this reaction is as follows:
+

− −
C H3 C O2 H(aq) + OH (aq) → C H3 C O (aq) + H2 O(l)
2

The initial numbers of millimoles of OH −

and C H 3 C O2 H are as follows:
25.00 mL(0.200 mmol OH−mL=5.00 mmol OH −

50.00 mL(0.100C H3 C O2 H L = 5.00mmol C H3 C O2 H

The number of millimoles of OH −

equals the number of millimoles of C H 3 C O2 H , so neither species is present in excess.
B Because the number of millimoles of OH added corresponds to the number of millimoles of acetic acid in solution, this is
−

the equivalence point. The results of the neutralization reaction can be summarized in tabular form.
− −
C H3 C O2 H(aq) + OH ⇌ C H3 C O (aq) + H2 O(l)
(aq) 2

results of the neutralization reaction

ICE [CH CO H]
3 2
[OH
−
] [CH CO
3
−
2
]

initial 5.00 mmol 5.00 mmol 0 mmol

6.6.8 https://chem.libretexts.org/@go/page/43435
 ICE [CH CO H]
3 2
[OH
−
] [CH CO
3
−
2
]

change −5.00 mmol −5.00 mmol +5.00 mmol

final 0 mmol 0 mmol 5.00 mmol

C Because the product of the neutralization reaction is a weak base, we must consider the reaction of the weak base with water
to calculate [H+] at equilibrium and thus the final pH of the solution. The initial concentration of acetate is obtained from the
neutralization reaction:
−
5.00 mmol C H3 C O
2 −2
[ CH CO ] = = 6.67 × 10 M
3 2
(50.00 + 25.00) mL

The equilibrium reaction of acetate with water is as follows:

− −
−
CH CO2 (aq) + H O(l) ↽⇀
− CH CO H(aq) + OH (aq)
3 2 3 2

The equilibrium constant for this reaction is

Kw
Kb = (6.6.3)
Ka

where K is the acid ionization constant of acetic acid. We therefore define x as

a [ OH
−
] produced by the reaction of acetate
with water. Here is the completed table of concentrations:
− −
H2 O(l) + C H3 C O ⇌ C H3 C O2 H(aq) + OH
2(aq) (aq)

completed table of concentrations

− −
[CH CO ] [CH CO H] [OH ]
3 2 3 2

initial 0.0667 0 1.00 × 10−7

change −x +x +x

final (0.0667 − x) x x

D We can obtain K by substituting the known values into Equation 6.6.3:

b

−14
Kw 1.01 × 10
−10
Kb = = = 5.80 × 10 (6.6.4)
−5
Ka 1.74 × 10

Substituting the expressions for the final values from the ICE table into Equation 6.6.4 and solving for x:
2
x −10
= 5.80 × 10
0.0667
−−−−−−−−−−−−−−−−−−
−10
x = √ (5.80 × 10 )(0.0667)

−6
= 6.22 × 10

Thus [OH ] = 6.22 × 10 M and the pH of the final solution is 8.794 (Figure 6.6.3a). As expected for the titration of a
− −6

weak acid, the pH at the equivalence point is greater than 7.00 because the product of the titration is a base, the acetate ion,
which then reacts with water to produce OH . −

 Exercise 6.6.2
Calculate the pH of a solution prepared by adding 45.0 mL of a 0.213 M HCl solution to 125.0 mL of a 0.150 M solution of
ammonia. The pK of ammonia is 4.75 at 25°C.
b

Answer
9.23

6.6.9 https://chem.libretexts.org/@go/page/43435
As shown in part (b) in Figure 6.6.3, the titration curve for NH3, a weak base, is the reverse of the titration curve for acetic acid. In
particular, the pH at the equivalence point in the titration of a weak base is less than 7.00 because the titration produces an acid.
The identity of the weak acid or weak base being titrated strongly affects the shape of the titration curve. Figure 6.6.4 illustrates the
shape of titration curves as a function of the pK or the pK . As the acid or the base being titrated becomes weaker (its pK or
a b a

pK becomes larger), the pH change around the equivalence point decreases significantly. With very dilute solutions, the curve
b

becomes so shallow that it can no longer be used to determine the equivalence point.

Figure 6.6.4 : Effect of Acid or Base Strength on the Shape of Titration Curves. Unlike strong acids or bases, the shape of the
titration curve for a weak acid or base depends on the pK or pK of the weak acid or base being titrated. (a) Solution pH as a
a b

function of the volume of 1.00 M NaOH added to 10.00 mL of 1.00 M solutions of weak acids with the indicated pK values. (b) a

Solution pH as a function of the volume of 1.00 M HCl added to 10.00 mL of 1.00 M solutions of weak bases with the indicated
pK values. The shapes of the two sets of curves are essentially identical, but one is flipped vertically in relation to the other.
b

Midpoints are indicated for the titration curves corresponding to pK = 10 and pK = 10. (CC BY-SA-NC; Anonymous by request)
a b

The titration curves of weak acids with strong base and weak bases titrated with strong acid are inverses of each other. Three weak
acids and three weak bases with pKa and pKb of 4, 7, and 10 are used.
One point in the titration of a weak acid or a weak base is particularly important: the midpoint of a titration is defined as the point
at which exactly enough acid (or base) has been added to neutralize one-half of the acid (or the base) originally present and occurs
halfway to the equivalence point. The midpoint is indicated in Figures 6.6.4a and 6.6.4b for the two shallowest curves. By
definition, at the midpoint of the titration of an acid, [HA] = [A−]. Recall that the ionization constant for a weak acid is as follows:
+ −
[ H3 O ][ A ]
Ka =
[H A]

If [H A] = [A ], this reduces to K
−
a = [ H3 O
+
] . Taking the negative logarithm of both sides,

− log Ka = − log[ H3 O+]

From the definitions of pK and pH, we see that this is identical to

a

p Ka = pH (6.6.5)

Thus the pH at the midpoint of the titration of a weak acid is equal to the pK of the weak acid, as indicated in part (a) in Figure
a

6.6.4 for the weakest acid where we see that the midpoint for pK = 10 occurs at pH = 10. Titration methods can therefore be used
a

to determine both the concentration and the pK (or the pK ) of a weak acid (or a weak base).
a b

The pH at the midpoint of the titration of a weak acid is equal to the pK of the weak acid. a

6.6.5: Titrations of Polyprotic Acids or Bases

When a strong base is added to a solution of a polyprotic acid, the neutralization reaction occurs in stages. The most acidic group is
titrated first, followed by the next most acidic, and so forth. If the pK values are separated by at least three pK units, then the
a a

overall titration curve shows well-resolved “steps” corresponding to the titration of each proton. A titration of the triprotic acid
H P O with NaOH is illustrated in Figure 6.6.5 and shows two well-defined steps: the first midpoint corresponds to pK 1, and
3 4 a

6.6.10 https://chem.libretexts.org/@go/page/43435
the second midpoint corresponds to pK 2. Because HPO42− is such a weak acid,
a pKa 3 has such a high value that the third step
cannot be resolved using 0.100 M NaOH as the titrant.

Figure 6.6.5 : Titration Curve for Phosphoric Acid (H P O , a Typical Polyprotic Acid. The curve for the titration of 25.0 mL of a
3 4

0.100 M H P O solution with 0.100 M NaOH along with the species in solution at each Ka is shown. Note the two distinct
3 4

equivalence points corresponding to deprotonation of H P O at pH ≈ 4.6 and H P O at pH ≈ 9.8. Because H P O is a very

3 4 2
2−

4
2−

weak acid, the third equivalence point, at pH ≈ 13, is not well defined. (CC BY-SA-NC; Anonymous by request)
The titration curve for the reaction of a polyprotic base with a strong acid is the mirror image of the curve shown in Figure 6.6.5.
The initial pH is high, but as acid is added, the pH decreases in steps if the successive pK values are well separated. Table E1 lists
b

the ionization constants and pK values for some common polyprotic acids and bases.
a

 Example 6.6.3

Calculate the pH of a solution prepared by adding 55.0 mL of a 0.120 M NaOH solution to 100.0 mL of a 0.0510 M solution
of oxalic acid (HO CCO H), a diprotic acid (abbreviated as H ox). Oxalic acid, the simplest dicarboxylic acid, is found in
2 2 2

rhubarb and many other plants. Rhubarb leaves are toxic because they contain the calcium salt of the fully deprotonated form
of oxalic acid, the oxalate ion (O CCO , abbreviated ox ).Oxalate salts are toxic for two reasons. First, oxalate salts of
2
2 −
2
2 −

divalent cations such as Ca are insoluble at neutral pH but soluble at low pH. As a result, calcium oxalate dissolves in the
2 +

dilute acid of the stomach, allowing oxalate to be absorbed and transported into cells, where it can react with calcium to form
tiny calcium oxalate crystals that damage tissues. Second, oxalate forms stable complexes with metal ions, which can alter the
distribution of metal ions in biological fluids.

Given: volume and concentration of acid and base

Asked for: pH
Strategy:

6.6.11 https://chem.libretexts.org/@go/page/43435
A. Calculate the initial millimoles of the acid and the base. Use a tabular format to determine the amounts of all the species in
solution.
B. Calculate the concentrations of all the species in the final solution. Determine [H+] and convert this value to pH.
Solution:
A Table E5 gives the pK values of oxalic acid as 1.25 and 3.81. Again we proceed by determining the millimoles of acid and
a

base initially present:

0.510 mmol H2 ox
100.00 mL ( ) = 5.10 mmol H2 ox
mL

0.120 mmol N aOH

55.00 mL ( ) = 6.60 mmol N aOH
mL

The strongest acid (H ox ) reacts with the base first. This leaves (6.60 − 5.10) = 1.50 mmol of
2 OH
−
to react with Hox−,
forming ox2− and H2O. The reactions can be written as follows:
− −
H2 ox + OH → H ox + H2 O
5.10 mmol 6.60 mmol 5.10 mmol 5.10 mmol

− − 2−
H ox + OH → ox + H2 O
5.10 mmol 1.50 mmol 1.50 mmol 1.50 mmol

In tabular form,
Solutions to Example 17.3.3
− − 2 −
H ox OH Hox ox
2

initial 5.10 mmol 6.60 mmol 0 mmol 0 mmol

change (step 1) −5.10 mmol −5.10 mmol +5.10 mmol 0 mmol

final (step 1) 0 mmol 1.50 mmol 5.10 mmol 0 mmol

change (step 2) — −1.50 mmol −1.50 mmol +1.50 mmol

final 0 mmol 0 mmol 3.60 mmol 1.50 mmol

B The equilibrium between the weak acid (Hox ) and its conjugate base (ox ) in the final solution is determined by the
− 2 −

magnitude of the second ionization constant, K = 10 = 1.6 × 10 a2 . To calculate the pH of the solution, we need to
−3.81 −4

know [H ], which is determined using exactly the same method as in the acetic acid titration in Example 6.6.2:
+

final volume of solution = 100.0 mL + 55.0 mL = 155.0 mL

Thus the concentrations of Hox and ox − 2 −

are as follows:
−
−
3.60 mmol H ox −2
[H ox ] = = 2.32 × 10 M
155.0 mL

2−
2−
1.50 mmol ox −3
[ox ] = = 9.68 × 10 M
155.0 mL

We can now calculate [H+] at equilibrium using the following equation:

2− +
[ox ] [H ]
Ka2 =
−
[H ox ]

Rearranging this equation and substituting the values for the concentrations of Hox and ox − 2 −
,
− −4 −2
Ka2 [H ox ] (1.6 × 10 ) (2.32 × 10 )
+ −4
[H ] = = = 3.7 × 10 M
2− −3
[ox ] (9.68 × 10 )

So

6.6.12 https://chem.libretexts.org/@go/page/43435
 + −4
pH = − log[ H ] = − log(3.7 × 10 ) = 3.43

This answer makes chemical sense because the pH is between the first and second pK values of oxalic acid, as it must be. We
a

added enough hydroxide ion to completely titrate the first, more acidic proton (which should give us a pH greater than pK ), a1

but we added only enough to titrate less than half of the second, less acidic proton, with pK . If we had added exactly enough
a2

hydroxide to completely titrate the first proton plus half of the second, we would be at the midpoint of the second step in the
titration, and the pH would be 3.81, equal to pK . a2

 Exercise 6.6.3: Piperazine

Piperazine is a diprotic base used to control intestinal parasites (“worms”) in pets and humans. A dog is given 500 mg (5.80
mmol) of piperazine (pK = 4.27, pK = 8.67). If the dog’s stomach initially contains 100 mL of 0.10 M HCl (pH = 1.00),
b1 b2

calculate the pH of the stomach contents after ingestion of the piperazine.

Answer
pH=4.9

6.6.6: Indicators
In practice, most acid–base titrations are not monitored by recording the pH as a function of the amount of the strong acid or base
solution used as the titrant. Instead, an acid–base indicator is often used that, if carefully selected, undergoes a dramatic color
change at the pH corresponding to the equivalence point of the titration. Indicators are weak acids or bases that exhibit intense
colors that vary with pH. The conjugate acid and conjugate base of a good indicator have very different colors so that they can be
distinguished easily. Some indicators are colorless in the conjugate acid form but intensely colored when deprotonated
(phenolphthalein, for example), which makes them particularly useful.
We can describe the chemistry of indicators by the following general equation:
+ −
HIn(aq) −
↽⇀
− H (aq) + In (aq)

where the protonated form is designated by HIn and the conjugate base by −
In . The ionization constant for the deprotonation of
indicator HIn is as follows:
+ −
[H ][ In ]
KIn = (6.6.6)
[HIn]

The pK in (its pK ) determines the pH at which the indicator changes color.

a

Many different substances can be used as indicators, depending on the particular reaction to be monitored. For example, red
cabbage juice contains a mixture of colored substances that change from deep red at low pH to light blue at intermediate pH to
yellow at high pH. Similarly, Hydrangea macrophylla flowers can be blue, red, pink, light purple, or dark purple depending on the
soil pH (Figure 6.6.6). Acidic soils will produce blue flowers, whereas alkaline soils will produce pinkish flowers.
Irrespective of the origins, a good indicator must have the following properties:
The color change must be easily detected.
The color change must be rapid.
The indicator molecule must not react with the substance being titrated.
To minimize errors, the indicator should have a pK that is within one pH unit of the expected pH at the equivalence point of
in

the titration.

6.6.13 https://chem.libretexts.org/@go/page/43435
 Figure 6.6.6 : Naturally occurring pH indicators can be found in red cabbage and Hydrangea macrophylla flowers. Red Cabbage
image (CC BY-SA 3.0; KENPEI via Wikipedia) and Hydrangea macrophylla flowers (pixabay).
Synthetic indicators have been developed that meet these criteria and cover virtually the entire pH range. Figure 6.6.7 shows the
approximate pH range over which some common indicators change color and their change in color. In addition, some indicators
(such as thymol blue) are polyprotic acids or bases, which change color twice at widely separated pH values.

Figure 6.6.7 : Some Common Acid–Base Indicators. Approximate colors are shown, along with pK in values and the pH range over
which the color changes. (CC BY-SA-NC; Anonymous by request)
It is important to be aware that an indicator does not change color abruptly at a particular pH value; instead, it actually undergoes a
pH titration just like any other acid or base. As the concentration of HIn decreases and the concentration of In− increases, the color
of the solution slowly changes from the characteristic color of HIn to that of In−. As we will see later, the [In−]/[HIn] ratio changes
from 0.1 at a pH one unit below pKin to 10 at a pH one unit above pKin. Thus most indicators change color over a pH range of
about two pH units.
We have stated that a good indicator should have a pKin value that is close to the expected pH at the equivalence point. For a
strong acid–strong base titration, the choice of the indicator is not especially critical due to the very large change in pH that occurs
around the equivalence point. In contrast, using the wrong indicator for a titration of a weak acid or a weak base can result in
relatively large errors, as illustrated in Figure 6.6.8. This figure shows plots of pH versus volume of base added for the titration of
50.0 mL of a 0.100 M solution of a strong acid (HCl) and a weak acid (acetic acid) with 0.100 M N aOH . The pH ranges over
which two common indicators (methyl red, pK = 5.0 , and phenolphthalein, pK = 9.5 ) change color are also shown. The
in in

horizontal bars indicate the pH ranges over which both indicators change color cross the HCl titration curve, where it is almost
vertical. Hence both indicators change color when essentially the same volume of NaOH has been added (about 50 mL), which
corresponds to the equivalence point. In contrast, the titration of acetic acid will give very different results depending on whether
methyl red or phenolphthalein is used as the indicator. Although the pH range over which phenolphthalein changes color is slightly
greater than the pH at the equivalence point of the strong acid titration, the error will be negligible due to the slope of this portion
of the titration curve. Just as with the HCl titration, the phenolphthalein indicator will turn pink when about 50 mL of NaOH has
been added to the acetic acid solution. In contrast, methyl red begins to change from red to yellow around pH 5, which is near the

6.6.14 https://chem.libretexts.org/@go/page/43435
midpoint of the acetic acid titration, not the equivalence point. Adding only about 25–30 mL of NaOH will therefore cause the
methyl red indicator to change color, resulting in a huge error.

Figure 6.6.8 : Choosing the Correct Indicator for an Acid–Base Titration. (CC BY-SA-NC; Anonymous by request)
If the pH of the solution is between 4.95 and 6 then methyl red should be used. If the pH is between 8,2 and 10 then
phenolphthalein should be used.
The graph shows the results obtained using two indicators (methyl red and phenolphthalein) for the titration of 0.100 M solutions
of a strong acid (HCl) and a weak acid (acetic acid) with 0.100 M N aOH . Due to the steepness of the titration curve of a strong
acid around the equivalence point, either indicator will rapidly change color at the equivalence point for the titration of the strong
acid. In contrast, the pKin for methyl red (5.0) is very close to the pK of acetic acid (4.76); the midpoint of the color change for
a

methyl red occurs near the midpoint of the titration, rather than at the equivalence point.
In general, for titrations of strong acids with strong bases (and vice versa), any indicator with a pKin between about 4.0 and 10.0
will do. For the titration of a weak acid, however, the pH at the equivalence point is greater than 7.0, so an indicator such as
phenolphthalein or thymol blue, with pKin > 7.0, should be used. Conversely, for the titration of a weak base, where the pH at the
equivalence point is less than 7.0, an indicator such as methyl red or bromocresol blue, with pKin < 7.0, should be used.
The existence of many different indicators with different colors and pKin values also provides a convenient way to estimate the pH
of a solution without using an expensive electronic pH meter and a fragile pH electrode. Paper or plastic strips impregnated with
combinations of indicators are used as “pH paper,” which allows you to estimate the pH of a solution by simply dipping a piece of
pH paper into it and comparing the resulting color with the standards printed on the container (Figure 6.6.9).

Figure 6.6.9 : pH Paper. pH paper contains a set of indicators that change color at different pH values. The approximate pH of a
solution can be determined by simply dipping a paper strip into the solution and comparing the color to the standards provided. (CC
BY-SA-NC; Anonymous by request)

6.6.15 https://chem.libretexts.org/@go/page/43435
 pH Indicators

pH Indicators: pH Indicators(opens in new window) [youtu.be]

6.6.7: Summary and Takeaway

Plots of acid–base titrations generate titration curves that can be used to calculate the pH, the pOH, the pK , and the pK of the
a b

system. The shape of a titration curve, a plot of pH versus the amount of acid or base added, provides important information about
what is occurring in solution during a titration. The shapes of titration curves for weak acids and bases depend dramatically on the
identity of the compound. The equivalence point of an acid–base titration is the point at which exactly enough acid or base has
been added to react completely with the other component. The equivalence point in the titration of a strong acid or a strong base
occurs at pH 7.0. In titrations of weak acids or weak bases, however, the pH at the equivalence point is greater or less than 7.0,
respectively. The pH tends to change more slowly before the equivalence point is reached in titrations of weak acids and weak
bases than in titrations of strong acids and strong bases. The pH at the midpoint, the point halfway on the titration curve to the
equivalence point, is equal to the pK of the weak acid or the pK of the weak base. Thus titration methods can be used to
a b

determine both the concentration and the pK (or the pK ) of a weak acid (or a weak base). Acid–base indicators are compounds
a b

that change color at a particular pH. They are typically weak acids or bases whose changes in color correspond to deprotonation or
protonation of the indicator itself.

6.6: Acid-Base Titration Curves is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
17.3: Acid-Base Titrations is licensed CC BY-NC-SA 3.0.

6.6.16 https://chem.libretexts.org/@go/page/43435
6.7: Polyprotic Acids
 Learning Objectives
Extend previously introduced equilibrium concepts to acids and bases that may donate or accept more than one proton

We can classify acids by the number of protons per molecule that they can give up in a reaction. Acids such as HCl, HNO , and 3

HCN that contain one ionizable hydrogen atom in each molecule are called monoprotic acids. Their reactions with water are:

+ −
HCl(aq) + H O(l) ⟶ H O (aq) + Cl (aq)
2 3

+ −
HNO (aq) + H O(l) ⟶ H O (aq) + NO3 (aq)
3 2 3

+ −
HCN(aq) + H O(l) ⟶ H O (aq) + CN (aq)
2 3

Even though it contains four hydrogen atoms, acetic acid, CH CO H

3 2
, is also monoprotic because only the hydrogen atom from
the carboxyl group (−COOH ) reacts with bases:

This image contains two equilibrium reactions. The first shows a C atom bonded to three H atoms and another C atom. The second
C atom is double bonded to an O atom and also forms a single bond to another O atom. The second O atom is bonded to an H atom.
There is a plus sign and then the molecular formula H subscript 2 O. An equilibrium arrow follows the H subscript 2 O. To the
right of the arrow is H subscript 3 O superscript positive sign. There is a plus sign. The final structure shows a C atom bonded the
three H atoms and another C atom. This second C atom is double bonded to an O atom and single bonded to another O atom. The
entire structure is in brackets and a superscript negative sign appears outside the brackets. The second reaction shows C H subscript
3 C O O H ( a q ) plus H subscript 2 O ( l ) equilibrium arrow H subscript 3 O ( a q ) plus C H subscript 3 C O O superscript
negative sign ( a q ).
Similarly, monoprotic bases are bases that will accept a single proton.

6.7.1: Diprotic Acids

Diprotic acids contain two ionizable hydrogen atoms per molecule; ionization of such acids occurs in two steps. The first ionization
always takes place to a greater extent than the second ionization. For example, sulfuric acid, a strong acid, ionizes as follows:
The first ionization is
+ −
H SO (aq) + H O(l) ⇌ H O (aq) + HSO 4 (aq)
2 4 2 3

with K a1
2
> 10 ; complete dissociation .
The second ionization is
− + 2 −
HSO (aq) + H O(l) ⇌ H O (aq) + SO (aq)
4 2 3 4

with K a2 = 1.2 × 10
−2
.
This stepwise ionization process occurs for all polyprotic acids. When we make a solution of a weak diprotic acid, we get a solution
that contains a mixture of acids. Carbonic acid, H CO , is an example of a weak diprotic acid. The first ionization of carbonic acid
2 3

yields hydronium ions and bicarbonate ions in small amounts.

First Ionization
+ −
H CO (aq) + H O(l) ⇌ H O (aq) + HCO3 (aq)
2 3 2 3

with

6.7.1 https://chem.libretexts.org/@go/page/43436
 + −
[H O ][ HCO ]
3 3 −7
KH CO = = 4.3 × 10
2 3
[ H CO ]
2 3

The bicarbonate ion can also act as an acid. It ionizes and forms hydronium ions and carbonate ions in even smaller quantities.
Second Ionization
− + 2−
HCO (aq) + H O(l) ⇌ H O (aq) + CO (aq)
3 2 3 3

with
+ 2−
[H O ][ CO ]
3 3 −11
KHCO− = = 4.7 × 10
3 −
[ HCO3 ]

KH
2
CO
3
is larger than K by a factor of 104, so H2CO3 is the dominant producer of hydronium ion in the solution. This means
HCO
−

that little of the HCO formed by the ionization of H2CO3 ionizes to give hydronium ions (and carbonate ions), and the
−

concentrations of H3O+ and HCO are practically equal in a pure aqueous solution of H2CO3.
−

If the first ionization constant of a weak diprotic acid is larger than the second by a factor of at least 20, it is appropriate to treat the
first ionization separately and calculate concentrations resulting from it before calculating concentrations of species resulting from
subsequent ionization. This can simplify our work considerably because we can determine the concentration of H3O+ and the
conjugate base from the first ionization, then determine the concentration of the conjugate base of the second ionization in a
solution with concentrations determined by the first ionization.

 Example 6.7.1: Ionization of a Diprotic Acid

When we buy soda water (carbonated water), we are buying a solution of carbon dioxide in water. The solution is acidic
because CO2 reacts with water to form carbonic acid, H2CO3. What are [H O ], [HCO ], and [CO ] in a saturated solution 3
+ −
3
2−
3

of CO2 with an initial [H2CO3] = 0.033 M?

+ − −7
H CO (aq) + H O(l) ⇌ H O (aq) + HCO (aq) Ka1 = 4.3 × 10 (equilibrium step 1)
2 3 2 3 3

− + 2− −11
HCO (aq) + H O(l) ⇌ H O (aq) + CO (aq) Ka2 = 4.7 × 10 (equilibrium step 2)
3 2 3 3

Solution
As indicated by the ionization constants, H2CO3 is a much stronger acid than HCO , so H −
3 2
CO
3
is the dominant producer of
hydronium ion in solution. Thus there are two parts in the solution of this problem:
1. Using the customary four steps, we determine the concentration of H3O+ and HCO produced by ionization of H2CO3. −

2. Then we determine the concentration of CO in a solution with the concentration of H3O+ and HCO determined in (1).
2−
3
−
3

To summarize:

Four tan rectangles are shown that are connected with right pointing arrows. The first is labeled “left bracket H subscript 2 C O
subscript 3 right bracket.” The second is labeled “left bracket H subscript 3 O superscript plus right bracket and left bracket H
C O subscript 3 superscript negative right bracket from H subscript 2 C O subscript 3.” The third is labeled “left bracket C O
subscript 3 superscript 2 negative right bracket from H C O subscript 3 superscript negative.”
1. First Ionization: Determine the concentrations of H 3
O
+
and HCO . −
3

Since equilibrium step 1 is has a much bigger K = 4.3 × 10 than K = 4.7 × 10

a1 for equilibrium step 2 , we can
−7
a2
−11

safely ignore the second ionization step and focus only on the first step (but address it in next part of problem).
+ − −7
H CO (aq) + H O(l) ⇌ H O (aq) + HCO3 (aq) Ka1 = 4.3 × 10
2 3 2 3

6.7.2 https://chem.libretexts.org/@go/page/43436
As for the ionization of any other weak acid:

Four tan rectangles are shown that are connected with right pointing arrows. The first is labeled “Determine the direction of
change.” The second is labeled “Determine x and the equilibrium concentrations.” The third is labeled “Solve for x and the
equilibrium concentrations.” The fourth is labeled “Check the math.”
An abbreviated table of changes and concentrations shows:
Abbreviated table of changes and concentrations
ICE Table H CO
2 3
(aq) H O(l)
2
H O
3
+
(aq) HCO
−
3
(aq)

Initial (M) 0.033 M - 0 0

Change (M) −x - +x +x

Equilibrium (M) 0.033 M − x - x x

Substituting the equilibrium concentrations into the equilibrium constant gives us:
+ −
[H O ][ HCO ] (x)(x)
3 3 −7
KH CO = = = 4.3 × 10
2 3
[ H CO ] 0.033 − x
2 3

Solving the preceding equation making our standard assumptions gives:

−4
x = 1.2 × 10

Thus:

[ H CO ] = 0.033 M
2 3

+ − −4
[H O ] = [ HCO ] = 1.2 × 10 M
3 3

2. Second Ionization: Determine the concentration of C O 2−

3
in a solution at equilibrium.
Since the equilibrium step 1 is has a much bigger K than equilibrium step 2 , we can the equilibrium conditions calculated
a

from first part of example as the initial conditions for an ICER Table for the equilibrium step 2 :
− + 2−
HCO (aq) + H O(l) ⇌ H O (aq) + CO (aq)
3 2 3 3

ICER Table for the equilibrium step 2:

ICE Table HCO
−
3
(aq) H O(l)
2
H O
3
+
(aq) CO
2−
3
(aq)

Initial (M) 1.2 × 10

−4
M - 1.2 × 10
−4
M 0

Change (M) −y - +y +y

Equilibrium (M) 1.2 × 10

−4
M −y - 1.2 × 10
−4
M +y y

+ 2−
[H O ][ CO ]
3 3
KHCO− =
3 −
[ HCO3 ]

−4
(1.2 × 10 M + y)(y)
=
−4
(1.2 × 10 M − y)

To avoid solving a quadratic equation, we can assume y ≪ 1.2 × 10 −4

M so
−4
(1.2 × 10 M )(y)
−11
KHCO− = 4.7 × 10 ≈
3 −4
(1.2 × 10 M)

6.7.3 https://chem.libretexts.org/@go/page/43436
 Rearranging to solve for y
−11 −4
(4.7 × 10 )(1.2 × 10 M)
y ≈
−4
1.2 × 10 M

2− −11
[ CO ] = y ≈ 4.7 × 10
3

To summarize:
In part 1 of this example, we found that the H 2
CO
3
in a 0.033-M solution ionizes slightly and at equilibrium
[ H CO ] = 0.033 M, , and M . In part 2, we determined that
+ −4 − −4
[ H O ] = 1.2 × 10 [ HCO3 ] = 1.2 × 10
2 3 3

M .
2− −11
[ CO ] = 5.6 × 10
3

 Exercise 6.7.2: Hydrogen Sulfide

The concentration of H S in a saturated aqueous solution at room temperature is approximately 0.1 M. Calculate
2 [H O
3
+
,
]

[ HS ], and [ S ] in the solution:

− 2 −

+ − −8
H S(aq) + H O(l) ⇌ H O (aq) + HS (aq) Ka1 = 8.9 × 10
2 2 3

− + 2− −19
HS (aq) + H O(l) ⇌ H O (aq) + S (aq) Ka2 = 1.0 × 10
2 3

Answer
[ H S] = 0.1M
2
, [H 3
O
+
] = [H S
−
] = 0.0001 M [ S , 2−
] = 1 × 10
−19
M

We note that the concentration of the sulfide ion is the same as Ka2. This is due to the fact that each subsequent dissociation
occurs to a lesser degree (as acid gets weaker).

6.7.2: Triprotic Acids

A triprotic acid is an acid that has three dissociable protons that undergo stepwise ionization: Phosphoric acid is a typical example:
The first ionization is
+ −
H PO (aq) + H O(l) ⇌ H O (aq) + H PO (aq)
3 4 2 3 2 4

with K a1 = 7.5 × 10
−3
.
The second ionization is
− + 2−
H PO (aq) + H O(l) ⇌ H O (aq) + HPO (aq)
2 4 2 3 4

with K a2 = 6.2 × 10
−8
.
The third ionization is
2− + 3−
HPO (aq) + H O(l) ⇌ H O (aq) + PO (aq)
4 2 3 4

with K a3 = 4.2 × 10
−13
.
As with the diprotic acids, the differences in the ionization constants of these reactions tell us that in each successive step the
degree of ionization is significantly weaker. This is a general characteristic of polyprotic acids and successive ionization constants
often differ by a factor of about 105 to 106. This set of three dissociation reactions may appear to make calculations of equilibrium
concentrations in a solution of H3PO4 complicated. However, because the successive ionization constants differ by a factor of 105
to 106, the calculations can be broken down into a series of parts similar to those for diprotic acids.
Polyprotic bases can accept more than one hydrogen ion in solution. The carbonate ion is an example of a diprotic base, since it can
accept up to two protons. Solutions of alkali metal carbonates are quite alkaline, due to the reactions:
2− − −
H O(l) + CO (aq) ⇌ HCO (aq) + OH (aq)
2 3 3

and

6.7.4 https://chem.libretexts.org/@go/page/43436
 − −
H O(l) + HCO (aq) ⇌ H CO (aq) + OH (aq)
2 3 2 3

Summary
An acid that contains more than one ionizable proton is a polyprotic acid. The protons of these acids ionize in steps. The
differences in the acid ionization constants for the successive ionizations of the protons in a polyprotic acid usually vary by roughly
five orders of magnitude. As long as the difference between the successive values of Ka of the acid is greater than about a factor of
20, it is appropriate to break down the calculations of the concentrations of the ions in solution into a series of steps.

Glossary
diprotic acid
acid containing two ionizable hydrogen atoms per molecule. A diprotic acid ionizes in two steps

diprotic base
base capable of accepting two protons. The protons are accepted in two steps

monoprotic acid
acid containing one ionizable hydrogen atom per molecule

stepwise ionization
process in which an acid is ionized by losing protons sequentially

triprotic acid
acid that contains three ionizable hydrogen atoms per molecule; ionization of triprotic acids occurs in three steps

6.7: Polyprotic Acids is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
14.5: Polyprotic Acids by OpenStax is licensed CC BY 4.0. Original source: https://openstax.org/details/books/chemistry-2e.

6.7.5 https://chem.libretexts.org/@go/page/43436
 6.8: A Deeper Look - Exact Treatment of Acid-Base Equilibria
 Learning Objectives
Understand the exact equations that are involves in complex acid-base equilibria in aqueous solutions

The methods for dealing with acid-base equilibria that we developed in the earlier units of this series are widely used in ordinary
practice. Although many of these involve approximations of various kinds, the results are usually good enough for most purposes.
Sometimes, however — for example, in problems involving very dilute solutions, the approximations break down, often because
they ignore the small quantities of H+ and OH– ions always present in pure water. In this unit, we look at exact, or "comprehensive"
treatment of some of the more common kinds of acid-base equilibria problems.

6.8.1: Strong acid-base systems

The usual definition of a “strong” acid or base is one that is completely dissociated in aqueous solution. Hydrochloric acid is a
common example of a strong acid. When HCl gas is dissolved in water, the resulting solution contains the ions H3O+, OH–, and
Cl–, but except in very concentrated solutions, the concentration of HCl is negligible; for all practical purposes, molecules of
“hydrochloric acid”, HCl, do not exist in dilute aqueous solutions. To specify the concentrations of the three species present in an
aqueous solution of HCl, we need three independent relations between them.
Limiting Conditions
These relations are obtained by observing that certain conditions must always hold for aqueous solutions:
1. The dissociation equilibrium of water must always be satisfied:
+ –
[H ][OH ] = Kw (6.8.1)

2. The undissociated acid and its conjugate base must be in mass balance. The actual concentrations of the acid and its conjugate
base can depend on a number of factors, but their sum must be constant, and equal to the “nominal concentration”, which we
designate here as C . For a solution of HCl, this equation would be
a

–
[H C l] + [C l ] = Ca (6.8.2)

Because a strong acid is by definition completely dissociated, we can neglect the first term and write the mass balance condition
as
–
[C l ] = Ca (6.8.3)

3. In any ionic solution, the sum of the positive and negative electric charges must be zero; in other words, all solutions are
electrically neutral. This is known as the electroneutrality principle.
+ – –
[H ] = [OH ] + [C l ] (6.8.4)

The next step is to combine these three limiting conditions into a single expression that relates the hydronium ion concentration to
C . This is best done by starting with an equation that relates several quantities and substituting the terms that we want to
a

eliminate. Thus we can get rid of the [C l ] term by substituting Equation 6.8.3 into Equation 6.8.4 :
–

+ –
[H ] = [OH ] + Ca (6.8.5)

The [OH –
] term can be eliminated by the use of Equation 6.8.1:

+
Kw
[H ] = Ca + (6.8.6)
[H + ]

This equation tells us that the hydronium ion concentration will be the same as the nominal concentration of a strong acid as long
as the solution is not very dilute. As the acid concentration falls below about 10–6 M, however, the second term predominates;
−−
−
[ H ] approaches √K or 10 M at 25 °C. The hydronium ion concentration can of course never fall below this value; no amount
+ –7
w

of dilution can make the solution alkaline!

No amount of dilution can make the solution of a strong acid alkaline!

6.8.1 https://chem.libretexts.org/@go/page/43437
 Notice that Equation 6.8.6 is a quadratic equation; in regular polynomial form it would be rewritten as
+ 2 +
[H ] – Ca [ H ]– Kw = 0 (6.8.7)

Most practical problems involving strong acids are concerned with more concentrated solutions in which the second term of
Equation 6.8.7 can be dropped, yielding the simple relation
+ –
[H ] ≈ [A ] (6.8.8)

Activities and Concentrated Solutions of Strong Acids

In more concentrated solutions, interactions between ions cause their “effective” concentrations, known as their activities, to
deviate from their “analytical” concentrations. Thus in a solution prepared by adding 0.5 mole of the very strong acid HClO4 to
sufficient water to make the volume 1 liter, freezing-point depression measurements indicate that the concentrations of hydronium
and perchlorate ions are only about 0.4 M. This does not mean that the acid is only 80% dissociated; there is no evidence of HClO4
molecules in the solution. What has happened is that about 20% of the H3O+ and ClO4– ions have formed ion-pair complexes in
which the oppositely-charged species are loosely bound by electrostatic forces. Similarly, in a 0.10 M solution of hydrochloric acid,
the activity of H+ is 0.81, or only 81% of its concentration. (See the green box below for more on this.)
Activities are important because only these work properly in equilibrium calculations. The relation between the concentration of a
species and its activity is expressed by the activity coefficient γ:
a = γC (6.8.9)

As a solution becomes more dilute, γ approaches unity. At ionic concentrations below about 0.001 M, concentrations can generally
be used in place of activities with negligible error. Recall that pH is defined as the negative logarithm of the hydrogen ion activity,
not its concentration.

Activities of single ions cannot be determined, so activity coefficients in ionic solutions

are always the average, or mean, of those for all ionic species present. This quantity is
denoted as γ . ±

At very high concentrations, activities can depart wildly from concentrations. This is a practical consideration when dealing with
strong mineral acids which are available at concentrations of 10 M or greater. In a 12 M solution of hydrochloric acid, for example,
the mean ionic activity coefficient* is 207. This means that under these conditions with [H+] = 12, the activity {H+} = 2500,
corresponding to a pH of about –3.4, instead of –1.1 as might be predicted if concentrations were being used. These very high
activity coefficients also explain another phenomenon: why you can detect the odor of HCl over a concentrated hydrochloric acid
solution even though this acid is supposedly "100% dissociated".
At these high concentrations, a pair of "dissociated" ions H and C l will occasionally find themselves so close together that they
+ –

may momentarily act as an HCl unit; some of these may escape as \(HCl(g)\) before thermal motions break them up again. Under
these conditions, “dissociation” begins to lose its meaning so that in effect, dissociation is no longer complete. Although the
concentration of \(HCl(aq)\) will always be very small, its own activity coefficient can be as great as 2000, which means that its
escaping tendency from the solution is extremely high, so that the presence of even a tiny amount is very noticeable.

6.8.2: Weak monoprotic acids and bases

Most acids are weak; there are hundreds of thousands of them, whereas there are no more than a few dozen strong acids. We can
treat weak acid solutions in exactly the same general way as we did for strong acids. The only difference is that we must now
include the equilibrium expression for the acid. We will start with the simple case of the pure acid in water, and then go from there
to the more general one in which strong cations are present. In this exposition, we will refer to “hydrogen ions” and [H ] for +

brevity, and will assume that the acid H A dissociates into H and its conjugate base A .
+ −

6.8.3: Pure acid in water

In addition to the species H+, OH–, and A− which we had in the strong-acid case, we now have the undissociated acid HA; four
variables, requiring four equations.
Equilibria

6.8.2 https://chem.libretexts.org/@go/page/43437
 + –
[H ][OH ] = Kw (6.8.10)

+ –
[H ][ A ]
Ka = (6.8.11)
[H A]

Mass balance
–
Ca = [H A] + [ A ] (6.8.12)

Charge balance
+ – –
[H ] = [OH ] + [H A ] (6.8.13)

To eliminate [HA] from Equation 6.8.11 , we solve Equation 6.8.13 for this term, and substitute the resulting expression into the
numerator:
+ + −
[H ]([ H ] − [OH ])
Ka = (6.8.14)
Ca − ([ H + ] − [OH − ])

The latter equation is simplified by multiplying out and replacing [H+][OH–] with Kw. We then get rid of the [OH–] term by
replacing it with Kw/[H+]
+ + 2 + – + –
[H ] Cb + [ H ] – [H ][OH ] = Ka Ca – Ka [ H ] + Ka [OH ] (6.8.15)

+ 2 + 3 + +
Ka Kw
[H ] Cb + [ H ] – [H ] Kw = Ka Ca – Ka [ H ]+ (6.8.16)
[H + ]

Rearranged into standard polynomial form, this becomes

+ 3 + 2 +
[H ] + Ka [ H ] – (Kw + Ca Ka )[ H ]– Ka Kw = 0 (6.8.17)

For most practical applications, we can make approximations that eliminate the need to solve a cubic equation.

6.8.3.1: Approximation 1: Neglecting Hydroxide Population

Unless the acid is extremely weak or the solution is very dilute, the concentration of OH– can be neglected in comparison to that of
[H+]. If we assume that [OH–] ≪ [H+], then Equation 6.8.17 can be simplified to
+ 2
[H ]
Ka ≈ (6.8.18)
+
Ca − [ H ]

which is a quadratic equation:

+ 2 +
[H ] + Ka [ H ]– Ka Ca ≈ 0 (6.8.19)

and thus, from the quadratic formula,

−−−−−−−−− −
Ka + √ Ka + 4 Ka Ca
+
[H ] ≈ (6.8.20)
2

 Example 6.8.1: Acetic Acid

Calculate the pH of a 0.0010 M solution of acetic acid, K a = 1.74 × 10

–5
.
Solution
First approximation:
−−−−−−−−−−−−−−−−−−−−− − −−−−−− − −
+ –3 –5 –8 –4
[H ] = √ (1.0 × 10 ) × (1.74 × 10 = √ 1.74 × 10 = 1.3 × 10 M.

Applying the "5% test",

–4
1.3 × 10
= 0.13
–3
1.0 × 10

6.8.3 https://chem.libretexts.org/@go/page/43437
 This exceeds 0.05, so we must explicitly solve the quadratic Equation 6.8.19 to obtain two roots: +1.2 × 10
–4
and
– 1.4 × 10 . Taking the positive root, we have
−4

–4
pH =– log(1.2 × 10 ) = 3.9

6.8.3.2: Approximation 2: Very Concentrated Acids

If the acid is fairly concentrated (usually more than 10–3 M), a further simplification can frequently be achieved by making the
assumption that [H ] ≪ C . This is justified when most of the acid remains in its protonated form [HA], so that relatively little H+
+
a

is produced. In this event, Equation 6.8.18 reduces to

+ 2
[H ]
Ka ≈ (6.8.21)
Ca

or
+ −−−−−
[H ] ≈ √Ka Ca (6.8.22)

 Example 6.8.2

Calculate the pH and percent ionization of 0.10 M acetic acid "HAc" (CH3COOH), K a
–5
= 1.74 × 10 .
Solution:
It is usually best to start by using Equation 6.8.21 as a first approximation:
−−−−−−−−−−−−−−− − −−−−−− − −
+ –5 –6 –3
[H ] = √ (0.10)(1.74 × 10 ) = √ 1.74 × 10 = 1.3 × 10 M

This approximation is generally considered valid if [H+] is less than 5% of Ca; in this case, [H+]/Ca = 0.013, which is smaller
than 0.05 and thus within the limit. This same quantity also corresponds to the ionization fraction, so the percent ionization is
1.3%. The pH of the solution is
−3
pH =– log 1.2 × 10 = 2.9

6.8.3.3: Approximation 3: Very Weak and Acidic

If the acid is very weak or its concentration is very low, the H produced by its dissociation may be little greater than that due to
+

the ionization of water. However, if the solution is still acidic, it may still be possible to avoid solving the cubic equation 6.8.17 by
assuming that the term ([H ] − [OH ]) ≪ C in Equation 6.8.14:
+ –
a

+ 2
[H ]
Ka = (6.8.23)
+
Ca − [ H ]

This can be rearranged into standard quadratic form

+ 2 +
[H ] + Ka [ H ]– Ka Ca = 0 (6.8.24)

For dilute solutions of weak acids, an exact treatment may be required. With the aid of a computer or graphic calculator, solving a
cubic polynomial is now far less formidable than it used to be. However, round-off errors can cause these computerized cubic
solvers to blow up; it is generally safer to use a quadratic approximation.

 Example 6.8.3: Boric Acid

Boric acid, B(OH)3 ("H3BO3") is a weak acid found in the ocean and in some natural waters. As with many boron compounds,
there is some question about its true nature, but for most practical purposes it can be considered to be monoprotic with
K = 7.3 × 10
a :
–10

+
Bi(OH )3 + 2 H2 O ⇌ Bi(OH )– + H3 O
4

Find the [H+] and pH of a 0.00050 M solution of boric acid in pure water.
Solution

6.8.4 https://chem.libretexts.org/@go/page/43437
 Because this acid is quite weak and its concentration low, we will use the quadratic form Equation 6.8.19, which yields the
positive root 6.12 × 10 , corresponding to pH = 6.21. Notice that this is only six times the concentration of H present in
–7 +

pure water!
It is instructive to compare this result with what the quadratic approximation would yield, which yield [H +
] = 6.04 × 10
–7
so
pH = 6.22.

6.8.4: Weak bases

The weak bases most commonly encountered are:
anions A– of weak acids:
– –
A + H2 O ⇌ H A + OH (6.8.25)

2– –
CO + H2 O ⇌ H C O– + OH (6.8.26)
3 3

ammonia
+ –
N H3 + H2 O ⇌ N H + OH (6.8.27)
4

amines, e.g. methylamine

+
C H3 N H2 + H2 O ⇌ C H3 N H + H2 O (6.8.28)
3

6.8.4.1: Solution of an anion of a weak acid

Note that, in order to maintain electroneutrality, anions must be accompanied by sufficient cations to balance their charges. Thus
for a Cb M solution of the salt NaA in water, we have the following conditions:
Species
Na+, A–, HA, H2O, H+, OH–
Equilibria
+ –
[H ][OH ] = Kw (6.8.29)

−
[H A][OH ]
Kb = (6.8.30)
−
[A ]

Mass balance
+ –
Cb = [N a ] = [H A] + [ A ] (6.8.31)

Charge balance
+ + – –
[N a ] + [H ] = [OH ] + [A ] (6.8.32)

Replacing the [Na+] term in Equation 6.8.31 by C and combining with

b Kw and the mass balance, a relation is obtained that is
analogous to that of Equation 6.8.14 for weak acids:
− − +
[OH ]([OH ] − [H ])
Kb = (6.8.33)
− +
Cb − ([OH ] − [H ])

The approximations
− 2
[OH ]
Kb ≈ (6.8.34)
−
Cb − [OH ]

and
– −−−−−
[OH ] ≈ √Kb Cb (6.8.35)

can be derived in a similar manner.

6.8.5 https://chem.libretexts.org/@go/page/43437
  Example 6.8.4: Methylamine

Calculate the pH and the concentrations of all species in a 0.01 M solution of methylamine, CH3NH2 (K b = 4.2 × 10
–4
).
Solution
We begin by using the simplest approximation Equation 6.8.30:
−−−−− −−−−−−−−−−−−−−
– −4 –2 –3
[OH ] = √(Kb Cb − = √ (4.2 × 10 )(10 ) = 2.1 × 10

To see if this approximation is justified, we apply a criterion similar to what we used for a weak acid: [OH–] must not exceed
5% of Cb. In this case,
– −3
[OH ] (2.1 × 10
= = 0.21
–2
Cb 10

so we must use the quadratic form Equation 6.8.24 that yields the positive root 1.9 × 10 –3
which corresponds to [OH –
]

−14
Kw 1 × 10
+ −12
[H ] = = = 5.3 × 10
– –3
[OH 1.9 × 10

and
–12
pH =– log 5.3 × 10 = 11.3.

From the charge balance equation, solve for

– + – –12
[C H3 N H2 ] = [OH ]– [ H ] ≈ [OH ] = 5.3 × 10 M.

For the concentration of the acid form (methylaminium ion CH3NH3+), use the mass balance equation:
+
[C H3 N H ] = Cb – [C H3 N H2 ] = 0.01– 0.0019 = 0.0081 M .
3

6.8.5: Mixtures of Acids

Many practical problems relating to environmental and physiological chemistry involve solutions containing more than one acid. In
this section, we will restrict ourselves to a much simpler case of two acids, with a view toward showing the general method of
approaching such problems by starting with charge- and mass-balance equations and making simplifying assumptions when
justified. In general, the hydrogen ions produced by the stronger acid will tend to suppress dissociation of the weaker one, and both
will tend to suppress the dissociation of water, thus reducing the sources of H+ that must be dealt with.
Consider a mixture of two weak acids HX and HY; their respective nominal concentrations and equilibrium constants are denoted
by Cx , Cy , Kx and Ky ,
Starting with the charge balance expression
+ – – –
[H ] = [X ] + [Y ] + [OH ] (6.8.36)

We use the equilibrium constants to replace the conjugate base concentrations with expressions of the form
[H X]
−
[X ] = Kx (6.8.37)
+
[H ]

to yield
[H X] [H Y ]
+
[H ] = + + Kw (6.8.38)
Kx Ky

If neither acid is very strong or very dilute, we can replace equilibrium concentrations with nominal concentrations:
−−−−−−−−−−−−−−
+
[H ] ≈ √ Cc Kx + Cy Ky Kw (6.8.39)

6.8.6 https://chem.libretexts.org/@go/page/43437
  Example 6.8.5: Acetic Acid and Formic Acid

Estimate the pH of a solution that is 0.10M in acetic acid (K a = 1.8 × 10

–5
) and 0.01M in formic acid (Ka = 1.7 × 10
–4
).
Solution
Because Kw is negligible compared to the CaKa products, we can simplify \Equation ref 3 − 4 :
−−−−−−−−−−−−−−−−− −
+ –6 −6
[H ] = √ 1.8 × 10 + 1.7 × 10 = 0.0019

Which corresponds to a pH of – log 0.0019 = 2.7

Note that the pH of each acid separately at its specified concentration would be around 2.8. However, if 0.001 M chloroacetic
acid (Ka= 0.0014) is used in place of formic acid, the above expression becomes
−−−−−−−−−−−−−−−−−−− −
+ −6 −14
[H ] ≈ √ 1.4 × 10 + 1.75 × 10 = 0.00188 (6.8.40)

which exceeds the concentration of the stronger acid; because the acetic acid makes a negligible contribution to [H+] here, the
simple approximation given above \Equation 6.8.38 is clearly invalid. We now use the mass balance expression for the stronger
acid
–
[H X] + [ X ] = Cx (6.8.41)

to solve for [X–] which is combined with the equilibrium constant Kx to yield
+ ]
[H ][ X
−
[X ] = Cx − (6.8.42)
Kx

Solving this for [X–] gives

−
Cx Kx
[X ] = (6.8.43)
Kx + [ H + ]

The approximation for the weaker acetic acid (HY) is still valid, so we retain it in the substituted electronegativity expression:
Cx Kx Cy Ky
+
[H ] + (6.8.44)
+ +
Kx + [ H ] [H ]

which is a cubic equation that can be solved by approximation.

Several methods have been published for calculating the hydrogen ion concentration in solutions containing an arbitrary number of
acids and bases. These generally involve iterative calculations carried out by a computer. See, for example, J. Chem. Education
67(6) 501-503 (1990) and 67(12) 1036-1037 (1990).

6.8.6: Equilibria of Polyprotic Acids

Owing to the large number of species involved, exact solutions of problems involving polyprotic acids can become very
complicated. Thus for phosphoric acid H3PO4, the three "dissociation" steps yield three conjugate bases:

Fortunately, it is usually possible to make simplifying assumptions in most practical applications. In the section that follows, we
will show how this is done for the less-complicated case of a diprotic acid. A diprotic acid HA can donate its protons in two steps,
yielding first a monoprotonated species HA– and then the completely deprotonated form A2–.

Since there are five unknowns (the concentrations of the acid, of the two conjugate bases and of H+ and OH–), we need five
equations to define the relations between these quantities. These are
Equilibria
+ –
[H ][OH ] = Kw (6.8.45)

6.8.7 https://chem.libretexts.org/@go/page/43437
 + −
[H ][H A ]
K1 = (6.8.46)
[ H2 A]

+ 2−
[H ][H A ]
K1 = (6.8.47)
−
[H A ]

Mass balance
– 2–
Ca = [ H2 A] + [H A ] + [ A ] (6.8.48)

Charge balance
+ – – 2–
[H ] = [OH ] + [H A ] + 2[ A ] (6.8.49)

(It takes 2 moles of H +

to balance the charge of 1 mole of A ) 2–

Solving these five equations simultaneously for K yields the rather intimidating expression
1

+ −
2 K2 [ H ] − [OH ]
+ + −
[H ] ([ H ] − [OH ] )
+
[H + 2 K2
K1 = (6.8.50)
+ −
K2 [ H ] − [OH ]
+ −
Ca − ([ H ] − [OH ] )
+
[H ] + 2 K2

which is of little practical use except insofar as it provides the starting point for various simplifying approximations.
If the solution is even slightly acidic, then ([H+] – [OH–]) ≈ [H+] and
+
2 K2 [ H ]
+ +
[H ] ([ H ] )
+
[H + 2 K2
K1 = (6.8.51)
+
K2 [ H ]
+
Ca − ([ H ] )
[ H + ] + 2 K2

For any of the common diprotic acids, K is much smaller than K . If the solution is sufficiently acidic that K ≪ [H ] , then a
2 1 2
+

further simplification can be made that removes K from Equation 6.8.51; this is the starting point for most practical calculations.
2

+ 2
[H ]
K1 ≈ (6.8.52)
Ca − [ H + ]

Finally, if the solution is sufficiently concentrated and K sufficiently small so that [H

1
+
] ≪ Ca , then Equation 6.8.52 reduces to:
+ −−−−−
[H ] ≈ √Ka Ca (6.8.53)

6.8.7: Acid with conjugate base: Buffer solutions

Solutions containing a weak acid together with a salt of the acid are collectively known as buffers. When they are employed to
control the pH of a solution (such as in a microbial growth medium), a sodium or potassium salt is commonly used and the
concentrations are usually high enough for the Henderson-Hasselbalch equation to yield adequate results.

6.8.7.1: Exact solution

In this section, we will develop an exact analytical treatment of weak acid-salt solutions, and show how the H–H equation arises as
an approximation. A typical buffer system is formed by adding a quantity of strong base such as sodium hydroxide to a solution of
a weak acid HA. Alternatively, the same system can be made by combining appropriate amounts of a weak acid and its salt NaA. A
system of this kind can be treated in much the same way as a weak acid, but now with the parameter Cb in addition to Ca.
Species
Na+, A–, HA, H2O, H+, OH–
Equilibria
+ –
[H ][OH ] = Kw (6.8.54)

6.8.8 https://chem.libretexts.org/@go/page/43437
 + −
[H ][ A ]
Ka = (6.8.55)
[H A]

Mass balance
–
Ca + C − b = [H A] + [ A ] (6.8.56)

+
Cb = [N a ] (6.8.57)

Charge balance
+ + – –
[N a ] + [H ] = [OH ] + [A ] (6.8.58)

Substituting Equation 6.8.57 into Equation 6.8.58 yields an expression for [A–]:
– + –
[ A ] = Cb + [ H ]– [OH ] (6.8.59)

Inserting this into Equation 6.8.56 and solving for [HA] yields
+ –
[H A] = Cb + [ H ]– [OH ] (6.8.60)

Finally, we substitute these last two expressions into the equilibrium constant (Equation 6.8.55):
+ −
Ca − [ H ] + [OH ]
+
[H ] = Ka (6.8.61)
+ −
Cb + [ H ] − [OH ]

which becomes cubic in [H+] when [OH–] is replaced by (Kw / [H+]).

+ 3 + 2 +
[H ] + (Cb + Ka )[ H ] – (Kw + Ca Ka )[ H ]– Ka Kw = 0 (6.8.62)

6.8.7.2: Approximations
In almost all practical cases it is possible to make simplifying assumptions. Thus if the solution is known to be acidic or alkaline,
then the [OH–] or [H+] terms in Equation 6.8.61 can be neglected. In acidic solutions, for example, Equation 6.8.61 becomes
+
Ca − [ H ]
+
[H ] = Ka (6.8.63)
+
Cb + [ H ]

which can be rearranged into a quadratic in standard polynomial form:

+ 2 +
[H ] + (Cb + Ca ) [ H ]– Ka Ca = 0 (6.8.64)

If the concentrations Ca and Cb are sufficiently large, it may be possible to neglect the [H+] terms entirely, leading to the
commonly-seen Henderson-Hasselbalch Approximation.
Ca
+
[H ] ≈ Ka (6.8.65)
Cb

It's important to bear in mind that the Henderson-Hasselbalch Approximation is an "approximation of an approximation" that is
generally valid only for combinations of Ka and concentrations that fall within the colored portion of this plot.

6.8.9 https://chem.libretexts.org/@go/page/43437
Most buffer solutions tend to be fairly concentrated, with Ca and Cb typically around 0.01 - 0.1 M. For more dilute buffers and
larger Ka's that bring you near the boundary of the colored area, it is safer to start with Equation 6.8.63.

 Example 6.8.6: Chlorous Acid Buffer

Chlorous acid HClO2 has a pKa of 1.94. Calculate the pH of a solution made by adding 0.01 M/L of sodium hydroxide to a -.02
M/L solution of chloric acid.
Solution
In the resulting solution, Ca = Cb = 0.01M. On the plots shown above, the intersection of the log Ca = –2 line with the plot for
pKa = 2 falls near the left boundary of the colored area, so we will use the quadratic form 6.8.64.
Substitution in Equation 6.8.64 yields
+ + –1.9 –2
H + 0.02 H – (10 x 10 ) =0

which yields a positive root 0.0047 = [H+] that corresponds to pH = 2.3.

Note: Using the Henderson-Hassalbach Approximateion (Equation 6.8.65) would give pH = pKa = 1.9.

6.8: A Deeper Look - Exact Treatment of Acid-Base Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.
13.7: Exact Calculations and Approximations by Stephen Lower is licensed CC BY 3.0. Original source:
http://www.chem1.com/acad/webtext/virtualtextbook.html.

6.8.10 https://chem.libretexts.org/@go/page/43437
6.9: Organic Acids and Bases - Structure and Reactivity
 Learning Objectives
To understand how molecular structure affects the strength of an acid or base.

We have seen that the strengths of acids and bases vary over many orders of magnitude. In this section, we explore some of the
structural and electronic factors that control the acidity or basicity of a molecule.

6.9.1: Bond Strengths

In general, the stronger the A– H or B– H bond, the less likely the bond is to break to form H
+ +
ions and thus the less acidic the
substance. This effect can be illustrated using the hydrogen halides:

Relative Acid Strength HF HCl HBr HI

H–X Bond Energy

570 432 366 298
(kJ/mol)

pKa 3.20 −6.1 −8.9 −9.3

The trend in bond energies is due to a steady decrease in overlap between the 1s orbital of hydrogen and the valence orbital of the
halogen atom as the size of the halogen increases. The larger the atom to which H is bonded, the weaker the bond. Thus the bond
between H and a large atom in a given family, such as I or Te, is weaker than the bond between H and a smaller atom in the same
family, such as F or O. As a result, acid strengths of binary hydrides increase as we go down a column of the periodic table. For
example, the order of acidity for the binary hydrides of Group 16 elements is as follows, with pK values in parentheses:
a

H2 O(14.00 = p Kw ) < H2 S(7.05) < H2 Se(3.89) < H2 T e(2.6) (6.9.1)

6.9.2: Stability of the Conjugate Base

Whether we write an acid–base reaction as AH ⇌ A + H or as BH ⇌ B + H , the conjugate base (A or B ) contains
− + + + −

one more lone pair of electrons than the parent acid (AH or BH ). Any factor that stabilizes the lone pair on the conjugate base
+

favors dissociation of H and makes the parent acid a stronger acid. Let’s see how this explains the relative acidity of the binary
+

hydrides of the elements in the second row of the periodic table. The observed order of increasing acidity is the following, with
pKa values in parentheses:
C H4 ( 50) ≪ N H3 ( 36) < H2 O(14.00) < H F (3.20) (6.9.2)

Consider, for example, the compounds at both ends of this series: methane and hydrogen fluoride. The conjugate base of C H is 4

C H , and the conjugate base of H F is F . Because fluorine is much more electronegative than carbon, fluorine can better
− −
3

stabilize the negative charge in the F ion than carbon can stabilize the negative charge in the CH3− ion. Consequently, HF has a
−

greater tendency to dissociate to form H and F than does methane to form H and C H , making HF a much stronger acid
+ − + −

than C H . 4

The same trend is predicted by analyzing the properties of the conjugate acids. For a series of compounds of the general formula
H E , as the electronegativity of E increases, the E–H bond becomes more polar, favoring dissociation to form E and H . Due to− +

both the increasing stability of the conjugate base and the increasing polarization of the E–H bond in the conjugate acid, acid
strengths of binary hydrides increase as we go from left to right across a row of the periodic table.

Acid strengths of binary hydrides increase as we go down a column or from left to right across a row of the periodic table.

 the strongest acid Known: The hydrohelium Cation

The stornger acid, the weaker the covalent bond to a hydrogen atom. So the strongest acid possible is the molecule with the
weakest bond. That is the hydrohelium (1+) cation, HeH , which is a positively charged ion formed by the reaction of a proton
+

with a helium atom in the gas phase. It was first produced in the laboratory in 1925 and is isoelectronic with molecular
hydrogen (\ce{H2}}). It is the strongest known acid, with a proton affinity of 177.8 kJ/mol.

6.9.1 https://chem.libretexts.org/@go/page/43438
 Ball and stick model of the hydrohelium ion. (CC BY-SA 3.0; CCoil).
HeH
+
cannot be prepared in a condensed phase, as it would protonate any anion, molecule or atom with which it were
associated. However it is possible to estimate a hypothetical aqueous acidity using Hess's law:

HHe+(g) → H+(g) + He(g) +178 kJ/mol

HHe+(aq) → HHe+(g) +973 kJ/mol

+ +
H (g) → H (aq) −1530 kJ/mol

He(g) → He(aq) +19 kJ/mol

HHe+(aq) → H+(aq) + He(aq) −360 kJ/mol

A free energy change of dissociation of −360 kJ/mol is equivalent to a pKa of −63.

It has been suggested that HeH should occur naturally in the interstellar medium, but it has not yet been detected.
+

6.9.3: Inductive Effects

Atoms or groups of atoms in a molecule other than those to which H is bonded can induce a change in the distribution of electrons
within the molecule. This is called an inductive effect, and, much like the coordination of water to a metal ion, it can have a major
effect on the acidity or basicity of the molecule. For example, the hypohalous acids (general formula HOX, with X representing a
halogen) all have a hydrogen atom bonded to an oxygen atom. In aqueous solution, they all produce the following equilibrium:
+ −
H OX(aq) ⇌ H + OX (aq) (6.9.3)
(aq)

The acidities of these acids vary by about three orders of magnitude, however, due to the difference in electronegativity of the
halogen atoms:

HOX Electronegativity of X pKa

HOCl 3.0 7.40

HOBr 2.8 8.55

HOI 2.5 10.5

As the electronegativity of X increases, the distribution of electron density within the molecule changes: the electrons are drawn
more strongly toward the halogen atom and, in turn, away from the H in the O–H bond, thus weakening the O–H bond and
allowing dissociation of hydrogen as H .+

The acidity of oxoacids, with the general formula H OXO (with n = 0−3), depends strongly on the number of terminal oxygen
n

atoms attached to the central atom X. As shown in Figure 6.9.1, the K values of the oxoacids of chlorine increase by a factor of
a

about 10 to 10 with each oxygen as successive oxygen atoms are added. The increase in acid strength with increasing number of
4 6

terminal oxygen atoms is due to both an inductive effect and increased stabilization of the conjugate base.

Any inductive effect that withdraws electron density from an O–H bond increases the
acidity of the compound.
Because oxygen is the second most electronegative element, adding terminal oxygen atoms causes electrons to be drawn away
from the O–H bond, making it weaker and thereby increasing the strength of the acid. The colors in Figure 6.9.1 show how the

6.9.2 https://chem.libretexts.org/@go/page/43438
electrostatic potential, a measure of the strength of the interaction of a point charge at any place on the surface of the molecule,
changes as the number of terminal oxygen atoms increases. In Figure 6.9.1 and Figure 6.9.2, blue corresponds to low electron
densities, while red corresponds to high electron densities. The oxygen atom in the O–H unit becomes steadily less red from H C lO
to H C lO (also written as H OC lO , while the H atom becomes steadily bluer, indicating that the electron density on the O–H
4 3

unit decreases as the number of terminal oxygen atoms increases. The decrease in electron density in the O–H bond weakens it,
making it easier to lose hydrogen as H ions, thereby increasing the strength of the acid.
+

Figure 6.9.1 : The Relationship between the Acid Strengths of the Oxoacids of Chlorine and the Electron Density on the O–H Unit.
These electrostatic potential maps show how the electron density on the O–H unit decreases as the number of terminal oxygen
atoms increases. Blue corresponds to low electron densities, whereas red corresponds to high electron densities. Source: Chlorine
oxoacids pKa values from J. R. Bowser, Inorganic Chemistry (Pacific Grove, CA: Brooks-Cole,1993).
At least as important, however, is the effect of delocalization of the negative charge in the conjugate base. As shown in Figure
6.9.2, the number of resonance structures that can be written for the oxoanions of chlorine increases as the number of terminal

oxygen atoms increases, allowing the single negative charge to be delocalized over successively more oxygen atoms.

Electron delocalization in the conjugate base increases acid strength.

The electrostatic potential plots in Figure 6.9.2 demonstrate that the electron density on the terminal oxygen atoms decreases
steadily as their number increases. The oxygen atom in ClO− is red, indicating that it is electron rich, and the color of oxygen
progressively changes to green in C lO , indicating that the oxygen atoms are becoming steadily less electron rich through the
+
4

series. For example, in the perchlorate ion (C lO ), the single negative charge is delocalized over all four oxygen atoms, whereas in
−
4

the hypochlorite ion (OC l ), the negative charge is largely localized on a single oxygen atom (Figure 6.9.2). As a result, the
−

perchlorate ion has no localized negative charge to which a proton can bind. Consequently, the perchlorate anion has a much lower
affinity for a proton than does the hypochlorite ion, and perchloric acid is one of the strongest acids known.

6.9.3 https://chem.libretexts.org/@go/page/43438
As the number of terminal oxygen atoms increases, the number of resonance structures that can be written for the oxoanions of
chlorine also increases, and the single negative charge is delocalized over more oxygen atoms. As these electrostatic potential plots
demonstrate, the electron density on the terminal oxygen atoms decreases steadily as their number increases. As the electron
density on the oxygen atoms decreases, so does their affinity for a proton, making the anion less basic. As a result, the parent
oxoacid is more acidic.
Similar inductive effects are also responsible for the trend in the acidities of oxoacids that have the same number of oxygen atoms
as we go across a row of the periodic table from left to right. For example, H P O is a weak acid, H SO is a strong acid, and
3 4 2 4

H C lO is one of the strongest acids known. The number of terminal oxygen atoms increases steadily across the row, consistent
4

with the observed increase in acidity. In addition, the electronegativity of the central atom increases steadily from P to S to C l,
which causes electrons to be drawn from oxygen to the central atom, weakening the O– H bond and increasing the strength of the
oxoacid.

Careful inspection of the data in Table 6.9.1 shows two apparent anomalies: carbonic acid and phosphorous acid. If carbonic acid
(H C O ) were a discrete molecule with the structure (HO) C=O, it would have a single terminal oxygen atom and should be
2 3 2

comparable in acid strength to phosphoric acid (H P O ), for which pKa1 = 2.16. Instead, the tabulated value of pK for carbonic
3 4 a1

acid is 6.35, making it about 10,000 times weaker than expected. As we shall see, however, H C O is only a minor component of
2 3

the aqueous solutions of C O that are referred to as carbonic acid. Similarly, if phosphorous acid (H P O ) actually had the
2 3 3

structure (H O) P , it would have no terminal oxygen atoms attached to phosphorous. It would therefore be expected to be about as
3

strong an acid as H OC l (pKa = 7.40). In fact, the pK for phosphorous acid is 1.30, and the structure of phosphorous acid is
a1

(HO) P(=O)H with one H atom directly bonded to P and one P=O bond. Thus the pKa1 for phosphorous acid is similar to that
2

of other oxoacids with one terminal oxygen atom, such as H P O . Fortunately, phosphorous acid is the only common oxoacid in
3 4

which a hydrogen atom is bonded to the central atom rather than oxygen.
Table 6.9.1 : Values of pKa for Selected Polyprotic Acids and Bases

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 Polyprotic Acids Formula pKa1 pKa2 pKa3

carbonic acid* “H 2 C O3 ” 6.35 10.33

citric acid 3.13

H O2 CCH − 2C(OH)(C O2 H)C H2 C O2 H 4.76 6.40

malonic acid HO − 2CC H2 C O2 H 2.85 5.70

oxalic acid H O2 CC O2 H 1.25 3.81

phosphoric acid H3 P O4 2.16 7.21 12.32

phosphorous acid H3 P O3 1.3 6.70

succinic acid H O2 CC H2 C H2 C O2 H 4.21 5.64

sulfuric acid H2 S O4 −2.0 1.99

sulfurous acid* “H 2 S O3 ” 1.85 7.21

Polyprotic Bases Formula pKb1 pKb2

ethylenediamine H2 N (C H2 )2 N H2 4.08 7.14

piperazine HN (C H2 C H2 )2 N H 4.27 8.67

propylenediamine H2 N (C H2 )3 N H2 3.45 5.12

*H C O and H S O are at best minor components of aqueous solutions of

2 3 2 3 CO2(g) and SO
2(g) , respectively, but such solutions are commonly
referred to as containing carbonic acid and sulfurous acid, respectively.

Inductive effects are also observed in organic molecules that contain electronegative substituents. The magnitude of the electron-
withdrawing effect depends on both the nature and the number of halogen substituents, as shown by the pKa values for several
acetic acid derivatives:

p Ka C H3 C O2 H 4.76 < C H2 C lC O2 H 2.87 < C H C l2 C O2 H 1.35 < C C l3 C O2 H 0.66 < C F3 C O2 H 0.52

As you might expect, fluorine, which is more electronegative than chlorine, causes a larger effect than chlorine, and the effect of
three halogens is greater than the effect of two or one. Notice from these data that inductive effects can be quite large. For instance,
replacing the – CH group of acetic acid by a – CF group results in about a 10,000-fold increase in acidity!
3 3

 Example 6.9.1

Arrange the compounds of each series in order of increasing acid or base strength.
a. sulfuric acid [H SO , or (H O) SO ], fluorosulfonic acid (F SO
2 4 2 2 3H , or F SO 2 OH ), and sulfurous acid [H 2 S O3 , or
(H O) SO ] 2

b. ammonia (N H ), trifluoramine (N F ), and hydroxylamine (N H

3 3 2 OH )
The structures are shown here.

Given: series of compounds

6.9.5 https://chem.libretexts.org/@go/page/43438
 Asked for: relative acid or base strengths
Strategy:
Use relative bond strengths, the stability of the conjugate base, and inductive effects to arrange the compounds in order of
increasing tendency to ionize in aqueous solution.
Solution:
Although both sulfuric acid and sulfurous acid have two –OH groups, the sulfur atom in sulfuric acid is bonded to two terminal
oxygen atoms versus one in sulfurous acid. Because oxygen is highly electronegative, sulfuric acid is the stronger acid because
the negative charge on the anion is stabilized by the additional oxygen atom. In comparing sulfuric acid and fluorosulfonic
acid, we note that fluorine is more electronegative than oxygen. Thus replacing an –OH by –F will remove more electron
density from the central S atom, which will, in turn, remove electron density from the S–OH bond and the O–H bond. Because
its O–H bond is weaker, F SO H is a stronger acid than sulfuric acid. The predicted order of acid strengths given here is
3

confirmed by the measured pKa values for these acids:

−2
pKaH2 S O3 1.85 < H2 S O < F S O3 H − 10
4

The structures of both trifluoramine and hydroxylamine are similar to that of ammonia. In trifluoramine, all of the hydrogen
atoms in NH3 are replaced by fluorine atoms, whereas in hydroxylamine, one hydrogen atom is replaced by OH. Replacing the
three hydrogen atoms by fluorine will withdraw electron density from N, making the lone electron pair on N less available to
bond to an H ion. Thus N F is predicted to be a much weaker base than N H . Similarly, because oxygen is more
+
3 3

electronegative than hydrogen, replacing one hydrogen atom in N H by OH will make the amine less basic. Because oxygen
3

is less electronegative than fluorine and only one hydrogen atom is replaced, however, the effect will be smaller. The predicted
order of increasing base strength shown here is confirmed by the measured pK values: b

p Kb N F3 — << N H2 OH 8.06 < N H3 4.75

Trifluoramine is such a weak base that it does not react with aqueous solutions of strong acids. Hence its base ionization
constant has never been measured.

 Exercise 6.9.1

Arrange the compounds of each series in order of

a. decreasing acid strength: H P O , C H P O H , and H C lO .
3 4 3 3 2 3

b. increasing base strength: C H S , OH , and C F S .

3
− −
3
−

Answer a
H C lO − 3 > C H3 P O3 H2 > H3 P O4

Answer a
− − −
C F3 S < C H3 S < OH

6.9.4: Summary
Inductive effects and charge delocalization significantly influence the acidity or basicity of a compound. The acid–base strength of
a molecule depends strongly on its structure. The weaker the A–H or B–H+ bond, the more likely it is to dissociate to form an H +

ion. In addition, any factor that stabilizes the lone pair on the conjugate base favors the dissociation of H , making the conjugate
+

acid a stronger acid. Atoms or groups of atoms elsewhere in a molecule can also be important in determining acid or base strength
through an inductive effect, which can weaken an O– H bond and allow hydrogen to be more easily lost as H ions. +

6.9.6 https://chem.libretexts.org/@go/page/43438
6.9.5: Contributors and Attributions
Anonymous

6.9: Organic Acids and Bases - Structure and Reactivity is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.
16.8: Molecular Structure and Acid-Base Behavior is licensed CC BY-NC-SA 4.0.

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6.10: Lewis Bases as Nucleophilic Reactants in Organic Reactions
The basis of chemistry is that opposite charges attract and like charges repel, and that in reactions, electrons flow from “electron
rich” areas to “electron poor” areas. A name to the types of species that are considered “electron rich“ and “electron poor”. They
are called nucleophiles and electrophiles.

6.10.1: Nucleophiles
A nucleophiles (from “nucleus loving”, or “positive-charge loving”) is a reactant that provides a pair of electrons to form a new
covalent bond. This is the exact definition of a Lewis base discussed earlier. Hence, nucleophiles are Lewis bases. When the
nucleophile donates a pair of electrons to a proton, it’s called a Brønsted base, or simply, “base”. As you can see, nucleophiles all
have pairs of electrons to donate, and tend to be rich in electrons. Here are some examples of Lewis bases you are probably familiar
with.

Figure 6.10.1 : Examples of Lewis bases

When the nucleophile donates a pair of electrons to a proton, it’s called a Brønsted base.
How is nucleophilicity different from basicity? Well, since it’s not limited to simply forming a bond to hydrogen anymore, this
leads to some extra complications. Let’s just talk about the measurement problem first. Many reactions of nucleophiles are not
reversible. A bond forms, a bond breaks, and that’s the end of the reaction. The problem with this from a measurement standpoint is
that we often cannot determine an equilibrium constant for a reaction. And if we can’t do that, then we cannot develop a reactivity
scale based on equilibria. If we can’t measure equilibria, then what do we do? Well, we use the next best measurement available: to
measure reaction rates, but that is discuss in the following chapters.

Figure 6.10.2 : A nucleophilic reaction with a nucleophile donating a pair of electrons to the the carbon

 Example 6.10.1: Basicity in Organic Chemistry Reactions

So how do reactions of nucleophiles at hydrogen differ from reactions of nucleophiles at carbon? Well, they’re more easily
reversible, for one thing. We can measure acidity (and, by extension, basicity) through the measure known as pKa, which is a
reflection of the position of the equilibrium between an acid and its conjugate base.

We can vaguely define “nucleophilicity” as “the extent to which a species can donate a pair of electrons”. A more precise definition
will be discussed in organic chemistry courses.

6.10.1 https://chem.libretexts.org/@go/page/44755
6.10.2: Electrophilicity
Similarly, the extent to which a species can accept a lone pair of electrons is called “electrophilicity”. An electrophile (from
“electron-loving”, or “negative-charge loving”) is a species that accepts a pair of electrons to form a new covalent bond. Again, this
should sound familiar: this is the definition of a Lewis acid. An electrophile that accepts an electron pair at hydrogen is called a
Brønsted acid, or just “acid”. Here are some examples of Lewis acids you’re familiar with.

Figure 6.10.3 : Lewis acids

Lewis acidity is essentially electrophilicity. Acidity (Brønsted acidity) is what we call it

when the electrophile is a proton.

 Example 6.10.1: The Hydroxide Ion

When hydroxide ion donates a pair of electrons to an electrophilic atom (such as carbon here) to form a new covalent bond, it
is acting as a nucleophile.

And as we’ve seen before, when hydroxide ion donates a pair of electrons to an (acidic) proton to form a new covalent bond,
we say it’s acting as a “base”.

The vast majority of the reactions you’ll see in organic chemistry (>95%) – will be reactions where a nucleophile donates a pair of
electrons to an electrophile (i.e., a nucleophile attacks an electrophile) with very few exceptions! This is why understanding where
electrons are, and how electrons flow is so important – because the electron richness (or poorness) of an atom (or molecule)
determines its nucleophilicity or electrophilicity, which in turn determines its reactivity. It’s not an exaggeration to say that
nucleophilicity and electrophilicity (and hence Lewis Acids and Bases) are the fundamental basis of chemical reactivity.

6.10.3: Summary
Basicity is a subset of nucleophilicity. While, all nucleophiles are Lewis bases since they donate a lone pair of electrons. A
(Brønsted) base is the name we give to a nucleophile since it forms a bond to a proton (H ). To summarize, when we’re talking
+

about basicity and nucleophilicity, we’re talking about these two types of events.

6.10.4: Contributors and Attributions

James Ashenhurst (MasterOrganicChemistry.com)

6.10: Lewis Bases as Nucleophilic Reactants in Organic Reactions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by LibreTexts.

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 CHAPTER OVERVIEW

VII: Solubility and Precipitation Equilibria

UC Davis: General Chemistry 4B

Winter 2024: Delmar Larsen
Unit I: Chemical Thermodynamics ● Unit II: Physical Equilibria ● Unit III: Chemical Equilibria
Agenda ● ADAPT ● Worksheets

Solubility equilibrium is a type of dynamic equilibrium. It exists when a chemical compound in the solid state is in chemical
equilibrium with a solution of that compound. The solid may dissolve unchanged, with dissociation or with chemical reaction with
another constituent of the solvent, such as acid or alkali. Each type of equilibrium is characterized by a temperature-dependent
equilibrium constant. Solubility equilibria are important in pharmaceutical, environmental and many other scenarios.
7.1: The Nature of Solubility Equilibria
7.2: Ionic Equilibria between Solids and Solutions
7.3: Precipitation and the Solubility Product
7.4: The Effects of pH on Solubility
7.5: Complex Ions and Solubility
7.6: A Deeper Look - Selective Precipitation of Ions

VII: Solubility and Precipitation Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
7.1: The Nature of Solubility Equilibria
 Learning Objectives
Understand the qualitative nature of dissolving a salt in water

Dissolution of a salt in water is a chemical process that is governed by the same laws of chemical equilibrium that apply to any
other reaction. There are, however, a number of special aspects of of these equilibria that set them somewhat apart from the more
general ones that are covered in the lesson set devoted specifically to chemical equilibrium. These include such topics as the
common ion effect, the influence of pH on solubility, supersaturation, and some special characteristics of particularly important
solubility systems... all explained in what follows.

7.1.1: The Dissolution of Salts in Water

Drop some ordinary table salt into a glass of water, and watch it "disappear". We refer to this as dissolution, and we explain it as a
process in which the sodium and chlorine units break away from the crystal surface, get surrounded by H2O molecules, and become
hydrated ions.
+
N aC l(s) → N a + C l– (7.1.1)
(aq) (aq)

The designation (aq) means "aqueous" and comes from aqua, the Latin word for water. It is used whenever we want to emphasize
that the ions are hydrated — that H2O molecules are attached to them.

Remember that solubility equilibrium and the calculations that relate to it are only meaningful when both sides (solids and
dissolved ions) are simultaneously present. But if you keep adding salt, there will come a point at which it no longer seems to
dissolve. If this condition persists, we say that the salt has reached its solubility limit, and the solution is saturated in NaCl. The
situation is now described by
+
N aC l(s) ⇌ N a + C l– (7.1.2)
(aq) (aq)

in which the solid and its ions are in equilibrium.

Salt solutions that have reached or exceeded their solubility limits (usually 36-39 g per 100 mL of water) are responsible for
prominent features of the earth's geochemistry. They typically form when NaCl leaches from soils into waters that flow into salt
lakes in arid regions that have no natural outlets; subsequent evaporation of these brines force the above equilibrium to the left,
forming natural salt deposits. These are often admixed with other salts, but in some cases are almost pure NaCl. Many parts of the
world contain buried deposits of NaCl (known as halite) that formed from the evaporation of ancient seas, and which are now
mined.

7.1.1.1: Expressing solubilities

Solubilities are most fundamentally expressed in molar (mol L–1 of solution) or molal (mol kg–1 of water) units. But for practical
use in preparing stock solutions, chemistry handbooks usually express solubilities in terms of grams-per-100 ml of water at a given
temperature, frequently noting the latter in a superscript. Thus 6.9 20 means 6.9 g of solute will dissolve in 100 mL of water at 20°
C.

7.1.1 https://chem.libretexts.org/@go/page/44749
When quantitative data are lacking, the designations "soluble", "insoluble", "slightly soluble", and "highly soluble" are used. There
is no agreed-on standard for these classifications, but a useful guideline might be that shown below.

7.1.1.2: What determines solubility?

The solubilities of salts in water span a remarkably large range of values, from almost completely insoluble to highly soluble.
Moreover, there is no simple way of predicting these values, or even of explaining the trends that are observed for the solubilities
of different anions within a given group of the periodic table.

Ultimately, the driving force for dissolution (and for all chemical processes) is determined by the Gibbs free energy change.
Dissolution of a salt is conceptually understood as a sequence of the two processes depicted above:
1. breakup of the ionic lattice of the solid (i.e., lattice energy)
2. followed by attachment of water molecules to the released ions (Solvation or Hydration Energy).
The first step consumes a large quantity of energy, something that by itself would strongly discourage solubility. But the second
step releases a large amount of energy and thus has the opposite effect. Thus the net energy change depends on the sum of two
large energy terms (often approaching 1000 kJ/mol) having opposite signs. Each of these terms will to some extent be influenced
by the size, charge, and polarizability of the particular ions involved, and on the lattice structure of the solid. This large number of
variables makes it impossible to predict the solubility of a given salt.
Nevertheless, there are some clear trends for how the solubilities of a series of salts of a given anion (such as hydroxides, sulfates,
etc.) change with a periodic table group. And of course, there are a number of general solubility rules.

 Solubility Rules
1. Salts containing Group I elements are soluble (Li+, Na+, K+, Cs+, Rb+). Exceptions to this rule are rare. Salts containing the
ammonium ion (NH4+) are also soluble.
2. Salts containing nitrate ion (NO3-) are generally soluble.
3. Salts containing Cl -, Br -, I - are generally soluble. Important exceptions to this rule are halide salts of Ag+, Pb2+, and
(Hg2)2+. Thus, AgCl, PbBr2, and Hg2Cl2 are all insoluble.
4. Most silver salts are insoluble. AgNO3 and Ag(C2H3O2) are common soluble salts of silver; virtually anything else is
insoluble.
5. Most sulfate salts are soluble. Important exceptions to this rule include BaSO4, PbSO4, Ag2SO4 and SrSO4 .
6. Most hydroxide salts are only slightly soluble. Hydroxide salts of Group I elements are soluble. Hydroxide salts of Group II
elements (Ca, Sr, and Ba) are slightly soluble. Hydroxide salts of transition metals and Al3+ are insoluble. Thus, Fe(OH)3,
Al(OH)3, Co(OH)2 are not soluble.
7. Most sulfides of transition metals are highly insoluble. Thus, CdS, FeS, ZnS, Ag2S are all insoluble. Arsenic, antimony,
bismuth, and lead sulfides are also insoluble.
8. Carbonates are frequently insoluble. Group II carbonates (Ca, Sr, and Ba) are insoluble. Some other insoluble carbonates
include FeCO3 and PbCO3.
9. Chromates are frequently insoluble. Examples: PbCrO4, BaCrO4
10. Phosphates are frequently insoluble. Examples: Ca3(PO4)2, Ag3PO4
11. Fluorides are frequently insoluble. Examples: BaF2, MgF2 PbF2.

A solution must be saturated to be in equilibrium with the solid. This is a necessary condition for solubility equilibrium, but it is
not by itself sufficient. True chemical equilibrium can only occur when all components are simultaneously present. A solubility

7.1.2 https://chem.libretexts.org/@go/page/44749
system can be in equilibrium only when some of the solid is in contact with a saturated solution of its ions. Failure to appreciate
this is a very common cause of errors in solving solubility problems.

 Undersaturated and supersaturated solutions

If the ion product is smaller than the solubility product, the system is not in equilibrium and no solid can be present. Such a
solution is said to be undersaturated. A supersaturated solution is one in which the ion product exceeds the solubility product.
A supersaturated solution is not at equilibrium, and no solid can ordinarily be present in such a solution. If some of the solid is
added, the excess ions precipitate out and until solubility equilibrium is achieved.

7.1.2: Solubility and Temperature

Solubility usually increases with temperature - but not always. This is very apparent from the solubility-vs.-temperature plots
shown in Figure 7.1.1. (Some of the plots are colored differently in order to make it easier to distinguish them where they crowd
together.) The temperature dependence of any process depends on its entropy change — that is, on the degree to which thermal
kinetic energy can spread throughout the system. When a solid dissolves, its component molecules or ions diffuse into the much
greater volume of the solution, carrying their thermal energy along with them. So we would normally expect the entropy to increase
— something that makes any process take place to a greater extent at a higher temperature.

Figure 7.1.1 : Solubility of select salts in water as a function of temperature.

So why does the solubility of cerium sulfate (green plot) diminish with temperature? Dispersal of the Ce3+ and SO42– ions
themselves is still associated with an entropy increase, but in this case the entropy of the waterdecreases even more owing to the
ordering of the H2O molecules that attach to the Ce3+ ions as they become hydrated. It's difficult to predict these effects, or explain
why they occur in individual cases — but they do happen.

7.1.3: Contributors and Attributions

Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook

7.1: The Nature of Solubility Equilibria is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

7.1.3 https://chem.libretexts.org/@go/page/44749
7.2: Ionic Equilibria between Solids and Solutions
 Learning Objectives
To calculate the solubility of an ionic compound from its Ksp

We begin our discussion of solubility and complexation equilibria—those associated with the formation of complex ions—by
developing quantitative methods for describing dissolution and precipitation reactions of ionic compounds in aqueous solution. Just
as with acid–base equilibria, we can describe the concentrations of ions in equilibrium with an ionic solid using an equilibrium
constant expression.

7.2.1: The Solubility Product

When a slightly soluble ionic compound is added to water, some of it dissolves to form a solution, establishing an equilibrium
between the pure solid and a solution of its ions. For the dissolution of calcium phosphate, one of the two main components of
kidney stones, the equilibrium can be written as follows, with the solid salt on the left:
2+ 3−
C a3 (P O4 )2(s) ⇌ 3C a + 2P O (7.2.1)
(aq) 4(aq)

As you will discover in more advanced chemistry courses, basic anions, such as S2−, PO43−, and CO32−, react with water to produce
OH− and the corresponding protonated anion. Consequently, their calculated molarities, assuming no protonation in aqueous
solution, are only approximate.
The equilibrium constant for the dissolution of a sparingly soluble salt is the solubility product (Ksp) of the salt. Because the
concentration of a pure solid such as Ca3(PO4)2 is a constant, it does not appear explicitly in the equilibrium constant expression.
The equilibrium constant expression for the dissolution of calcium phosphate is therefore
2+ 3 3− 2
[C a ] [PO ]
4
K = (7.2.2)
[C a3 (PO4 )2 ]

2+ 3 3− 2
[C a3 (PO4 )2 ]K = Ksp = [C a ] [PO ] (7.2.3)
4

At 25°C and pH 7.00, Ksp for calcium phosphate is 2.07 × 10−33, indicating that the concentrations of Ca2+ and PO43− ions in
solution that are in equilibrium with solid calcium phosphate are very low. The values of Ksp for some common salts are listed in
Table 7.2.1, which shows that the magnitude of Ksp varies dramatically for different compounds. Although Ksp is not a function of
pH in Equations 7.2.2 and 7.2.3, changes in pH can affect the solubility of a compound as discussed later.

As with K, the concentration of a pure solid does not appear explicitly in Ksp.
Table 7.2.1 : Solubility Products for Selected Ionic Substances at 25°C
Solid Color Ksp Solid Color Ksp

Acetates Iodides

Ca(O2CCH3)2·3H2O white 4× 10−3 Hg2I2* yellow 5.2 × 10−29

Bromides PbI2 yellow 9.8 × 10−9

AgBr off-white 5.35 × 10−13 Oxalates

Hg2Br2* yellow 6.40 × 10−23 Ag2C2O4 white 5.40 × 10−12

Carbonates MgC2O4·2H2O white 4.83 × 10−6

CaCO3 white 3.36 × 10−9 PbC2O4 white 4.8 × 10−10

PbCO3 white 7.40 × 10−14 Phosphates

Chlorides Ag3PO4 white 8.89 × 10−17

AgCl white 1.77 × 10−10 Sr3(PO4)2 white 4.0 × 10−28

*These contain the Hg22+ ion.

7.2.1 https://chem.libretexts.org/@go/page/44750
 Solid Color Ksp Solid Color Ksp

Hg2Cl2* white 1.43 × 10−18 FePO4·2H2O pink 9.91 × 10−16

PbCl2 white 1.70 × 10−5 Sulfates

Chromates Ag2SO4 white 1.20 × 10−5

CaCrO4 yellow 7.1 × 10−4 BaSO4 white 1.08 × 10−10

PbCrO4 yellow 2.8 × 10−13 PbSO4 white 2.53 × 10−8

Fluorides Sulfides

BaF2 white 1.84 × 10−7 Ag2S black 6.3 × 10−50

PbF2 white 3.3 × 10−8 CdS yellow 8.0 × 10−27

Hydroxides PbS black 8.0 × 10−28

Ca(OH)2 white 5.02 × 10−6 ZnS white 1.6 × 10−24

Cu(OH)2 pale blue 1 × 10−14

Mn(OH)2 light pink 1.9 × 10−13

Cr(OH)3 gray-green 6.3 × 10−31

Fe(OH)3 rust red 2.79 × 10−39

*These contain the Hg22+ ion.

Solubility products are determined experimentally by directly measuring either the concentration of one of the component ions or
the solubility of the compound in a given amount of water. However, whereas solubility is usually expressed in terms of mass of
solute per 100 mL of solvent, K , like K , is defined in terms of the molar concentrations of the component ions.
sp

A color photograph of a kidney stone, 8 mm in length. Kidney stones form from sparingly soluble calcium salts and are largely
composed of Ca(O2CCO2)·H2O and Ca3(PO4)2. from Wikipedia.

 Example 7.2.1: Kidney Stones

Calcium oxalate monohydrate [Ca(O2CCO2)·H2O, also written as CaC2O4·H2O] is a sparingly soluble salt that is the other
major component of kidney stones [along with Ca3(PO4)2]. Its solubility in water at 25°C is 7.36 × 10−4 g/100 mL. Calculate
its Ksp.
Given: solubility in g/100 mL
Asked for: Ksp
Strategy:
A. Write the balanced dissolution equilibrium and the corresponding solubility product expression.
B. Convert the solubility of the salt to moles per liter. From the balanced dissolution equilibrium, determine the equilibrium
concentrations of the dissolved solute ions. Substitute these values into the solubility product expression to calculate Ksp.

7.2.2 https://chem.libretexts.org/@go/page/44750
 Solution
A We need to write the solubility product expression in terms of the concentrations of the component ions. For calcium oxalate
monohydrate, the balanced dissolution equilibrium and the solubility product expression (abbreviating oxalate as ox2−) are as
follows:
2+ − − 2+ 2−
Ca(O2 CC O2 ) ⋅ H2 O(s) ⇌ C a (aq) + O2 CC O (aq) + H2 O(l) Ksp = [C a ][o x ]
2

Neither solid calcium oxalate monohydrate nor water appears in the solubility product expression because their concentrations
are essentially constant.
B Next we need to determine [Ca2+] and [ox2−] at equilibrium. We can use the mass of calcium oxalate monohydrate that
dissolves in 100 mL of water to calculate the number of moles that dissolve in 100 mL of water. From this we can determine
the number of moles that dissolve in 1.00 L of water. For dilute solutions, the density of the solution is nearly the same as that
of water, so dissolving the salt in 1.00 L of water gives essentially 1.00 L of solution. Because each 1 mol of dissolved calcium
oxalate monohydrate dissociates to produce 1 mol of calcium ions and 1 mol of oxalate ions, we can obtain the equilibrium
concentrations that must be inserted into the solubility product expression. The number of moles of calcium oxalate
monohydrate that dissolve in 100 mL of water is as follows:
−4
7.36 × 10 g
−6
= 5.04 × 10 mol Ca(O2 CC O2 ) ⋅ H2 O
146.1 g/mol

The number of moles of calcium oxalate monohydrate that dissolve in 1.00 L of the saturated solution is as follows:
−6
5.04 × 10 mol Ca(O2 CC O2 ⋅)H2 O 1000 mL −5 −5
( )( ) = 5.04 × 10 mol/L = 5.04 × 10 M
100 mL 1.00 L

Because of the stoichiometry of the reaction, the concentration of Ca2+ and ox2− ions are both 5.04 × 10−5 M. Inserting these values
into the solubility product expression,
2+ 2− −5 −5 −9
Ksp = [C a ][ox ] = (5.04 × 10 )(5.04 × 10 ) = 2.54 × 10

In our calculation, we have ignored the reaction of the weakly basic anion with water, which tends to make the actual solubility of
many salts greater than the calculated value.

 Exercise 7.2.1

One crystalline form of calcium carbonate (CaCO3) is the mineral sold as “calcite” in mineral and gem shops. The solubility of
calcite in water is 0.67 mg/100 mL. Calculate its Ksp.
Answer 4.5 × 10−9

The reaction of weakly basic anions with H 2O tends to make the actual solubility of many
salts higher than predicted.

A crystal of calcite (CaCO3), illustrating the phenomenon of double refraction. When a transparent crystal of calcite is placed over
a page, we see two images of the letters. Image used with permisison from Wikipedia
Calcite, a structural material for many organisms, is found in the teeth of sea urchins. The urchins create depressions in limestone
that they can settle in by grinding the rock with their teeth. Limestone, however, also consists of calcite, so how can the urchins
grind the rock without also grinding their teeth? Researchers have discovered that the teeth are shaped like needles and plates and
contain magnesium. The concentration of magnesium increases toward the tip, which contributes to the hardness. Moreover, each

7.2.3 https://chem.libretexts.org/@go/page/44750
tooth is composed of two blocks of the polycrystalline calcite matrix that are interleaved near the tip. This creates a corrugated
surface that presumably increases grinding efficiency. Toolmakers are particularly interested in this approach to grinding.
Tabulated values of Ksp can also be used to estimate the solubility of a salt with a procedure that is essentially the reverse of the one
used in Example 7.2.1. In this case, we treat the problem as a typical equilibrium problem and set up a table of initial
concentrations, changes in concentration, and final concentrations (ICE Tables), remembering that the concentration of the pure
solid is essentially constant.

 Example 7.2.2

We saw that the Ksp for Ca3(PO4)2 is 2.07 × 10−33 at 25°C. Calculate the aqueous solubility of Ca3(PO4)2 in terms of the
following:
a. the molarity of ions produced in solution
b. the mass of salt that dissolves in 100 mL of water at 25°C
Given: Ksp
Asked for: molar concentration and mass of salt that dissolves in 100 mL of water
Strategy:
A. Write the balanced equilibrium equation for the dissolution reaction and construct a table showing the concentrations of the
species produced in solution. Insert the appropriate values into the solubility product expression and calculate the molar
solubility at 25°C.
B. Calculate the mass of solute in 100 mL of solution from the molar solubility of the salt. Assume that the volume of the
solution is the same as the volume of the solvent.
Solution:
A. A The dissolution equilibrium for Ca3(PO4)2 (Equation 7.2.2) is shown in the following ICE table. Because we are starting
with distilled water, the initial concentration of both calcium and phosphate ions is zero. For every 1 mol of Ca3(PO4)2 that
dissolves, 3 mol of Ca2+ and 2 mol of PO43− ions are produced in solution. If we let x equal the solubility of Ca3(PO4)2 in
moles per liter, then the change in [Ca2+] will be +3x, and the change in [PO43−] will be +2x. We can insert these values into
the table.
Ca3(PO4)2(s) ⇌ 3Ca2+(aq) + 2PO43−(aq)
2 +
Ca (PO )
3 4 2
[Ca ] \ce{[PO4^{3−}}]

initial pure solid 0 0

change — +3x +2x

final pure solid 3x 2x

Although the amount of solid Ca3(PO4)2 changes as some of it dissolves, its molar concentration does not change. We
now insert the expressions for the equilibrium concentrations of the ions into the solubility product expression (Equation
17.2):
2+ 3 3− 2 3 2
Ksp = [C a ] [PO ] = (3x ) (2x )
4

−33 5
2.07 × 10 = 108x
−35 5
1.92 × 10 =x
−7
1.14 × 10 M =x

This is the molar solubility of calcium phosphate at 25°C. However, the molarity of the ions is 2x and 3x, which means that
[PO43−] = 2.28 × 10−7 and [Ca2+] = 3.42 × 10−7.
b. B To find the mass of solute in 100 mL of solution, we assume that the density of this dilute solution is the same as the density
of water because of the low solubility of the salt, so that 100 mL of water gives 100 mL of solution. We can then determine the
amount of salt that dissolves in 100 mL of water:

7.2.4 https://chem.libretexts.org/@go/page/44750
 −7
1.14 × 10 mol 1 L 310.18 g C a3 (PO4 )2
−6
( ) 100 mL ( )( ) = 3.54 × 10 g C a3 (PO4 )2
1 L 1000 mL 1 mol

 Exercise 7.2.2

The solubility product of silver carbonate (Ag2CO3) is 8.46 × 10−12 at 25°C. Calculate the following:
a. the molarity of a saturated solution
b. the mass of silver carbonate that will dissolve in 100 mL of water at this temperature

Answer a
1.28 × 10−4 M
Answer a
3.54 mg

7.2.2: Relating Solubilities to Solubility Constants

The solubility (by which we usually mean the molar solubility) of a solid is expressed as the concentration of the "dissolved solid"
in a saturated solution. In the case of a simple 1:1 solid such as AgCl, this would just be the concentration of Ag+ or Cl– in the
saturated solution. But for a more complicated stoichiometry such as as silver chromate, the solubility would be only one-half of
the Ag+ concentration.
For example, let us denote the solubility of Ag2CrO4 as S mol L–1. Then for a saturated solution, we have
+
[Ag ] = 2S
2–
[C rO ] =S
4

Substituting this into Eq 5b above,

2 3 –12
(2S ) (S) = 4 S = 2.76 × 10 (7.2.4)

1/3 −13 1/3 −4

S = (df rac Ksp 4) = (6.9 × 10 ) = 0.88 × 10 (7.2.5)

thus the solubility is 8.8 × 10 –5

M .
Note that the relation between the solubility and the solubility product constant depends on the stoichiometry of the dissolution
reaction. For this reason it is meaningless to compare the solubilities of two salts having the formulas A2B and AB2, say, on the
basis of their Ks values.

It is meaningless to compare the solubilities of two salts having different formulas on the basis of their Ks values.

 Example 7.2.2

The solubility of CaF2 (molar mass 78.1) at 18°C is reported to be 1.6 mg per 100 mL of water. Calculate the value of Ks under
these conditions.

Solution
moles of solute in 100 mL; S = 0.0016 g / 78.1 g/mol = 2.05 × 10 −5
mol
–5
2.05 × 10 mol
S =
0.100 L

−4
= 2.05 × 10 M

7.2.5 https://chem.libretexts.org/@go/page/44750
 2+ – 2
Ksp = [C a ][ F ]

2
= (S)(2S)

–4 3
= 4 × (2.05 × 10 )

–11
= 3.44 × 10

 Example 7.2.3

Estimate the solubility of La(IO3)3 and calculate the concentration of iodate in equilibrium with solid lanthanum iodate, for
which Ks = 6.2 × 10–12.

Solution
The equation for the dissolution is
3 + –
La (IO ) −
↽⇀
− La + 3 IO3
3 3

If the solubility is S, then the equilibrium concentrations of the ions will be

[La3+] = S and [IO3–] = 3S. Then Ks = [La3+][IO3–]3 = S(3S)3 = 27S4
27S4 = 6.2 × 10–12, S = ( ( 6.2 ÷ 27) × 10–12 )¼ = 6.92 × 10–4 M
[IO3–] = 3S = 2.08 × 10–5 (M)

 Example 7.2.4: Cadmium

Cadmium is a highly toxic environmental pollutant that enters wastewaters associated with zinc smelting (Cd and Zn
commonly occur together in ZnS ores) and in some electroplating processes. One way of controlling cadmium in effluent
streams is to add sodium hydroxide, which precipitates insoluble Cd(OH)2 (Ks = 2.5E–14). If 1000 L of a certain wastewater
contains Cd2+ at a concentration of 1.6E–5 M, what concentration of Cd2+ would remain after addition of 10 L of 4 M NaOH
solution?
Solution
As with most real-world problems, this is best approached as a series of smaller problems, making simplifying approximations
as appropriate.
Volume of treated water: 1000 L + 10 L = 1010 L
Concentration of OH– on addition to 1000 L of pure water:
(4 M) × (10 L)/(1010 L) = 0.040 M
2+
Initial concentration of Cd in 1010 L of water:
100
–5 –5
(1.6 × 10 M) ( ) ≈ 1.6 × 10 M (7.2.6)
101

The easiest way to tackle this is to start by assuming that a stoichiometric quantity of Cd(OH)2 is formed — that is, all of the
Cd2+ gets precipitated.

Concentrations [Cd2+], M [OH–], M

initial 1.6E–5 0.04

change –1.6E–5 –3.2E–5

final: 0 0.04 – 3.2E–5 ≈ .04

Now "turn on the equilibrium" — find the concentration of Cd2+ that can exist in a 0.04M OH– solution:

7.2.6 https://chem.libretexts.org/@go/page/44750
 Concentrations [Cd2+], M [OH–], M

initial o 0.04

change +x +2x

at equilibrium x .04 + 2x ≈ .04

Substitute these values into the solubility product expression:

Cd(OH)2(s) = [Cd2+] [OH–]2 = 2.5E–14
[Cd2+] = (2.5E–14) / (16E–4) = 1.6E–13 M
Note that the effluent will now be very alkaline:
pH = 14 + log0.04 = 12.6 (7.2.7)

so in order to meet environmental standards an equivalent quantity of strong acid must be added to neutralize the water before
it is released.

7.2.3: Summary
The solubility product (Ksp) is used to calculate equilibrium concentrations of the ions in solution, whereas the ion product (Q)
describes concentrations that are not necessarily at equilibrium. The equilibrium constant for a dissolution reaction, called the
solubility product (Ksp), is a measure of the solubility of a compound. Whereas solubility is usually expressed in terms of mass of
solute per 100 mL of solvent, Ksp is defined in terms of the molar concentrations of the component ions.

7.2: Ionic Equilibria between Solids and Solutions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

7.2.7 https://chem.libretexts.org/@go/page/44750
7.3: Precipitation and the Solubility Product
 Learning Objectives
Define Ksp, the solubility product.
Explain solid/solution equilibria using K and Qsp.
sp

Calculate molarity of saturated solution from Ksp.

Calculate K from molarity of saturated solution.
sp

Precipitation reactions occur when cations and anions in aqueous solution combine to form an insoluble ionic solid called a
precipitate. Whether or not such a reaction occurs can be determined by using the solubility rules for common ionic solids.
Because not all aqueous reactions form precipitates, one must consult the solubility rules before determining the state of the
products and writing a net ionic equation. The ability to predict these reactions allows scientists to determine which ions are
present in a solution, and allows industries to form chemicals by extracting components from these reactions.

7.3.1: Properties of Precipitates

Precipitates are insoluble ionic solid products of a reaction, formed when certain cations and anions combine in an aqueous
solution. The determining factors of the formation of a precipitate can vary. Some reactions depend on temperature, such as
solutions used for buffers, whereas others are dependent only on solution concentration. The solids produced in precipitate
reactions are crystalline solids, and can be suspended throughout the liquid or fall to the bottom of the solution. The remaining fluid
is called supernatant liquid (or just the supernate). The two components of the mixture (precipitate and supernate) can be
separated by various methods, such as filtration, centrifuging, or decanting.

Figure 7.3.1: Above is a diagram of the formation of a precipitate in solution. (Public Domain; ZabMilenko)
The use of solubility rules require an understanding of the way that ions react. Most precipitation reactions are single replacement
reactions or double replacement reactions. A double replacement reaction occurs when two ionic reactants dissociate and bond with
the respective anion or cation from the other reactant. The ions replace each other based on their charges as either a cation or an
anion. This can be thought of as a double displacement reaction where the partners "switching; that is, the two reactants each "lose"
their partner and form a bond with a different partner:

Figure 7.3.2 : A double replacement reaction

A double replacement reaction is specifically classified as a precipitation reaction when the chemical equation in question occurs
in aqueous solution and one of the of the products formed is insoluble. An example of a precipitation reaction is given below:
CdSO (aq) + K S(aq) → CdS(s) + K SO (aq) (7.3.1)
4 2 2 4

Both reactants are aqueous and one product is solid. Because the reactants are ionic and aqueous, they dissociate and are therefore
soluble. However, there are six solubility guidelines used to predict which molecules are insoluble in water. These molecules form
a solid precipitate in solution.

7.3.1 https://chem.libretexts.org/@go/page/44751
  Solubility Rules

Whether or not a reaction forms a precipitate is dictated by the solubility rules. These rules provide guidelines that tell which
ions form solids and which remain in their ionic form in aqueous solution. The rules are to be followed from the top down,
meaning that if something is insoluble (or soluble) due to rule 1, it has precedence over a higher-numbered rule.
1. Salts formed with group 1 cations and NH cations are soluble. There are some exceptions for certain Li salts.
+

4
+

2. Acetates (C H O ), nitrates (NO ), and perchlorates (ClO ) are soluble.

2 3
−
2
−
3
−

3. Bromides, chlorides, and iodides are soluble.

4. Sulfates (SO ) are soluble with the exception of sulfates formed with Ca , Sr , and Ba .
2 −
4
2 + 2 + 2 +

5. Salts containing silver, lead, and mercury (I) are insoluble.

6. Carbonates (CO ), phosphates (PO ), sulfides, oxides, and hydroxides (OH ) are insoluble. Sulfides formed with
2 −
3
3 −
4
−

group 2 cations and hydroxides formed with calcium, strontium, and barium are exceptions.

If the rules state that an ion is soluble, then it remains in its aqueous ion form. If an ion is insoluble based on the solubility rules,
then it forms a solid with an ion from the other reactant. If all the ions in a reaction are shown to be soluble, then no precipitation
reaction occurs.

7.3.2: Net Ionic Equations

To understand the definition of a net ionic equation, recall the equation for the double replacement reaction. Because this
particular reaction is a precipitation reaction, states of matter can be assigned to each variable pair:

AB(aq) + C D(aq) → AD(aq) + C B(s) (7.3.2)

The first step to writing a net ionic equation is to separate the soluble (aqueous) reactants and products into their respective cations
and anions. Precipitates do not dissociate in water, so the solid should not be separated. The resulting equation looks like that
below:
+ − + − + −
A (aq) + B (aq) + C (aq) + D (aq) → A (aq) + D (aq) + C B(s) (7.3.3)

In the equation above, A+ and D- ions are present on both sides of the equation. These are called spectator ions because they
remain unchanged throughout the reaction. Since they go through the equation unchanged, they can be eliminated to show the net
ionic equation:
− +
B (aq) + C (aq) → +C B(s) (7.3.4)

The net ionic equation only shows the precipitation reaction. A net ionic equation must be balanced on both sides not only in terms
of atoms of elements, but also in terms of electric charge. Precipitation reactions are usually represented solely by net ionic
equations. If all products are aqueous, a net ionic equation cannot be written because all ions are canceled out as spectator ions.
Therefore, no precipitation reaction occurs

7.3.3: Equilibrium and non-Equilibrium Conditions

The ion product (Q) of a salt is the product of the concentrations of the ions in solution raised to the same powers as in the
solubility product expression. It is analogous to the reaction quotient (Q) discussed for gaseous equilibria. Whereas Ksp describes
equilibrium concentrations, the ion product describes concentrations that are not necessarily equilibrium concentrations. An ion
product can in principle have any positive value, depending on the concentrations of the ions involved. Only in the special case
when its value is identical with Ks does it become the solubility product. A solution in which this is the case is said to be saturated.
Thus when
+ 2 2 − −12
[ Ag ] [ CrO ] = 2.76 × 10 (7.3.5)
4

at the temperature and pressure at which this value K sp of applies, we say that the "solution is saturated in silver chromate".

The ion product Q is analogous to the reaction quotient Q for gaseous equilibria.

As summarized in Figure 7.3.3, there are three possible conditions for an aqueous solution of an ionic solid:

7.3.2 https://chem.libretexts.org/@go/page/44751
 Q < Ksp . The solution is unsaturated, and more of the ionic solid, if available, will dissolve.
Q = Ksp . The solution is saturated and at equilibrium.
Q > Ksp . The solution is supersaturated, and ionic solid will precipitate.

Figure 7.3.3 : The Relationship between Q and Ksp. If Q is less than Ksp, the solution is unsaturated and more solid will dissolve
until the system reaches equilibrium (Q = Ksp). If Q is greater than Ksp, the solution is supersaturated and solid will precipitate until
Q = Ksp. If Q = Ksp, the rate of dissolution is equal to the rate of precipitation; the solution is saturated, and no net change in the
amount of dissolved solid will occur. (CC BY-SA-NC; Anonymous)
The process of calculating the value of the ion product and comparing it with the magnitude of the solubility product is a
straightforward way to determine whether a solution is unsaturated, saturated, or supersaturated. More important, the ion product
tells chemists whether a precipitate will form when solutions of two soluble salts are mixed.

 Example 7.3.3: barium milkshakes

Barium sulfate is used in medical imaging of the gastrointestinal tract. Its solubility product is 1.08 × 10 at 25°C, so it is −10

ideally suited for this purpose because of its low solubility when a “barium milkshake” is consumed by a patient. The pathway
of the sparingly soluble salt can be easily monitored by x-rays. Will barium sulfate precipitate if 10.0 mL of 0.0020 M Na2SO4
is added to 100 mL of 3.2 × 10−4 M BaCl2? Recall that NaCl is highly soluble in water.
Given: Ksp and volumes and concentrations of reactants
Asked for: whether precipitate will form
Strategy:
A. Write the balanced equilibrium equation for the precipitation reaction and the expression for Ksp.
B. Determine the concentrations of all ions in solution when the solutions are mixed and use them to calculate the ion product
(Q).
C. Compare the values of Q and Ksp to decide whether a precipitate will form.

Solution
A The only slightly soluble salt that can be formed when these two solutions are mixed is BaSO
4
because NaCl is highly
soluble. The equation for the precipitation of BaSO is as follows:
4

2 + 2 −
BaSO (s) −
↽⇀
− Ba (aq) + SO (aq)
4 4

The solubility product expression is as follows:

2 + 2 − −10
Ksp = [ Ba ][ SO ] = 1.08 × 10
4

B To solve this problem, we must first calculate the ion product:

2 + 2 −
Q = [ Ba ][ SO ]
4

using the concentrations of the ions that are present after the solutions are mixed and before any reaction occurs. The concentration
of Ba2+ when the solutions are mixed is the total number of moles of Ba2+ in the original 100 mL of BaCl solution divided by the 2

final volume (100 mL + 10.0 mL = 110 mL):

7.3.3 https://chem.libretexts.org/@go/page/44751
 −4
1 L 3.2 × 10 mol
2+ −5 2+
moles Ba = 100 mL ( )( ) = 3.2 × 10 mol Ba
1000 mL 1 L

−5 2+
3.2 × 10 mol Ba 1000 mL
2+ −4 2+
[Ba ] =( )( ) = 2.9 × 10 M Ba
110 mL 1 L

Similarly, the concentration of SO42− after mixing is the total number of moles of SO42− in the original 10.0 mL of Na2SO4 solution
divided by the final volume (110 mL):
1 L 0.0020 mol
2− −5 2−
moles SO = 10.0 mL ( )( ) = 2.0 × 10 mol SO
4 4
1000 mL 1 L

−5 2−
2.0 × 10 mol SO 4 1000 mL
2− −4 2−
[SO ] =( )( ) = 1.8 × 10 M SO
4 4
110 mL 1 L

We can now calculate \(Q\):

2 + 2 − −4 −4 −8
Q = [ Ba ][ SO ] = (2.9 × 10 )(1.8 × 10 ) = 5.2 × 10
4

C We now compare Q with the K . If Q > Ksp, then BaSO will precipitate, but if Q < Ksp, it will not. Because Q > Ksp, we
sp 4

predict that BaSO will precipitate when the two solutions are mixed. In fact, BaSO will continue to precipitate until the system
4 4

reaches equilibrium, which occurs when

2 + 2 − −10
[ Ba ][ SO ] = Ksp = 1.08 × 10 .
4

 Exercise 7.3.3

The solubility product of calcium fluoride (CaF ) is 3.45 × 10 . If 2.0 mL of a 0.10 M solution of NaF is added to 128 mL
2
−11

of a 2.0 × 10 M solution of Ca(NO ) , will CaF precipitate?

−5
3 2 2

Answer
Yes, since Q sp
−11
= 4.7 × 10 > Ksp .

A solution must be saturated to be in equilibrium with the solid. This is a necessary condition for solubility equilibrium, but it is
not by itself sufficient. True chemical equilibrium can only occur when all components are simultaneously present. A solubility
system can be in equilibrium only when some of the solid is in contact with a saturated solution of its ions. Failure to appreciate
this is a very common cause of errors in solving solubility problems.

 Undersaturated and supersaturated solutions

If the ion product is smaller than the solubility product, the system is not in equilibrium and no solid can be present. Such a
solution is said to be undersaturated. A supersaturated solution is one in which the ion product exceeds the solubility product.
A supersaturated solution is not at equilibrium, and no solid can ordinarily be present in such a solution. If some of the solid is
added, the excess ions precipitate out and until solubility equilibrium is achieved.
How to know the saturation status of a solution? Just comparing the ion product Qs with the solubility product Ksp. as shown in
Table 7.3.1.
Table 7.3.1 : relationship among Q , K sp sp and saturation
Qsp / Ksp Status

Product concentration too high for equilibrium; net reaction proceeds

>1
to left.

=1 System is at equilibrium; no net change will occur.

Product concentration too low for equilibrium; net reaction proceeds

<1
to right.

For example, for the system

7.3.4 https://chem.libretexts.org/@go/page/44751
 + 2 –
Ag CrO (s) −
↽⇀
− 2 Ag + CrO4 (7.3.6)
2 4

a solution in which Qs < Ks (i.e., Ks /Qs > 1) is undersaturated (blue shading) and the no solid will be present. The combinations
of [Ag+] and [CrO42–] that correspond to a saturated solution (and thus to equilibrium) are limited to those described by the
curved line. The pink area to the right of this curve represents a supersaturated solution.

Figure 7.3.4 : Equilibrium vs. non-equilibrium states for Ag 2

CrO (s)
4
. (CC BY; Stephen Lower).

For some substances, formation of a solid or crystallization does not occur automatically whenever a solution is saturated. These
substances have a tendency to form oversaturated solutions. For example, syrup and honey are oversaturated sugar solutions,
containing other substances such as citric acids. For oversatureated solutions, Qsp is greater than Ksp. When a seed crystal is
provided or formed, a precipitate will form immediately due to equilibrium of requiring Q to approach K . For example Sodium
sp sp

acetate trihydrate, NaCH COO ⋅ 3 H O , when heated to 370 K will become a liquid and stays as a liquid when cooled to room
3 2

temperature or even below 273 K (Video 7.3.1). As soon as a seed crystal is present, crystallization occurs rapidly. In such a
process, heat is released since this is an exothermic process ΔH < 0 .

hot ice (sodium acetate) beautiful scien…

scien…

Video 7.3.1 : "hot ice" (sodium acetate) crystallized from a non-equilibrium supersaturated (Q sp > Ksp ) solution

 Example 7.3.1

A sample of groundwater that has percolated through a layer of gypsum (CaSO ) with K = 4.9 × 10 = 10
4
) is found
sp
–5 –4.3

to have be 8.4 × 10 M in Ca2+ and 7.2 × 10 M in SO42–. What is the equilibrium state of this solution with respect to
–5 –5

gypsum?
Solution
The ion product
–5 −5 –4
Qs = (8.4 × 10 )(7.2 × 10 ) = 6.0 × 10

exceeds K , so the ratio K

sp sp / Qsp > 1 and the solution is supersaturated in CaSO . 4

7.3.4: Relating Solubilities to Solubility Constants

The solubility (by which we usually mean the molar solubility) of a solid is expressed as the concentration of the "dissolved solid"
in a saturated solution. In the case of a simple 1:1 solid such as AgCl, this would just be the concentration of Ag+ or Cl– in the

7.3.5 https://chem.libretexts.org/@go/page/44751
saturated solution. But for a more complicated stoichiometry such as as silver chromate, the solubility would be only one-half of
the Ag+ concentration.
For example, let us denote the solubility of Ag2CrO4 as S mol L–1. Then for a saturated solution, we have
+
[Ag ] = 2S
2–
[C rO ] =S
4

Substituting this into Eq 5b above,

2 3 –12
(2S ) (S) = 4 S = 2.76 × 10 (7.3.7)

1/3
Ksp
−13 1/3 −4
S =( ) = (6.9 × 10 ) = 0.88 × 10 (7.3.8)
4

thus the solubility is 8.8 × 10

–5
M .
Note that the relation between the solubility and the solubility product constant depends on the stoichiometry of the dissolution
reaction. For this reason it is meaningless to compare the solubilities of two salts having the formulas A2B and AB2, say, on the
basis of their Ks values.

It is meaningless to compare the solubilities of two salts having different formulas on the basis of their Ks values.

 Example 7.3.2

The solubility of CaF2 (molar mass 78.1) at 18°C is reported to be 1.6 mg per 100 mL of water. Calculate the value of Ks under
these conditions.
Solution
moles of solute in 100 mL; S = 0.0016 g / 78.1 g/mol = 2.05 × 10 −5
mol
–5
2.05 × 10 mol
−4
S = = 2.05 × 10 M (7.3.9)
0.100 L

2+ – 2 2 –4 3 –11
Ksp = [C a ][ F ] = (S)(2S ) = 4 × (2.05 × 10 ) = 3.44 × 10 (7.3.10)

 Example 7.3.3

Estimate the solubility of La(IO3)3 and calculate the concentration of iodate in equilibrium with solid lanthanum iodate, for
which Ks = 6.2 × 10–12.
Solution
The equation for the dissolution is
3+
La(I O3 )3 ⇌ La + 3I O– (7.3.11)
3

If the solubility is S, then the equilibrium concentrations of the ions will be

[La3+] = S and [IO3–] = 3S. Then Ks = [La3+][IO3–]3 = S(3S)3 = 27S4
27S4 = 6.2 × 10–12, S = ( ( 6.2 ÷ 27) × 10–12 )¼ = 6.92 × 10–4 M
[IO3–] = 3S = 2.08 × 10–5 (M)

 Example 7.3.4: Cadmium

Cadmium is a highly toxic environmental pollutant that enters wastewaters associated with zinc smelting (Cd and Zn
commonly occur together in ZnS ores) and in some electroplating processes. One way of controlling cadmium in effluent
streams is to add sodium hydroxide, which precipitates insoluble Cd(OH)2 (Ks = 2.5E–14). If 1000 L of a certain wastewater

7.3.6 https://chem.libretexts.org/@go/page/44751
 contains Cd2+ at a concentration of 1.6E–5 M, what concentration of Cd2+ would remain after addition of 10 L of 4 M NaOH
solution?
Solution
As with most real-world problems, this is best approached as a series of smaller problems, making simplifying approximations
as appropriate.
Volume of treated water: 1000 L + 10 L = 1010 L
Concentration of OH– on addition to 1000 L of pure water:
(4 M) × (10 L)/(1010 L) = 0.040 M
Initial concentration of Cd2+ in 1010 L of water:
100
–5 –5
(1.6 × 10 M) ( ) ≈ 1.6 × 10 M (7.3.12)
101

The easiest way to tackle this is to start by assuming that a stoichiometric quantity of Cd(OH)2 is formed — that is, all of the
Cd2+ gets precipitated.

Concentrations [ Cd
2 +
], M
–
[ OH ], M

initial 1.6E–5 0.04

change –1.6E–5 –3.2E–5

final: 0 0.04 – 3.2E–5 ≈ .04

Now "turn on the equilibrium" — find the concentration of Cd2+ that can exist in a 0.04M OH– solution:

Concentrations [ Cd
2 +
], M
–
[ OH ], M

initial o 0.04

change +x +2x

at equilibrium x .04 + 2x ≈ .04

Substitute these values into the solubility product expression:

Cd(OH)2(s) = [Cd2+] [OH–]2 = 2.5E–14
[Cd2+] = (2.5E–14) / (16E–4) = 1.6E–13 M
Note that the effluent will now be very alkaline:

pH = 14 + log 0.04 = 12.6 (7.3.13)

so in order to meet environmental standards an equivalent quantity of strong acid must be added to neutralize the water before
it is released.

7.3.5: The Common Ion Effect

It has long been known that the solubility of a sparingly soluble ionic substance is markedly decreased in a solution of another ionic
compound when the two substances have an ion in common. This is just what would be expected on the basis of the Le Chatelier
Principle; whenever the process
2+ –
C aF2(s) ⇌ C a + 2F (7.3.14)

is in equilibrium, addition of more fluoride ion (in the form of highly soluble NaF) will shift the composition to the left, reducing
the concentration of Ca2+, and thus effectively reducing the solubility of the solid. We can express this quantitatively by noting that
the solubility product expression
2+ – 2 –10
[C a ][ F ] = 1.7 × 10 (7.3.15)

7.3.7 https://chem.libretexts.org/@go/page/44751
must always hold, even if some of the ionic species involved come from sources other than CaF2(s). For example, if some quantity
x of fluoride ion is added to a solution initially in equilibrium with solid CaF2, we have
2+
[C a ] =S
–
[F ] = 2S + x

so that
2+ – 2 2
Ksp = [C a ][ F ] = S(2S + x ) . (7.3.16)

University-level students should be able to derive these relations for ion-derived solids of any stoichiometry. In most practical cases
x will be large compared to S so that the 2S term can be dropped and the relation becomes
2
Ksp ≈ S x (7.3.17)

Ksp
S = (7.3.18)
x2

The plots shown below illustrate the common ion effect for silver chromate as the chromate ion concentration is increased by
addition of a soluble chromate such as Na2CrO4.

What's different about the plot on the right? If you look carefully at the scales, you will see that this one is plotted logarithmically
(that is, in powers of 10.) Notice how a much wider a range of values can display on a logarithmic plot. The point of showing this
pair of plots is to illustrate the great utility of log-concentration plots in equilibrium calculations in which simple approximations
(such as that made in Equation 7.3.18) can yield straight-lines within the range of values for which the approximation is valid.

 Example 7.3.5: strontium sulfate

Calculate the solubility of strontium sulfate (Ks = 2.8 × 10–7) in

a. pure water and
b. in a 0.10 mol L–1 solution of Na2SO4.
Solution:
(a) In pure water, Ks = [Sr2+][SO42–] = S2
S = √Ks = (2.8 × 10–7)½ = 5.3 × 10–4
(b) In 0.10 mol L–1 Na2SO4, we have
Ks = [Sr2+][SO42–] = S × (0.10 + S) = 2.8 × 10–7
Because S is negligible compared to 0.10 M, we make the approximation
Ks = [Sr2+][SO42–] ≈ S × (0.10 M) = 2.8 × 10–7

7.3.8 https://chem.libretexts.org/@go/page/44751
 so S ≈ (2.8 × 10–7) / 0.10M = 2.8 × 10–6 M — which is roughly 100 times smaller than the result from (a).

 Note
The common ion effect usually decreases the solubility of a sparingly soluble salt.

 Example 7.3.6

Calculate the solubility of calcium phosphate [Ca3(PO4)2] in 0.20 M CaCl2.

Given: concentration of CaCl2 solution
Asked for: solubility of Ca3(PO4)2 in CaCl2 solution
Strategy:
A. Write the balanced equilibrium equation for the dissolution of Ca3(PO4)2. Tabulate the concentrations of all species
produced in solution.
B. Substitute the appropriate values into the expression for the solubility product and calculate the solubility of Ca3(PO4)2.

Solution
A The balanced equilibrium equation is given in the following table. If we let x equal the solubility of Ca3(PO4)2 in moles per
liter, then the change in [Ca2+] is once again +3x, and the change in [PO43−] is +2x. We can insert these values into the ICE
table.
2+ 3−
C a3 (P O4 )2(s) ⇌ 3C a (aq) + 2P O (7.3.19)
4(aq)

+
Ca (PO ) [Ca ] [PO −]
3 4 2 2 43

initial pure solid 0.20 0

change — +3x +2x

final pure solid 0.20 + 3x 2x

B The Ksp expression is as follows:

Ksp = [Ca2+]3[PO43−]2 = (0.20 + 3x)3(2x)2 = 2.07×10−33

Because Ca3(PO4)2 is a sparingly soluble salt, we can reasonably expect that x << 0.20. Thus (0.20 + 3x) M is approximately 0.20
M, which simplifies the Ksp expression as follows:
3 2 −33
Ksp = (0.20 ) (2x ) = 2.07 × 10 (7.3.20)

2 −32
x = 6.5 × 10 (7.3.21)
−16
x = 2.5 × 10 M (7.3.22)

This value is the solubility of Ca3(PO4)2 in 0.20 M CaCl2 at 25°C. It is approximately nine orders of magnitude less than its
solubility in pure water, as we would expect based on Le Chatelier’s principle. With one exception, this example is identical to
Example 7.3.2—here the initial [Ca2+] was 0.20 M rather than 0.

 Exercise 7.3.6

Calculate the solubility of silver carbonate in a 0.25 M solution of sodium carbonate. The solubility of silver carbonate in pure
water is 8.45 × 10−12 at 25°C.

Answer
2.9 × 10−6 M (versus 1.3 × 10−4 M in pure water)

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7.3.6: Applications and Examples
Precipitation reactions are useful in determining whether a certain element is present in a solution. If a precipitate is formed when a
chemical reacts with lead, for example, the presence of lead in water sources could be tested by adding the chemical and
monitoring for precipitate formation. In addition, precipitation reactions can be used to extract elements, such as magnesium from
seawater. Precipitation reactions even occur in the human body between antibodies and antigens; however, the environment in
which this occurs is still being studied.

 Example 7.3.7

Complete the double replacement reaction and then reduce it to the net ionic equation.

N aOH (aq) + M gC l2 (aq) →

First, predict the products of this reaction using knowledge of double replacement reactions (remember the cations and anions
“switch partners”).

2N aOH (aq) + M gC l2 (aq)

→ 2N aC l + M g(OH )2

Second, consult the solubility rules to determine if the products are soluble. Group 1 cations (N a ) and chlorides are soluble
+

from rules 1 and 3 respectively, so N aC l will be soluble in water. However, rule 6 states that hydroxides are insoluble, and
thus M g(OH ) will form a precipitate. The resulting equation is the following:
2

2N aOH (aq) + M gC l2 (aq) → 2N aC l(aq) + M g(OH )2 (s)

Third, separate the reactants into their ionic forms, as they would exist in an aqueous solution. Be sure to balance both the
electrical charge and the number of atoms:
+ − 2+ − + −
2N a (aq) + 2OH (aq) + M g (aq) + 2C l (aq) → M g(OH )2 (s) + 2N a (aq) + 2C l (aq)

Lastly, eliminate the spectator ions (the ions that occur on both sides of the equation unchanged). In this case, they are the
sodium and chlorine ions. The final net ionic equation is:
2+ −
Mg (aq) + 2OH (aq) → M g(OH )2(s)

 Example 7.3.8

Complete the double replacement reaction and then reduce it to the net ionic equation.

C oC l2 (aq) + N a2 S O4 (aq) →

Solution
The predicted products of this reaction are C oSO and N aC l. From the solubility rules, C oSO is soluble because rule 4
4 4

states that sulfates (SO ) are soluble. Similarly, we find that N aC l is soluble based on rules 1 and 3. After balancing, the
2−

resulting equation is as follows:

C oC l2 (aq) + N a2 S O4 (aq) → C oS O4 (aq) + 2N aC l(aq)

Separate the species into their ionic forms, as they would exist in an aqueous solution. Balance the charge and the atoms.
Cancel out all spectator ions (those that appear as ions on both sides of the equation.):
Co2- (aq) + 2Cl-(aq) + 2Na+ (aq) + SO42-(aq) → Co2- (aq) + SO42-(aq) + 2Na+ (aq) + 2Cl-(aq)
No precipitation reaction
This particular example is important because all of the reactants and the products are aqueous, meaning they cancel out of the
net ionic equation. There is no solid precipitate formed; therefore, no precipitation reaction occurs.

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 Example 7.3.9

Write the net ionic equation for the potentially double displacement reactions. Make sure to include the states of matter and
balance the equations.
a. F e(N O ) 3 + N aOH (aq) →
3 (aq)

b. Al (SO )
2 4 + BaC l
3 (aq)
→ 2 (aq)

c. H I (aq) + Zn(N O ) → 3 2 (aq)

d. C aC l +Na P O
2 (aq)
→3 4 (aq)

e. P b(N O ) 3 + K SO
2 (aq) → 2 4 (aq)

Solutions
a. Regardless of physical state, the products of this reaction are F e(OH ) and N aN O . The solubility rules predict that 3 3

N aN O is soluble because all nitrates are soluble (rule 2). However, F e(OH ) is insoluble, because hydroxides are insoluble
3 3

(rule 6) and F e is not one of the cations which results in an exception. After dissociation, the ionic equation is as follows:
3+ − + − + −
Fe (aq) + N O +Na (aq) + 3OH (aq) → F e(OH )3 (s) +Na (aq) + N O
3 (aq) 3 (aq)

Canceling out spectator ions leaves the net ionic equation:

3+ −
Fe (aq) + OH (aq) → F e(OH ) 3(s)

b. From the double replacement reaction, the products are AlC l and BaSO . AlC l is soluble because it contains a chloride
3 4 3

(rule 3); however, BaSO is insoluble: it contains a sulfate, but the Ba ion causes it to be insoluble because it is one of the
4
2+

cations that causes an exception to rule 4. The ionic equation is (after balancing):
3+ − 2+ 2− 3+ −
2Al (aq) + 6C l (aq) + 3Ba (aq) + 3S O → 2Al (aq) + 6C l (aq) + 3BaS O4 (s)
4 (aq)

Canceling out spectator ions leaves the following net ionic equation:
2+ 2−
Ba (aq) + S O → BaS O4 (s)
4 (aq)

c. From the double replacement reaction, the products H N O and ZnI are formed. Looking at the solubility rules, H N O is
3 2 3

soluble because it contains nitrate (rule 2), and ZnI is soluble because iodides are soluble (rule 3). This means that both the
2

products are aqueous (i.e. dissociate in water), and thus no precipitation reaction occurs.
d. The products of this double replacement reaction are C a (P O ) and N aC l. Rule 1 states that 3 4 2 N aC l is soluble, and
according to solubility rule 6, C a (P O ) is insoluble. The ionic equation is:
3 4 2

2+ − + 3− + −
Ca (aq) + C l (aq) + N a (aq) + P O → C a3 (P O4 )2 (s)
+Na (aq) + C l (aq)
4 (aq)

After canceling out spectator ions, the net ionic equation is given below:
2+ 3−
Ca (aq) + P O → C a3 (P O4 )2 (s)
4 (aq)

e. The first product of this reaction, P bSO , is soluble according to rule 4 because it is a sulfate. The second product, KN O ,
4 3

is also soluble because it contains nitrate (rule 2). Therefore, no precipitation reaction occurs.

7.3.7: References
1. Campbell, Dan, Linus Pauling, and Davis Pressman. "The Nature of the Forces Between Antigen and Antibody and of the
Precipitation Reaction." Physiological Reviews 23.3 (1943): 203-219. Online.
2. Harwood, William, F Herring, Jeffry Madura, and Ralph Petrucci. General Chemistry. 9th ed. Upper Saddle River: Pearson
Pretence Hall, 2007. Print.
3. Freeouf, J.L, Grischkowsky, D., McInturff, D.T., Warren, A.C., & Woodall, J.M. (1990). Arsenic precipitates and the semi-
insulating properties of gaas buffer layers grown by low-temperature molecular beam epitaxy. Applied Physics Letters, 57(13)
4. Petrucci, et al. General Chemistry: Principles & Modern Applications. 9th ed. Upper Saddle River, New Jersey 2007.

7.3.11 https://chem.libretexts.org/@go/page/44751
7.3.8: Summary
In contrast to K , the ion product (Q ) describes concentrations that are not necessarily equilibrium concentrations. Comparing Q
sp sp

and Ksp enables us to determine whether a precipitate will form when solutions of two soluble salts are mixed. Adding a common
cation or common anion to a solution of a sparingly soluble salt shifts the solubility equilibrium in the direction predicted by Le
Chatelier’s principle. The solubility of the salt is almost always decreased by the presence of a common ion.

7.3.9: Contributors and Attributions

Julie Schaffer (UCD), Corinne Herman (UCD)
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook

7.3: Precipitation and the Solubility Product is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

7.3.12 https://chem.libretexts.org/@go/page/44751
7.4: The Effects of pH on Solubility
 Learning Objectives
To understand why the solubility of many compounds depends on pH.

The solubility of many compounds depends strongly on the pH of the solution. For example, the anion in many sparingly soluble
salts is the conjugate base of a weak acid that may become protonated in solution. In addition, the solubility of simple binary
compounds such as oxides and sulfides, both strong bases, is often dependent on pH. In this section, we discuss the relationship
between the solubility of these classes of compounds and pH.

7.4.1: The Effect of Acid–Base Equilibria the Solubility of Salts

We begin our discussion by examining the effect of pH on the solubility of a representative salt, M +
A
−
, where A is the conjugate
−

base of the weak acid HA. When the salt dissolves in water, the following reaction occurs:
+ −
MA(s) ⇌ M (aq) + A (aq)

with
+ −
Ksp = [ M ][ A ]

The anion can also react with water in a hydrolysis reaction:

− −
A (aq) + H O(l) ⇌ OH (aq) + HA(aq) (7.4.1)
2

Because of the reaction described in Equation 7.4.1, the predicted solubility of a sparingly soluble salt that has a basic anion such
as S2−, PO43−, or CO32− is increased. If instead a strong acid is added to the solution, the added H+ will react essentially completely
with A− to form HA. This reaction decreases [A−], which decreases the magnitude of the ion product
+ −
Q = [M ][ A ] (7.4.2)

According to Le Chatelier’s principle, more MA will dissolve until Q = K . Hence an acidic pH dramatically increases the
sp

solubility of virtually all sparingly soluble salts whose anion is the conjugate base of a weak acid. In contrast, pH has little to no
effect on the solubility of salts whose anion is the conjugate base of a stronger weak acid or a strong acid, respectively (e.g.,
chlorides, bromides, iodides, and sulfates). For example, the hydroxide salt Mg(OH)2 is relatively insoluble in water:
2+ −
M g(OH )2(s) ⇌ M g (aq) + 2OH (aq) (7.4.3)

with
−12
Ksp = 5.61 × 10 (7.4.4)

When acid is added to a saturated solution that contains excess solid Mg(OH)2, the following reaction occurs, removing OH− from
solution:
+ −
H (aq) + OH (aq) → H2 O(l) (7.4.5)

The overall equation for the reaction of Mg(OH)2 with acid is thus
+ 2+
M g(OH )2(s) + 2 H (aq) ⇌ M g (aq) + 2 H2 O(l) (7.4.6)

As more acid is added to a suspension of Mg(OH)2, the equilibrium shown in Equation 7.4.6 is driven to the right, so more
Mg(OH)2 dissolves.
Such pH-dependent solubility is not restricted to salts that contain anions derived from water. For example, CaF2 is a sparingly
soluble salt:
2+ −
C aF2(s) ⇌ C a (aq) + 2 F (aq) (7.4.7)

with
−11
Ksp = 3.45 × 10 (7.4.8)

7.4.1 https://chem.libretexts.org/@go/page/44752
When strong acid is added to a saturated solution of CaF2, the following reaction occurs:
+ −
H (aq) + F (aq) ⇌ H F (aq) (7.4.9)

Because the forward reaction decreases the fluoride ion concentration, more CaF2 dissolves to relieve the stress on the system. The
net reaction of CaF2 with strong acid is thus
+ 2+
C aF2(s) + 2 H (aq) → C a (aq) + 2H F (aq) (7.4.10)

Example 7.4.1 shows how to calculate the solubility effect of adding a strong acid to a solution of a sparingly soluble salt.

Sparingly soluble salts derived from weak acids tend to be more soluble in an acidic
solution.

 Example 7.4.1

Lead oxalate (PbC2O4), lead iodide (PbI2), and lead sulfate (PbSO4) are all rather insoluble, with Ksp values of 4.8 × 10−10, 9.8
× 10−9, and 2.53 × 10−8, respectively. What effect does adding a strong acid, such as perchloric acid, have on their relative
solubilities?
Given: Ksp values for three compounds
Asked for: relative solubilities in acid solution
Strategy:
Write the balanced chemical equation for the dissolution of each salt. Because the strongest conjugate base will be most
affected by the addition of strong acid, determine the relative solubilities from the relative basicity of the anions.
Solution
The solubility Equilibria for the three salts are as follows:
2+ 2−
P b C2 O4(s) ⇌ P b (aq) + C2 O
4(aq)

2+ −
P b I2(s) ⇌ P b (aq) + 2 I (aq)

2+ 2−
P bS O4(s) ⇌ P b (aq) + S O
4(aq)

The addition of a strong acid will have the greatest effect on the solubility of a salt that contains the conjugate base of a weak
acid as the anion. Because HI is a strong acid, we predict that adding a strong acid to a saturated solution of PbI2 will not
greatly affect its solubility; the acid will simply dissociate to form H+(aq) and the corresponding anion. In contrast, oxalate is
the fully deprotonated form of oxalic acid (HO2CCO2H), which is a weak diprotic acid (pKa1 = 1.23 and pKa2 = 4.19).
Consequently, the oxalate ion has a significant affinity for one proton and a lower affinity for a second proton. Adding a strong
acid to a saturated solution of lead oxalate will result in the following reactions:
2− + −
C2 O +H (aq) → H O2 C C O
4(aq) 2(aq)

− +
H O2 C C O +H (aq) → H O2 C C O2 H (aq)
2(aq)

These reactions will decrease [C2O42−], causing more lead oxalate to dissolve to relieve the stress on the system. The pKa of
HSO4− (1.99) is similar in magnitude to the pKa1 of oxalic acid, so adding a strong acid to a saturated solution of PbSO4 will
result in the following reaction:
2− + −
SO +H (aq) ⇌ H S O
4(aq) 4(aq)

Because HSO4− has a pKa of 1.99, this reaction will lie largely to the left as written. Consequently, we predict that the effect of
added strong acid on the solubility of PbSO4 will be significantly less than for PbC2O4.

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  Exercise 7.4.1

Which of the following insoluble salts—AgCl, Ag2CO3, Ag3PO4, and/or AgBr—will be substantially more soluble in 1.0 M
HNO3 than in pure water?

Answer
Ag2CO3 and Ag3PO4

Solubility Products and pH

Solubility Products and pH: https://youtu.be/XJ0s5SATZgQ

Caves and their associated pinnacles and spires of stone provide one of the most impressive examples of pH-dependent solubility
Equilbria(part (a) in Figure 7.4.1:). Perhaps the most familiar caves are formed from limestone, such as Carlsbad Caverns in New
Mexico, Mammoth Cave in Kentucky, and Luray Caverns in Virginia. The primary reactions that are responsible for the formation
of limestone caves are as follows:
+ −
CO (aq) + H O(l) ⇌ H (aq) + HCO (aq) (7.4.11)
2 2 3

− + 2 −
HCO (aq) ⇌ H (aq) + CO (aq) (7.4.12)
3 3

2 + 2 −
Ca (aq) + CO (aq) ⇌ CaCO (s) (7.4.13)
3 3

Limestone deposits that form caves consist primarily of CaCO3 from the remains of living creatures such as clams and corals,
which used it for making structures such as shells. When a saturated solution of CaCO3 in CO2-rich water rises toward Earth’s
surface or is otherwise heated, CO2 gas is released as the water warms. CaCO3 then precipitates from the solution according to the
following equation (part (b) in Figure 7.4.1:):
2+ −
Ca (aq) + 2H C O ⇌ C aC O3(s) + C O2(g) + H2 O(l) (7.4.14)
3(aq)

The forward direction is the same reaction that produces the solid called scale in teapots, coffee makers, water heaters, boilers, and
other places where hard water is repeatedly heated.

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 Figure 7.4.1 : The Chemistry of Cave Formation. (a) This cave in Campanet, Mallorca, Spain, and its associated formations are
examples of pH-dependent solubility equilibriums. (b) A cave forms when groundwater containing atmospheric CO2, forming an
acidic solution, dissolves limestone (CaCO3) in a process that may take tens of thousands of years. As groundwater seeps into a
cave, water evaporates from the solution of CaCO3 in CO2-rich water, producing a supersaturated solution and a shift in
equilibrium that causes precipitation of the CaCO3. The deposited limestone eventually forms stalactites and stalagmites.
When groundwater-containing atmospheric CO2 (Equations 7.4.11 and 7.4.12) finds its way into microscopic cracks in the
limestone deposits, CaCO3 dissolves in the acidic solution in the reverse direction of Equation 7.4.14. The cracks gradually enlarge
from 10–50 µm to 5–10 mm, a process that can take as long as 10,000 yr. Eventually, after about another 10,000 yr, a cave forms.
Groundwater from the surface seeps into the cave and clings to the ceiling, where the water evaporates and causes the equilibrium
in Equation 7.4.14 to shift to the right. A circular layer of solid CaCO3 is deposited, which eventually produces a long, hollow
spire of limestone called a stalactite that grows down from the ceiling. Below, where the droplets land when they fall from the
ceiling, a similar process causes another spire, called a stalagmite, to grow up. The same processes that carve out hollows below
ground are also at work above ground, in some cases producing fantastically convoluted landscapes like that of Yunnan Province in
China (Figure 7.4.2).

Figure 7.4.2 : Solubility Equilbriain the Formation of Karst Landscapes. Landscapes such as the steep limestone pinnacles of the
Stone Forest in Yunnan Province, China, are formed from the same process that produces caves and their associated formations.

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7.4.2: Acidic, Basic, and Amphoteric Oxides and Hydroxides
One of the earliest classifications of substances was based on their solubility in acidic versus basic solution, which led to the
classification of oxides and hydroxides as being either basic or acidic. Basic oxides and hydroxides either react with water to
produce a basic solution or dissolve readily in aqueous acid. Acidic oxides or hydroxides either react with water to produce an
acidic solution or are soluble in aqueous base. There is a clear correlation between the acidic or the basic character of an oxide and
the position of the element combined with oxygen in the periodic table. Oxides of metallic elements are generally basic oxides, and
oxides of nonmetallic elements are acidic oxides. Compare, for example, the reactions of a typical metal oxide, cesium oxide, and a
typical nonmetal oxide, sulfur trioxide, with water:
+ −
C s2 O(s) + H2 O(l) → 2C s (aq) + 2OH (aq) (7.4.15)

S O3(g) + H2 O(l) → H2 S O4(aq) (7.4.16)

Cesium oxide reacts with water to produce a basic solution of cesium hydroxide, whereas sulfur trioxide reacts with water to
produce a solution of sulfuric acid—very different behaviors indeed

Metal oxides generally react with water to produce basic solutions, whereas nonmetal
oxides produce acidic solutions.
The difference in reactivity is due to the difference in bonding in the two kinds of oxides. Because of the low electronegativity of
the metals at the far left in the periodic table, their oxides are best viewed as containing discrete Mn+ cations and O2− anions. At the
other end of the spectrum are nonmetal oxides; due to their higher electronegativities, nonmetals form oxides with covalent bonds
to oxygen. Because of the high electronegativity of oxygen, however, the covalent bond between oxygen and the other atom, E, is
usually polarized: Eδ+–Oδ−. The atom E in these oxides acts as a Lewis acid that reacts with the oxygen atom of water to produce
an oxoacid. Oxides of metals in high oxidation states also tend to be acidic oxides for the same reason: they contain covalent bonds
to oxygen. An example of an acidic metal oxide is MoO3, which is insoluble in both water and acid but dissolves in strong base to
give solutions of the molybdate ion (MoO42−):
− 2−
M oO3(s) + 2OH (aq) → M oO + H2 O(l) (7.4.17)
4(aq)

Figure 7.4.3 : Classification of the Oxides of the Main Group Elements According to Their Acidic or Basic Character. There is a
gradual transition from basic oxides to acidic oxides from the lower left to the upper right in the periodic table. Oxides of metallic
elements are generally basic oxides, which either react with water to form a basic solution or dissolve in aqueous acid. In contrast,
oxides of nonmetallic elements are acidic oxides, which either react with water to form an acidic solution or are soluble in aqueous
base. Oxides of intermediate character, called amphoteric oxides, are located along a diagonal line between the two extremes.
Amphoteric oxides either dissolve in acid to produce water or dissolve in base to produce a soluble complex ion. (Radioactive
elements are not classified.)
As shown in Figure 7.4.3, there is a gradual transition from basic metal oxides to acidic nonmetal oxides as we go from the lower
left to the upper right in the periodic table, with a broad diagonal band of oxides of intermediate character separating the two
extremes. Many of the oxides of the elements in this diagonal region of the periodic table are soluble in both acidic and basic
solutions; consequently, they are called amphoteric oxides (from the Greek ampho, meaning “both,” as in amphiprotic).

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Amphoteric oxides either dissolve in acid to produce water or dissolve in base to produce a soluble complex. As shown in Video
7.4.1, for example, mixing the amphoteric oxide Cr(OH)3 (also written as Cr2O3•3H2O) with water gives a muddy, purple-brown

suspension. Adding acid causes the Cr(OH)3 to dissolve to give a bright violet solution of Cr3+(aq), which contains the
[Cr(H2O)6]3+ ion, whereas adding strong base gives a green solution of the [Cr(OH)4]− ion. The chemical equations for the
reactions are as follows:
+ 3+
Cr(OH)3 (s) + 3 H (aq) → C r (aq) + 3 H2 O(l) (7.4.18)
violet

− −
Cr(OH)3 (s) + OH (aq) → [Cr(OH)4 ] (aq) (7.4.19)
green

Complex Ions: Adding NaOH solution to …

Video 7.4.1 : Chromium(III) Hydroxide [Cr(OH)3 or Cr2O3•3H2O] is an Example of an Amphoteric Oxide. All three beakers
originally contained a suspension of brownish purple Cr(OH)3(s) (center). When concentrated acid (6 M H2SO4) was added to the
beaker on the left, Cr(OH)3 dissolved to produce violet [Cr(H2O)6]3+ ions and water. The addition of concentrated base (6 M
NaOH) to the beaker on the right caused Cr(OH)3 to dissolve, producing green [Cr(OH)4]−ions. For a more complete description,
see https://www.youtube.com/watch?v=IQNcLH6OZK0

 Example 7.4.2

Aluminum hydroxide, written as either Al(OH)3 or Al2O3•3H2O, is amphoteric. Write chemical equations to describe the
dissolution of aluminum hydroxide in (a) acid and (b) base.
Given: amphoteric compound
Asked for: dissolution reactions in acid and base
Strategy:
Using Equations 7.4.18 and 7.4.19 as a guide, write the dissolution reactions in acid and base solutions.
Solution
a. An acid donates protons to hydroxide to give water and the hydrated metal ion, so aluminum hydroxide, which contains
three OH− ions per Al, needs three H+ ions:
+ 3+
Al(OH )3(s) + 3 H (aq) → Al (aq) + 3 H2 O(l)

In aqueous solution, Al3+ forms the complex ion [Al(H2O)6]3+.

b. In basic solution, OH− is added to the compound to produce a soluble and stable poly(hydroxo) complex:
− −
Al(OH )3(s) + OH (aq) → [Al(OH )4 ] (aq)

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  Exercise 7.4.2
Copper(II) hydroxide, written as either Cu(OH)2 or CuO•H2O, is amphoteric. Write chemical equations that describe the
dissolution of cupric hydroxide both in an acid and in a base.

Answer
+ 2+
C u(OH )2(s) + 2 H (aq) → C u (aq) + 2 H2 O(l)

− 2
C u(OH )2(s) + 2OH (aq) → [C u(OH )4 ]
−(aq)

7.4.3: Selective Precipitation Using pH

Many dissolved metal ions can be separated by the selective precipitation of the cations from solution under specific conditions. In
this technique, pH is often used to control the concentration of the anion in solution, which controls which cations precipitate.

The concentration of anions in solution can often be controlled by adjusting the pH,
thereby allowing the selective precipitation of cations.
Suppose, for example, we have a solution that contains 1.0 mM Zn2+ and 1.0 mM Cd2+ and want to separate the two metals by
selective precipitation as the insoluble sulfide salts, ZnS and CdS. The relevant solubility equilbria can be written as follows:
2+ 2−
ZnS(s) ⇌ Z n (aq) + S (aq) (7.4.20)

with
−24
Ksp = 1.6 × 10 (7.4.21)

and
2+ 2−
C dS(s) ⇌ C d (aq) + S (aq) (7.4.22)

with
−27
Ksp = 8.0 × 10 (7.4.23)

Because the S2− ion is quite basic and reacts extensively with water to give HS− and OH−, the solubility equilbria are more
accurately written as M S(s) ⇌ M (aq) + H S (aq) + OH
2+ −
rather than M S(s) ⇌ M (aq) + S (aq) . Here we use the
− 2+ 2−

simpler form involving S2−, which is justified because we take the reaction of S2− with water into account later in the solution,
arriving at the same answer using either equilibrium equation.
The sulfide concentrations needed to cause ZnS and C dS to precipitate are as follows:
2+ 2−
Ksp = [Z n ][ S ] (7.4.24)

−24 2−
1.6 × 10 = (0.0010 M )[ S ] (7.4.25)

−21 2−
1.6 × 10 M = [S ] (7.4.26)

and
2+ 2−
Ksp = [C d ][ S ] (7.4.27)

−27 2−
8.0 × 10 = (0.0010 M )[ S ] (7.4.28)

−24 2−
8.0 × 10 M = [S ] (7.4.29)

Thus sulfide concentrations between 1.6 × 10−21 M and 8.0 × 10−24 M will precipitate CdS from solution but not ZnS. How do we
obtain such low concentrations of sulfide? A saturated aqueous solution of H2S contains 0.10 M H2S at 20°C. The pKa1for H2S is
6.97, and pKa2 corresponding to the formation of [S2−] is 12.90. The equations for these reactions are as follows:
+ −
H2 S(aq) ⇌ H (aq) + H S (aq) (7.4.30)

7.4.7 https://chem.libretexts.org/@go/page/44752
with
−7
p Ka1 = 6.97 and hence Ka1 = 1.1 × 10 (7.4.31)

− + 2−
HS (aq) ⇌ H (aq) + S (aq) (7.4.32)

with
−13
p Ka2 = 12.90 and hence Ka2 = 1.3 × 10 (7.4.33)

We can show that the concentration of S2− is 1.3 × 10−13 by comparing Ka1 and Ka2 and recognizing that the contribution to [H+]
from the dissociation of HS− is negligible compared with [H+] from the dissociation of H2S. Thus substituting 0.10 M in the
equation for Ka1 for the concentration of H2S, which is essentially constant regardless of the pH, gives the following:
+ − 2
[H ][HS ] x
−7
Ka1 = 1.1 × 10 = = (7.4.34)
[ H2 S] 0.10 M

−4 + −
x = 1.1 × 10 M = [H ] = [HS ]

Substituting this value for [H+] and [HS−] into the equation for Ka2,
+ 2− −4
[H ][ S ] (1.1 × 10 M)x
−13 2−
Ka2 = 1.3 × 10 = = = x = [S ] (7.4.35)
− −4
[HS ] 1.1 × 10 M

Although [S2−] in an H2S solution is very low (1.3 × 10−13 M), bubbling H2S through the solution until it is saturated would
precipitate both metal ions because the concentration of S2− would then be much greater than 1.6 × 10−21 M. Thus we must adjust
[S2−] to stay within the desired range. The most direct way to do this is to adjust [H+] by adding acid to the H2S solution (recall Le
Chatelier's principle), thereby driving the equilibrium in Equation 7.4.33 to the left. The overall equation for the dissociation of
H2S is as follows:
+ 2−
H2 S(aq) ⇌ 2 H (aq) + S (aq) (7.4.36)

Now we can use the equilibrium constant K for the overall reaction, which is the product of Ka1 and Ka2, and the concentration of
H2S in a saturated solution to calculate the H+ concentration needed to produce [S2−] of 1.6 × 10−21 M:
+ 2 2−
[H ] [S ]
−7 −13 −20
K = Ka1 Ka2 = (1.1 × 10 )(1.3 × 10 ) = 1.4 × 10 = (7.4.37)
[ H2 S]

−20
K[ H2 S] (1.4 × 10 )(0.10 M)
+ 2
[H ] = = = 0.88 (7.4.38)
2− −21
[S ] 1.6 × 10 M
+
[H ] = 0.94 (7.4.39)

Thus adding a strong acid such as HCl to make the solution 0.94 M in H+ will prevent the more soluble ZnS from precipitating
while ensuring that the less soluble CdS will precipitate when the solution is saturated with H2S.

 Example 7.4.3

A solution contains 0.010 M Ca2+ and 0.010 M La3+. What concentration of HCl is needed to precipitate La2(C2O4)3•9H2O but
not Ca(C2O4)•H2O if the concentration of oxalic acid is 1.0 M? Ksp values are 2.32 × 10−9 for Ca(C2O4) and 2.5 × 10−27 for
La2(C2O4)3; pKa1 = 1.25 and pKa2 = 3.81 for oxalic acid.
Given: concentrations of cations, Ksp values, and concentration and pKa values for oxalic acid
Asked for: concentration of HCl needed for selective precipitation of La2(C2O4)3
Strategy:
A. Write each solubility product expression and calculate the oxalate concentration needed for precipitation to occur.
Determine the concentration range needed for selective precipitation of La2(C2O4)3•9H2O.
B. Add the equations for the first and second dissociations of oxalic acid to get an overall equation for the dissociation of
oxalic acid to oxalate. Substitute the [ox2−] needed to precipitate La2(C2O4)3•9H2O into the overall equation for the
dissociation of oxalic acid to calculate the required [H+].

7.4.8 https://chem.libretexts.org/@go/page/44752
 Solution
A Because the salts have different stoichiometries, we cannot directly compare the magnitudes of the solubility products.
Instead, we must use the equilibrium constant expression for each solubility product to calculate the concentration of oxalate
needed for precipitation to occur. Using ox2− for oxalate, we write the solubility product expression for calcium oxalate as
follows:
2+ 2− 2− −9
Ksp = [C a ][ox ] = (0.010)[ox ] = 2.32 × 10

2− −7
[ox ] = 2.32 × 10 M

The expression for lanthanum oxalate is as follows:

3+ 2 2− 3 2 2− 3 −27
Ksp = [La ] [ox ] = (0.010 ) [ox ] = 2.5 × 10

2− −8
[ox ] = 2.9 × 10 M

Thus lanthanum oxalate is less soluble and will selectively precipitate when the oxalate concentration is between
M and 2.32 × 10 M.
−8 −7
2.9 × 10

B To prevent Ca2+ from precipitating as calcium oxalate, we must add enough H+ to give a maximum oxalate concentration of
2.32 × 10−7 M. We can calculate the required [H+] by using the overall equation for the dissociation of oxalic acid to oxalate:
+ 2−
H O2 C C O2 H (aq) ⇌ 2 H (aq) + C2 O (7.4.40)
4(aq)

K = Ka1Ka2 = (10−1.25)(10−3.81) = 10−5.06 = 8.7×10−6

Substituting the desired oxalate concentration into the equilibrium constant expression,
+ 2 2− + 2 −7
[H ] [o x ] [H ] (2.32 × 10 )
−6
8.7 × 10 = = (7.4.41)
[HO2 CC O2 H] 1.0

+
[H ] = 6.1 M (7.4.42)

Thus adding enough HCl to give [H+] = 6.1 M will cause only La2(C2O4)3•9H2O to precipitate from the solution.

 Exercise 7.4.3

A solution contains 0.015 M Fe2+ and 0.015 M Pb2+. What concentration of acid is needed to ensure that Pb2+ precipitates as
PbS in a saturated solution of H2S, but Fe2+ does not precipitate as FeS? Ksp values are 6.3 × 10−18 for FeS and 8.0 × 10−28 for
PbS.

Answer
0.018 M H+

7.4.4: Summary
The anion in sparingly soluble salts is often the conjugate base of a weak acid that may become protonated in solution, so
the solubility of simple oxides and sulfides, both strong bases, often depends on pH. The anion in many sparingly soluble salts
is the conjugate base of a weak acid. At low pH, protonation of the anion can dramatically increase the solubility of the salt. Oxides
can be classified as acidic oxides or basic oxides. Acidic oxides either react with water to give an acidic solution or dissolve in
strong base; most acidic oxides are nonmetal oxides or oxides of metals in high oxidation states. Basic oxides either react with
water to give a basic solution or dissolve in strong acid; most basic oxides are oxides of metallic elements. Oxides or hydroxides
that are soluble in both acidic and basic solutions are called amphoteric oxides. Most elements whose oxides exhibit amphoteric
behavior are located along the diagonal line separating metals and nonmetals in the periodic table. In solutions that contain
mixtures of dissolved metal ions, the pH can be used to control the anion concentration needed to selectively precipitate the desired
cation.

7.4.9 https://chem.libretexts.org/@go/page/44752
7.4.5: Contributors and Attributions
Anonymous

7.4: The Effects of pH on Solubility is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
18.7: Solubility and pH is licensed CC BY-NC-SA 4.0.

7.4.10 https://chem.libretexts.org/@go/page/44752
7.5: Complex Ions and Solubility
 Learning Objectives
To be introduced to complex ions, including ligands.

Previously, you learned that metal ions in aqueous solution are hydrated—that is, surrounded by a shell of usually four or six water
molecules. A hydrated ion is one kind of a complex ion (or, simply, complex), a species formed between a central metal ion and
one or more surrounding ligands, molecules or ions that contain at least one lone pair of electrons, such as the [Al(H2O)6]3+ ion.
A complex ion forms from a metal ion and a ligand because of a Lewis acid–base interaction. The positively charged metal ion acts
as a Lewis acid, and the ligand, with one or more lone pairs of electrons, acts as a Lewis base. Small, highly charged metal ions,
such as Cu2+ or Ru3+, have the greatest tendency to act as Lewis acids, and consequently, they have the greatest tendency to form
complex ions.
As an example of the formation of complex ions, consider the addition of ammonia to an aqueous solution of the hydrated Cu2+ ion
{[Cu(H2O)6]2+}. Because it is a stronger base than H2O, ammonia replaces the water molecules in the hydrated ion to form the
[Cu(NH3)4(H2O)2]2+ ion. Formation of the [Cu(NH3)4(H2O)2]2+ complex is accompanied by a dramatic color change, as shown in
Figure 7.5.1. The solution changes from the light blue of [Cu(H2O)6]2+ to the blue-violet characteristic of the [Cu(NH3)4(H2O)2]2+
ion.

Figure 7.5.1: The Formation of Complex Ions. An aqueous solution of CuSO consists of hydrated Cu2+ ions in the form of pale
4

blue [Cu(H2O)6]2+ (left). The addition of aqueous ammonia to the solution results in the formation of the intensely blue-violet
[Cu(NH3)4(H2O)2]2+ ions, usually written as [Cu(NH3)4]2+ ion (right) because ammonia, a stronger base than H2O, replaces water
molecules from the hydrated Cu2+ ion. For a more complete description, see www.youtube.com/watch?v=IQNcLH6OZK0.

7.5.1: The Formation Constant

The replacement of water molecules from [Cu(H2O)6]2+ by ammonia occurs in sequential steps. Omitting the water molecules
bound to Cu2+ for simplicity, we can write the equilibrium reactions as follows:
2+ 2+
Cu (aq) + NH3(aq) ⇌ [Cu(NH3 )] K1 (7.5.1)
(aq)

2+ 2+
[Cu(NH3 )] + NH3(aq) ⇌ [Cu(NH3 )2 ] K2 (7.5.2)
(aq) (aq)

2+ 2+
[Cu(NH3 )2 ] + NH3(aq) ⇌ [Cu(NH3 )3 ] K3 (7.5.3)
(aq) (aq)

2+ 2+
[Cu(NH3 )3 ] + NH3(aq) ⇌ [Cu(NH3 )4 ] K4 (7.5.4)
(aq) (aq)

The sum of the stepwise reactions is the overall equation for the formation of the complex ion: The hydrated Cu2+ ion contains six
H2O ligands, but the complex ion that is produced contains only four NH ligands, not six.
3

2+ 2+
Cu + 4N H3(aq) ⇌ [C u(N H3 )4 ] (7.5.5)
(aq) (aq)

The equilibrium constant for the formation of the complex ion from the hydrated ion is called the formation constant (Kf). The
equilibrium constant expression for Kf has the same general form as any other equilibrium constant expression. In this case, the
expression is as follows:
2+
[[Cu(NH3 )4 ] ]
13
Kf = = 2.1 × 10 = K1 K2 K3 K4 (7.5.6)
2+ 4
[C u ][NH3 ]

7.5.1 https://chem.libretexts.org/@go/page/44754
 The formation constant (Kf) has the same general form as any other equilibrium constant
expression.
Water, a pure liquid, does not appear explicitly in the equilibrium constant expression, and the hydrated Cu2+(aq) ion is represented
as Cu2+ for simplicity. As for any equilibrium, the larger the value of the equilibrium constant (in this case, Kf), the more stable the
product. With Kf = 2.1 × 1013, the [Cu(NH3)4(H2O)2]2+ complex ion is very stable. The formation constants for some common
complex ions are listed in Table 7.5.1.
Table 7.5.1 : Common Complex Ions
Complex Ion Equilibrium Equation Kf

[Ag(NH3)2]+ Ag+ + 2NH3 ⇌ [Ag(NH3)2]+ 1.1 × 107

Ammonia Complexes [Cu(NH3)4]2+ Cu2+ + 4NH3 ⇌ [Cu(NH3)4]2+ 2.1 × 1013

[Ni(NH3)6]2+ Ni2+ + 6NH3 ⇌ [Ni(NH3)6]2+ 5.5 × 108

[Ag(CN)2]− Ag+ + 2CN− ⇌ [Ag(CN)2]− 1.1 × 1018

Cyanide Complexes [Ni(CN)4]2− Ni2+ + 4CN− ⇌ [Ni(CN)4]2− 2.2 × 1031

[Fe(CN)6]3− Fe3+ + 6CN− ⇌ [Fe(CN)6]3− 1 × 1042

[Zn(OH)4]2− Zn2+ + 4OH− ⇌ [Zn(OH)4]2− 4.6 × 1017

Hydroxide Complexes
[Cr(OH)4]− Cr3+ + 4OH− ⇌ [Cr(OH)4]− 8.0 × 1029

[HgCl4]2− Hg2+ + 4Cl− ⇌ [HgCl4]2− 1.2 × 1015

Halide Complexes [CdI4]2− Cd2+ + 4I ⇌ [CdI4]2− 2.6 × 105

[AlF6]3− Al3+ + 6F− ⇌ [AlF6]3− 6.9 × 1019

[Ag(S2O3)2]3− Ag+ + 2S2O32− ⇌ [Ag(S2O3)2]3− 2.9 × 1013

Other Complexes
[Fe(C2O4)3]3− Fe3+ + 3C2O42− ⇌ [Fe(C2O4)3]3− 2.0 × 1020

*Reported values are overall formation constants. Source: Data from Lange’s Handbook of Chemistry, 15th ed. (1999).

 Example 7.5.1

If 12.5 g of Cu(NO )
3 2
∙6H O
2
is added to 500 mL of 1.00 M aqueous ammonia, what is the equilibrium concentration of
Cu2+(aq)?
Given: mass of Cu2+ salt and volume and concentration of ammonia solution
Asked for: equilibrium concentration of Cu2+(aq)
Strategy:
A. Calculate the initial concentration of Cu2+ due to the addition of copper(II) nitrate hexahydrate. Use the stoichiometry of
the reaction shown in Equation 7.5.5 to construct a table showing the initial concentrations, the changes in concentrations,
and the final concentrations of all species in solution.
B. Substitute the final concentrations into the expression for the formation constant (Equation 7.5.6) to calculate the
equilibrium concentration of Cu2+(aq).

Solution
Adding an ionic compound that contains Cu2+ to an aqueous ammonia solution will result in the formation of [Cu(NH3)4]2+
(aq), as shown in Equation 7.5.5. We assume that the volume change caused by adding solid copper(II) nitrate to aqueous
ammonia is negligible.
A The initial concentration of Cu2+ from the amount of added copper nitrate prior to any reaction is as follows:

7.5.2 https://chem.libretexts.org/@go/page/44754
 1 mol 1 1000 mL
12.5 g Cu(NO3 )2 ⋅ 6 H2 O ( )( )( ) = 0.0846 M (7.5.7)
295.65 g 500 mL 1 L

Because the stoichiometry of the reaction is four NH3 to one Cu2+, the amount of NH3 required to react completely with the
Cu2+ is 4(0.0846) = 0.338 M. The concentration of ammonia after complete reaction is 1.00 M − 0.338 M = 0.66 M. These
results are summarized in the first two lines of the following table. Because the equilibrium constant for the reaction is large
(2.1 × 1013), the equilibrium will lie far to the right. Thus we will assume that the formation of [Cu(NH3)4]2+ in the first step is
complete and allow some of it to dissociate into Cu2+ and NH3 until equilibrium has been reached. If we define x as the amount
of Cu2+ produced by the dissociation reaction, then the stoichiometry of the reaction tells us that the change in the
concentration of [Cu(NH3)4]2+ is −x, and the change in the concentration of ammonia is +4x, as indicated in the table. The final
concentrations of all species (in the bottom row of the table) are the sums of the concentrations after complete reaction and the
changes in concentrations.
2 + 2 +
Cu + 4 NH −
↽⇀
− [Cu(NH ) ]
3 3 4

[Cu2+] [NH3] [[Cu(NH3)4]2+]

initial 0.0846 1.00 0

after complete reaction 0 0.66 0.0846

change +x +4x −x

final x 0.66 + 4x 0.0846 − x

B Substituting the final concentrations into the expression for the formation constant (Equation 7.5.6) and assuming that x <<
0.0846, which allows us to remove x from the sum and difference,
2+
[[Cu(NH3 )4 ] ] 0.0846 − x 0.0846 13
Kf = = ≈ = 2.1 × 10
[C u2+ ][NH3 ]4 x(0.66 + 4x)4 x(0.66)4

−14
x = 2.1 × 10

The value of x indicates that our assumption was justified. The equilibrium concentration of Cu2+(aq) in a 1.00 M ammonia
solution is therefore 2.1 × 10−14 M.

 Exercise 7.5.1

The ferrocyanide ion {[Fe(CN)6]4−} is very stable, with a Kf of 1 × 1035. Calculate the concentration of cyanide ion in
equilibrium with a 0.65 M solution of K4[Fe(CN)6].

Answer
2 × 10−6 M

7.5.2: The Effect of the Formation of Complex Ions on Solubility

What happens to the solubility of a sparingly soluble salt if a ligand that forms a stable complex ion is added to the solution? One
such example occurs in conventional black-and-white photography. Recall that black-and-white photographic film contains light-
sensitive microcrystals of AgBr, or mixtures of AgBr and other silver halides. AgBr is a sparingly soluble salt, with a Ksp of 5.35 ×
10−13 at 25°C. When the shutter of the camera opens, the light from the object being photographed strikes some of the crystals on
the film and initiates a photochemical reaction that converts AgBr to black Ag metal. Well-formed, stable negative images appear
in tones of gray, corresponding to the number of grains of AgBr converted, with the areas exposed to the most light being darkest.
To fix the image and prevent more AgBr crystals from being converted to Ag metal during processing of the film, the unreacted
AgBr on the film is removed using a complexation reaction to dissolve the sparingly soluble salt.
The reaction for the dissolution of silver bromide is as follows:
+ −
AgBr(s) ⇌ Ag + Br (7.5.8)
(aq) (aq)

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with
−13
Ksp = 5.35 × 10 at 25°C (7.5.9)

The equilibrium lies far to the left, and the equilibrium concentrations of Ag+ and Br− ions are very low (7.31 × 10−7 M). As a
result, removing unreacted AgBr from even a single roll of film using pure water would require tens of thousands of liters of water
and a great deal of time. Le Chatelier’s principle tells us, however, that we can drive the reaction to the right by removing one of
the products, which will cause more AgBr to dissolve. Bromide ion is difficult to remove chemically, but silver ion forms a variety
of stable two-coordinate complexes with neutral ligands, such as ammonia, or with anionic ligands, such as cyanide or thiosulfate
(S2O32−). In photographic processing, excess AgBr is dissolved using a concentrated solution of sodium thiosulfate.

The reaction of Ag+ with thiosulfate is as follows:

+ 2− 3−
Ag + 2 S2 O ⇌ [Ag(S2 O3 )2 ] (7.5.10)
(aq) 3(aq) (aq)

with
13
Kf = 2.9 × 10 (7.5.11)

The magnitude of the equilibrium constant indicates that almost all Ag+ ions in solution will be immediately complexed by
thiosulfate to form [Ag(S2O3)2]3−. We can see the effect of thiosulfate on the solubility of AgBr by writing the appropriate
reactions and adding them together:
+ − −13
AgBr(s) ⇌ Ag (aq) + Br (aq) Ksp = 5.35 × 10 (7.5.12)

+ 2− 3− 13
Ag (aq) + 2 S2 O (aq) ⇌ [Ag(S2 O3 )2 ] (aq) Kf = 2.9 × 10 (7.5.13)
3

2− 3− −
AgBr(s) + 2 S2 O (aq) ⇌ [Ag(S2 O3 )2 ] (aq) + Br (aq) K = Ksp Kf = 15 (7.5.14)
3

Comparing K with Ksp shows that the formation of the complex ion increases the solubility of AgBr by approximately 3 × 1013.
The dramatic increase in solubility combined with the low cost and the low toxicity explains why sodium thiosulfate is almost
universally used for developing black-and-white film. If desired, the silver can be recovered from the thiosulfate solution using any
of several methods and recycled.

If a complex ion has a large Kf, the formation of a complex ion can dramatically increase
the solubility of sparingly soluble salts.

 Example 7.5.2

Due to the common ion effect, we might expect a salt such as AgCl to be much less soluble in a concentrated solution of KCl
than in water. Such an assumption would be incorrect, however, because it ignores the fact that silver ion tends to form a two-
coordinate complex with chloride ions (AgCl2−). Calculate the solubility of AgCl in each situation:
a. in pure water
b. in 1.0 M KCl solution, ignoring the formation of any complex ions
c. the same solution as in part (b) except taking the formation of complex ions into account, assuming that AgCl2− is the only
Ag+ complex that forms in significant concentrations
At 25°C, Ksp = 1.77 × 10−10 for AgCl and Kf = 1.1 × 105 for AgCl2−.
Given: Ksp of AgCl, Kf of AgCl2−, and KCl concentration
Asked for: solubility of AgCl in water and in KCl solution with and without the formation of complex ions
Strategy:
A. Write the solubility product expression for AgCl and calculate the concentration of Ag+ and Cl− in water.
B. Calculate the concentration of Ag+ in the KCl solution.

7.5.4 https://chem.libretexts.org/@go/page/44754
 C. Write balanced chemical equations for the dissolution of AgCl and for the formation of the AgCl2− complex. Add the two
equations and calculate the equilibrium constant for the overall equilibrium.
D. Write the equilibrium constant expression for the overall reaction. Solve for the concentration of the complex ion.

Solution
a. A If we let x equal the solubility of AgCl, then at equilibrium [Ag+] = [Cl−] = x M. Substituting this value into the
solubility product expression,
Ksp = [Ag+][Cl−] = (x)(x) = x2 =1.77×10−10

x = 1.33×10−5
Thus the solubility of AgCl in pure water at 25°C is 1.33 × 10−5 M.
b. B If x equals the solubility of AgCl in the KCl solution, then at equilibrium [Ag+] = x M and [Cl−] = (1.0 + x) M. Substituting
these values into the solubility product expression and assuming that x << 1.0,
Ksp = [Ag+][Cl−] = (x)(1.0 + x) ≈ x(1.0) = 1.77×10−10 = x
If the common ion effect were the only important factor, we would predict that AgCl is approximately five orders of
magnitude less soluble in a 1.0 M KCl solution than in water.
c. C To account for the effects of the formation of complex ions, we must first write the equilibrium equations for both the
dissolution and the formation of complex ions. Adding the equations corresponding to Ksp and Kf gives us an equation that
describes the dissolution of AgCl in a KCl solution. The equilibrium constant for the reaction is therefore the product of Ksp and
Kf:
+ − −10
AgCl(s) ⇌ Ag (aq) + C l (aq) Ksp = 1.77 × 10 (7.5.15)

+ − − 5
Ag (aq) + 2C l ⇌ [AgC l2 ] Kf = 1.1 × 10 (7.5.16)

− − −5
AgCl(s) + C l ⇌ [AgC l2 ] K = Ksp Kf = 1.9 × 10 (7.5.17)

D If we let x equal the solubility of AgCl in the KCl solution, then at equilibrium = x and [AgCl2−] [Cl−] = 1.0 − x. Substituting
these quantities into the equilibrium constant expression for the net reaction and assuming that x << 1.0,
−
[AgC l ] x
2 −5
K = = ≈ 1.9 × 10 =x
− 1.0 − x
[C l ]

That is, AgCl dissolves in 1.0 M KCl to produce a 1.9 × 10−5 M solution of the AgCl2− complex ion. Thus we predict that AgCl
has approximately the same solubility in a 1.0 M KCl solution as it does in pure water, which is 105 times greater than that
predicted based on the common ion effect. (In fact, the measured solubility of AgCl in 1.0 M KCl is almost a factor of 10 greater
than that in pure water, largely due to the formation of other chloride-containing complexes.)

 Exercise 7.5.2

Calculate the solubility of mercury(II) iodide (HgI2) in each situation:

a. pure water
b. a 3.0 M solution of NaI, assuming [HgI4]2− is the only Hg-containing species present in significant amounts
Ksp = 2.9 × 10−29 for HgI2 and Kf = 6.8 × 1029 for [HgI4]2−.

Answer a
1.9 × 10−10 M
Answer a
1.4 M

Complexing agents, molecules or ions that increase the solubility of metal salts by forming soluble metal complexes, are common
components of laundry detergents. Long-chain carboxylic acids, the major components of soaps, form insoluble salts with Ca2+ and

7.5.5 https://chem.libretexts.org/@go/page/44754
Mg2+, which are present in high concentrations in “hard” water. The precipitation of these salts produces a bathtub ring and gives a
gray tinge to clothing. Adding a complexing agent such as pyrophosphate (O3POPO34−, or P2O74−) or triphosphate (P3O105−) to
detergents prevents the magnesium and calcium salts from precipitating because the equilibrium constant for complex-ion
formation is large:

2 + 4 − 2 −
Ca (aq) + O POPO (aq) ⇌ [Ca(O POPO )] (aq) (7.5.18)
3 4 3 3

with
4
Kf = 4 × 10 (7.5.19)

However, phosphates can cause environmental damage by promoting eutrophication, the growth of excessive amounts of algae in a
body of water, which can eventually lead to large decreases in levels of dissolved oxygen that kill fish and other aquatic organisms.
Consequently, many states in the United States have banned the use of phosphate-containing detergents, and France has banned
their use beginning in 2007. “Phosphate-free” detergents contain different kinds of complexing agents, such as derivatives of acetic
acid or other carboxylic acids. The development of phosphate substitutes is an area of intense research.
Commercial water softeners also use a complexing agent to treat hard water by passing the water over ion-exchange resins, which
are complex sodium salts. When water flows over the resin, sodium ion is dissolved, and insoluble salts precipitate onto the resin
surface. Water treated in this way has a saltier taste due to the presence of Na+, but it contains fewer dissolved minerals.

Figure 7.5.2: An MRI Image of the Heart, Arteries, and Veins. When a patient is injected with a paramagnetic metal cation in the
form of a stable complex known as an MRI contrast agent, the magnetic properties of water in cells are altered. Because the
different environments in different types of cells respond differently, a physician can obtain detailed images of soft tissues.
Another application of complexing agents is found in medicine. Unlike x-rays, magnetic resonance imaging (MRI) can give
relatively good images of soft tissues such as internal organs. MRI is based on the magnetic properties of the 1H nucleus of
hydrogen atoms in water, which is a major component of soft tissues. Because the properties of water do not depend very much on
whether it is inside a cell or in the blood, it is hard to get detailed images of these tissues that have good contrast. To solve this
problem, scientists have developed a class of metal complexes known as “MRI contrast agents.” Injecting an MRI contrast agent
into a patient selectively affects the magnetic properties of water in cells of normal tissues, in tumors, or in blood vessels and
allows doctors to “see” each of these separately (Figure 7.5.2). One of the most important metal ions for this application is Gd3+,
which with seven unpaired electrons is highly paramagnetic. Because Gd3+(aq) is quite toxic, it must be administered as a very
stable complex that does not dissociate in the body and can be excreted intact by the kidneys. The complexing agents used for
gadolinium are ligands such as DTPA5− (diethylene triamine pentaacetic acid), whose fully protonated form is shown here.

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7.5.3: Summary
The formation of complex ions can substantially increase the solubility of sparingly soluble salts if the complex ion has a large Kf.
A complex ion is a species formed between a central metal ion and one or more surrounding ligands, molecules or ions that contain
at least one lone pair of electrons. Small, highly charged metal ions have the greatest tendency to act as Lewis acids and form
complex ions. The equilibrium constant for the formation of the complex ion is the formation constant (Kf). The formation of a
complex ion by adding a complexing agent increases the solubility of a compound.

7.5: Complex Ions and Solubility is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

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7.6: A Deeper Look - Selective Precipitation of Ions
 Learning Objectives
To know how to separate metal ions by selective precipitation.
To understand how several common metal cations can be identified in a solution using selective precipitation.

The composition of relatively complex mixtures of metal ions can be determined using qualitative analysis, a procedure for
discovering the identity of metal ions present in the mixture (rather than quantitative information about their amounts). The
procedure used to separate and identify more than 20 common metal cations from a single solution consists of selectively
precipitating only a few kinds of metal ions at a time under given sets of conditions. Consecutive precipitation steps become
progressively less selective until almost all of the metal ions are precipitated, as illustrated in Figure 7.6.1.

Figure 7.6.1 : Steps in a Typical Qualitative Analysis Scheme for a Solution That Contains Several Metal Ions

7.6.1: Group 1: Insoluble Chlorides

Most metal chloride salts are soluble in water; only Ag , Pb , and Hg
+ 2 +
form chlorides that precipitate from water. Thus the
2 +
2

first step in a qualitative analysis is to add about 6 M HCl, thereby causing AgCl, PbCl , and/or Hg Cl to precipitate. If no
2 2 2

precipitate forms, then these cations are not present in significant amounts. The precipitate can be collected by filtration or
centrifugation.

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7.6.2: Group 2: Acid-Insoluble Sulfides
Next, the acidic solution is saturated with H S gas. Only those metal ions that form very insoluble sulfides, such as As , Bi ,
2
3 + 3 +

Cd
2 +
, Cu , Hg , Sb , and Sn , precipitate as their sulfide salts under these acidic conditions. All others, such as Fe
2 + 2 + 3 + 2 + 2 +

and Zn , remain in solution. Once again, the precipitates are collected by filtration or centrifugation.
2 +

7.6.3: Group 3: Base-Insoluble Sulfides (and Hydroxides)

Ammonia or NaOH is now added to the solution until it is basic, and then (NH ) S is added. This treatment removes any 4 2

remaining cations that form insoluble hydroxides or sulfides. The divalent metal ions Co , Fe , Mn , Ni , and Zn 2 + 2 + 2 + 2 + 2 +

precipitate as their sulfides, and the trivalent metal ions Al and Cr precipitate as their hydroxides: Al(OH) and Cr(OH) .
3 + 3 +

3 3

If the mixture contains Fe , sulfide reduces the cation to Fe , which precipitates as FeS.
3 + 2 +

7.6.4: Group 4: Insoluble Carbonates or Phosphates

The next metal ions to be removed from solution are those that form insoluble carbonates and phosphates. When Na CO is added 2 3

to the basic solution that remains after the precipitated metal ions are removed, insoluble carbonates precipitate and are collected.
Alternatively, adding (NH ) HPO causes the same metal ions to precipitate as insoluble phosphates.
4 2 4

7.6.5: Group 5: Alkali Metals

At this point, we have removed all the metal ions that form water-insoluble chlorides, sulfides, carbonates, or phosphates. The only
common ions that might remain are any alkali metals (Li , Na , K , Rb , and Cs ) and ammonium (NH ). We now take a
+ + + + + +

second sample from the original solution and add a small amount of NaOH to neutralize the ammonium ion and produce NH . 3

(We cannot use the same sample we used for the first four groups because we added ammonium to that sample in earlier steps.)
Any ammonia produced can be detected by either its odor or a litmus paper test. A flame test on another original sample is used to
detect sodium, which produces a characteristic bright yellow color. The other alkali metal ions also give characteristic colors in
flame tests, which allows them to be identified if only one is present.
Metal ions that precipitate together are separated by various additional techniques, such as forming complex ions, changing the pH
of the solution, or increasing the temperature to redissolve some of the solids. For example, the precipitated metal chlorides of
group 1 cations, containing Ag , Pb , and Hg , are all quite insoluble in water. Because PbCl is much more soluble in hot
+ 2 + 2 +

2 2

water than are the other two chloride salts, however, adding water to the precipitate and heating the resulting slurry will dissolve
any PbCl present. Isolating the solution and adding a small amount of Na CrO solution to it will produce a bright yellow
2 2 4

precipitate of PbCrO if Pb were in the original sample (Figure 7.6.2).

4
2 +

Figure 7.6.2 : When a small amount of Na CrO solution is added to a sample containing
2 4
Pb
2 +
ions in water, a bright yellow
precipitate of PbCrO forms. (CC BY-SA 3.0 Unported; PRHaney via Wikipedia).
4

As another example, treating the precipitates from group 1 cations with aqueous ammonia will dissolve any AgCl because Ag
+

+
forms a stable complex with ammonia: [Ag(NH ) ] . In addition, Hg Cl disproportionates in ammonia.
3 2 2 2

2 + 2 +
2 Hg → Hg + Hg
2

to form a black solid that is a mixture of finely divided metallic mercury and an insoluble mercury(II) compound, which is
separated from solution:
+ −
Hg Cl (s) + 2 NH (aq) → Hg(l) + Hg(NH )Cl(s) + NH (aq) + Cl (aq)
2 2 3 2 4

Any silver ion in the solution is then detected by adding HCl , which reverses the reaction and gives a precipitate of white AgCl

that slowly darkens when exposed to light:

7.6.2 https://chem.libretexts.org/@go/page/44753
 + + − +
[Ag (NH ) ] (aq) + 2 H (aq) + Cl (aq) → AgCl(s) + 2 NH (aq)
3 2 4

Similar but slightly more complex reactions are also used to separate and identify the individual components of the other groups.

7.6.6: Summary
In qualitative analysis, the identity, not the amount, of metal ions present in a mixture is determined. The technique consists of
selectively precipitating only a few kinds of metal ions at a time under given sets of conditions. Consecutive precipitation steps
become progressively less selective until almost all the metal ions are precipitated. Other additional steps are needed to separate
metal ions that precipitate together.

7.6: A Deeper Look - Selective Precipitation of Ions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.
17.7: Qualitative Analysis for Metallic Elements by Anonymous is licensed CC BY-NC-SA 3.0.

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Index
A H Phase transition
acid strength heat 3.5: Phase Transitions
6.3: Acid and Base Strength 1.2: Heat as a Mechanism to Transfer Energy
azeotropes Heat capacity Q
4.5: Separating Volatile Solutions - Distillation 1.5: Heat Capacity and Calorimetry qualitative analysis
Hess's law 7.6: A Deeper Look - Selective Precipitation of Ions
B 1.8: Indirect Determination of ΔH - Hess's Law
base strength R
6.3: Acid and Base Strength I refining
intermolecular forces 4.5: Separating Volatile Solutions - Distillation
C 3.2: Intermolecular Forces - Origins in Molecular
calorimetry Structure S
1.5: Heat Capacity and Calorimetry
ion pair solid phase
3.2: Intermolecular Forces - Origins in Molecular 3.8: The Solid State
Structure
D specific heat capacity
distillation 1.5: Heat Capacity and Calorimetry
L spontaneous change
4.5: Separating Volatile Solutions - Distillation
Law of Dulong and Petit 2.4: Entropy Changes and Spontaneity
1.6: Molecules as Energy Carriers and Converters
E lever rule
Enthalpies of Formation T
4.5: Separating Volatile Solutions - Distillation
1.9: Standard Enthalpies of Formation The Solubility Product
extensive property 7.2: Ionic Equilibria between Solids and Solutions
M
1.5: Heat Capacity and Calorimetry
metallic bonding W
3.9: Bonding in Metals
F weak acids
first law of thermodynamics 6.4: Equilibria Involving Weak Acids and Bases
P weak bases
1.4: The First Law of Thermodynamics
phase diagrams 6.4: Equilibria Involving Weak Acids and Bases
fractional distillation 3.6: Phase Diagrams
4.5: Separating Volatile Solutions - Distillation
phase equilibrium
fuels 3.4: Phase Equilibrium
1.10: Fuels as Sources of Energy

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Glossary
Sample Word 1 | Sample Definition 1

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