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2. THERMODYNAMICS OF
CHEMICAL PROCESSES

Prof. Dr. Ing. Ileana Rau

Thermodynamics (Greek: therm = heat;

dynamys = power) studies the effects of
changes in temperature, pressure and volume
on physical systems at the macroscopic scale
by analysing the collective motion of their
particles by using statistical methods.

Thermodynamics - studies energy balance

of chemical processes, chemical equilibrium,
reaction yield, phase transformations with
applications to mixtures and solutions.

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Main Objectives
• the thermal effects of chemical transformation;
• the quantity of work, accompanying thermodynamic
process which can include a chemical reaction;
• the laws describing the processes in which the energy
pass from one state to another;
• the possibility, the direction and the limits of natural and
industrial process;
• the organization or disorganization state of
thermodynamic systems;
• the chemical system and thermal equilibrium after
physical – chemical transformations;
• establish the determining conditions for equilibrium.

2.1. Thermodynamic systems

Thermodynamic system: a part of the
universe separated by a real or imaginary
boundary from the rest of the universe. The
surroundings comprises the region outside the
system, where we make our measurements.
Phase – part of a system having the same
properties in all its points and separated from
the rest of the system by a separation surface.
Surrounding

System

Boundary

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Thermodynamic systems are classified as follows:

– from physical point of view
– homogenous – formed from only one phase. It has the
same properties in all its points (gas, solution, mixture of
gases)
– heterogenous – formed from 2 phases or many (ex.
Physical equilibrium H2OL H2OV – the properties vary in
at least 2 points)

– from point of view of interaction with the environment

– isolated system, there is no energy or mass exchange
with the environment;
– no isolated or open system – it changes energy and mass
with the environment;
– closed system – it does not exchange mass but it can
exchange energy
» Diathermic system - the system allows energy to
escape as heat system;
» Adiabatic system – there is no change of heat with
the environment, only other types of energy.

The properties of a system could be:

• intensive – they do not depend on quantity
of substance: pressure, temperature;
• extensive – they depend on quantity of
substance: internal energy (U), enthalpy
(H), Gibbs free energy (G), Helmholtz free
energy (A or F).
In order to describe a thermodynamic process
state equations are used (f(P,V,T) = 0)

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Thermodynamic process – the energetic

evolution of a thermodynamic system proceeding
from an initial state to a final state. This evolution
is determined by the variation of one or more
state parameters.
The thermodynamic processes are classified as
follows:
• reversible – the process passes spontaneously
from the initial state to the final state and from
the final state to the initial state through the
same sequence of intermediate states;
• irreversible – the process in which the system
can not come back from the final state to the
initial state through the same sequence of
intermediate states.

2.2. The Thermodynamics laws

2.2.1 Zeroth law of thermodynamics

• If two systems are in thermal equilibrium with a

third system, then they must be in thermal
equilibrium with each other.
• This principle introduces the temperature
parameter, T.
• When two different systems are in thermal contact,
the big body called also thermostat preserves
unchanged its properties while the small body,
called also thermometer varies its properties.

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Temperature units and notations

• t  C (Celsius degrees)
• T  K (Kelvin degrees) (T = t + 273,16)
• °F = 9/5 °C + 32 (Fahrenheit degrees)
(anglosaxon system)

2.2.2. First law of thermodynamics

Energy is neither created nor destroyed; it changes from one
form to another.
Consequences
• It is impossible to create a perpetual motion machine
of I type (machine which produces energy from nothing) –
Helmholtz 1847;
• If a quantity of energy disappears from a system, a new
form of energy, in an equivalent quantity appears in its
place;
• The internal energy of an isolated system is constant 
Equivalence Law of Joule
W1 W2
  const  4.18 J / cal
Q1 Q2

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• The first law of thermodynamic postulate that U – the

change in internal energy of the system is given by:
U  Q  W

• The change in internal energy of a closed system is equal to

the energy that passes through its boundary as heat or/and
work.

• All these dimensions are expressed in J (Joule) or cal

(calorie):
1cal = 4,186 J

• The internal energy is a state function. It is depending on

the initial and final state and not on the way (being thus a
state function), while the heat and the work are functions
which depend on the followed way.
2

U  U 2  U1 U   dU  U 2  U1
1

Sign convention
(+) any quantity which increases the energy of the system;
(-) any energy lost by the system.

Examples:
– Heat:
(+) received by the system (evaporation, endothermic
reaction)
(-) lost by the system (solidification, exothermic reaction)
– Work:
(+) performed by the surrounding on the system
(compression)
(-) performed by the system (expansion)

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Exemples :
• Reversible Processes (perfect gaz):
– Isotherm process (constant temperature)
– Isochoric process (constant volume)
– Adiabatic process
– Isobar process (constant pressure):
A new state function is introduced in order to characterize
the isobar process: H – Enthalpy, calorific function of Gibbs
The thermal effects of all process which take place at
constant pressure (chemical reactions, phase transitions,
solubilization) represent the change in enthalpy for that
system

2.2.2.1. Applications of the first

law to the material constants
• Heat capacity represents the amount of heat necessary to increase the temperature of
the system by 1C.
• Specific heat capacity (specific heat) – of a substance represents the heat capacity
divided by the mass, usually in grams or, in other words, it represents the heat
quantity necessary to increase the temperature of one gram of substance by 1C
Q
c
mT
• Molar heat capacity – heat quantity necessary to increase the temperature of one
mole of substance by 1C:

Q m
C n
nT M

• Cv – the molar heat capacity at constant volume - the change of the molar internal
energy of the substance with the temperature, at constant volume
• Cp – the molar heat capacity at constant pressure - the change of the molar
enthalpy of the substance with the temperature, at constant pressure

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CV and Cp are state functions

For certain temperature range Cp = a + bT + cT2 +…….

Cp – Cv = R - Mayer equation

R= 1.987 cal / mol K

R = 8.31 J/ mol K
R = 0.082 L atm / mol K

2.2.2.2 Thermochemistry
In thermodynamics and physical chemistry,
themochemistry is the study of the heat
evolved or absorbed in chemical reactions.
Thermochemistry, generally, is concerned with
the heat exchange accompanying
transformations, such as mixing, phase
transitions, chemical reactions, etc, which
include calculations of quantities such as the
heat capacity, heat of absorption, heat of
formation, etc.

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 1 A1  2 A2   3 A3  ...  i Ai  ...   1' A1'  2' A2'  ... i' Ai'  ....  r H
If r H is (+) the reaction is endothermic reactions
and if r H is (–) the reaction is exothermic.
r H T , P   i' H i'   i H i
prod react

where vi is the number of moles for ith reactant; Hi is

the molar enthalpy of ith reactant; v’i is the number
of moles for ith product; H’i is the molar enthalpy of
ith product.

N 2  3H 2  2NH 3
Exemple
r H T , P  2 H NH 3  3H H 2  H N 2

a) Heat of formation
r HT , P   i'f H i'   i f H i
prod react

• In tables  f H 298
0
- standard enthalpy of formation
• The standard enthalpy of formation of a substance is
the standard reaction enthalpy for the formation of the
compound from its elements in their reference states.

• c. s. : t = 25C si p = 1 atm.
• c. n. : t = 0C si p = 1 atm.
• c. b. : t = 37C si p = 1 atm.

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b) Heat of combustion
• The heat of combustion is the energy
released as heat when one mol of a
compound undergoes complete combustion
to upper stable oxides.

Exemple:
CH 4(g)  2O 2(g)  CO 2 (g)  2H 2 O (l) c H 298
0
 212,79 kcal / mol

r H T , P  
react
i c
H i   i
prod

' c
H i
'

• Other heat type:

– heat of solubilization
– heat of decomposition
– heat of neutralization
– heat from bond energy

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2.2.2.3 The laws of thermochemistry

a) Hess’s law (1840)

• The heat exchange accompanying a transformation is
the same, independently whether the process occurs
in one or several steps.
• The standard enthalpy of an overall reaction is the
sum of the standard enthalpies of the individual
reactions into which a reaction may be divided.
• The thermal effects of one reaction depend only on the
nature and the state of the reactants and products and
not on the way in which takes place the reaction.

CO
rH2 rH3
½ O2 ½ O2
rH1
C CO2
O2

C( s )  O2 ( g )  CO2 ( g ) r H1  94030 cal

C( s )  1 / 2O2 ( g )  CO( g ) r H 2  26390 cal
CO( g )  1 / 2O2 ( g )  CO2 ( g ) r H 3  67640 cal

r H 1  r H 2  r H 3

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b) Kirchhoff’ s law

The variation with temperature of the thermal

effects of a chemical reaction is equal to the
stoechiometric molar heat capacity of the
system (constant pressure).
T2

 HT2 , P   HT1, P   rCPdT

r r

T1

integral form of Kirchhoff equation

CP  a  bT  cT 2
r CP  r a  r bT  r cT 2  ...

Generally: T1 = 298K şi P = 1 atm. (standard heat of formation)

Δ 𝐻 =Δ 𝐻 + Δ 𝑎 + Δ 𝑏𝑇 + Δ 𝑐𝑇2+. . . 𝑑𝑇

r C p  0 T rH

r C p  0 T rH

r C p  0 T rH - constant

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If phase transitions take place in the

temperature range considered, the enthalpies of
transition should be taken into account.
Ttr T2

r HT02  r HT01   r CP1 dT  vi tr Hi   r CP2 dT

T1 Ttr
where i represents the mole numbers of the
substance undergoing the phase transition. The
transition enthalpy will be positive when a product
is phase transformed and will be negative when a
reactant undergoes a phase transition. rCp1 and
rCp2 are the change in heat capacity calculated with
the values of heat capacity function of the phase.

c) Lavoisier and Laplace’s law (1782)

The heat exchange accompanying a transformation is equal in

absolute value and opposite in sign to the heat exchange
accompanying the reverse transformation.

Exemple:
CH 4 (g)  2O 2 (g)  CO 2 (g)  H 2O (l) r H1

CO 2 (g)  2H 2O (l)  CH 4 (g)  2O2 (g) r H 2

r H1  212.7 kcal / mol

r H 2  212.7 kcal / mol

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Consequence

When one mole of a chemical compound is decomposed into

chemical elements quantity of heat is absorbed or evolved a
quantity of heat equal to the heat evolved or absorbed when
one mole is formed from the constituent elements.

 f H  d H

2.2.3 The second law of thermodynamics

• Clausius formulation (1850)
Heat cannot spontaneously flow from a colder to a
hotter material.
No machine whose working fluid undergoes a cycle can
absorb heat from one system, reject heat to another
system and produce no other effect
• Kelvin and Planck formulation
No process is possible in which the sole result is the
absorption of heat from a reservoir and its complete
conversion into work. Such a kind of machine will be a
perpetual Motion Machine of IInd type.
No (heat) engine whose working fluid undergoes a cycle
can absorb heat from a single reservoir, deliver an
equivalent amount of work, and deliver no other effect

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Hot body Q1 Engine Q2 Cold body

T1 T2

A heat engine is a mechanical device that provides useful

work based on the difference in temperature of two bodies.
In other words, a heat engine is a mechanical device that
continuously transforms heat into an useful work. Therefore
in order to function such an engine necessarily has to be
endowed with two heat reservoirs: a hot source (T1) and a
cold source (sink) (T2)
During the functioning of this engine some heat Q1 is
absorbed from the hot source, a part is transformed into
work and the rest Q2 is transferred to the sink.

Hot body Q1 Engine Q2 Cold body

T1 T2

Sign convention W
(+) – for heat received by the system
(-) – for heat lost by the system
W  Q1 (Q2)  Q1Q2
The efficiency is given by: W Q1  Q2
 
Q1 Q1
Sadi Carnot (1824) established the ideal efficiency of heat
engines for an engine which work through cycles formed
from two isotherm transformations (constant temperature)
and two adiabatic transformations (Q = ct). Such a cycle is
called Carnot cycle. T T
 1 2
T1

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• Consequence: The maximum efficiency of a

heat engine does not depend on the nature
of substance which follows the
transformations. It is determined only by
the temperature of the two sources.
• For an irreversible cycle the efficiency will
be lower than the ideal efficiency.

Q1  Q2 T1  T2   for irreversible process 

  
Q1 T1   for reversible process 

2.2.3.1. State functions introduced

by the IInd Law of Thermodynamics
a) The Entropy
Q1  Q2 T1  T2 Q2 T Q2 Q Q1 Q2
  1  1 2   1   0
Q1 T1 Q1 T1 T2 T1 T1 T2

S – function, introduced by Clausius in

Qrev 1894, called entropy
 dS The entropy is a state function
T The entropy is an extensive function.
The units are cal/molK or J/molK.
Qirev
 dS
T

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Q the most general mathematical

 dS formulation of the second law of
T thermodynamics

Q  TdS
TdS  dU  pdV
Q  dU  pdV st
( I law)
the correlation expression
between Ist law and IInd law of
thermpdynamics

If U and V are constant  dS U ,V  0

the entropy change of an isolated system is positive for
spontaneous processes or nule at equilibrium state.

• In nature, at constant U and V, take place

spontaneously only the phenomena in which an
increase of entropy, exists.
• Thus the IInd law of thermodynamics can be
formulate in terms of entropy as follows:
“In one isolated system the entropy of the
system can not decrease, it is constant (dSU,V=0
if in the system only reversible processes take
place, and it increases (dSU,V>0) in any
irreversible process.”
This is why the IInd law of thermodynamics is
called also the entropy law.

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Entropy for a chemical reaction

 1 A1  2 A2  .......  i Ai  ....   1' A1'  2' A2'  ..... i' Ai'  ..........
r S   i' S i'   i S i
prod react

When some phase transitions take place:

Q
dS  dH
T  dS 
T
QP =H  Q  dH
tr H
For a finite process: tr S  S 2  S1 
For a chemical reaction:
Ttr
Ttr
CP tr H CP T2

 ST   ST   dT   i 
r r 1
dT 2

2 1
T1 T Ttr T T tr

Exemplu:
Să se calculeze entropia reacţiei:
Al2O3 + 3C  2Al + 3CO
la 1000 K şi 1 atm.
Se cunoaşte:r S 0 298  138,88 cal / K , temperatura de topire a
aluminiului 930 K, top H Al0  2500 cal / mol

Substance Cp, cal/molK

Al2O3 22 + 810-3T
CO 6,6 + 1,210-3T
C 2,7 + 2,610-3T
Al(s) 4,8 + 3,2 10-3 T
Al(l) 7

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b) Thermodynamic potentials
Helmholtz Free Energy (A or F),
Gibbs Free Energy (G)
The Helmholtz free energy is a
U  TS  A thermodynamic potential which measures
the “useful” work obtainable from a closed
thermodynamic system at a constant
temperature.
In a system, at constant temperature and
pressure can take place spontaneously
G  H  TS only the processes in which the Gibbs free
energy is decreasing dG T , P  0
At equilibrium the Gibbs free energy
of the system is minimum and it is
maintained constant G T , P  0

 r G 
 G   H  T 
r r

 T  P
Gibbs – Helmholtz equation establishes the
connection between the chemical affinity, r G
and the reaction heat r H

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2.2.4. Third Law of thermodynamics

• The Nernst heat Theorem:
The entropy change accompanying any physical or chemical
transformation approaches zero as the temperature approaches
zero: S0 as T0 provided all the substances involved are
perfectly ordered.

• Planck affirmation:
At 0 K not only S is zero but also the molar entropy (S) of any
crystalline pure element is zero.

S0 = 0 represents the mathematical expression of the IIIrd law

of thermodynamic.

• Summarized Third Law of thermodynamics is: The entropy of all

perfect crystalline substances is zero at T = 0 K.

2.2.5. Chemical Potential

In open systems formed from many substances, (so the
composition is varying due to the changes with the
surroundings), the expressions of the thermodynamics
functions established in the frame of Ist and IInd Laws should be
completed with composition variables:
U  U (V , S , n1 , n 2 ,......, ni .....)
H  H ( P , S , n1 , n 2 ,......, ni .....)
F  F (V , S , n1 , n 2 ,......, ni .....)
G  G (T , P, n1 , n 2 ,......, ni .....)
The elementary variation for the Gibbs free energy will be:
 G   G   G 
dG   SdT  VdP    dn1    dn2    dni  ...
 n1 T , P , n 2 , n3 ,..., ni  n2 T , P.n , n
1 3 ,.., n i
 ni T , P , n j ( j i )

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 G   G   G 
dG   SdT  VdP    dn1    dn2   
 dni  ...
 n1 T , P , n 2 , n3 ,..., ni  n2 T , P.n , n ,.., n
1 3 i
 ni T , P , n j ( j i )

The partial molar function:

 G 
Gi   
  i
n
 i T , P , n  j j i 

is called chemical potential (Gibbs)

 dG   SdT  VdP   i dni

i

2.3. Chemical equilibrium

In a chemical process, chemical equilibrium is the
state in which the chemical activities or
concentrations of the reactants and products
have no net change over time. Usually, this state
results when the forward chemical process
proceeds at the same rate as their reverse
reaction. The reactions rates of the forward and
reverse reactions are generally not zero but,
being equal, there are no net changes in any of
the reactant or product concentrations.

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2.3.1. Thermodynamical condition of

chemical equilibrium. Reaction isotherm
v1 A1  v2 A2  ...  vi Ai  ... v '1 A'1  v ' 2 A' 2  ...  v 'i A'i  ...
1 2 i ’1  ’2  ’i

 G 
r
T ,P   vi' i'   vi i  0
the thermodynamical
condition of the chemical
prod react
equilibrium

r G 0T  v 
prod
'
i i
0'
  vi i0
react
standard Gibbs
energy of the reaction

r GT0   RT ln K a
Ka – is the equilibrium constant, calculated with activities

 ai'
vi'

ai is the activity of ith component at

Ka  prod
equilibrium. It is a kind of “effective”
a
react
vi
i mole fraction

pi is the vapor pressure of ith component

(at equilibrium) when it is a component
pi
ai  of solution and
pi* pi* – vapor pressure of pure ith component
at equilibrium

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 pi'
v i'

ideal gas mixture: ai = pi Ka = Kp  Kp  prod

p
vi
i
react
For very diluted solutions activities can be replaced by
corresponding concentrations
Ka Kx or Ka  Km or Ka  Kc
ci – molar
xi – molar ratio mi – molal concentration
at equilibrium concentration (mols of
ni (moles of substance in 1L
xi  substance in 1 kg
nt of solution) at
of solvent) at equilibrium
equilibrium
r GT0   RT ln K x (r GT0 ) m   RT ln K m (r GT0 ) c   RT ln K c

 G    G    G 
r 0
T
r 0
T m
r 0
T c

2.3.2 Expression of equilibrium

constants for reactions among gases
v1' v 2' v i'
p1'  p2' ... pi'
Kp 
p1v  p2v  ... piv
1 2 i

pi  xi P pi is partial pressure of ith component at equilibrium,

a) P is the total pressure
xi is molar ratio of ith component at equilibrium

v v v '
v '
v ' '
'
i
x1' x2' x3' ... xi' ... P
1 2 3 i
i

 Kp  v v v   K x P v
v
x1 x2 x3 ... xi ...
1 2 v 3 i i

P i

v   vi'  v i
Prod React

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b) piV  ni RT
1'  2'  3'  i'
 RT 
'
c1' c2' c3' ... ci' ... 
i

 K c RT 

Kp  
1  2  3
c1 c2 c3 ... ci ... i
RT  i

R = 0.082 Latm / molK


   P 
c) KxP  K c (RT )  Kc  K  
 RT 
X

v  0  K p  K x  Kc

Exemple

For the reaction

COCl2 CO + Cl2,
at equilibrium, at 550C and 1 atm 77% of
COCl2 is dissociated. Calculate Kx, Kp and Kc.

Prof. Habil. Dr. Ing. Ileana Rau 24

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2.3.3 Estimation of the equilibrium

constant from thermodynamic data
r GT0
r GT0   RT ln K a ln K a  
RT
r GT0  r H T0  Tr S T0 T
r H T0  r H 298   c
0 r
p dT
298

r H T0 r S T0
T
r C p
r ST0  r S 298  
0
ln K a    dT
RT R 298 T

r ST0 1  1 r C p 
T T
r H 298
0
ln K a        C p dT  
r
dT 
RT R R  T 298 298
T 
This equation solves the most important problem of chemical equilibrium:
the integral calculus of equilibrium constant from thermodynamical data -
reaction heat, molar heat capacities, and entropies

2.3.4. The shift of chemical equilibrium;

Le Chatelier (1884) – Brawn (1887) principle

• If a dynamic equilibrium is disturbed by

changing the conditions (p, T and
composition), the position of equilibrium
shifts in order to counteract the change.
• A system at equilibrium, when subjected to
a disturbance, responds in a way that tends
to minimize its the effect.

Prof. Habil. Dr. Ing. Ileana Rau 25

 12/11/2019

2.3.4.1. Temperature influence on the

equilibrium constant. Equation Van’t Hoff

 r G 0 
d  
1 r G 0 d ln K a 1  T 
ln K a   
R T dT R dT
 r G 0 
d  
 T   H
r 0
Gibbs Helmholtz Equation
dT RT 2

d ln K a r H
 van’t Hoff equation
dT RT 2

d ln K a r H

dT RT 2
So the increase of the
H 0
r 0
;T Ka temperature will have as
effect the shift of the
reaction to the right side

Thus the increase of the

H 0
r 0
;T Ka temperature will result in
the shift of the reaction to
the left side

Prof. Habil. Dr. Ing. Ileana Rau 26

 12/11/2019

2.3.4.2. Pressure influence on

the equilibrium constant
r G 0
ln K p  
RT
Since rG0 is not depending on pressure Kp is not depending
on pressure. However the pressure has influence on the
equilibrium composition: K  K  P  v
x p

v  0 ; P Kx

v  0 ; P Kx

v  0

Exemple

For the reaction :

CO(g)  SO3(g) CO2  SO2(g)
the values for standard enthalpy and free Gibbs
energy are: : r H 298
0
 44.14 kcal and r G298
0
 44.72 kcal .
Calculate r G400
0
and Kp at 400 K, supposing that
C p  0 cal/K for the temperature range 298 -
400K, and an ideal gases behavior.

Prof. Habil. Dr. Ing. Ileana Rau 27