Chemistry, The Central Science, 10th edition AP edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 14: Chemical Kinetics

John D. Bookstaver, St. Charles Community College, St. Peters, MO,
 2006, Prentice Hall, Inc.

(ppt modified for our requirements)

Chemical
Kinetics
 Resources and Activities
Kinetics • Textbook - chapter 14 & ppt file
• Online practice quiz
Studies the rate • Lab activities
at which a • POGIL activities
chemical process • Chem Guy video lecture series on
Chemical Kinetics (several)
occurs. http://www.cosmolearning.com/courses/ap-
chemistry-with-chemguy/video-lectures/
• Chemtour videos from Norton &
Besides information about the speed
Animations from Glencoe
at which reactions occur, kinetics also
sheds light on the reaction mechanism
(exactly how the reaction occurs).
 Activities and Problem set for chapter 14 (due date_______)

Lab activities: Chapter 14 reading guide and practice

problems packet
 Kinetics of a reaction (wet lab)
 Virtual lab (Iodine-Clock expt.) In class preview and then Independent work -
students to view animations & interactive
 http://www.chem.iastate.edu activities (5 in total from Norton) and write
summary notes on each. These summaries are
/group/Greenbowe/sections/ to be included in your portfolio.
projectfolder/flashfiles/kineti
cs2/iodine_clock.html Animations to view in class and at home:
http://www.wwnorton.com/college/chemistry/gilbert2/co
ntents/ch14/studyplan.asp
(Reaction rates, Reaction order, Arrhenius
POGILS (2) : Chemical Kinetics; equation, Collision Theory, Reaction
mechanisms)
Reaction Mechanisms

Additional resources to explore (summaries not

Online practice quiz ch 14 due mandatory)
by_____ http://glencoe.mcgraw-
hill.com/sites/0023654666/student_view0/chapter1
3/animations_center.html#
(catalysis, Kinetics simulation)
 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular

Mechanisms scale processes.

Chemical
Kinetics
 Vocabulary terms
Reaction rate
(units M• s-1 ≡ mol• L-1• s-1) Reaction mechanisms
• Instantaneous rate  Elementary
• Initial rate (instantaneous rate at t = 0) reactions/processes
• Average rate of reaction  Molecularity
• Rate constant (diff units possible  Unimolecular, bimolecular,
depending on molecularity of reaction) termolecular
Reaction orders Catalysts
• Overall reaction order  Homogeneous &
• 1st order heterogeneous
• 2nd order  Adsorption vs absorbtion
Collision Model/theory  Enzymes, substrates, active
• Activation energy (Ea) sites, lock& key model
• Activated complex/transition state
• Arrhenius equation
 Important equations
aA + bB cC+ dD Rate = k [A]x[B]y
_____________________________________
For a first order reaction A → products

D[A]
rate = - ln [A]t = − kt + ln [A]0
Dt
rate = k [A]

Because [A] at t1/2 is one-half of the original [A], [A]t = ½[A]0=0.5[A]0

0.5 [A]0 0.693

ln = −kt = t1/2
[A]0 1/2 k
 Important equations
For a second order reaction A + B → products
D[A]
rate = - rate = k [A] [B] rate = k [A]2
Dt

Half life for second order reaction

1
= t1/2
k[A]0
 Important equations (to complete)
Arrhenius equation k = A e−Ea/RT

ln(k) = ln A - Ea /RT

Chemical
Kinetics
Factors That Affect Reaction Rates
• Physical State of the Reactants
 In order to react, molecules must come in contact with
each other.
 The more homogeneous the mixture of reactants, the
faster the molecules can react.
• Concentration of Reactants
 As the concentration of reactants increases, so does the
likelihood that reactant molecules will collide.
• Temperature
 At higher temperatures, reactant molecules have more
kinetic energy, move faster, and collide more often and
with greater energy.
Factors That Affect Reaction Rates
• Presence of a Catalyst
 Catalysts speed up reactions by changing the
mechanism of the reaction.
 Catalysts are not consumed during the course of the
reaction.

Chemical
Kinetics
 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt

13.1
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

In this reaction, the

concentration of
butyl chloride,
C4H9Cl, was
measured at various
times.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

The average rate of

the reaction over
each interval is the
change in
concentration divided
by the change in time:
D[C4H9Cl]
Average rate = Dt
Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• Note that the average

rate decreases as the
reaction proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• A plot of concentration
vs. time for this reaction
yields a curve like this.
• The slope of a line
tangent to the curve at
any point is the
instantaneous rate at
that time.

Chemical
Kinetics
 Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• All reactions slow down

over time.
• Therefore, the best
indicator of the rate of a
reaction is the
instantaneous rate near
the beginning.

Chemical
Kinetics
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio

of C4H9Cl to C4H9OH is
1:1.
• Thus, the rate of
disappearance of
C4H9Cl is the same as
the rate of appearance
of C4H9OH.

-D[C4H9Cl] D[C4H9OH]
Rate = =
Dt Dt Chemical
Kinetics
Reaction Rates and Stoichiometry

• What if the ratio is not 1:1?

2 HI(g)  H2(g) + I2(g)
•Therefore,
Rate = − 1 D[HI] = D[I2]
2 Dt Dt

Chemical
Kinetics
 Reaction Rates and Stoichiometry

• To generalize, then, for the reaction

aA + bB cC + dD

1 D[A] 1 D[B] 1 D[C] 1 D[D]

Rate = − =− = =
a Dt b Dt c Dt d Dt

Chemical
Kinetics
 Concentration and Rate
One can gain information about the rate of a reaction by
seeing how the rate changes with changes in
concentration.

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Comparing Experiments 1 and 2, when [NH4+]
doubles, the initial rate doubles.
 Concentration and Rate

NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Likewise, comparing Experiments 5 and 6,

when [NO2−] doubles, the initial rate doubles.
Chemical
Kinetics
 Concentration and Rate
• This means
Rate  [NH4+]
Rate  [NO2−]
Rate  [NH ] [NO2 ]
+ −

or
Rate = k [NH4+] [NO2−]
• This equation is called the rate law, and
k is the rate constant.
Chemical
Kinetics
 Rate Laws
• A rate law shows the relationship between the
reaction rate and the concentrations of reactants.
• The exponents tell the order of the reaction with
respect to each reactant.
• This reaction is
First-order in [NH4+]
First-order in [NO2−]
• The overall reaction order can be found by adding
the exponents on the reactants in the rate law.
• This reaction is second-order overall.
 The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD

Rate = k [A]x[B]y

reaction is xth order in A

reaction is yth order in B
reaction is (x +y)th order overall
Chemical
Kinetics
13.2
 F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant

Rate doubles
x=1

Quadruple [ClO2] with [F2] constant rate = k [F2][ClO2]

Rate quadruples
Chemical
y=1 Kinetics
13.2
 Run # Initial [A] Initial [B] Initial Rate (v0)
([A]0) ([B]0)
1 1.00 M 1.00 M 1.25 x 10-2 M/s
2 1.00 M 2.00 M 2.5 x 10-2 M/s
3 2.00 M 2.00 M 2.5 x 10-2 M/s

What is the order with respect to A? 0

What is the order with respect to B? 1

What is the overall order of the 1

reaction?

Chemical
Kinetics
 Initial Rate
[Cl2(g)] (mol dm-
[NO(g)] (mol dm-3) 3) (mol dm-3 s-
1)

0.250 0.250 1.43 x 10-6

0.250 0.500 2.86 x 10-6
0.500 0.500 1.14 x 10-5
What is the order with respect to Cl2? 1

What is the order with respect to NO? 2

What is the overall order of the

reaction? 3

Chemical
Kinetics
 Rate Laws

• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1
Chemical
Kinetics
13.2
 Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate
Experiment [S2O82-] [I-]
(M/s) rate = k [S2O82-]x[I-]y
1 0.08 0.034 2.2 x 10-4 y=1
2 0.08 0.017 1.1 x 10-4 x=1
3 0.16 0.017 2.2 x 10-4 rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2)

Double [S2O82-], rate doubles (experiment 2 & 3)

rate 2.2 x 10-4 M/s

k= 2- -
= = 0.08/M•s Chemical
[S2O8 ][I ] (0.08 M)(0.034 M) Kinetics
13.2
 Integrated Rate Laws
Using calculus to integrate the rate law
for a first-order process gives us

[A]t
ln = −kt
[A]0
Where
[A]0 is the initial concentration of A.

[A]t is the concentration of A at some time, t,

during the course of the reaction.
 Integrated Rate Laws

Manipulating this equation produces…

[A]t
ln = −kt
[A]0
ln [A]t − ln [A]0 = − kt
ln [A]t = − kt + ln [A]0
…which is in the form
y = mx + b
Chemical
Kinetics
 First-Order Processes

ln [A]t = -kt + ln [A]0

Therefore, if a reaction is first-order, a

plot of ln [A] vs. t will yield a straight
line, and the slope of the line will be -k.

Chemical
Kinetics
 First-Order Reactions (other forms of equations)

D[A]
rate = - rate = k [A] [A] = [A]0e-kt
Dt

[A] is the concentration of A at any time t

ln[A] - ln[A]0 = - kt
[A]0 is the concentration of A at time t=0
First-Order Processes

Consider the process in

which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

Chemical
Kinetics
 First-Order Processes
CH3NC CH3CN

This data was

collected for this
reaction at
198.9°C.

Chemical
Kinetics
 First-Order Processes

• When ln P is plotted as a function of time, a

straight line results.
• Therefore,
 The process is first-order.
Chemical
 k is the negative slope: 5.1  10-5 s−1. Kinetics
 The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?
[A] = [A]0e-kt
[A]0 = 0.88 M
ln[A] - ln[A]0 = - kt [A] = 0.14 M
ln[A]0 - ln[A] = kt
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1

Chemical
Kinetics
13.3
 First-Order Reactions

The half-life, t½, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.

t½ = t when [A] = [A]0/2

[A]0
ln
[A]0/2 ln 2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
t½ = ln 2 = 0.693
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1

How do you know decomposition is first order?

units of k (s-1)
 First-order reaction
A product

# of
half-lives [A] = [A]0/n
1 2

2 4

3 8

4 16
Chemical
Kinetics
13.3
 Second-Order Reactions

D[A]
rate = - rate = k [A]2 [A] is the concentration of A at any time t
Dt [A]0 is the concentration of A at time t=0

1 1 Half life for second order

- = kt
[A] [A]0 t½ = t when [A] = [A]0/2
1
t½ =
k[A]0

Chemical
Kinetics

13.3
 Second-Order Processes

Similarly, integrating the rate law for a

process that is second-order in reactant
A, we get
1 1
= −kt +
[A]t [A]0
also in the form
y = mx + b
Chemical
Kinetics
 Second-Order Processes
1 1
= −kt +
[A]t [A]0
So if a process is second-order in A, a
plot of 1/[A] vs. t will yield a straight line,
and the slope of that line is k.

Chemical
Kinetics
 Second-Order Processes
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields data comparable to this:

Time (s) [NO2], M

0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481 Chemical
300.0 0.00380 Kinetics
 Second-Order Processes
• Graphing ln [NO2] vs. t
yields:
• The plot is not a straight
line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 −4.610
50.0 0.00787 −4.845
100.0 0.00649 −5.038
200.0 0.00481 −5.337 Chemical
300.0 0.00380 −5.573 Kinetics
 Second-Order Processes
• Graphing ln
1/[NO2] vs. t,
however, gives this
plot.
• Because this is a
Time (s) [NO2], M 1/[NO2] straight line, the
0.0 0.01000 100
process is second-
order in [A].
50.0 0.00787 127
100.0 0.00649 154
200.0 0.00481 208 Chemical
Kinetics
300.0 0.00380 263
Half-Life

• Half-life is defined
as the time required
for one-half of a
reactant to react.
• Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.
 Half-Life
For a first-order process, this becomes
0.5 [A]0
ln
[A]0 = −kt 1/2

ln 0.5 = −kt1/2

−0.693 = −kt1/2
0.693
NOTE: For a first-order = t1/2
k
process, the half-life
Chemical
does not depend on [A]0. Kinetics
 Half-Life
For a second-order process,
1 1
= kt1/2 +
0.5 [A]0 [A]0

2 1
= kt1/2 +
[A]0 [A]0

2 − 1 = 1 = kt
1/2
[A]0 [A] 0

1
= t1/2
k[A]0 Chemical
Kinetics
Temperature and Rate

• Generally, as temperature
increases, so does the
reaction rate.
• This is because k is
temperature dependent.

Chemical
Kinetics
 The Collision Model

• In a chemical reaction, bonds are

broken and new bonds are formed.
• Molecules can only react if they collide
with each other.

Chemical
Kinetics
 The Collision Model

Furthermore, molecules must collide with the

correct orientation and with enough energy to
cause bond breakage and formation.

Chemical
Kinetics
 Activation Energy
• In other words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll
up the hill with enough energy, a reaction cannot
occur unless the molecules possess sufficient energy
to get over the activation energy barrier.

Chemical
Kinetics
 Reaction Coordinate Diagrams

It is helpful to
visualize energy
changes
throughout a
process on a
reaction coordinate
diagram like this
one for the
rearrangement of
methyl isonitrile.
Chemical
Kinetics
 Reaction Coordinate Diagrams
• It shows the energy of
the reactants and
products (and,
therefore, DE).
• The high point on the
diagram is the transition
state.
• The species present at the transition state is
called the activated complex.
• The energy gap between the reactants and the
activated complex is the activation energy
Chemical
barrier. Kinetics
Maxwell–Boltzmann Distributions

• Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.
• At any temperature there is a wide
distribution of kinetic energies. Chemical
Kinetics
Maxwell–Boltzmann Distributions

• As the temperature
increases, the curve
flattens and
broadens.
• Thus at higher
temperatures, a
larger population of
molecules has
higher energy.
Chemical
Kinetics
Maxwell–Boltzmann Distributions
• If the dotted line represents the activation
energy, as the temperature increases, so does
the fraction of molecules that can overcome
the activation energy barrier.

• As a result, the
reaction rate
increases.

Chemical
Kinetics
 Maxwell–Boltzmann Distributions
This fraction of molecules can be found through the
expression −E /RT
f=e a

where R is the gas constant and T is the Kelvin

temperature.

Chemical
Kinetics
 Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:

k = A e−Ea/RT

where A is the frequency factor, a number that

represents the likelihood that collisions would
occur with the proper orientation for reaction.
Chemical
Kinetics
 Arrhenius Equation
Taking the natural
logarithm of both
sides, the equation
becomes
1
ln k = -Ea ( ) + ln A
RT
y = mx + b

Therefore, if k is determined experimentally at

several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T. Chemical
Kinetics
 Reaction Mechanisms
The sequence of events that describes
the actual process by which reactants
become products is called the reaction
mechanism.

• Reactions may occur all at once or

through several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary
process.
 Reaction Mechanisms

The molecularity of a process tells how many

molecules are involved in the process.

Chemical
Kinetics
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product

formation is the reaction mechanism.

2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the reaction!

Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Chemical
Overall reaction: 2NO + O2 2NO2 Kinetics
13.5
 Multistep Mechanisms

• In a multistep process, one of the steps will

be slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.

Chemical
Kinetics
 Slow Initial Step
NO2 (g) + CO (g)  NO (g) + CO2 (g)

• The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
• This suggests the reaction occurs in two steps.
Chemical
Kinetics
 Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second
step.
• As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.

Chemical
Kinetics
 Fast Initial Step
2 NO (g) + Br2 (g)  2 NOBr (g)

• The rate law for this reaction is found to

be
Rate = k [NO]2 [Br2]
• Because termolecular processes are
rare, this rate law suggests a two-step
mechanism.
Chemical
Kinetics
 Fast Initial Step

• A proposed mechanism is
Step 1: NO + Br2 NOBr2 (fast)
Step 2: NOBr2 + NO  2 NOBr (slow)

Step 1 includes the forward and reverse reactions.

Chemical
Kinetics
 Fast Initial Step

• The rate of the overall reaction depends

upon the rate of the slow step.
• The rate law for that step would be

Rate = k2 [NOBr2] [NO]

• But how can we find [NOBr2]?

Chemical
Kinetics
 Fast Initial Step

• NOBr2 can react two ways:

With NO to form NOBr
By decomposition to reform NO and Br2
• The reactants and products of the first
step are in equilibrium with each other.
• Therefore,
Ratef = Rater
Chemical
Kinetics
 Fast Initial Step

• Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

• Solving for [NOBr2] gives us

k1
k−1
[NO] [Br 2] = [NOBr2]
Chemical
Kinetics
 Fast Initial Step

Substituting this expression for [NOBr2]

in the rate law for the rate-determining
step gives
k2k1
Rate = [NO] [Br2] [NO]
k−1

= k [NO]2 [Br2]

Chemical
Kinetics
 Catalysts
• Catalysts increase the rate of a reaction by
decreasing the activation energy of the
reaction.
• Catalysts change the mechanism by which
the process occurs.

Chemical
Kinetics
 Catalysts

One way a
catalyst can
speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.

Chemical
Kinetics
 Catalytic Converters

catalytic
CO + Unburned Hydrocarbons + O2 converter
CO2 + H2O

catalytic
2NO + 2NO2 converter 2N2 + 3O2

Chemical
Kinetics
13.6
Enzyme Catalysis

Chemical
Kinetics
13.6