Chemical Kinetics

Chapter 2

Dr. Harminder Singh

 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.
Dr. Harminder Singh
13.1
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt

Dr. Harminder Singh

13.1
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

Br2 (aq)

393 nm
393 nm Detector
light
D[Br2] a DAbsorption
Dr. Harminder Singh
13.1
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent
slope of
tangent

D[Br2] [Br2]final – [Br2]initial

average rate = - =-
Dt tfinal - tinitial
instantaneous rate = rate for specific
Dr. Harminder Singh instance in time
13.1
 rate a [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
Dr. Harminder Singh
13.1
 2H2O2 (aq) 2H2O (l) + O2 (g)

PV = nRT
n
P= RT = [O2]RT
V
1
[O2] = P
RT

D[O2] 1 DP
rate = =
Dt RT Dt

measure DP over time

Dr. Harminder Singh
13.1
2H2O2 (aq) 2H2O (l) + O2 (g)

Dr. Harminder Singh

13.1
 Reaction Rates and Stoichiometry

2A B

Two moles of A disappear for each mole of B that is formed.

1 D[A] D[B]
rate = - rate =
2 Dt Dt

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

Dr. Harminder Singh

13.1
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

D[CH4] 1 D[O2] D[CO2] 1 D[H2O]

rate = - =- = =
Dt 2 Dt Dt 2 Dt

Dr. Harminder Singh

13.1
 Factors That Affect Reaction Rates
• 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.
• Catalysts
– Speed rxn by changing
mechanism.
• Nature of the reactants
• Radiation
• Surface area

Dr. Harminder Singh

Dr. Harminder Singh
 Molecularity
NH4NO2 → N2 + 2H2O
2HI → H2 + I2
2NO + O2 → 2NO2
Suppose
2NO + 2H2 → N2 + 2H2O
Mechanism:
2NO + H2 → N2 + H2O2
H 2O 2 + H2 → 2H2O
2NO + 2H 2 →
Dr. Harminder Singh
N 2 + 2H2O
 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

Dr. Harminder Singh

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
y=1 Dr. Harminder Singh
13.2
 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

Dr. Harminder Singh

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
[S2O8 ][I ] (0.08 M)(0.034 M)
Dr. Harminder Singh
13.2
 First-Order Reactions
D[A]
A product rate = - rate = k [A]
Dt
D[A]
rate M/s - = k [A]
k= =
M
= 1/s or s-1 Dt
[A]
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

[A] = [A]0exp(-kt) ln[A] = ln[A]0 - kt

Dr. Harminder Singh

13.3
 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]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]
[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

Dr. Harminder Singh

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 ln2 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 = ln2 = 0.693
= 1200 s = 20 minutes
k -4
5.7 x 10 s -1

How do you know decomposition is first order?

Dr. Harminder Singh
units of k (s-1) 13.3
 First-order reaction
A product

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

2 4

3 8

4 16

Dr. Harminder Singh

13.3
 Second-Order Reactions
D[A]
A product rate = - rate = k [A]2
Dt

rate M/s D[A]

k= = = 1/M•s - = k [A]2
[A] 2 M 2
Dt

1 1 [A] is the concentration of A at any time t

= + kt
[A] [A]0 [A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

1
t½ =
k[A]0

Dr. Harminder Singh

13.3
 Zero-Order Reactions
D[A]
A product rate = - rate = k [A]0 = k
Dt

rate D[A]
k= = M/s - =k
[A] 0 Dt

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

[A] = [A]0 - kt
[A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

[A]0
t½ =
2k

Dr. Harminder Singh

13.3
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2

k
1 1 1
2 rate = k [A]2 = + kt t½ =
[A] [A]0 k[A]0

Dr. Harminder Singh

13.3
 Activation Energy
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.

Dr. Harminder Singh

 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.
Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bond breakage and formation.

Dr. Harminder Singh

 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.

Dr. Harminder Singh

 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 barrier. Dr. Harminder Singh
 A+B C+D

Exothermic Reaction Endothermic Reaction

The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
Dr. Harminder Singh
13.4
Temperature Dependence of the Rate Constant

k = A • exp( -Ea/RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

Ea 1
lnk = - + lnA
R T

Dr. Harminder Singh

13.4
 Ea 1
lnk = - + lnA
R T

Dr. Harminder Singh

13.4
 Reaction Mechanisms
• Reactions may occur all at once or through
several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary process.

Dr. Harminder Singh

 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 N 2O 2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Dr. Harminder Singh
13.5
Intermediates are species that appear in a reaction
mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary step
and consumed in a later elementary step.

Elementary step: NO + NO N 2O 2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

The molecularity of a reaction is the number of molecules

reacting in an elementary step.
• Unimolecular reaction – elementary step with 1 molecule
• Bimolecular reaction – elementary step with 2 molecules
• Termolecular reaction – elementary step with 3 molecules
Dr. Harminder Singh
13.5
 Reaction Mechanisms

• The molecularity of a process tells how many molecules

are involved in the process.
• The rate law for an elementary step is written directly
from that step.
Dr. Harminder Singh
 Rate Laws and Elementary Steps

Unimolecular reaction A products rate = k [A]

Bimolecular reaction A+B products rate = k [A][B]

Bimolecular reaction A+A products rate = k [A]2

Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.
The rate-determining step is the slowest step in the
sequence of steps leading to product formation.
Dr. Harminder Singh
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.

Dr. Harminder Singh

 The experimental rate law for the reaction between NO2
and CO to produce NO and CO2 is rate = k[NO2]2. The
reaction is believed to occur via two steps:
Step 1: NO2 + NO2 NO + NO3
Step 2: NO3 + CO NO2 + CO2
What is the equation for the overall reaction?
NO2+ CO NO + CO2
What is the intermediate?
NO3

What can you say about the relative rates of steps 1 and 2?
rate = k[NO2]2 is the rate law for step 1 so
step 1 mustDr.be slower than step 2
Harminder Singh
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.

Dr. Harminder Singh

 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.

Dr. Harminder Singh

 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.

Dr. Harminder Singh

 Fast Initial Step

• The rate law for this reaction is found

(experimentally) to be

• Because termolecular (= trimolecular) processes

are rare, this rate law suggests a two-step
mechanism.
Dr. Harminder Singh
 Fast Initial Step
• A proposed mechanism is

Step 1 is an equilibrium-
it includes the forward and reverse reactions.

Dr. Harminder Singh

 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

• But how can weDr.find [NOBr

Harminder Singh 2]?
 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
Dr. Harminder Singh
 Fast Initial Step

• Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
k−1
[NO] [Br 2 ] = [NOBr 2 ]
Dr. Harminder Singh
 Fast Initial Step

Substituting this expression for [NOBr2] in

the rate law for the rate-determining step
gives

Dr. Harminder Singh

A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k = A • exp( -Ea/RT ) Ea k

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

Ea‘ < Ea
Dr. Harminder Singh
13.6
In heterogeneous catalysis, the reactants and the catalysts
are in different phases.

• Haber synthesis of ammonia

• Ostwald process for the production of nitric acid
• Catalytic converters

In homogeneous catalysis, the reactants and the catalysts

are dispersed in a single phase, usually liquid.

• Acid catalysis
• Base catalysis

Dr. Harminder Singh

13.6
 Haber Process

Fe/Al2O3/K2O
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst

Dr. Harminder Singh

13.6
 Ostwald Process
Pt catalyst
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)

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

2NO2 (g) + H2O (l) HNO2 (aq) + HNO3 (aq)

Hot Pt wire
Pt-Rh catalysts used over NH3 solution
Dr. Harminder Singh
in Ostwald process 13.6
 Catalytic Converters

catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O

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

Dr. Harminder Singh

13.6
Enzyme Catalysis

Dr. Harminder Singh

13.6
 enzyme
uncatalyzed catalyzed

Dr. Harminder Singh

13.6