Chapter 11

Chemical Kinetics

1
Rates of Chemical Reaction
• Chemical kinetics deals with the rates of reactions.
• In a chemical process, reactant/reactants are consumed up as time
elapses and the product or products are formed
• Eg. A (Reactants) B (Products)
• Every reaction has a rate and is unique in respect of chemical kinetic study

2
• The rate of a reaction is defined as change in concentration of reactants or products per unit time

A (Reactants) B (Products)

• Rate of a reaction =

• Rate of a reaction =

• The kinetics of a chemical reaction can be studied either with respect to the reactants or products.

• Rate = -
 Units
• mol L1 s1 , M/s, M/min, or M/h

3
Stoichiometry and Rate Rate 5 Change in concentration
Elapsed time

N2 + 2O2 2NO2

Rate = -

 The increase in the concentration of the product, the rate of a reaction is a positive number.
 The decrease in the concentration of the reactant, the rate of a reaction is a negative number.

Rate = Rate = 

= the stoichiometric coefficient of the product

react = the stoichiometric coefficient of the reactant

4
Example Problem 11.1
The production of NO2 from nitrogen and oxygen, N2 + 2O2 2NO2, was studied in an experiment, and the
rate of nitrogen consumption was measured as 2.5  105 mol L1 s1. What was the rate of NO2 production in
this experiment?
solution
N2 + 2O2 2NO2

Rate = -

- = 2.5  105 mol L1 s1

2.5  105 mol L1 s1 =

= 2(2.5  105 mol L1 s1)

= 5.0  105 mol L1 s1

5
 Check Your Understanding
Nitrogen forms a number of different oxides. Dinitrogen pentoxide decomposes to form O2 (along with
nitrogen dioxide) by the reaction 2N2O5 4NO2 + O2. If the rate of disappearance of N2O5 is 4.0  106
mol L1 s1, what is the rate of appearance of each product?

Average Rate and Instantaneous Rate

 For the average rate, two concentrations are measured at times separated by a finite difference, and
the slope of the line between them gives the rate.
 The instantaneous rate refers to the rate at a single moment, and it is given by the slope of a line
tangent to the curve defined by the change in concentration versus time.

6
 Rate Laws and the Concentration Dependence of Rates
 Rate law for a chemical reaction is a mathematical expression that provides a relationship between
the rate of the reaction and the concentration of the reactants participating in it.
 A rate law are two forms of (i) differential rate law (ii) integrated rate law.
 Differential rate law - The reaction rate in terms of changes in the concentration of one or more reactants over a
specific time interval.

 For a reaction X + Y Z, the rate of reaction can be described by an equation of the form
Rate = k[X]m[Y]n

 where the rate depends on a rate constant (k) and the reactant concentrations [X] and [Y].
 m and norder of reaction
 For example, if m = 1, the reaction is first order with respect to reactant X; if m = 2, the reaction is second
order with respect to X.
A + B C
Rate = k[A][B]
 second order overall but first order with respect to reactant A and first order with respect to reactant B .

7
  If the rate constant is small, the reaction is likely to proceed slowly.
 A large rate constant indicates a rapid reaction.
 The value of the rate constant depends on the temperature of the reaction.
 The units for k of a first-order reaction s 1, for second-order reaction L mol1 s1.

Example Problem 11.2

In the following rate laws, determine the orders with respect to each substance and the overall order of the
reaction. (a) Rate = k[A]2[B], (b) Rate = k[A][B]1/2
solution
The order with respect to A = 2. The order with respect to B = 1. The overall order = 3.
The order with respect to A = 1. The order with respect to B = 1/2. The overall order = 3/2

Check Your Understanding

The following reactions were studied in the laboratory, and their respective rate laws were determined. Find
the orders with respect to each reactant and the overall order for each of the following reactions.
H2(g) + Br2(g) 2HBr; rate = k[H2][Br2]
2N2O5 4NO2 + O2; rate = k[N2O5]
8
 Determination of the Rate Law

 The simple reaction in which some substance A is the only reactant.

A B
Rate = k[A]n

 The order of reaction (n) is usually an integer and is rarely greater than two (0, 1, 2).

 1. If n = 0, doubling the concentration of A does not change the rate at all because any quantity raised to the 0
power is 1.
 2. If n = 1, doubling the concentration of A doubles the rate.
 3. If n = 2, doubling the concentration of A increases the rate by a factor of 4 (because 22 = 4).

9
 In a zero-order reaction, the rate of the reaction is completely independent of the reactant concentration. This
means that the rate is always equal to the rate constant, regardless of the reactant concentration.

 In a first-order reaction, the rate of the reaction is directly proportional to the reactant concentration.
A B
The rate law for this reaction is, Rate = kA
If you doubling the concentration of A, the rate of the reaction will also double.
Rate = k2A = 2kA

 In a second-order reaction, the rate of the reaction is proportional to the square of the reactant concentration.
2A B
The rate law for this reaction is, Rate = kA2
If you doubling the concentration of A, the rate of the reaction will quadruple.
Rate = k2A2 = 4kA2

10
Example Problem 11.3
The decomposition of N2O5:
2N2O5(g) 4NO2(g) + O2(g)
Consider the following data for the kinetics of this reaction:
Experiment Initial [N2O5] Initial Rate of Reaction
(mol L-1) (mol L-1s-1)

1 3.0103 9.0107

2 9.0103 2.7106

Determine the rate law and rate constant for this reaction at the temperature of these experiments.
Solution
The initial concentration triples from the first to the second experiment: 3(3.0103) = 9.0103 mol L1
the rate also triples: 3(9.0107) = 2.7106 mol L1 s
the reaction must be first order with respect to N2O5: Rate = k[N2O5]

11
7 1 1 3 1
Check Your Understanding
Would the result change if we used Experiment 2 to determine the rate constant?

Example Problem 11.4

In the sort of complex mixture of gases we might find in urban air, many chemical reactions may occur. For
example, NO2, which we’ve mentioned as a key species in the formation of ozone, can also react with ozone.
NO2+O3 NO3+O2
In a study of this reaction, three experiments were run at the same temperature, and the following data obtained:
Experiment Initial [NO2] Initial [O3] Initial Rate of Reaction
(mol L-1) (mol L-1) (mol L-1s-1)
1 2.3105 3.0105 1.0105
2 4.6105 3.0105 2.1105
3 4.6105 6.0105 4.2105

Determine the rate law and rate constant for this reaction.
Solution
 Order with respect to NO2
From Experiments 1 and 2, if we double [NO2] while holding [O3] constant, we double the rate.
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The order in NO2 is 1.
 Order with respect to O3
From Experiments 2 and 3, if we double [O3] while holding [NO2] constant, we double the rate. Thus the
order in O3 is 1. The rate law is
Rate = k[NO2][O3]

2.1105 mol L1 s1 = k(4.6105 mol L1)(3.0105 mol L1)

k = 1.5104 L mol1 s1

Check Your understanding

Why are the units for k in this example different from the units in Example Problem 11.3?

13
 Different Types of Order of Reaction
 1st Order Reactions
Reactions in which the rate varies with concentration of a single species, and the change in
concentration is exponential, so that a plot of ln (concentration) vs time is linear. The stoichiometric
coefficient is 1. e.g. Radioactive decay
 2nd Order Reactions of Class I
Reaction in which the rate varies with concentration of a single species, but the stoichiometric
coefficient is 2. the rate varies with the reciprocal of the concentration so that a plot of 1/(concentration) vs
time is linear.
 2nd Order Reactions of Class II
Reactions in which the rate varies with the concentration of two substances, each of which has a
stoichiometric coefficient of 1. A pot of on (conc. A/ conc. B) vs time is linear.
 Higher Order reactions
Reactions in which more than two species are involved, or on species reacts with stoichiometric
coefficient
 Zero Order Reactions
Many reactions in biochemistry appear to occur at a rate independent of substrate concentration.
In enzyme-catalyzed reaction, the rate is determined by the concentration of enzyme, as long as the
14
substrate is in excess, so that the rate is saturated.
Integrated Rate Laws Tim

 The form of the integrated rate law depends on the order of reaction.

Zero-Order Integrated Rate Law

 The simplest rate law is for a zero-order reaction:
Rate = k[A]0 = k
 The rate of the reaction will not change as the reactants are consumed. The integrated rate law is given by
[A]t = [A]0  kt
[A]t = kt + [A]0
[N2O]
y = mx + b For a zero-order reaction, a plot of
reactant concentration vs. time is
(Derivation, Page; 373) linear. The slope of the line is k

time
Figure The decomposition of N2O over gold is a zero-order process, for which the reactant concentration decreases linearly
as a function of time
15
st-Order Integrated Rate Law
or a first-order reaction with a single reactant, A, the integrated rate law is given by the equations

ln = kt or [A]t = [A]0ekt

A]0 represents the initial concentration of the reactant at time t = 0

ln[A] = kt + ln[A]0

y = mx + b

For a first-order reaction, plotting the natural log

ln[NO2] of the concentration vs. time gives a straight line.
The slope of that line is equal to -k

Time
Figure The first-order integrated rate law predicts that a plot of the natural logarithm of reactant concentration versus time
should be linear. 16
Example Problem 11.5
The photodissociation of NO2 by ultraviolet wavelengths of sunlight initiates the formation of photochemical smog. It is a
first-order reaction with a rate constant of 2.95  10–3 min–1 at a given level of light exposure.
NO2 + h NO + O
Consider a laboratory experiment in which a sample of nitrogen dioxide is exposed to UV radiation at an intensity chosen to
mimic conditions for the formation of smog on a summer day. ◂ If the initial concentration of NO 2 is 7.5 mM, what will the
concentration be after 2 hours?
Solution
2.0 hour() = 120 min

[NO2] = [NO2]0 ekt

= 7.5 mM (
= 5.3 mM

Check Your understanding

Another important photochemical reaction occurs in the stratosphere, where ozone interacts with UV radiation and is broken
down into O2 and O atoms. At 40 km above the Earth’s surface, this reaction proceeds with a first- order rate constant of 1.0
 103 s1. If an experiment were to simulate these conditions, how long would it take for an initial ozone concentration of 5.0
mM to fall to 2.1 mM?
17
Second-Order Integrated Rate Law
 For second-order reactions, the mathematical form of the integrated rate law is quite different from the first-order
reactions. For the consumption of reactant A, the integrated rate law is
 = kt
 [A]t is the concentration of X at time t and [A]0 is the initial concentration.
 The form of the integrated rate law for second-order kinetics suggests the nature of a linear plot; in this case, we must plot
1/[A] versus time.

Example Problem 11.6

Photodissociation by UV radiation is not the only possible fate of NO 2 in urban air. An ordinary decomposition reaction, in
which NO2 reacts to form NO and O2, is also possible. This reaction was studied at 370°C by a student, and the following data
were obtained:
Time (s) [NO2] (mol L-1)
0.0 3.0010-1
5.0 1.9710-2
10.0 1.0010-2
15.0 7.0010-3
20.0 5.2010-3
25.0 4.1010-3
30.0 3.5010-3 18
Based on these data, determine the order of this reaction and the rate constant.
Solution
See Page 377 and 378.

Check Your understanding

N2O5(g) can decompose to form NO2 and O2. The following data were obtained for this decomposition at 300°C. Determine the
order of the reaction and the rate constant.
Time (s) [N2O5] (mol L-1)

0.0 0.1500

300.0 0.0729

600.0 0.0316

900.0 0.0203

1200.0 0.0108

1500.0 0.0051

1800.0 0.0020
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Half-Life
 The half-life of a reactant is the time it takes for its concentration to fall to one-half its original value.
 The interaction of stratospheric ozone with UV light leads to the reaction:
O3 + h O + O2
1

0.8

0.6
PO3 (atm)
0.4
0.2

0
0 20 40 60 80 100
Time (h)

 The experiment begins with PO3 =1 atm and then PO3 drops off as time goes by.
 The dashed lines in the figure show that the partial pressure reaches one-half its initial value after about 19 hours.
 The reaction continues, and the pressure falls further, reaching 0.25 atm, or one-fourth of its initial value after about 38
hours.
 In the first 19-hour period, the ozone pressure decreased by one-half its value, from 1 to 0.5. Between about 19 hours and
38 hours on the graph, the pressure again decreased by one-half, this time falling from 0.5 to 0.25. 20
Mathematical expression for the half-life of a first-order reaction, when the reaction has been proceeding for one half-life
(t1/2), the concentration of the reactant must be [A] = [A] 0.
By substituting the first-order integrated rate law,
ln = kt

ln() = kt1/2

ln() = kt1/2

ln =  kt1/2

ln 1  ln 2 = kt1/2

ln 2 = kt1/2

t1/2 = = (The units of rate constant , k and the half-life, t1/2 are consistent.)
 k does not depend on the amount of substance present, neither does t1/2.
 The half-life is most used to describe the kinetics of nuclear decay. All radioactive decay processes follow first-order
kinetics. (For nuclear decay, the half-life is also independent of temperature).
 The t1/2 of first-order reaction is independent of initial concentration of reactant. If the rate constant is small, the half-life
must be long. 21
Example Problem 11.7
The rate of the photodissociation of ozone in the example shown in Figure 11.7 may seem slow. But it is actually tremendously
faster than what we would see in the absence of ultraviolet light. The rate constant, k, for the thermal decomposition of ozone
in the dark at 25°C is just 3  1026 s1. What is the half-life of ozone under these conditions?
Solution
t1/2 = = = 2  s

Check Your understanding

The half-life of the photochemical decomposition of N2O5 in the stratosphere (at 40 km) is roughly 43,000 s. What
is the rate constant for the reaction?

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 Factors Affecting the Rate of Reaction

 Concentration of Reactants
- Differential rate Law & order of reaction
- Integrated rate Law & order of reaction
 Temperature
- Collision model
- Arrhenius equation
 Presence of a Catalyst
 Surface Area of the Reactants

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Temperature and Kinetics
Temperature Effects and Molecules That React
 The kinetic-molecular theory says that molecules interact with one another only through collisions. So, for two molecules to
react, first they must collide.
At lower temperatures,
molecular speeds are

Number of molecules
lower.
Low T
High T At higher temperatures,
more molecules will be
moving with the higher
speeds needed to
produce reactive
collisions.

This is the minimum velocity Speed

needed to produce a collision with
sufficient kinetic energy to allow
 Higher temperatures mean molecules possess more kinetic energy, leading to faster movement and more frequent
reaction.

collisions.
 At the higher temperature, a larger fraction of the molecules moves at high speeds. Thus, at higher temperatures, reactions
tend to proceed more quickly because more of the collisions between reactants have the high energies needed to bring
about reaction. As temperature increases, the reaction rate increases.
 Why do reactions require high-energy collisions?
Chemical reactions involve the breaking and forming of chemical bonds. From thermodynamics, breaking bonds require
energy input and forming bonds liberates energy. Before new bonds can form, old ones must break, or at least begin24to break.
So, many chemical reactions need energy input at the outset to start breaking bonds in reactants.
 The activation energy is
sometimes called an
activation barrier because on
a graph like this it looks like a
barrier that the reactants
Activation energ must overcome to produce
If an O atom strikes the nitrogen products.
Reactants
end of an N2O molecule, it cannot
react to form molecular oxygen.

Energy
‡

Products

Reaction progress is a
If the O atom strikes the oxygen end measure of the extent of bond Reaction progress
of an N2O molecule, it is able to form
breaking and forming as a
an O=O bond, leading to N2 and O2 as
reaction proceeds.
products.
 Effective collisions: For a reaction to occur, molecules must collide with sufficient energy (activation energy) and proper
orientation. (The minimum energy required to initiate a chemical reaction is called the activation energy, Ea. The value of
Ea varies within reactions. The energy barrier between the starting molecule and the highest energy along the reaction
pathway is the activation energy, Ea. The particular arrangement of atoms at the top of the barrier – the activated complex
or transition state.)
 In Figure , a collision between a molecule of N2O and an oxygen atom may or may not lead to a reaction, depending on the
geometry of the collision.
 At the moment of an effective collision, both bond breaking and bond formation are occurring.
 For an instant, as bond rearrangement is occurring, an unstable intermediate species, called an activated complex, exists
in the reaction mixture. The activated complex represents the highest energy point along the route from reactants 25 to
-15
Arrhenius equation
 What is Arrhenius Behavior?
Most chemical reactions speed up when you increase the temperature. The Arrhenius equation describes the relationship
between temperature and rate constant (k) of a reaction.
k = Ae  Ea/RT
where, Ea = the activation energy
R = the universal gas constant (8.314 J/mol.K)
T = the temperature (in kelvins),
A = a proportionality constant called the frequency factor or pre-exponential factor
 The rate of reaction is exponentially related to the temperature. This means that a small change in temperature can lead
to a big change in reaction rate. The Arrhenius equation can be used to determine the activation energy and predict the
reaction rate.
As increases, k will be smaller, and smaller rate constants correspond to slower reactions..
Taking natural log of both sides,
ln k = + ln A
ln k =
y = mx + b
Y axis = ln k
X axis = 1/T
Slope =
Intercept = ln A
(The plot of ln k versus 1/T should be a straight line).
26
Example Problem 11.8
Once ozone forms in photochemical smog, there are a number of reactions by which it is subsequently destroyed. One such
reaction occurs when ozone molecules encounter hydroxyl radicals:
HO  (g) O3(g) HO2  (g) + O2(g)
The following values for the rate constant, k, for this reaction were measured in experiments at various temperatures:

k (L mol-1 s-1) Temperature (K)

1.0107 220
5.1107 340
1.1108 450

(a) Does this reaction display Arrhenius behavior? (b) Estimate the activation energy from these data.
Solution

k (L mol-1 s-1) Ln k Temperature (K) 1/T (K-1)

1.0107 16.1 220 4.5103
5.1107 17.7 340 2.9103
1.1108 18.5 450 2.2103

27
 19.0
ln
k
18.5

18.0

17.5

ln k 17.0

16.5

16.0

15.5 0.005
0 0.001 0.002 0.003 0.004
1/T (K–1)

(a) Yes, the reaction does exhibit Arrhenius behavior.

(b) Slope =
= 1.04 K

= (1.04K) (8.314 J K-1 mol-1 )

= 8.7 J mol-1 = 8.7 kJmol-1

28
Check Your understanding
Once generated, HO2 may react with carbon monoxide to reform the hydroxyl radical and carbon dioxide. This reaction
plays a role in ozone pollution in major cities. Assume that an experiment to determine the rate constant of this reaction
provides the data tabulated here. What is the activation energy of this reaction?

k (L) Temperature (K)

5.9 301
4.7 650

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Reaction Mechanisms
Chapman cycle
 The Chapman cycle is a series of reactions that occur in the stratosphere, where oxygen molecules and ultraviolet rays
interact to create ozone. The cycle is responsible for the concentration of ozone in the stratosphere.
 The importance of the Chapman cycle lies in the detailed steps involved.
 The Chapman cycle can be described by the following series of individual reactions:
O2 + h O+O
O + O2 + M , O3 + M*
O3 + h O2 + O
O + O3 2 O2

 In the second reaction, we include an unidentified species, written as “M.”

 The M* designation on the right-hand side of that reaction means that species M is in a higher energy state.
 This set of steps represent the reaction mechanism for the Chapman cycle.
 A mechanism is a collection of one or more molecular steps that account for the way reactants become products.

30
Elementary Steps and Reaction Mechanisms
Elementary Steps
 The individual steps in a reaction mechanism are called elementary steps.
 Three types of elementary steps are likely to occur, those involving one, two, or three molecules.
 Steps with one reactant are called unimolecular, and those with two and three reactants are called bimolecular and
termolecular.
 The number of reactant molecules in an elementary step is its molecularity. The molecularity tells us the overall order of
the rate law for the elementary step, as summarized in following table.

Table: Types of elementary reactions

Summary of molecularity of elementary reactions

type of elementary reaction Molecularity rate law

A products Unimolecular Rate =k[A]
A+B products Bimolecular Rate = k[A][B]
2A products Rate = k[A]2
A + B +C products Termolecular Rate = k[A][B][C
2 A+ B products Rate = k[A]2[B]
A + B+ C+ D products Not observed

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Mechanism for the formation of nitrogen monoxide at high temperatures
O + N2 NO + N
N + O2 NO + O
Net: N2 + O2 2 NO
1. The N atom generated in the first reaction is consumed in the second reaction. A chemical species that is generated in one
step and consumed in a later step is called an intermediate or a reactive intermediate. Many mechanisms involve one or more
intermediates. Intermediates are formed in one elementary step and consumed in another. They are unstable and short-lived.
2. When the steps of the mechanism are properly summed, they give the observed stoichiometry of the overall reaction.

Example Problem 11.9

The decomposition of N2O5 is given by the equation
2 N2O5(g) 4 NO2(g) + O2(g)
The following mechanism is proposed for this reaction:
N2O5 NO2 + NO3
NO2 + NO3 NO2 + NO + O2
NO + NO3 2 NO2
(a) Does this mechanism as written provide the correct stoichiometry? If not how does it need adjustment? (b) Identify all
intermediates in the mechanism. (c) Identify the molecularity of each step in the mechanism.
Solution
(a) A simple sum of the mechanism yields
N2O5 + NO3 O2 + 3 NO2
This is not the desired stoichiometry, but if we multiply the first step by 2, 32
2 N2O5 2 NO2 + 2 NO3
 2 N2O5 2 NO2 + 2 NO3
NO2 + NO3 NO2 + NO + O2
NO + NO3 2 NO2

yields
2 N2O5 O2 + 4 NO2

he mechanism does provide the correct stoichiometry, as long as we realize that some steps may need to occur more than
others.
(b) The intermediates are NO3 and NO.
(c) The first step is unimolecular, whereas steps two and three are bimolecular.

Check Your understanding

The following mechanism was once proposed for the decomposition of N 2O5:
N2O5 N2O3 + O2
N2O3 NO2 + NO
NO + N2O5 3 NO2
(a) Is this mechanism plausible?
(b) Identify the intermediates in the reaction.
33
(c) Determine the molecularity of each step.
Mechanisms and Rate
Rate-Determining Step
 The slow step is called the rate-determining step and it dictates the rate law. It determines the overall rate of reaction.
2A + B C
A possible mechanism could be:
1. A + B X (fast)
2. A + X C (slow)
 Each step is an elementary step, and X is an intermediate. The second step is the rate-determining step.
Rate = kAX
Since X is an intermediate, from the first step we can assume that X is proportional to AB.
Therefore, Rate = k A2B (k = new rate constant)

Catalysis
 Catalysis is a process in which a reaction rate is influenced by the presence of substances that are neither reactants nor
products in the overall equation.

Types of Catalysis
1. Homogeneous Catalysis: The catalyst and reactants are in the same phase (e.g., both liquids).
2. Heterogeneous Catalysis: The catalyst and reactants are in different phases (e.g., a solid catalyst with liquid or gaseous
reactants).
3. Enzyme Catalysis: Enzymes are biological catalysts, typically proteins, that catalyze reactions in living organisms.
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Catalyst
 A catalyst is a substance that increases the rate of the reaction but is neither created nor destroyed in the process.

Homogeneous and Heterogeneous Catalysts

 Homogeneous catalysts are those that are in the same phase as the reacting substances, whereas heterogeneous
catalysts are in a different phase from the reacting species.
 For gas-phase reactions, the heterogeneous catalyst typically is a solid surface. Both types of catalysis are important in
atmospheric processes.

Characteristics of Catalysts
 Increased reaction rate
 Equilibrium unaffected

35