Chapter 11: Chemical Kinetics

Chemical kinetics includes investigations

of how different experimental conditions can
Section 11.1 Reaction Rates influence the speed of a chemical
reaction and yield information about
the reaction's mechanism and transition
states, as well as the construction
of mathematical models that can describe
Reaction Rate the characteristics of a chemical reaction.
• Change in concentration of a reactant or product per
unit time.

concentration of A at time t2  concentration of A at time t1

Rate =
t2  t1

 A
=
t

[A] means concentration of A in mol/L;

1
A is the reactant or product being considered.
The Decomposition of Nitrogen Dioxide

2
 300 oC
2 NO2  2 NO + O2

NO and O2 are colorless

Figure 11.1
Starting with a flask of
nitrogen dioxide at 300 oC,
the concentrations of
nitrogen dioxide, nitric
oxide, and oxygen are
plotted versus time

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 Instantaneous Rate

• Value of the rate at a particular time.

• Can be obtained by computing the slope of a line
tangent to the curve at that point.

Section 11.2 Rate Laws: An Introduction

Rate Law
• Shows how the rate depends on the concentrations of
reactants.
• For the decomposition of nitrogen dioxide:
2NO2(g) → 2NO(g) + O2(g)
Rate = k[NO2]n:
 k = rate constant
 n = order of the reactant 4
Rate = k[NO2]n
• The concentrations of the products do not appear in the rate
law because the reaction rate is being studied under
conditions where the reverse reaction does not contribute to
the overall rate.
• The value of the exponent n must be determined by
experiment; it cannot be written from the balanced equation.

Types of Rate Laws

• Differential Rate Law (rate law) – shows how the rate of a

reaction depends on concentrations.

• Integrated Rate Law – shows how the concentrations of

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species in the reaction depend on time.
Rate Laws: A Summary

• Because we typically consider reactions only under conditions

where the reverse reaction is unimportant, our rate laws will
involve only concentrations of reactants.
• Because the differential and integrated rate laws for a given
reaction are related in a well–defined way, the experimental
determination of either of the rate laws is sufficient.
• Experimental convenience usually dictates which type of rate
law is determined experimentally.
• Knowing the rate law for a reaction is important mainly
because we can usually infer the individual steps involved in
the reaction from the specific form of the rate law.
• Determine experimentally the power to which each reactant
concentration must be raised in the rate law.

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Section 11.3 Determining the Form of the Rate Law
• Determine experimentally the power to which each reactant
concentration must be raised in the rate law.
2NO2(g) → 2NO(g) + O2(g)
Rate = k[NO2]n
We typically consider reactions only under
conditions where the reverse reaction is
unimportant, our rate laws will involve only
concentrations of reactants.

Method of Initial Rates

• The value of the initial rate is determined for each experiment
at the same value of t as close to t = 0 as possible.
• Several experiments are carried out using different initial
concentrations of each of the reactants, and the initial rate is
determined for each run.
• The results are then compared to see how the initial rate
depends on the initial concentrations of each of the reactants.7
Overall Reaction Order
• The sum of the exponents in the reaction rate equation.

Rate = k[A]n[B]m

Overall reaction order = n + m

k = rate constant
[A] = concentration of reactant A
[B] = concentration of reactant B

Concept Check
How do exponents (orders) in rate laws compare to
coefficients in balanced equations?

Why?
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Section 11.4 The Integrated Rate Law

First-Order

• Rate = k[A]
• Integrated:
ln[A] = –kt + ln[A]o

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A

Plot of ln[N2O5] vs Time

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10
First-Order
• Half–Life:
0.693 ln[A] = –kt + ln[A]o
t1 =
2 k From this equation, we can figure out t1/2
k = rate constant

• Half–life does not depend on the concentration of

reactants.

Exercise
A first order reaction is 35% complete at the end of 55 minutes.
What is the value of k?
From the above equation, we can get
the answer.

k = 7.8 x 10–3 min–1

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Second-Order

• Rate = k[A]2
• Integrated: 1 1
= kt +
A  A 0
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A

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Plot of ln[C4H6] vs Time and Plot of 1/[C4H6] vs Time

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 1 1
Second-Order = kt +
A  A 0
From this equation, we can figure out t1/2

• Half–Life: 1
t1 =
2 k  A 0
k = rate constant
[A]o = initial concentration of A

• Half–life gets longer as the

reaction progresses and the
concentration of reactants
decrease.
• Each successive half–life is
double the preceding one.

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Exercise

For a reaction aA  Products,

[A]0 = 5.0 M, and the first two half-lives are 25 and 50 minutes,
respectively.
a) Write the rate law for this reaction.
rate = k[A]2
1 1
= kt +
b) Calculate k.   A   A0
k = 8.0 x 10-3 M–1min–1
c) Calculate [A] at t = 525 minutes.
[A] = 0.23 M

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Zero-Order

• Rate = k[A]0 = k
• Integrated:
[A] = –kt + [A]o

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A

Plot of [A] vs Time

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Figure 11.7
The decomposition reaction 2N2O(g)  2N2(g) + O2(g) takes place on a
platinum surface. Although [N2O] is 3 times as great in (b) as in (a), the
rate of decomposition of N2O is the same in both cases because the
platinum surface can accommodate only a certain number of molecules. 17
As a result, this reaction is zero order.
Zero-Order [A] = –kt + [A]o

• Half–Life: t1 =
 A 0 From this equation,
we can figure out t1/2
2 2k
k = rate constant
[A]o = initial concentration of A

• Half–life gets shorter as the reaction progresses and the

concentration of reactants decrease.

Concept Check
How can you tell the difference among 0th, 1st, and 2nd order
rate laws from their graphs?
For the zero-order reaction, the graph of concentration versus time is a
straight line with a negative slope. For a first-order graph, the graph is a
natural log function. The second-order graph looks similar to the first-
order, but with a greater initial slope. Students should be able to write a
conceptual explanation of how the half-life is dependent on concentration
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(or in the case of first-order reactions, not dependent
For a zero order
reaction

For a first order

reaction

For a second
order reaction

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Integrated Rate Laws for Reactions with More Than One
Reactant

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Summary of the Rate Laws

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Section 11.5 Reaction Mechanism

Reaction Mechanism
• Most chemical reactions occur by a series of elementary
steps.
• An intermediate is formed in one step and used up in a
subsequent step and thus is never seen as a product in
the overall balanced reaction.

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A Molecular Representation of the Elementary Steps in the
Reaction of NO2 and CO
NO2(g) + CO(g) → NO(g) + CO2(g)

k1
Elementary step

k2
Elementary step

Rate = k [NO2]2

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 Molecularity in chemistry is the number
of molecules that come together to react
in an elementary (single-step)
reaction[1] and is equal to the sum
Elementary Steps (Molecularity) of stoichiometric coefficients of reactants
in this elementary reaction.
• Unimolecular – reaction involving one molecule; first order.
• Bimolecular – reaction involving the collision of two species;
second order.
• Termolecular – reaction involving the collision of three species;
third order.

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Rate-Determining Step
• A reaction is only as fast as its slowest step.
• The rate-determining step (slowest step) determines the
rate law and the molecularity of the overall reaction.

NO2(g) + CO(g) → NO(g) + CO2(g)

k1
Elementary step
(slow, rate-determining)

k2
Elementary step
(fast)

Rate = k [NO2]2

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Reaction Mechanism Requirements
• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The mechanism must agree with the experimentally
determined rate law.

Decomposition of N2O5

2N2O5(g)  4NO2(g) + O2(g)

Step 1: 2( N2O5 → NO2 + NO3 ) (slow)

Step 2: NO2 + NO3 → NO + O2 + NO2 (fast)
Step 3: NO3 + NO → 2NO2 (fast)
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Concept Check

The reaction A + 2B  C has the following proposed

mechanism:
A+B D (fast equilibrium)
D+BC (slow)
Write the rate law for this mechanism.

rate = k[A][B]2

A+B D fast equilibrium - assuming K is the equilibrium constant

D+BC slow - assuming a rate constant k1
[D]
We have K = [D] = K [A] [B]
[A] [B]
k in the answer is k1K
and
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rate = k1 [D] [B] rate = k1 [D] [B] = k1K [A] [B]2
Section 11.6 A model for Chemical Kinetics

Collision Model
• Molecules must collide to react.
• Main Factors:
 Activation energy, Ea
 Temperature
 Molecular orientations

Activation Energy, Ea
• Energy that must be overcome to produce a chemical
reaction.

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Change in Potential Energy

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Plot showing the number of collisions with a particular energy at T1 and T2. 30
Arrhenius Equation
 Ea / RT
k = Ae
A = frequency factor
Ea = activation energy
R = gas constant
(8.3145 J/K·mol)
T = temperature (in K)

Rate = k[A]n[B]m
k: rate constant
A plot showing the exponential
dependence of the rate constant
on absolute temperature.
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Linear Form of Arrhenius Equation
Ea  1 
ln(k ) =    + ln  A 
R T

obtained from
 Ea / RT
k = Ae

An example of
obtaining activation
energy

Measuring k at
different temperature!
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Exercise

Chemists commonly use a rule of thumb that an increase of 10

K in temperature doubles the rate of a reaction. What must the
activation energy be for this statement to be true for a
temperature increase from 25°C to 35°C?

Ea = 53 kJ

ln(2) = (Ea / 8.3145 J/K·mol)[(1/298 K) – (1/308 K)]

Ea  1 
ln(k1) =    + ln  A  (1)
Ea  1  R  T1
ln(k ) =    + ln  A 
R T Ea  1 
ln(k2) =    + ln  A  (2)
R  T2
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Eq (2) – Eq(2)
Section 11.7 Catalysis

Catalyst
• A substance that speeds up a reaction without being
consumed itself.
• Provides a new pathway for the reaction with a lower
activation energy.

Energy Plots for a Catalyzed and an Uncatalyzed Pathway

for a Given Reaction

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Effect of a Catalyst on the Number of Reaction-Producing
Collisions

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Heterogeneous Catalyst
• Most often involves gaseous reactants being adsorbed
on the surface of a solid catalyst.
• Adsorption – collection of one substance on the surface
of another substance.

1. Adsorption and activation of the reactants.

2. Migration of the adsorbed reactants on the surface.
3. Reaction of the adsorbed substances.
4. Escape, or desorption, of the products.

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37
The exhaust gases from an automobile engine are passed through a
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catalytic converter to minimize environmental damage
 Homogeneous Catalyst
• Exists in the same phase as the reacting molecules.
• Enzymes are nature’s catalysts.

Illustration of an enzyme catalysing hydrolysis of a protein chain to 39

remove the end amino acid