Chemical Kinetics

Chapter 13

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

[A]
rate = -
t

[B]
rate =
t

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

time

t1 < t2 < t 3

393 nm Detector
light
[Br2]  Absorption
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 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent slope of
tangent

[Br2] [Br2]final – [Br2]initial

average rate = - =-
t tfinal - tinitial
instantaneous rate = rate for specific instance in time 5
 Reaction Rates and Stoichiometry

2A B

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

1 [A] [B]
rate = - rate =
2 t t

aA + bB cC + dD

1 [A] 1 [B] 1 [C] 1 [D]

rate = - =- = =
a t b t c t d t

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Example 13.1
Write the rate expressions for the following reactions in terms of
the disappearance of the reactants and the appearance of the
products:
Example 13.2
Consider the reaction

Suppose that, at a particular moment during the reaction,

molecular oxygen is reacting at the rate of 0.024 M/s.

(a)At what rate is N2O5 being formed?

(b)At what rate is NO2 reacting?

 Review of Concepts
Write a balanced chemical equation for a gas-
phase reaction whose rate is given by

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RATE LAW

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

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 rate  [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
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 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

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 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

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

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant

Rate doubles
x=1
rate = k [F2][ClO2]
Quadruple [ClO2] with [F2] constant
Rate quadruples
y=1 16
Example 13.3
The reaction of nitric oxide with hydrogen at 1280°C is

From the following data collected at this temperature, determine

(a) the rate law
(b) the rate constant
(c) the rate of the reaction when [NO] = 12.0 × 10−3 M and [H2]
= 6.0 × 10 −3 M
Example 13.3
Example 13.3
INTEGRATED RATE LAW

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 First-Order Reactions
[A]
A product rate = - rate = k [A]
t
[A]
rate M/s - = k [A]
k= = = 1/s or s-1 t
[A] M
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

[A] = [A]0e−kt ln[A] = ln[A]0 - kt

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Example 13.4
The conversion of cyclopropane to propene in the gas phase is a
first-order reaction with a rate constant of 6.7 × 10 −4 s−1 at 500°C.

(a)If the initial concentration of cyclopropane was 0.25 M, what is

the concentration after 8.8 min?

(b)How long (in minutes) will it take for the concentration of

cyclopropane to decrease from 0.25 M to 0.15 M?

(c)How long (in minutes) will it take to convert 74 percent of the

starting material?
Example 13.4
Graphical Determination of k

2N2O5 4NO2 (g) + O2 (g)

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Example 13.5
The rate of decomposition of azomethane (C2H6N2) is studied by
monitoring the partial pressure of the reactant as a function of
time:

The data obtained at 300°C are shown in the following table:

Are these values consistent with first-order kinetics? If so,

determine the rate constant.
Example 13.5
 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

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First-order reaction
A product

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

2 4

3 8

4 16

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Example 13.6
The decomposition of ethane (C2H6) to methyl radicals is a first-
order reaction with a rate constant of 5.36 × 10−4 s−1 at 700°C:

Calculate the half-life of the reaction in minutes.

 Review of Concepts
Consider the first-order reaction A B in which A
molecules (blue spheres) are converted to B molecules
(orange spheres). (a) What are the half-life and rate constant
for the reaction? (b) How many molecules of A and B are
present at t = 20s and t = 30s?

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 Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t

rate M/s [A]

k= = 2 = 1/M•s
- = k [A]2
[A] 2 M t

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

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Example 13.7
Iodine atoms combine to form molecular iodine in the gas
phase

This reaction follows second-order kinetics and has the high

rate constant 7.0 × 109/M · s at 23°C.

(a)If the initial concentration of I was 0.086 M, calculate the

concentration after 2.0 min.

(b)Calculate the half-life of the reaction if the initial

concentration of I is 0.60 M and if it is 0.42 M.
 Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t

rate [A]
k= = M/s - =k
[A] 0
t

[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

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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 = ln 2

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

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 Rate Laws Summary
1. Assume rxn studied under conditions
where only forward rxn is important
2. Two types of rate laws
a. Differential rate law
b. Integrated rate law
3. Use method of initial rates to obtain rate
law

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TEMPERATURE DEPENDENCE
OF THE RATE CONSTANT 36
 Collision Theory
• Parameters
1. Collision frequency
2. Energy of collisions
3. Orientation of collisions
• Temp velocities frequency

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 A+B AB++ C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea ) is the minimum amount of

energy required to initiate a chemical reaction.
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 # of collisions

Amount of Kinetic Energy

energy

The area under the curve after the

activation energy are the collisions
that resulted in a reaction. The
higher temperature has more area,
more collisions that result in a
reaction. 39
Importance of Molecular Orientation

effective collision

ineffective collision
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Arrhenius equation

k  A  e ( Ea / RT )
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

Alternate format:

Ea 1
ln k = - + lnA
R T

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Example 13.8
The rate constants for the decomposition of acetaldehyde

were measured at five different temperatures. The data are

shown in the table. Plot ln k versus 1/T, and determine the
activation energy (in kJ/mol) for the reaction. Note that the
reaction is “3/2” order in CH3CHO, so k has the units of
1/M½ ·s.
Example 13.8
 Alternate Form of the Arrhenius Equation

At two temperatures, T1 and T2

or

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Example 13.9
The rate constant of a first-order reaction is 3.46 × 10−2 s−1 at
298 K.

What is the rate constant at 350 K if the activation energy for

the reaction is 50.2 kJ/mol?
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k  A  e ( Ea / RT ) Ea k
Uncatalyzed Catalyzed

ratecatalyzed > rateuncatalyzed

Ea′ < Ea 46
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

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 Haber Process

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

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 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)

Pt-Rh catalysts used

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in Ostwald process
 Catalytic Converters

catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O
catalytic
2NO + 2NO2 converter 2N2 + 3O2

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Enzyme Catalysis

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Binding of Glucose to Hexokinase

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 Enzyme Kinetics

[P]
rate =
t

rate = k [ES]

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 Factors that affect rxn rate
1. Temperature
2. Concentration
3. Surface area / physical state
4. presence of a catalyst

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What does a chemical equation
tell you?

CO (g) + NO2 (g) CO2 (g) + NO (g)

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 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 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
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 2NO (g) + O2 (g) 2NO2 (g)
Mechanism:

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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 2 O2
+ 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
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 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.
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60
Sequence of Steps in Studying a Reaction Mechanism

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Example 13.10
The gas-phase decomposition of nitrous oxide (N2O) is believed
to occur via two elementary steps:

Experimentally the rate law is found to be rate = k[N2O].

•Write the equation for the overall reaction.

•Identify the intermediate.

•What can you say about the relative rates of steps 1 and 2?
 Example
CO (g) + NO2 (g) CO2 (g) + NO (g)

• NO3 is detected
• Experimental rate law: rate=k[NO2]2
• Give a plausible mechanism

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 Review of Concepts
The rate law for the reaction H2 + 2IBr I2 + 2HBr is
rate=k[H2][IBr]. Given that HI is and intermediate, write
a two-step mechanism for the reaction.

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