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
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.
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 A B

D[A]
rate = -
Dt

D[B]
rate =
Dt

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

time

t 1< t 2 < t 3

393 nm Detector
light
D[Br2] a D Absorption
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 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 instance in time 5
 rate a [Br2]
rate = k [Br2]
rate
k= = rate constant
[Br2]
= 3.50 x 10-3 s-1
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 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

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8
 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

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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

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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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 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 12
 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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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)
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 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]0e−kt ln[A] = ln[A]0 - kt

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Graphical Determination of k

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

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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

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 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 5.7 x 10 s-4 -1

How do you know decomposition is first order?

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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

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 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

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 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

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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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 +
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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Temperature Dependence of the Rate Constant

k  A  e( 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

Alternate format:

Ea 1
ln k = - + lnA
R T
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 Alternate Form of the Arrhenius Equation

At two temperatures, T1 and T2

or

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Importance of Molecular Orientation

effective collision

ineffective collision
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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 2O 2
+ 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 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
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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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Sequence of Steps in Studying a Reaction Mechanism

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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 must be slower than step 2 32
 Chemistry In Action: Femtochemistry

• •
CH2 CH2 CH2 CH2 CH2 CH2
2 CH2 CH2
CH2 CH2 CH2 CH2 CH2 CH2

2 CH2 CH2

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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 34
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

D[P]
rate =
Dt

rate = k [ES]

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