Chemical Kinetics

The area of chemistry that

concerns reaction rates.
 Reaction Rate
Change in concentration (conc) of a reactant
or product per unit time.

conc of A at time t2 − conc of A at time t1

Rate =
t2 − t1
∆A
=
∆t
12_291
0.0100

NO 2

0.0075
Concentrations (mol/L)

0.0026 ∆[NO 2 ]
0.0006

∆t 70s
0.005
110 s

NO

0.0003
0.0025 70s

O2

50 100 150 200 250 300 350 400

Time (s)
12_1575

Time Time

(a) (b) (c)

 Rate Laws

Rate = k[NO2]n

k = rate constant
n = rate order
 Types of Rate Laws

Differential Rate Law: expresses how rate

depends on concentration.

Integrated Rate Law: expresses how

concentration depends on time.
C4H9Cl + H2O → C4H9OH + HCl
 Method of Initial Rates

Initial Rate: the “instantaneous rate” just

after the reaction begins.

The initial rate is determined in several

experiments using different initial
concentrations.
NH4+(aq) + NO2-(aq) → N2(g) 2H2O(l)
 Overall Reaction Order

Sum of the order of each component in the

rate law.

rate = k[H2SeO3][H+]2[I−]3

The overall reaction order is 1 + 2 + 3 = 6.

 2ClO2 + 2OH- → ClO3- + ClO2- + H2O

Experiment [ClO2] M [OH-] M Rate, M s-1

1 0.060 0.030 0.0248
2 0.020 0.030 0.00276
3 0.020 0.090 0.00828

1. Determine the rate law for the reaction.

2. Calculate the rate constant.
3. What is the overall reaction order?
ICA
 First-Order Rate Law

For aA → Products in a 1st-order reaction,

−∆ A
Rate = =k A
∆t

Integrated first-order rate law is

ln[A] = −kt + ln[A]o
 CH3NC → CH3CN
Conversion of methyl isonitrile to acetonitrile
 Half-Life of a First-Order
Reaction
0.693
t1/2 =
k
t1/2 = half-life of the reaction
k = rate constant

For a first-order reaction, the half-life does

not depend on concentration.
 Half-Life of a First Order Rx
12_294

[N2O5]0 0.1000
0.0900

0.0800
0.0700
[N2O5] (mol/L)

0.0600
[N2O5]0 0.0500
2
0.0400

0.0300
[N2O5]0
4 0.0200
[N2O5]0
0.0100
8

50 100 150 200 250 300 350 400

t1/2 t1/2 t1/2

Time (s)
O (g) + NO2 (g) → NO (g) + O2 (g)

P se u d o -F irst O rd e r R ate L aw s
y = -1 0 0 .1 5 x + 2 2 .3 4 5
2 3 .0 0
2 2 .0 0
ln [O]

2 1 .0 0
2 0 .0 0
1 9 .0 0
0 0 .0 1 0 .0 2 0 .0 3 0 .0 4
tim e (s )
Types of Radioactive Decay

alpha production (α ): helium nucleus42 He

92 U → 2 He +
238 4 234
90Th

beta production (β ):−10 e

90Th → 91Pa +
234 234 0
−1e
 Types of Radioactive Decay

gamma ray production (γ ):

92 U → 2 He + + 20 γ
238 4 234 0
90Th

High energy photon

 Decay Series

A radioactive nucleus reaches a

stable state by a series of steps.

series of decays 208

90Th   → 82 Pb
232
21_475

202
120 80 Hg (1.53:1 ratio)

100 Unstable region

atio
(too many neutrons; r
n
Number of neutrons (A–Z)

spontaneous beta oto

- pr
production)
80 n -to
t ro

e
u

h
ne

i ty t
bil s in
1
1:
60 s t a de
of ucli
110
Cd
ne n

48
zo able

(1.29:1 ratio)
St

40
Unstable region
(too many protons;
spontaneous positron
20 production)
6
3 Li (1:1 ratio)
0
0 20 40 60 80 100
Number of protons (Z)
21_476
U
238
236
Th Pa U
234
232
230 Th
228
Mass number (A)

226 Ra
224
222 Rn
220
218 Po
216
214 Pb Bi Po
212
210 Pb Bi Po
208
206 Pb
204
0 82 83 84 85 86 87 88 89 90 91 92 93
Atomic number (Z)
 Rate of Decay

rate = kN
The rate of decay is proportional to the
number of nuclides. This represents a first-
order process.
 Decay of Strontium-90
21_477

10.0

8.0
Mass of38 Sr (g)

6.0 1 half-
life
90

4.0 2 half-
lives
3 half-
2.0 lives 4 half-
lives

0
20 40 60 80 100 120
t1/ 2 = 2 8.8 t1/2 = 2 8.8 t 1/2 = 2 8.8 t 1/ 2 = 2 8.8
Time (yr)
Radioactive Decay
 Second-Order Rate Law
For aA → products in a second-order reaction,
−∆ A
Rate = =k A 2
∆t

Integrated rate law is

1 1
= kt +
A Ao
 Half-Life of a Second-Order
Reaction
1
t1/2 =
kA o

t1/2 = half-life of the reaction

k = rate constant
Ao = initial concentration of A

The half-life is dependent upon the initial concentration.

Zero Order Rate Laws
Rate = k [A]0

Integrated Form

[A] = -kt + [A]o

 A Summary

1. Simplification: Conditions are set such

that only forward reaction is important.
2. Two types: differential rate law
integrated rate law
3. Which type? Depends on the type of
data collected - differential and
integrated forms can be interconverted.
 A Summary
(continued)

4. Most common: method of initial rates.

5. Concentration v. time: used to determine
integrated rate law, often graphically.
6. For several reactants: choose conditions
under which only one reactant varies
significantly (pseudo n-order conditions).
12_06T

Table 12.6 Summary of the Kinetics for Reactions of the Type aA → Products That Are
Zero, First, or Second Order in [A]

Order

Zero First Second

Rate law Rate = k Rate = k[A] Rate = k[A]2

1 1
Integrated rate law [A] = -kt + [A]0 ln[A] = -kt + ln[A]0 = kt +
[A] [A]0
1
Plot needed to give a straight line [A] versus t ln[A] versus t versus t
[A]
Relationship of rate constant
to the slope of straight line Slope = -k Slope = -k Slope = k

Half-life [A]0 0.693 1

t1/2 = t1/2 = t1/2 =
2k k k[A]0
 Reaction Mechanism

- The series of steps by which a chemical

reaction occurs.

- A chemical equation does not tell us how

reactants become products - it is a
summary of the overall process.
 Reaction Mechanism
(continued)

- The reaction

O3 + O → 2O2

has several steps in the reaction

mechanism.
 Often Used Terms
Intermediate: formed in one step and used up in
a subsequent step and so is never seen as a
product.
Molecularity: the number of species that must
collide to produce the reaction indicated by that
step.
Elementary Step: A reaction whose rate law can
be written from its molecularity.
uni, bi and termolecular
Rate-Determining Step

In a multistep reaction, it is the

slowest step. It therefore
determines the rate of reaction.
 Collision Model

Key Idea: Molecules must collide to react.

However, only a small fraction of

collisions produces a reaction. Why?

Arrhenius: An activation energy must be

overcome.
 Arrhenius Equation

- Collisions must have enough energy to

produce the reaction (must equal or exceed
the activation energy).

- Orientation of reactants must allow

formation of new bonds.
 Temperature and Ea
12_300

T1
T2 > T 1
T2

0
0 Ea
Energy
 Arrhenius Equation
(continued)

− Ea / RT
k = Ae

k = rate constant
A = frequency factor
Ea = activation energy
T = temperature
R = gas constant
 Catalysis
Catalyst: A substance that speeds up a reaction
without being consumed

Enzyme: A large molecule (usually a protein)

that catalyzes biological reactions.

Homogeneous catalyst: Present in the same

phase as the reacting molecules.

Heterogeneous catalyst: Present in a different

phase than the reacting molecules.
 Lower Ea for Catalyzed Rx
12_303

Uncatalyzed
pathway
Energy

Catalyzed
pathway

Products

∆E

Reactants

Reaction progress
 Heterogeneous Catalysis
Steps:
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.
END