CHEMICAL

KINETICS

INTRODUCTION

Chemical kinetics is the study of chemical

(or biological) systems whose composition
changes with time.
Explores the rates and mechanisms of
chemical reactions.

CHEMICAL KINETICS

TOPIC OBJECTIVES

Definition of reaction rate and techniques

for its measurement
Analysis of results of such measurements
differential equations
Solutions of diffential equations to predict
the concentration of species at anytime
after the start of the reaction

CHEMICAL KINETICS

Any chemical process may be broken down

into a sequence of one or more single-step
processes known either as elementary
processes, elementary reactions, or
elementary steps.

CHEMICAL KINETICS

Elementary reactions usually involve either:

a single reactive collision between two
molecules, which we refer to as a a
bimolecular step, or

dissociation/isomerisation of a single
reactant molecule, which we refer to as a
unimolecular step.

CHEMICAL KINETICS

An important point to recognise is that many

reactions that are written as a single reaction
equation in actual fact consist of a series of
elementary steps.
This will become extremely important as we
learn more about the theory of chemical reaction
rates.

EMPIRICAL KINETICS

The first step in the kinetic analysis of

reactions is establishment of the
stoichiometry of the reaction and
identification of any side reactions.

Basic Data of Chemical Kinetics:

[reactants]*

[products]*
*At different times after the reaction has
beeen initiated

EMPIRICAL KINETICS
NB: Most reactions ate temperature sensitive
hence temperature must be held constant
throughout the reaction.

EMPIRICAL KINETICS
EXPERIMENTAL TECHNIQUES

Several techniques are used to monitor the rates of

chemical reactions.
Spectrophotometry

The measurement of the intensity of the absorption of

radiation in a particular spectral region is widely
applicable to correlate to the concentration of the
analyte.

Other methods include titration, mass spectrometry,

gas chromatography, magnetic resonance.

EMPIRICAL KINETICS

Read on quenching methods, flow methods,

stopped flow technique and flash photolysis.

RATES OF REACTIONS

Rate is dependent on the composition and

the temperature of the reaction mixture.
Consider a reaction of the form:
A + B C

in which at some instant the

concentrations of the participants are [A],
[B], and [C].

RATES OF REACTIONS

Measures of the rate of the reaction are:

1. Rate of formation of product

2. Rate of consumption of the reactant(s)

RATES OF REACTIONS

The rate of consumption of A is,

= -d[A]/dt

And the rate of formation of the product C is:

= d[C]/dt

NB: The reaction stoichiometry implies that the

rate of formation of C is equal to the rate of
consumption of A or B.

RATES OF REACTIONS

Consider the reaction:

A +

2B

3C + D

Rate of formation of C

3 x rate of consumption of A,

d[D]/dt = 1/3d[C]/dt = -d[A]/dt = -1/2d[B]/dt

In general rate, can be defined as:

= (1/ j) d[J]/dt

where j = stoichiometric coefcient of substance

J( with j ve for reactants and +ve for products).

RATES OF REACTIONS

Example: Reporting rates of reaction

The rate of formation of NO in the reaction

2NOBr(g) 2NO(g) + Br2 was reported as

1.6 x 10-4 mol L-1s-1.

What is the rate of reaction, and the rate of

consumption of NOBr ?

RATES OF REACTIONS

Solution

Write the equation in the form:

0 = products - reactants and identify the
stoichiometric numbers.
From equation = (1/ j) d[J]/dt
d[NO]/dt = 1.6 x 10-4 mol L-1 s-1
0 = 2NO (g)

Br2 (g) - 2NOBr (g)

RATES OF REACTIONS

Therefore NO = +2.
= 1/2d[NO]/dt = x 1.6 x 10-4 mol L-1 s-1
= 8.0 x 10-5 mol L-1 s-1

RATES OF REACTION

Since NOBr = -2 ,

the rate at which the concentration of NOBr

change is
d[NOBr]/dt = NOBr x
= -2 x (8.0 x 10-5 mol L-1 s-1)
= -1,6 x 10 -4 mol L-1 s-1

RATES OF REACTIONS

Rate Laws and rate constants

The rate of a reaction is proportional to

the concentrations of reactants raised to a
power.
Rate may be proportional to the
concentrations of two reactants e.g.
= k[A][B] where k is the rate constant.

RATES OF REACTIONS

A practical application of the rate law is

that once it is known the rate of reaction
from the composition of the mixture can be
predicted.
It is also a guide to the mechanism of the
reaction.

RATES OF REACTIONS

The determination of rate laws

Experimental investigation identification
of all products, intermediates and any side
reactions involved.
Read on methods of initial rates

RATES OF REACTIONS

INTEGRATED RATE LAW

The methods of initial rates might not
reveal the full rate law, for example in a
complex reaction the products may
participate in the reaction and affect the
rate once they have been formed.
Rate laws are differential equations
therefore must be integrated to find the
concentrations as a function of time.

RATES OF REACTIONS

First order reactions

The 1st order-rate law for the

consumption of a reactant A

d[A]/dt = -k[A]
In([A]/A]0)

= -kt

[A] = [A]0e-kt

RATES OF REACTIONS

HALF - LIFE
A useful indication of the rate of a first order chemical
reaction is the half life, t1/2

t1/2 the time it takes for the concentration

half the initial value.

to fall to

The time it takes for substance [A] to

decrease from
[A]0 to [A]0 in a first order reaction is expressed as
kt1/2 = - In(1/2[A]0/[A]0) = In2
t1/2 = In2/k

REACTION KINETICS

Second Order Reactions

The integrated rate law of the second order

rate law:
d[A]/dt = k[A]2

is
1/[A] 1/[A]0 = kt

[A] = [A]0/(1 + k[A]0)

REACTION KINETICS

Another type of second order reaction is

one that is first order in each of the two
reactants A and B:
d[A]/dt = -k[A][B]

NB: The above rate law cannot be

integrated until information on how the [B]
is related to that of [A].

RATES OF REACTIONS

Show that for the reaction:

A + B

Products

kt = 1/([B]0 [A]0) x In(([B]/[B]0)/[A]/[A]0)

RATES OF REACTIONS

Temperature Dependence of Reaction Rates

Rates of chemical reactions increase as

the temperature is raised.

The Arrhenius parameters

An empirical observation is that many

reactions have rate constants that follow the
Arrhenius equation.

RATES OF REACTIONS

Arrhenius equation:
Ink = InA Ea/RT or k = Ae-Ea/RT

A plot of Ink vs 1/T gives a straight line.

A pre-exponential or frequency factor

Ea activation energy

RATES OF REACTIONS

Accounting For the Rate Laws

Elementary reactions

Most reactions occur in a sequence of

steps called elementary reactions.

RATES OF REACTIONS

A typical elementary reaction is :

H +

Br2

HBr +

Br

Molecularity - The molecularity of an

elementary reaction is the number of
molecules coming to react together.

RATES OF REACTIONS
Unimolecular reaction a single
molecule rearranges itself to form a
different molecule.
Bimolecular reaction a pair of
molecules collides and exchange energy,
atoms or groups of atoms.
NB: Reaction order is an empirical quantity,
and obtained from the experimental rate law.

RATES OF REACTIONS
Molecularity refers to an elementary reaction
proposed as an individual step in a mechanism.
The rate law of an elementary reaction can be
written from its chemical equation.
E.g. the rate law of a unimolecular elementary
reaction is 1st order in the reactant:
A

Products

d[A]/dt = -k[A]
NB: A unimolecuar reaction is 1st order and a
bimolecular reaction is second order

RATES OF REACTIONS

Read on consecutive elementary

reactions and the rate determining
a reaction.

step of

RATES OF RAECTIONS

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RATES OF REACTIONS

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RATES OF REACTIONS

The steady- state approximation

It assumes that, during the major part of

the reaction, the rates of change of
concentrations of all reactions intermediates
are negligibly small.
d[intermediate]/dt

RATES OF REACTIONS
Account for the rate law for the
decomposition of N2O5

2N2O5(g) 4NO2(g)
+
O2(g)
= k[N2O5]
On the basis of the following mechanism

RATES OF REACTIONS

N2 O5

NO2 + NO3

NO2 + NO3 N2O5

ka

ka

NO2 + NO3 NO2 + O2 + NO

NO +

N 2 O5

3NO2

kb
kc

RATES OF REACTIONS

Solution

1. Identify the intermediate species.

2. Write expressions for their net rates of
formation.
3. Use the steady state approximation
4. Solve the resulting equations
algebraically.

RATES OF REACTIONS
d[NO]/dt = kb[NO2][NO3] kc[NO][N2O5]
d[NO3]/dt = kb[N2O5] ka[NO2][NO3]
kb[NO2][NO3]

RATES OF REACTIONS

Set the equations to zero:

Kb[NO2][NO3] - kc[NO][N2O5]

kb[N2O5] ka[NO2][NO3] kb[NO2][NO3]

0

RATES OF REACTIONS

The net rate of change of

concentration of N2O5 is

d[N2O5]/dt

= - ka[N2O5] + ka[NO2][NO3]

Kc [NO][N2O5]

RATES OF REACTIONS

Replacing the concentrations of the

intermediates by using the equations
above gives

d[N2O5]/dt

-2kakb[N2O5]/(ka+kb)

it follows that the rate is

= k[N2O5]

,where k = -2kakb/(ka+kb)

RATES OF REACTIONS

Read on pre-equilibria

RATES OF REACTIONS

CHAIN REACTIONS

Many gas phase reactions and liquidphase reactions are chain reactions.

In a chain reaction an intermediate

produced in one step generates an
intermediate in a subsequent step,
then that intermediate generates
another intermediate, etc.

RATES OF REACTIONS
The

structure of chain reactions

Intermediates responsible for the

propagation of a chain reaction are
called chain carriers.

Classification of Reaction steps

Initiation
Propagation
Termination.

RATES OF REACTIONS
Polymerization

Kinetics

Chain polymerization results in the

rapid growth of an individual polymer
for each activated monomer.

Examples include addition

polymerization of ethane, methyl
methacrylate, and styrene.

RATES OF REACTIONS

The central feature of the kinetic

analysis is that the rate of
polymerization is proportional to the
square root of the initiator
concentration:

k[I]1/2[M]

RATES OF REACTIONS

There are three basic steps in a chain

polymerization process.

Initiation

2R.
R.

M .1

k[I]I

RATES OF REACTION
Propagation

M + M. 1

M + M. 2
M + M.n-1

M.2
M.3
M.n

kp[M][M.]

Since the chain reaction propagates quickly,

the rate at which the total concentration of
radicals grows is equal to the rate of the ratedetermining step.

RATES OF REACTIONS

It follows that d[M.]/dt = 2ki[I]

where is the yield from the initiation
step, the fraction of radicals R. That
successfully initiates a chain.

Termination

M. + M.m

M.n+ m

RATES OF REACTIONS

Assumption: the rate of termination is

independent of chain length, it follows
that:

= kt[M.]2 and the rate of change

of radical concentration by this
process is

d[M.]/dt

= -2kt[M.]2

RATES OF REACTIONS

NB: In practice, other termination

steps may intervene e.g. side
reactions.

The total radical concentration is

approximately constant throughout the
main part of the polymerization.

RATES OF REACTIONS

Using the steady state approximation

d[M.]/dt = 2ki[I] - 2kt[M.]2 = 0

The steady state concentration of

radical chains is:

[M.] = (ki/kt)1/2 x [I]1/2

RATES OF REACTIONS

Since the rate of propagation of the

chain is

d[M]/dt

= -kp[M.][M]

It follows that

d[M]/dt

= -kp(ki/kt)1/2 x [I]1/2 x [M]

which has the form of

k[I]1/2[M]

RATES OF REACTIONS
Kinetic Chain Length,

It is a measure of the efficiency of chain

propagation mechanism.

It is also defined as the ratio of the

number of monomer units consumed
per active centre produced in the
initiation step:
= no. of monomer units consumed
no. of active centres produced.

RATES OF REACTIONS

The kinetic chain length is therefore

equal to the ratio of the propagation
and initiation rates
=

propagation rate
initiation rate

RATES OF REACTIONS

Since the initiation rate is equal to the

termination rate it follows that

= kp[M.][M]
2kt[M.]2

kp[M.]
2kt[M.]

RATES OF REACTIONS

When the steady state expression is

substituted for the radical
concentration , it follows that

=
1/2

kp[M.][I]-1/2 where k = kp/[2(kikt)-

NB: the slower the initiation of the

chain (the smaller the initiator
concentration and the smaller the
initiation rate constant), the greater
the kinetic chain length.

RATES OF REACTIONS

Stepwise Polymerization

This type of polymerization commonly

proceeds by a condensation reaction, in
which a molecule is eliminated in each
step.

Production of nylon-66 proceeds by

stepwise polymerization.

RATES OF REACTIONS
The Rate Law of Stepwise Polymerization

Consider the step wise polymerization of

polyester.

The condensation can be expected to be overall

second order in the concentration of the -OH and
COOH or (A) groups.
d[A]/dt = -k[-OH][A]

Since there is one OH for each COOH group,

this equation is the same as
d[A]/dt = -k[A]2

RATES OF REACTIONS

Assuming that the rate constant for the

condensation is independent of the
chain length and then k remains
constant throughout the reaction.

The solution for the rate law is:

[A] = [A]0/(1 + k[A]0)

RATES OF REACTIONS

The fraction p of the COOH groups

that have condensed at time t is
p =( [A]0 - [A])/[A]0)
p =(kt [A]0 /(1+kt[A]0)