INTRODUCTION

Chemical kinetics is the study of reaction rates,

factors that affect the reaction rates and reaction

mechanisms.
In

terms of the physical state of the reacting chemical

substance
Chemical

reaction can be classified into 4 different types:

Gas phase reaction
Liquid phase reaction
Solid phase reaction
Heterogeneous reaction of different phases such as gassolid interface.

 In

terms of the speed of reaction

Chemical

reaction is divided into:

Explosive
It involves examination of reaction mechanism
& determination of condition under which chemical
system under go very fast reacion.

Non explosive

REACTION RATE
The

rate of reaction is the rate at which products are formed or the

rate at which reactants are used up in the reaction.

Rates

vary immensely from reaction to reaction.

Many

ionic reactions take place instantaneously.

For ex, the following neutralization reaction is instantaneous :
+

H (aq) + OH (aq) H2O(l)

In

other cases, reactions keep on going for months or even years.

For ex-The fermentation of grape juice to form wine can take place
many months to complete.

 For the reaction

A B

There are two ways of measuring rate:

(1) the speed at which the reactants disappear
(2) the speed at which the products appear

Both give same result.

The most useful (and general) way of measuring the rate of the
reaction is in terms of change in concentration per unit time

[A]
rate = t

[A] = change in concentration of A over

time period t

[B]
rate =
t

[B] = change in concentration of B over

time period t
Because [A] decreases with time, [A] is negative .

Most

Common Units Rate =M/sec= moles/m sec

M= moles/m
3

time
[A]
rate = t
[B]
rate =
t

REACTION RATE..

Heres an another example of a reaction

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

We can plot [C4H9Cl] versus time

The average rate of a reaction

decreases with time.

The rate at any instant in time

(instantaneous rate) is the slope
of the tangent to the curve.

Instantaneous rate is different

from average rate, so when we
refer to the rate of a reaction, we
will be assuming its the
instantaneous rate unless
otherwise told.

Consider the reaction,

2 NO(g) + O2(g) 2 NO2(g).

We might try to write the rate as,

or as

but these are not the same because each

molecule of O2 gives two molecules of NO2.

SO,
RATE

The negative sign tells us that species is being

consumed
The fractions take care of the stoichiometry.
Any one of the three derivatives can be used to define
the rate of the reaction.

For a general reaction,

a A + b B c C + d D

The rate can be written in a number of different

but equivalent ways,
Rate

The stoichiometry is preserved by dividing the rate of

change of concentration of each substance by its
stoichiometric coefficient

QUES

Consider the decomposition of N2O5 to give NO2

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

Determine the rate

SOL.

Consider at t = 300 to 400 s

(0.0049-0.0040)
Rate values differ

-not account of the stoichiometry

coff.

To compare the rates must account for the stoichiometry

EX-2

(a) How is the rate at which ozone disappears

related to the rate at which oxygen appears in the
reaction

Sol.

b) If the rate at which O2 appears,

is 6.0 X 105 M/s at a particular instant,
at what rate is O3 disappearing at this same
time, [O3] / t?

PRACTICE QUESTION
The decomposition of N2O5 proceeds according to the following
equation:
If the rate of decomposition of N2O5 at a particular instant in a
reaction vessel is 4.2 X 107 M/s, what is the rate
of appearance of (a) NO2, (b) O2?

Answers: (a) 8.4 X10 7 M/s, (b) 2.1 X10 7 M/s

FACTORS INFLUENCING
REACTION RATE

Basically for a chemical reaction to occur :

1. The reactants must collide together; and

2. The reactants must have the right amount of energy.

For a new substance to be made, some of the bonds in

the original substance have to be broken before new
bonds can be formed.
Bond

breaking requires energy.

The minimum energy that chemicals must have before
they can change to products is called the activation
energy.

THE FACTORS WHICH CAN AFFECT THE

RATES OF CHEMICAL REACTIONS.

( 1 ) Effect of concentration on reaction rate

An increase in concentration of reactants will
give more particles per unit volume and hence
more collisions per unit time, thus increasing the
chance of reaction.

2 ) Effect of pressure on reaction rate

For reactions involving gases, an increase in
pressure will have the same effect of increasing
the number of particles per unit volume.
This again increases the number of collisions per
unit time, and hence the rate of the reaction.

( 3 ) EFFECT OF SURFACE AREA ON REACTION RATE

Increasing the surface area of solid reactants

speeding up reactions.

is a convenient way of

The

greater the surface area of a solid, the greater the area of contact
open to reactants.

Example : The reaction between marble chips and hydrochloric acid

CaCO3(s) + 2 HCl(aq) CO2(g) + H2O(l) + CaCl2(aq)

If equal masses of powdered marble and marble chips are added

separately to equal volumes of 1 mol dm-3 hydrochloric acid at the
same temperature,
The ground up powder of marble can be seen to react more readily
with hydrochloric acid, since it takes a shorter time for the reaction
to reach completion.

( 4 ) EFFECT OF TEMPERATURE ON
REACTION RATE

At higher temperatures, reactant molecules have more

kinetic energy, move faster, and collide more often and
with greater energy.
( 5 ) Effect of catalyst on reaction rate

A catalyst speeds up a reaction by providing an alternative

mechanism (pathway) for a reaction.
The alternative mechanism has a lower activation energy
than the original route, so that at a given temperature,
more molecules can react.
Example : Catalytic decomposition of hydrogen peroxide by
MnO2
2 H2O2(aq)
O2(g) + 2 H2O(l)
Cat. MnO2(s)

( 6 ) EFFECT OF LIGHT ON REACTION RATE

Light affects the rates of certain chemical reactions by

providing suitable frequencies of electromagnetic radiation
which can effect photochemical breakdown of covalent bonds,
or
Excite the outer electrons of atoms to result in their ionization.

Example : The reaction between bromine and hexane

The reaction of bromine with hexane proceeds quite

quickly under a lamp but much more slowly in dark.

RATE LAW

The reaction rate law expression relates the

rate of a reaction to the concentrations of the
reactants.
Each concentration is expressed with an order
(exponent).
The rate constant converts the concentration
expression into the correct units of rate (Ms1).
(It also has deeper significance, which will be
discussed later)

For the general reaction:

aA+bBcC+dD

x and y are the

reactant orders
determined from
experiment.
The overall order of reaction
is therefore
x+y

x and y are NOT the

stoichiometric
coefficients.

Consider the

NH4+(aq) + NO2-(aq) N2(g) + 2H2O(l)

Lets say that the following observations from several

experiments were made

following reaction:

as [NH4+] doubles the rate doubles with [NO2-] constant.

as [NO2-] doubles the rate doubles with [NH4+] constant.

The rate of this reaction would be expressed as.

Rate = k[NH4+][NO2-]

The reaction is said to be first order with respect to [NH4+] and

first order with respect to [NO2-].

But the overall order of the reaction is said to be second order.

Reaction rates come from experiment data, not stoichiometry!

Units for the rate constant:

The units of a rate constant will change depending upon
the overall order.
3

The units of rate are always M/s or moles/m sec

To find the units of a rate constant for a particular rate
law, simply divide the units of rate by the units of
molarity in the concentration term of the rate law.
Rate (M/s) = k[A]

1st order
3

Where M=moles/m

(A)WHAT ARE THE OVERALL REACTION

ORDERS FOR THE RATE LAWS
DESCRIBED IN EQUATIONS 1 AND 2?

Ans. The rate of the reaction in Equation 1 is

first order in N2O5 and first order overall. The
reaction in Equation 2 is first order in CHCl3 and
one-half order in Cl2. The overall reaction order
is three halves.
(b) What are the units of the rate constant for the rate law for
Equation 1?

ANS.

So,

Notice that the units of the rate constant

change as the overall order of the reaction
changes

ORDER OF REACTIONS
First Order Reactions
A reaction is 1st order if doubling the concentration
causes the rate to double.

products
Rate = k1 [A]

The proportionality constant k1 is called the rate

constant for the reaction.
ExO2
2O

SECOND ORDER REACTIONS.

There are two types of second order reaction. The most obvious is
that where:

Rate = k2 [A] [B]

Alternatively, the rate may depend upon the square of the
concentration of only one of the species:

Rate = k2 [A]

A reaction is 2nd order if doubling the concentration causes a quadruple increase

in rate.

Ex- 2HI

H2+I2

Rate = k[H2 ][I2 ]

ZERO ORDER REACTIONS

Under special circumstances, reactions can proceed at

a constant rate which is unaffected by reactant
concentrations. These are called zero order
reactions.

Ex 2NH3

N2+3H2

INTEGRATED RATE LAWS

product

First-Order Reactions

[A]
rate = t
rate = k [A]
So,

[A]
= k [A]
t
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

k = rate = M/s = 1/s or s-1

M
[A]

[A] = [A]0exp(-kt)

ln[A] = ln[A]0 - kt

Shows how [A] depends on time. If initial [A] and

rate constant are known then [A] at any time can
be calculated
Equation is in the form y=mx +b

For a 1st order rxn plotting the natural log of [] vs. time
always gives a straight line
Slope of the line is -k
If the plot is not a straight line the rxn is not first order
in A can be expressed as a ratio of [A] and [A]0
ln([A]0/[A]) = kt

HALF-LIFE. T1/2

The time required for a reactant to reach half of its original [ ] is called the half-life.
t1/2

For

a A products

In 1st order reaction

ln([A]0/[A]) = kt
When

t = t1/2
[A] = [A] /2
0

Integrated

rate law becomes

ln([A] /[A] /2) = kt
0
0
1/2
ln(2) = kt
1/2

Substitute

the value on ln2 and solve for t 1/2

t
1/2 = 0.693/k
General equation for the half-life of a 1 st order reaction

QUESTION: USING 1ST ORDER INTEGRAL RATE LAW

The decomposition of a certain insecticide in water

follows first-order kinetics with a rate constant of 1.45
-1
yr at 12C. A quantity of this insecticide is washed
into a lake on June 1, leading to a concentration of
5.0 X107 g/cm3. Assume that the average temperature
of the lake is 12C.
(a) What is the concentration of the insecticide
on June 1 of the following year?
(b) How long will it take for the concentration
of the insecticide to drop to 3.0 X107 g/cm3?

ln [A]t = -kt + ln [A]0

sol.(a)
Substituting the known quantities into Equation

(b) Again substituting into Equation , with

[A]t=[insecticide]t = 3.0X 107 g/cm3, gives

Solving for t gives

2ND ORDER RATE LAWS

a A products
Rate

= -[A] = k[A]2

t
On Integrating
1/[A]

= kt + 1/[A]0

A plot of 1/[A] versus t will produce a straight line with a slope equal
to k
[A] depends on time and the equation can be used to calculate [A] at
any time t, provided k and [A]o are known.

2ND ORDER HALF-LIFE

[A] = [A]0/2

1/[A]0/2 = kt1/2 + 1/[A]0

2/[A]0-1/[A]0 = kt1/2

1/[A]0 = kt1/2

Solve for t1/2

t1/2 =

1/k[A]o

The expression for the half-life of a 2nd order reaction

QUESTION

A second order reaction involving reactants with the

initial concentration of 0.05 M is found to be 25 %
complete in 150 sec. calculate
a) The reaction rate constant.
b) The half life of the reaction
c) The time it would take for the reaction to be 25%
complete if the initial concentration where 0.005 M

SOL.(A)
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

X = concentration of A which is reacted.

[A]= [A]0 (1

100

[A]= 0.05 (1

- 25
100

[A]=0.0375

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

From Slide
number 38

Putting the value of [A]0 , [A] & t=150s in the above

equation;
We get,
k=0.044

(1 / M-sec)

(b)
half life of second order reaction is
t1/2 = 1/k[A] o
t1/2 =222.5 sec

[A]o =0.005 M

(c)
if [A]o =0.005 M
[A] =(1-25/100)*0.005
[A]=0.00375

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

k= 0.044

Then time for the reaction to be 255 complete is given by

t= 1500 sec

DIFFERENCES IN HALF-LIVES

1st order

Depends

only on k
Constant time for each reduction by

2nd order

Depends

on k and [A]o
Successive half-lives are not constant time
Each successive half-life is double the preceding one

ZERO-ORDER RATE LAWS

Rate

= -[A] = k[A]0 = k(1) = k

Rate

is constant

Integrated rate law

[A]
A

= -kt + [A]0

plot of [A] vs. t gives a straight line of slope -k

ZERO-ORDER HALF-LIFE

[A] = [A]0/2
[A]0/2
t1/2

= -kt1/2 + [A]0

= [A]o/2k

Solving for t1/2

t1/2

= [A]0/2k

Four of the simplest rate laws are given below in both their differential
and integrated form.

In the above [A]0 and [B]0 represent the initial concentrations of A and
B i.e. their concentrations at the start of the reaction.

THE METHOD OF INITIAL RATES

question
The initial rate of a reaction
was
measured for several different starting concentrations
of A and B, and the results are as follows:

Using these data, determine

(a) the rate law for the reaction,
(b) the magnitude of the rate constant,
(c) the rate of the reaction when [A] = 0.050 M and [B] =
0.100 M

Sol.(a)

(b) Using the rate law and the data from

experiment 1, we have

(c) Using the rate law from part (a) and the rate
constant from part (b), we have

PRACTICE EXERCISE

The following data were measured for the reaction

of nitric oxide with hydrogen:

(a) Determine the rate law for this reaction. (b) Calculate the
rate constant. (c) Calculate the rate when
[NO] = 0.050 M and [H2] = 0.150 M.
2
Answers: (a) rate = k[NO] [H2]; (b) k =1.2 M2s1; (c) rate =
4.5 x 104 M/s

DETERMINING REACTION ORDER:

THE METHOD OF INITIAL RATES
The reaction of nitric oxide with hydrogen at
1280C is:
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
From the following data, determine the rate law
and rate constant.

SOL.

The rate law for the reaction is given by:

x

Rate(M/min) = k [NO] [H2]

Taking the ratio of the rates of runs 3 and 1 one

finds:

2=

Taking log on both side

Taking the ratio of the rates of runs 1 and 2 one finds:

THE RATE LAW IS:

Rate(M/min) = k [NO] [H2]

To find the rate constant, choose one set of data
and solve:
3

0.0120 M/min= k (0.0100M) (0.0200M)

5

k= 6.00 x 10

ELEMENTARY STEPS & MOLECULARITY

Elementary step: any process that occurs in a single step.
Molecularity: the number of molecules present in an
elementary step.
Unimolecular: one molecule in the elementary
step,
Bimolecular: two molecules in the elementary
step, and
Termolecular: three molecules in the elementary
step.
(It is uncommon to see termolecular processes
statistically improbable for an effective collision to
occur.)

UNIMOLECULAR REACTION
STEPS

The elementary reaction step

is unimolecular because there is only one

molecule reacting, that is, molecule "A" is
reacting.
This unimolecular reaction step implies the rate
law,

or, equivalently,

An elementary reaction step may be reversible or

irreversible

This reversible unimolecular step implies the following

rate laws,

Or

(Either one of these may be used, depending on whether

we are trying to account for the disappearance of
reactant, A, or the appearance of product, B, in our
mechanism for a particular reaction.)

BIMOLECULAR REACTION STEPS

There are several varieties of bimolecular steps.

For example

implies the rate law

Or

REVERSIBLE BIMOLECULAR
STEPS

The bimolecular reaction

implies the rate law

If the reversible bimolecular reaction,

implies

TERMOLECULAR REACTION
STEPS

A typical termolecular process might be,

with its implied rate law

CONSECUTIVE REACTIONS

The simplest complex reaction consists of two

consecutive, irreversible elementary steps e.g.

An example of such a process is radioactive

Decay.
To solve the rate equations analytically the
following initial conditions hold

To determine the concentrations of [A], [B], and [C]

as a function of time. The rate equations for the
concentrations of A, B, and C are:

Integrating (1) gives

Substituting this into (2) gives

a differential equation with the solution

Finally, since [C] = [A]0[B][A],

By substituting values of [A] & [B] we get

We will consider two special cases for a pair of

sequential reactions:

CASE 1: K1 >> K2

In this case, all of the A initially present is rapidly

converted into B, which is then slowly used up to form
C. Since k2 becomes negligible in comparison with k1,
the equation for [C] becomes

i.e. the rate of production of C becomes independent of

k1 (apart from at the very beginning of the reaction).
In other words, the second step is the rate determining
step.

CASE 2: K2 >> K1

In this case, B is consumed as soon as it is produced,

and since k1 becomes negligible in comparison with k2,
the equation for [C] simplifies to

i.e. the overall rate now depends only on k1, and the
first step is rate determining.

CHAIN REACTIONS
Chain reactions are complex reactions that
involve chain carriers, reactive intermediates
which react to produce further reactive
intermediates.
The elementary steps in a chain reaction may be
classified into
Initiation
Propagation
Inhibition
Termination steps.

As an example, consider the reaction by which

chlorofluorocarbons (CFCs) destroy ozone:

Initiation step
Reaction is initiated either thermally or photo chemically.
The first reactive intermediates/chain carriers (in this
case a Cl radical) are produced.

PROPAGATION STEP
Reaction of a radical leads to formation of another
radical another reactive intermediate.
In the first propagation step above,
reacts to
form
; in the second step
reacts to form
.

Termination step
Chain carriers are deactivated.
Often
this occurs through radical-radical
recombination, reaction with walls, or reaction
with another molecule to create an inactive
product

Some chain reactions involve inhibition steps, in which

product molecules are destroyed.
Inhibition

steps.

steps are also sometimes referred to as retardation

The chain length in a chain reaction is defined as the

number of propagation steps per initiation step,
or
alternatively as the rate of propagation divided by the
rate of initiation

ACTIVATION ENERGY

A threshold energy that must be overcome to

produce a chemical reaction

A+B
Exothermic Reaction

AB++

C+D
Endothermic Reaction

The activation energy (Ea ) is the minimum amount of

energy required to initiate a chemical reaction.

ARRHENIUS EQUATION

Svante Arrhenius developed a mathematical

relationship between k (the rate constant) and Ea:

the rate constant is depend on temperature

where A is the frequency factor, a number that

represents the likelihood that collisions would occur
with the proper orientation for reaction.
E=empirical constant
R =universal gas constant
T =absolute temperature

The temperature dependence of the rate constant k is best

described by the Arrhenius equation:

Taking the natural logarithm of both sides, the

equation becomes

ln k = ln A E / R T

If we know the constant k at two or more temperatures

At temperatures T1 and T2 the rate constant is k1 and
k2
Then

Substract eq(1) &eq(2)

Example
For a 2nd order reaction the value of the reaction constant k at the
given temperature are as follows:
Temperature (deg c)

K(1/Ms)

330

78 x 1o^2

355

180 x 1o^2

380

410 x 1o^2

385

475 x 1o^2

Calculate the activation energy of reaction E

SOL.
At temperature T1

At temperature T2

Subtracting the equation ,we get

Convert the temperatures to Kelvin

Selecting the value of k at
T1=330+273 =603 k
k1=78 x 10
T2= 355+273=628 k
k2=180 x 10

Substituting in the equation

E=26,800 cal/mole

COLLISION THEORY

In a chemical reaction, bonds are broken and new

bonds are formed.
Molecules can only react if they collide with each
other.
Collision means that the centre of the reactant
molecules must come close enough to have a
distance equal to the sum of gas-kinetic radii
The rate of reaction is related to the number of
collision between molecules.

Furthermore, molecules must collide with the correct

orientation and with enough energy to cause bond
breakage and formation

KINETICS OF CHEMICAL CHAIN

REACTION
Reaction Of Hydrogen With Oxygen

Hydrogen- oxygen reaction is an example of

branch chain reaction.
The reaction rate of the reaction of Hydrogenoxygen is dependent to a large extent on the
pressure & temperature.
The reaction is studied between 450 600 deg C.

Fig illustrates effect of total pressure on reaction rate at

constant temperature 550 deg C

At low pressure the rate of reaction increases as expected .

As the pressure increased by few mm of Hg, the mixture
explodes .
This

pressure is known as first explosion limit ,indicated by

point B.

BETWEEN

pressure B & D the reaction is explosive.

At

E it again becomes slow & increases in the normal way up to

pressure F

Pressure

E is known as second explosion

Pressure

F is known as third explosion

second explosion limit 100 mm of Hg

The position of the explosion changes if the
temperature is changed.
The first & second explosion limit are not a thermal
explosion but because of branched chain reaction the
rate of reaction becomes very high.
In the range of AB & EF
The

chain terminating reaction are as fast as the chain

initiation & propagation reaction.

FIG. BETWEEN PRESSURE &

TEMPERATURE

REACTION MECHANISM

The reaction is explosive at 600 deg C & is given as

2H2+

O2

2 H 2O

It is third order reaction.

Reaction mechanism is divided in to three parts:
1. mechanism below the first explosion limit .
2. Between the second & third limit.
3. Near the third limit.

I.

H2 + O 2

2OH

II.

OH + H2

H 2O + H

PROPAGATION

III.

H + O2

OH + O

BRANCHING

IV.

O + H2

OH + H

BRANCHING

V.

H + O2 +M

VI.

HO2

HO2 +M

INITIATION

TERMINATION

DESTRUCTION BY WALL

HO2 radical is quite inactive and it diffuses to the wall

where it is absorbed & destroyed by the reaction with
another HO2 radical