UNIT- IV CHEMICAL KINETICS

Introduction : Speed in the process of chemical change is a

very important factor. Some reaction are very slow; for
example the rusting (oxidation) of iron is a fairly slow reaction.
Other reactions such as those between acids and bases, are
normally very fast Chemical kinetics is concerned not only with
the velocity of reactions but also with the intermediate steps by
which reactants are ultimately converted into products.
Velocity of Reaction : The velocity of a reaction is defined as
the rate at which the concentrations of reacting substances
change with time. The velocity of a chemical reaction is
measured by the amount of substance in unit volume changed
in unit time. The amount measured in gram moles. Since the
rate of reaction falls as the substance is used up, we cannot
get the velocity of a reaction by dividing the amount of
substance changed by time taken for the change. We,
therefore, consider a very small interval of time dt. During this
small interval the velocity is assumed constant. Let dx be the
amount of substance changed in time dt.
Then at that interval
dx
velocity or rate of reaction = dt

Velocity Constant : Let us consider a simple chemical change

A  B suppose we start with a gram mol of substance A and
let x gram moles undergo change into product B in time t then
concentration after time t will be (a - x)
A  B
a o ..........Initial concentration

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 (a - x) x  concentration after time t
Now according to law of mass action the rate of reaction
after time t should be proportional to the concentration (a - x)
Rate of reaction  (a - x) = K (a - x)
dx
But rate of reaction is given by dt
dx
therefore = K (a - x)
dt

The constant K is called velocity constant of the reaction.

Factors Affecting Rates of Reaction : Rate of chemical
reaction depends on:-
(1) Nature of reactants
(2) The temperature
(3) Concentration of the reacting substances
(4) Particle size or surface Area of the substances
(5) Catalyst
(1) Nature of reactants : The rate of a chemical reaction is
influenced by the chemical nature of the reactants. For
example, Fluorine and hydrogen react explosively even at
room temperature, but iodine unites very slowly with
hydrogen even when heated. This is due to differences in
their chemical energies and the differences in the structure
of their atoms and molecules.
Ni and Fe in the atmosphere corrode at different rates
even when the temperature and concentration are the
same for both. In a relatively short time iron oxide (rust)

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 can be seen on the iron while the surface of nickel
remains unchanged.
(2) The temperature : The rate of a chemical reaction in
general increases by increasing the temperature.
Consequently, reaction are often carried out at elevated
temperatures so that a good yield of the products can be
obtained in a reasonable time.
(3) Concentration of the reacting substances : Increasing
the concentration of a reactant normally causes an
increase in the rate of a reaction. Further more, the
different reactants concentration effect the rate of a
particular reactions in different ways. For example when
nitric oxide reacts with the oxygen
2 NO + O2  2 NO2
the reaction rate doubles when the oxygen concentration
doubles, but doubling the concentration of No quadruples
the rate of reaction.
(4) Particle size or surface area of the substance :
Reactions between the substances take place at the
surface of contact. The reactions that occur between
solids or immiscible liquids, if greater is the total surface
area exposed for the reaction, the faster is the reaction.
The reaction velocity is greater in a finely ground mixture
of solid reactants than it is in a coarsely ground one.
In reactions that involve soluble liquids or gases. The
reacting particles are intimately mixed. The rate of such
reactions will therefore be much more rapid than those
that involve surface reactions.
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(5) Catalyst : A catalytic agent may increase or decrease the
speed at which a chemical reaction proceeds without
undergoing any chemical change itself. Although catalysts
are not consumed in reactions, they are believed to
participate by forming intermediate compounds in the
conversion of reactants to products.
Molecularity : The molecularity of a reaction is given by the
sum of number of atom or molecules of all the species
participating in the reaction as given by the stoichiometric
equation.
A unimolecular reaction is one in which only one molecule
reacts at a time. Examples are
PCl5  PCl3 + Cl2
Br2   Br + Br
A bimolecular reaction is one in which two molecules
(either of the same or of different kinds) react. Examples are -
2 HI  H2 + I2
H2 + Br2  2 HBr
A termolecular reaction takes place as a result of the
simultaneous collision of three molecules. Examples are -
2 NO + O2  2 NO2
2 CO + O2  2 CO2
Order of Reaction : It has been known by quantitative
measurement of reaction velocity that rate of reaction is not
influenced by all the molecules as represented by a chemical
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equation but is influenced by those molecules whose
concentration actually alters during the course of chemical
reaction. For example inversion of sucrose
C12H22O11 + H2O  C6H12O6 + C6H12O6
Sucrose glucose fructose
The molecularity of this reaction is 2 but measurable
change in concentration of only one molecule (C12H22O11)
takes place. Water is in so much excess that its change in
concentration is not measurable. Thus, this is first order
reaction.These type of reactions are known as
Pseudounimolecular reactions.
The order of a reaction is defined as the no. of molecules
whose concentration changes as a result of chemical change.
Let us consider the general reaction
mA + nB  aX + bY
dx
The velocity will be given by the expression
dt

dx
= K [A]m [B]n
dt

and the order of the reaction will be (m + n).

The order of reaction can be known only experimentally
and not totally by the chemical equations.
Reaction are classified in the following orders :-
(i) Zero order reactions
(ii) First order reactions

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 (iii) Second order reactions
(iv) Third order reactions
(i) First order reactions : (Unimolecular reaction) when only
one molecule undergoes a change in concentration as a result
of chemical change, the reaction is of the first order. Examples
are -
N2O5  N2O4 + ½ O2
H2O2  H2O + ½ O2
C12H22O11 + H2O  C6H12O6 + C6H12O6
sucrose glucose fructose
Suppose we start with a gram mole/lit of A and x gram
mole/litre undergo change in time t.
Since, velocity of reactions  Molecular concentration
after time t
 dx
 (a - x) [Concentration of A after time t]
dt
dx
= K (a - x) .......(1)
dt

This is a differential equations. In order to know the value

of k, by integrating the above equation.
dx
 ( a  x )   Kdt.
– ln (a - x) = Kt + C .......(2)
Before the start of reaction when
t = 0, then x = 0
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 Putting these values in equation (2)

– ln a = 0 + C

or – ln a = C

Thus – ln (a - x) = Kt – ln a

ln a – ln (a - x) = Kt

a
ln ax
= Kt

1 a
or K = t Ln a  x

This equation is known as the kinetic equation for a

reaction of the first order. This can also be written in the
following alternate form
1 a
K = x 2.303 log
t ax

2.303 a
or K = log .......(3)
t ax

Here the initial concentration of the reaction is represented

by a and the amount, reacted in time t is represented by x,
then (a - x) is the concentration remaining after time t.
All first order reactions obey this equation.
Units of k  time–1
Special Cases :

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(1) Sometimes it is not convenient to know the initial
concentration a because the exact time at which reaction
starts is not definite. Under such conditions the value of k
is determined at two moments t1 and t2 while the
concentration are
(a - x1) and (a - x2) respectively. Under such conditions
we get the following first order reaction.
2.303 a  x1
k  log
t 2  t1 a  x 2 ........(4)

This equation can thus be used to calculate the value of k

by taking any pair of concentrations of the reactants at any
two time intervals. Reasonably constant values for k are
obtained which verify the first order reaction.
(2) Half life period : One of the important characteristics of
first order reaction is that the time used for the completion
of a definite part of reaction is not dependent on the initial
concentration. For example, the time necessary, for half of
a given quantity of a substance to react is as follows -
Since half of the given quantity of substance is changed,
so
x = a/2
2.303 a
Then kK  log
t 1/ 2 ( a  a / 2)
2.303 a
 log
t 1/ 2 a/2
or 2.303
 log 2
t 1/ 2

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 or 2.303
t 1/ 2  log 2
k
2.303
 x 0.3013
k

0. 693 ........(5)
t 1/ 2 
k
It is clear from equation (5) that time required to complete
half or any other fraction of the reaction is independent of initial
concentration. t½ is known as half life period.
Second order reaction : When the concentration of two
substance changes as a result of chemical change, the
reaction is called of the second order (bimolecular)
Following are the examples of second order reaction :
CH3 COOC2H5 + NaOH  CH3COONa + C2H5OH

C2H4 + H2  C2H6
2 O3  3 O2
Let us consider a second order reaction of the type
A + B  AB
Suppose the initial concentration of A and B is a gram
mole/liter. Let (a - x) be their concentrations after a time t.
Since the rate of a reaction is proportional to the concentration,
then we have
Rate of reaction  (a - x) (a - x) after a time t
or dx
 (a -x) (a - x)
dt

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 or dx
= K (a - x)2 .......(i)
dt

Integrating equation (i) we get

dx
 ( a  x) 2
 k  dt
1
 kt  C .......(ii)
a x

in which C = Constant of integration

The value of C can be calculated by setting x = 0 when t
= 0 in equation (ii) then
C = 1/a
Substituting the value of C in equation (ii) we get
1 1
 kt 
a x a

1 1
or   kt
a x a
1 x
k  x .......( iii )
t a( a  x)

Where k is the velocity constant and time is expressed in

moles/lit. k has the units of conc.–1 time–1 i.e. (mole L–1) –1
sec –1 or L mol –1 sec –1.
When half of the original material has reacted x = a/2
and
1 a/2 1 1
k 
t 1/ 2 a ( a  a / 2 ) t 1/ 2 a

1
t 1/ 2 
or ka .......(iv)
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 It must be remembered that equation (iii) and (iv) apply
only when initial concentration of A and B substances are the
same i.e. a.
If the initial concentration of A and B are different i.e. a
and b are respectively, then
dx
= K (a - x) (b - x)
dt

Its integrations gives the following equation (after

evaluating the integrations constants and converting to
common logarithm)
2.303 b( a  x)
k log
t( a  b) a(b  x) .......(v)
Determination of order of a Reaction: Various important
methods available for the determination of the reaction order
are as follows –
(1) Integration method: The reaction under study is
performed by taking different initial concentration of the
reactant (a) and noting the concentration (a - x) after
regular time intervals (t). The experimental values of a, (a -
x) and t are then substituted into the integrated rate
equation for the first, second and third order reactions.
The rate equations which gives a constant value of k
corresponds to the correct order of the Reaction. This
method of ascertating the order of reaction is essentially a
method of hit and trial but was the first to be employed. It
is still used extensively to find the order of simple
reactions.
2.303 a
For first order k log
t a x
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 1 x
Second order k 
t a( a  x )
(2) Half period method: In this, the time t1/2 required to
complete half of the reaction is determined and
experiment repeated with different, but equal initial
molecular concentrations of the reactants. If half life period
is found to be (i) independent of initial concentration (a).
The reaction is of first order (ii) inversely proportional to
the initial concentration (a) of the reactants, the reaction is
of second order.
In generl if t½ and t1½ are the times for the half life period
with initial concentration a1 and a2 respectively, then
order of reaction (n) is given by
n 1
t 1/ 2  a2 
  
t 11/ 2  a1 

Taking logarithms we get,

Log (t½/t1½) = (n -1) Log a2 / a1

Log ( t 1/ 2 / t 11/ 2 ) Log t 1/ 2  Logt 11/ 2

or (n -1) = 
Log( a 2 / a 1 ) Loga 2  Loga 1

Since a1, a2, t½ and t1½ are known, so order of reaction

(n) can be calculated.

(3) Graphical Method: In case of first order

a
Log  kt
a x

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 Simplifying it becomes
Log a - Log(a-x) = Kt
Log (a - x) = –kt + Log a
  
y = mx + c
Thus the two variables in the first order rate equation are:
Log a - x and t
Hence if Log a - x is plotted against t, a straight line
results.
In case of second order
1 1
 kt 
a x a
 
y = mx + c
This is the equation of a straight line y = mx + c. Here the
two variables are 1/a-x and t.
Thus when 1/a-x is plotted against t, we get straight line.
The reactions is of second order.
(4) Ostwald’s Isolation Method: This method is applicable
particularly, in the case of reaction in which there are two
or more reactants. The method consist in performing a
series of experiments in which all but one of the reactants
are taken in large excess turn by turn, so that its
concentration does not vary sensible during the course of
the reaction. Then order of reaction is determined with
respect to isolated reactant (i.e. which is taken in small
amount) in each case. Evidently, the order of reaction, so

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 determined is with respect to isolated reactant only. The
sum of the individual order, when each reactant is taken
separately in small amount, is the overall order of reaction.
For example, in the reaction.
2 FeCl3 + SnCl2  2 FeCl2 + SnCl4
(i) When FeCl3 is taken in large excess, the velocity
with respect to SnCl2 is preportional to the first
power of concentration of SnCl2 on the other
hand.
(ii) When SnCl2 is taken in large excess the velocity
with respect to FeCl3 is proportional to the
square of concentration of FeCl3.
Hence, the order of the above reaction is 1 + 2 = 3 i.e.
3rd order reaction.
Activation Energy:
According to collision theory of reaction rates, the rate of
reaction is governed by two factors –
(i) The total no. of collisions between the reactant particles
(molecules, atoms or ions), when concentration of any
reactant (s) is increased, the no. of collisions per unit time
increases, because of presence of greater no. of particles
per unit volume. The increasing no. of collisions implies a
greater reaction rate.
(ii) However, only a small fraction of the total no. of collisions
is effective in bringing about chemical change, because
only those collisions which involve particles having
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 sufficiently high kinetic energy are likely to result in
reaction. “Effective collisions” involve particles having
an energy content equal to or higher than a certain
minimum value. The minimum amount of energy from
zero level the reacting molecules must possess in
order to react is called the “Threshold energy.” Also
the molecules must be properly oriented, besides having
energy greater than or equal to threshold energy.
However, it is observed that only a small fraction of
molecules possess energy equal to or higher than this value.
Thus the rate of reaction in terms of no. of collisions can be
expressed as
No. of properly oriented Fraction of molecules
Rate = molecules per unit volume X with kinetic energy equal
per unit time to or greater than threshold
energy
The activation energy (Ea) may be defined as the
additional amount of energy to be supplied to the reactant
molecules to reach the “threshold energy state” or
activated energy state, so that their collisions may result
in an actual chemical change. In other words:
Activation energy (Ea) = [Threshold energy] – [Energy already possessed by the molecules]

Significance of activation energy:

In order to react, the colliding molecules must have a total
kinetic energy equal to or greater than the activation energy
(Ea), which is the minimum amount of energy required to
initiate a chemical reaction. Lacking this energy, the molecules
remains intact, and no change results from the collisions. The
species temporarily formed by the reactant molecules as a

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result of collision before forming the product (s) is called
activated complex.

Arrhenius Equation: The relationship between the value of

the rate constant and the absolute temperature is defined by
the Arrhenius equation:
K = Ae– Ea/RT ...........(i)
where k = rate constant; T = absolute temperature;
R = gas constant; Ea = activation energy and
e = base of natural logarithm.
Thus, e–Ea/RT represents the fraction of molecules
having energies equal to or greater than the energy of
activation.
Taking logarithm, we get
ln k = ln A – Ea / RT ..........(ii)

If k1 and k2 are the rate constants of a reaction at

temperatures T1 and T2 Respectively, then from eq. (ii) we get

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 Ea
ln k 1  ln A 
RT1 ..........(iii)
Ea
and ln k 2  ln A  ..........(iv)
RT2
on subtracting (iii) from (iv) we get,
lnk2 – lnk1 = Ea  Ea 
   
RT2  RT1 

Ea Ea
=  
RT2 RT1

Ea  1 1 
=   
R  T1 T2 

k E a  T2  T 1 
 
2
ln  
k1 R  T1 T 2 
or
k2 E a  T2  T1 
log   
k1 2 .303R  T1 T2 
or .........(v)
But R = 1.987 cal k–1 mol–1
4.576T1T2 log k 2  log k1 
Ea = cal mol -1 .........(vi)
T2  T1 
Thus equation (vi) can be used for evaluating the
activation energy (Ea) by determining the Rate constants of a
reaction at two different temperatures.

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