Consider the Reaction : 2 N2O5(g) 4NO2(g) + O2 (g).

When a reaction proceeds, the concentration of a reactant decreases while that of a product
increases with time. The rate of change of concentration of a reactant is called rate of consumption
or disappearance of the reactant.
Average rate of consumption of N 2O5

N 2O5
t

since [N2O5] is a negative quantity, it is multiplied by 1 to make the rate a positive

quantity.
Similarly, rates of formation of NO2 and O2 are given by
Average rate of formation of NO2
Average rate of formation of O2

NO2
t
O2
t

These rates can be equated if we divide the rate of change of concentration of a reactant or
a product by its stoichiometric coefficient appearing in balanced chemical equation, that is,
Average rate (rav)/or rate

O2
1 N 2O5
1 NO2


2
t
4
t
t

Rate of a reaction at time t is known as the instantaneous rate of reaction.

As t 0, rinst or rate

d O2
1 d N 2O5
1 d NO2


2
dt
4
dt
dt

For the Reaction

5 Br (aq) + BrO3 (aq) + 6H+ (aq) 3Br2 (aq) + 3H2O(l)
We do not use the concentration term for water for expressing the rate of reaction since
change in the concentration of water is negligibly small because the reaction is occurring in aqueous
medium. Hence, the rate of reaction is given as below :

Rate

BrO3
1 Br
1 H
1 Br2



5
t
t
6
t
3
t

Order and Molecularity of Reaction

Rate law : Consider a general reaction : a A + b B c C + d D
25

Chemistry

The rate law for this reaction is :

Rate = k [A]x [B]y where x and y may or may not be equal to the stoichiometric coefficients a
and b of the reactants.
Rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation. It is determined experimentally.
x = order of reaction w.r.t. the reactant A
y = order of reaction w.r.t. the reactant B
and

x + y = overall order of the reaction.

Units of rate constant depend upon the order or reaction.

Rate = k [A]x [B]y

Rate

A x B y

If x + y = n = order of reaction, then we have

unit of k

Concn. 1 n
concentration
1
M1 n

time
time
s
concentration n

For zero order reaction (n = 0), unit of k is mol L1 s1 or Ms1

For first order reaction (n = 1), unit of k is s1
For second order reaction (n = 2), unit of k is L mol1 s1 or M1 s1.
Molecularity is the number of reacting species taking part in an elementary reaction, i.e., the
number of species that collide simultaneously in order to bring about a chemical reaction.
For a bimolecular or trimolecular elementary reactions, the order of reaction is the same as
its molecularity and order w.r.t. each reactant is equal to its stoichiometric coefficient.
For unimolecular elementary reactions, the order of reaction is one at high concentration or
pressure. At low pressure the reaction becomes second order but then the reaction is no longer an
elementary reaction. Order of reaction can be zero, 1, 2, 3 or even a fraction but molecularity can
never be zero or a non-integer. Order is applicable to elementary as well as complex reactions. For
complex reaction, molecularity has no meaning. For complex reaction, order of reaction is given by
slowest step and generally molecularity of the slowest step is the same as the order of the overall
reaction.
Zero Order Reaction : The rate of zero order reaction is independent of the concentration
change.

Rate

d R
0
k R k
dt

R 0 R
t

where

R 0 Initial concentration
R Concentration at time t

Half-life of a reaction is the time in which one-half of the initial concentration of the reactant
is consumed.

t1 2

R 0
2k

or t1 2 R 0
26

Chemistry

The decomposition of gaseous ammonia on hot platinum surface is a zero order reaction at
high pressure.
Rate = k [NH3]0 = k
First Order Reaction : 2N2O5 4NO2 is an example of first order reaction. For the reaction:
R P

d R
k R
dt

R 0
R 1
1
1
ln
or t2 t1
ln
R
R 2
k
k

These relationships can be expressed in exponential form as given below

[R] = [R]0ekt
Equation (ii) can be rewritten as :

R 0
R 1
2.303
2.303
log
or t2 t1
log
R
R 2
k
k

Expression for half-life for first order reaction :

t1 2

0.693
k

[R]

log

[R]0

Half-life period of first order reaction is independent of initial concentration of the reactant.

27

Chemistry

Rseudo First Order Reaction is a reaction which is first order w.r.t. each of the two
reactants but becomes first order reaction under certain experimental conditions, i.e., if one of the
reactants is taken in excess.
Note : Half-life period of nth order reaction in inversely proportional to initial concentration
of reactant raised to power (n 1)

t1 2

R n0 1

Dependence of rate of reaction on temperature is described by Arrhenius equation :

k = AeEa/RT where
Ea = Activation energy and is given by energy difference between the activated complex and
the reactant molecules.
A = Arrhenius factor or pre-exponential factor or frequency factor that has the units of rate
constant.
Natural logarithm of both sides of Arrehenius equation gives :

ln k

Ea
ln A
RT

The plot of ln k and

1
E
gives a straight line of slope a .
T
R

If k1 and k2 are rate constants at temperature T1K and T2K then we have

log

Ea
k2

k1
2.303 R

Ea
T2 T1
1
1
T T 2.303 R T T
1
2
2 1

(Plot between ln k and 1/T)

(Solid line denotes the reaction path without

catalyst and dotted line, with catalyst)

Effect of Catalyst : A catalyst provides an alternative reaction path or reaction mechanism

by reducing the activation energy between reactants and products by lowering the potential energy
barrier. A catalyst can catalyse those reactions for which rG < 0. It does not affect the equilibrium
state, increases the rates of forward as well as reverse reactions in the same proportion without
affecting the rH and the equilibrium is attained sooner.
28

Chemistry

Collision Theory of Chemical Reactions : The molecules are assumed to be hard spheres and
the reaction is postulated to occur when molecules collides with each other. The rate of reaction
for the following bimolecular elementry reaction : A + B Products, is given by
Rate = ZAB eEa/RT

where

ZAB = Collision frequency of the reactants, A and B.

eEa/R = Fraction of molecules with energy equal to or greater than Ea.
The collisions in which molecules collide with sufficient kinetic energy (or threshold energy)
and proper orientation are called effective collisions.
To account for effective collisions, another factor P, called the probability factor or steric factor
is introduced, i.e.,
Rate = pZABeEa/RT

29

Chemistry