CHEMICAL KINETICS

Chemical Kinetics is a branch of Physical chemistry which deals with the rate of reactions.
The study of Chemical Kinetics deals with:
(1) The rate of the reactions and rate laws. (2) The factors as temperature, pressure, concentration
and catalyst, that influence the rate of a reaction. (3) The mechanism or the sequence of steps by
which a reaction occurs.
The knowledge of the rate of reactions is very important

 To understand the mechanism of chemical reactions.

 To select optimum conditions for an industrial process so that the reaction proceeds at a
rate to offer maximum yield.

Terms involved in kinetics:

REACTION RATE: The rate of reactions is defined as the change in concentration of any of
reactants or products per unit time.
Let us consider a simple reaction A B
rate of reaction = rate of disappearance of A
= rate of appearance of B
−d [ A ] +d [ B]
Rate= ∨ d[A] represents the concentration in moles per litre
dt dt
d represents infinitesimally small change in concentration
UNITS OF RATE:
Reactions rate has the units of concentration divided by time.
concentrations in moles per litre (mol/litre or mol/1 or mol 1–1)
time may be given in any convenient unit second (s), minutes (min), hours (h), days (d)
or possible years. Therefore, the units of reaction rates may be
mole/litre sec or mol l–1 s-1 or mole/litre min or mol 1–1 min–1 or mole/litre hour or mol 1–1 h–1 and,
so on.
Average Rate of Reaction:
Average rate of reaction is defined as change in the concentration of reactants (or products)
during large interval of time. If ΔC is the change in the concentration of reactants and products in
Δt time, then
 Change∈the concentration of reactants∨ products
Average reaction rate=
Time
∆C C 2−C 1
¿± =±
∆t t 2−t 1
Units of concentration gram /mole −1 −1
Units for averagereaction rate= = =gmol L S
Unit of time time
Instantaneous Rate of Reaction: Instantaneous rate of reaction is defined as the average
reaction rate during a very short interval of time or rate of reaction at a particular time.
∆ C dC
Instantaneous rate=± lim =
∆ t →0 ∆t dt
Expression of Rate of Reaction:
For a general reaction n1A + n2B → m1C + m2D
−1 d [ A ] −1 d [B] +1 d [C] +1 d [ D]
Reaction rate= = = =
n 1 dt n 2 dt m1 dt m2 dt
NOTE: Rate of reaction and rate of concentration change of a reactant (or product) are two
different terms. Rate of reaction is equal to the rate of change of concentration of a reactant (or
a product) divided by the corresponding stoichiometric coefficient. The rate of reaction and rate
of concentration change are equal only when the stoichiometric coefficients involved are unity.
RATE CONSTANT:
Consider a simple reaction A→B
At a particular instant, if CA is the molar concentration or active mass of A, then
dx dx
∝C A ∨ =k .C A
dt dt
where k is a proportionality constant, called velocity constant or rate constant or specific reaction
rate.
At a fixed temperature, if CA = 1, then rate = dx/dt = k
Thus, rate constant can be defined as rate of reaction at unit concentration of the reactants. Let us
consider a general reaction aA + bB Product

Rate= ( dxdt )∝[ A ] [B]

a b

When [A]=[B]=1mol/L then rate = k

Units of Rate Constant

For reactions of different order, unit for rate constant is as follows:

[ ]
n−1
1
Unit of rate constant = x time−1
unit of concentration

[ ] [ ]
n−1 n −1
1 −1 litre
¿ x sec = x sec−1
mol mol
litre
Where, n = order of the reaction
ORDER OF A REACTION: The order of a reaction is defined as the sum of the powers of
concentration terms in the rate law.
Let us consider the example of a reaction which has the rate law pA + qB
Products
rate = k [A]m [B]n ...(1)
The reaction order with respect to A is m and
The reaction order with respect to B is n.
The overall order of reaction (m + n)

 Order can be zero, fractional or integer.

 Stoichiometric coefficients p and q of the reactants are always not equal to orders m and
n

The chemical reaction can be classified as first order, second order etc., based on the order

rate law order Type of order

rate = k [N2O5] 1 First order reaction
rate = k [H2] [I2] 1+1=2 Second order reaction
rate = k [NO2]2 2 Second order reaction
rate = k [[H2] [NO]2 2+1=3 Third order reaction
MOLECULARITY OF A REACTION: It is defined as the number of molecules, atom or
radicals that participate in the reaction. Depending on the number of participating molecules,
the reaction can be unimolecular, bimolecular, trimolecular, etc.

 Molecularity of a reaction is mostly between 1 to 3, but never zero. It is rare that

molecularity exceeds 3.
  Order and molecularity are not same and order may or may not be equal to molecularity
of the reaction.

Differences between order and molecularity

Order of reaction Molecularity

It is the sum of powers of molar It is the total number of reacting molecules
concentrations of the reacting molecules in (atoms or ions) take part in the reaction.
the rate equation of the reaction.
It may be a whole number, zero, fractional, It cannot have zero value and always a whole
positive or negative. number
It is always experimentally determined. It is a theoretical concept.
It is meant for the reaction and not for itsIt is meaningful only for simple reactions or
individual steps. individual steps of a complex reaction. It is
meaningless for overall complex reaction.
Order of the reaction can change with Molecularity is invariant for a chemical
condition such as pressure, temperature and equation
concentration

FIRST ORDER KINETICS:

Rate of the reaction is proportional to the first power of the concentration of the reactant is
known as first order reaction. For example
−dA 1
A B Rate (r )= =K[A]
dt
Initial time t=0 a0
At time t=t at = a0-x x = bt

−dA +dB dx
r= = = =K ( a 0−x )
dt dt dt
dx
=K .dt
( a0 −x )
On integration
x t

∫ a dx−x =∫ K . dt
0 0 0

[−ln ( a0−x ) ]=K [ t ]

−ln ( a0−x ) + ln a0=K . t
 ln
( a
a0−x
=K .t
)
1
K= ln
t
a0
a0 −x ( )
K=
2.303
t
log
a0
a 0−x ( )
Half life of first order reaction:
Reaction rates can also be expressed in terms of half-life or half-life period. It is defined as the
time required for the concentration of a reactant to decrease to half its initial value. Or
half-life is the time required for one-half of the reaction to be completed. It is represented by the
symbol t1/2 or t0.5
−dA 1
A B Rate (r )= =K[A]
dt
Initial time t=0 a0
At half time t=t1/2 at = a0/2 x = a0/2
Substituting these in fist order rate constant expression
1
K= ln
t
a0
a0 −x ( )
( )
1 a0
K= ln
t 1/ 2 a0
a 0−
2

ln 2 0.693
t 1/ 2= =
K K

It is clear from this relation that:

(1) half-life for a first order reaction is independent of the initial concentration.
(2) it is inversely proportional to k, the rate-constant
Second order kinetics: The rate of the reaction depends on the 2nd power of the concentration.
For a general reaction 2A Products r=k[A]2
Initial conc. At t=0 a0
Con. at time t t=t a0-x at
 −dA dx 2
r= = =k .[ A]
dt dt
dx 2
=k (a0−x )
dt
dx
2
=k . dt
(a 0−x )
On integration
x t

∫ (a dx
−x )2
=∫ k . dt
0 0 0

[ ]
x
dx t
2
=k [ t ] 0
(a0 −x) 0
1 1
− =k .t
a0 − x a 0
a0− ( a0 −x )
=k .t
a0 ( a0 −x )

1 x
k= .
t a 0 ( a0−x )

When the reaction consists two reactants and their initial concentrations are differ
rent
A+B Products r = k.[A]1[B]1
Initial conc. At t=0 a b
Conc. At time t=t a-x b-x x
−dA dB
r= = =k . [ A ][B]
dt dt
dx
=k ( a−x ) (b−x )
dt
dx
=kdt
( a−x ) (b−x )
On integration
x t

∫ ( a−xdx =∫ k . dt
) (b−x) 0
0
 [ ]
x t
1 1 1
∫ − =∫ k . dt
b−a 0 a−x b−x 0
1 x

b−a
[ −ln ( a−x ) + ln ⁡(b−x) ]0 =k . [ t ] 0
t

1
=[ −ln ( a−x ) +lna+ ln ( b−x ) −lnb ] =k . t
b−a

1 1 a(b−x )
k= ln
t b−a b(a−x )