Chemical Kinetics

Chemical kinetics gives information about how fast the

reaction proceeds. Global reactions, as given below,
are employed to describe the initial and final states.
2 2 2 2 2 18 8
47 9 8 ) 76 . 3 ( 5 . 12 N O H CO N O H C p
In reality, these global reactions take place in several
steps. An elementary reaction is one which can take
place in a single step.
Molecularity of a Reaction
Molecularity of a reaction is the number of molecules
or atoms taking part in each act leading to chemical
reaction. It is defined for an elementary reaction only.
N
2
O
5
N
2
O
4
+ O
2
, a unimolecular reaction
2HI H
2
+ I
2
, is a bimolecular reaction
CO
2
+ H
2
CO + H
2
O, is a bimolecular reaction
2NO + O
2
2NO
2
, is a termolecular reaction
Most reactions are bimolecular, since there is higher
probability for two molecules to collide.
Order of a Reaction
Order of a reaction is the power index of concentration
that determines the reaction rate.
Molecularity gives insight into the mechanism of a
reaction.
For the uni-molecular reaction N
2
O
5
N
2
O
4
+ O
2
, the
rate is given by d[N
2
O
5
]/dt = -k
1
[N
2
O
5
], indicating that
the reaction is first order.
In 2NO
2
2NO + O
2
, the rate is given by d[NO
2
]/dt = -
k
2
[NO
2
]
2
, indicating that the reaction is second order.
Order of a Reaction
The reaction between methylamine and ethyl bromine,
(C
2
H
5
)
3
N + C
2
H
5
Br (C
2
H
5
)
4
NBr is second order; its
rate is d[C
2
H
5
Br]/dt = -k
2
[C
2
H
5
Br] [(C
2
H
5
)
3
N].
The reaction 2NO + O
2
2NO
2
, is third order as the
reaction rate depends on concentrations of two NO
molecules and one oxygen molecule.
The order for global reaction steps may be fractional;
for example, d[CH3CHO]/dt = -k [CH3CHO]
1.5
.
For elementary reactions order and molecularity are
usually the same.
Order of a Reaction
There are also some zero order reactions. The rates
of these reactions do not depend upon the quantity of
the unconsumed reactants.
For hydro-carbons burning in oxygen, the overall order
of the reaction is known to lie between 1.7 to 2.2; the
order with respect to oxygen is near unity.
The order of a reaction being equal to 3 or more is
very rare, as the probability of 3 molecules to collide at
the same location is very less.
Collision theory of reactions
A
B
C
V
A
(d
A
+ d
B
)
A + B C
Collision theory of reactions
) (
B A AB
d d d + =
)
B A A B AB
AB
AB
C C T n n V
d
Z o
z

'
+

'

=
4
2
Consider a cylinder of diameter d
AB
around an A particle
A
AB
V
d
4
2
z
The volume covered by the A particle in unit time
B A
AB
n
d
4
2
T
= No. of collisions for one A particle with B per sec.
A
A
m
T
V
O 3
= Velocity of an A particle
No. of collisions between A and B per unit vol. per sec.
Collision theory of reactions
? A
? A? A
B A
A
C C k
dt
C d
!
All the Z
AB
collisions are not fruitful. Only those which
can provide activation energy for creating active radicals
will be fruitful.

'
+

'

RT
E
a
AB
exp
Number of fruitful collisions =
Finally the rate of a reaction A + B C is given as
The rate constant k E

'
+

'

RT
E
a
exp T
1/2
Collision theory of reactions
Law of Mass Action: The rate of a reaction is
proportional to the product of reactant
concentrations.
The proportionality constant (k) is known as
the Rate constant. It is actually a strong
function of the temperature T.
B A B A
a A
C C k C C
RT
E
T a
dt
dC
=

'
+

'

= exp
Rate Constant
From experimental data, k is usually evaluated in a
form k = a T
m
exp{-E
a
/RT}
Here a is called the pre-exponential factor, m is the
temperature power index and E
a
is the activation
energy
E
a
Q
comb
E
t
H
2
H + H
O
2
O + O
Such active species are
required for combustion
reactions to proceed
Rate Constant
In Arrhenius type reactions, k = a exp{-E
a
/ RT}. The
term T
m
is usually unimportant and its effect can be
absorbed in the stronger exponential term.
Only in low temperature pre-combustion reactions,
the T
m
term may have to be considered.
ln k
1/T
Intercept = ln(a)
Slope = -E
a
/R
Reaction Rate
D C B A
D C B A
R R R R + +
Consider the reaction
? A ? A
B A
B A
C C k
R R
[ !
y
? A ? A
B A
B A
D
D
C
C
B
B
A
A
C C k
R R
R
[
R
[
R
[
R
[
[ ! ! !

!
y y y y
y
For the reactants, the reaction rate is negative and
for the products it is positive
Concentration variation with time
For a first order reaction A B, the rate of
consumption of A
? A
? A A k
dt
A d
=
? A
? A
dt k
A
A d
=
? A ? A } exp{
0
kt A A !
k k
t
693 . 0 2 ln
2 / 1
= =
t
A
0
Concentration variation with time
For a second order reaction A + A A
2
? A
? A
2
2
1
A k
dt
A d
=
? A
? A
dt k
A
A d
2
2
=

? A ? A
t k
A A
2
1 1
0
!
Concentration variation with time
For a second order reaction A + B C, let
there be x moles of C formed. Also, let a
and b be the initial number of moles of A
and B present. Then we can write
dt k
x b x a
dx
!
) )( (
? A
? A? A ) ( ) ( x b x a k B A k
dt
dx
dt
C d
= = =
dt k dx
x b
C
dx
x a
C
=

) ( ) (
2 1
Where C
1
= -C
2
= 1/(b-a)
3 2 1
) ln( ) ln( C kt x b C x a C + =
Concentration variation with time
For a third order reaction A + B + C D, let
there be x moles of D formed. Also, let
a,b and c be the initial number of moles
of A,B and C present. Then we can write
dt k
x c x b x a
dx
=
) )( )( (
? A
? A? A? A ) )( ( ) ( x c x b x a k C B A k
dt
dx
dt
D d
= = =
The above equation can be solved using the
method of partial fractions
Multi-step Reactions
O H H OH
OH H O
O O O
H H H
k
k
k k
k k
b f
b f
2
,
2
,
2
4
3
2 2
1 1
+
+
+
+
? A
? A ? A ? A? A ? A? A
H OH H O H b H f
H
C C k C C k C k C k
dt
C d
4 3
2
1 1
2 2
2
!
Multi-step Reactions
For multi-step reactions, a particular species may be
consumed or produced from more than one reaction
step and so it is necessary to find the net rate of
production of each species.
For the set of reaction steps shown for the hydrogen-
oxygen system, six species (H
2
, O
2
, H, O, OH and
H
2
O) are present and hence a set of six coupled
ordinary differential equations can be formulated.
The coupled set of ODEs can be solved numerically
by time- marching methods like the Runge- Kutta
schemes.
Quasi- steady state assumption
Reactants
Products
Intermediates
C
t
Many intermediate species
have a short life time and
they may reach a quasi-
steady state. That is, the
net reaction rate is equal
to zero for these species.
With quasi- steady assumption, the temporal variation of an
intermediate species can be determined in terms of the other
species concentrations, by taking the net rate as zero.
Multi-step Reactions
A multi- step reaction scheme can be categorized
as chain- initiation, chain- branching or chain-
propagation and chain- termination steps.
Steps like H
2
2H are chain initiation steps.
Steps like H + O OH are chain- branching.
Steps like OH + H are chain- terminating.
If the rate at which active species are formed is
faster than chain- termination, an explosive reaction
will result.
Chemical Equilibrium
Consider
H H H
b f
k k
+
1 1
,
2
Forward reaction rate ? A
2 , 1
H k R
f f
=

Backward reaction rate ? A

2
, 1
H k R
b b
!

At chemical equilibrium, forward rate = backward rate

? A
2 , 1
H k R
f f
=

= ? A
2
, 1
H k R
b b
=

? A
? A
2
2
, 1
, 1
H
H
k
k
K
b
f
eq
! !
K
eq
= f(T) only