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6690-7-24E

AID: 1112 | 30/08/2016

The rate law expression is as follows:


x
y
r k A B

Where k is the rate constant,


and
and y are the partial orders of a reaction.

are the concentration of the species A and B, x

The rate of a chemical reaction is defined as the rate of change of concentration of


reactants and products which is given by the expression:
d R
rate
dt
d P

dt

Where,
denotes the concentration of reactant and
denotes the concentration of
product.
Rate of the reaction for the reaction given below is represented as follows:
A 2B
d[product]
d[reactant]
rate=

dt
dt
1 d[B]
d[A]
rate

k [A]
2 dt
dt
Where k is the rate constant. Consider this reaction given below,
k
*
1) A + B k 1
A
1

2) A* +C Product
A+ B +C Product

Here, in this reaction A represents the molecule which reacts with B to form an
intermediate and is in equilibrium. Formation of product follows a certain mechanism
given above as follows:
Step 1) represents an equilibrium reaction.
Step 2) represents the further reaction of A* with C.

Here A* is a steady variable which is present in the reaction but neither as reactant nor
product in the overall reaction and thus the rate of reaction of such intermediate is
considered almost equal to zero in accordance to the steady state approximation. The
concentration term of intermediate does not appear in rate law expression for formation
of product.
The given acid catalyzed reaction is as follows:

1 HA H kk1
HAH fast
1

HAH B

k2

BH

HA slow

In the first reaction, as the reaction is in equilibrium so, rate of forward reaction is equal
to rate of backward reaction written as follows:

k1 HA H k 1 HAH
HAH
k1

k1 HA H
k
HAH 1 HA H

k 1

HAH

is the intermediate here and is involved in rapid pre equilibrium.


k
HAH 1 HA H

k1

(1)

The rate of formation of product is,


d BH
rate
dt
k2
The rate law expression for the formation of product with rate constant
d BH
r
k2 HAH B
dt

Substitute

HAH

is as follows:

from equation (1) in the above expression as follows:

d BH
kk
2 1 HA H
dt
k1

B
(2)
d BH
kk
2 1 HA H
dt
k1

Hence, the rate law expression is

B
.

The above expression is the rate of formation of product and contains the term
H
H

, the

rate law expression can become independent of


if the source of
is the acid
H
HA
HA
, then another equilibrium represents the ionization of acid
to give
as
follows:
K
H A
HA a
Ka
The equilibrium constant
H A

Ka
HA

is given as follows:

It is considered that equal concentrations of proton and anion is released by the acid so,
H
A

So, the expression for equilibrium constant for the ionization of acid HA becomes,
H A

Ka
HA
2

HA

H K a HA

Substitute

obtained in the above expression in equation (2) as follows:

d BH
kk
2 1 HA H
dt
k1

Hence,

the

d BH
dt

k2 k1
HA K a HA B
k1
k2 k1 K a

1/2

HA B
3/2

k1

rate

k2 k1 K a

1/2

expression

HA B
3/2

k1
.

independent

of

the

term

is