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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
(1)
Substitute
HAH
is as follows:
d BH
kk
2 1 HA H
dt
k1
B
(2)
d BH
kk
2 1 HA H
dt
k1
B
.
The above expression is the rate of formation of product and contains the term
H
H
, the
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
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