The units of rate constant for a reaction of third order are conc

.-2
time
-1
i.e. mol
-2
L
2
s
-1
. for a
gaseous reaction the units will be atm
-2
s
-1
.

iv) Zero order reactions: a reaction A products is said to be of zero order when its rate
law is given by
Rate =k [A]0 = k
Obviously, in a zero order reaction, the rate does not depend upon the concentration of
reactants and remains constant throughout the course of reaction when the concentration of a
reactant is changed, the rate does not change i.e. the reaction proceeds with a constant rate.
Some examples of zero order reactions are as follows.

0 0
2 2 2 2
2 ; [ ] [ ] H Cl HCl rate k H Cl k
0
3 2 2 3
2 3 ; [ ] NH N H rate k NH k
The units of rate constant for a zero order reaction are conc. Time
-1
ie.e. mol L
-1
s
-1.
For a
gaseous reaction the units are atm s
-1
.

v) Reaction of fractional order: some examples of reactions having fractional
orders are as follows.
3/ 2
3 4 3
; [ ] 3/ 2 CH CHO CH CO rate k CH CHO order
1/ 2
2 2 2 2
2 ; [ ][ ] 3/ 2 H Br HBr rate k H Br order
3/ 2
2 2 2
; [ ] 3/ 2 COCl CO Cl rate k COCl order
2 1/ 2
2 2 2
; [ ] [ ] 5 / 2 CO Cl COCl rate k CO Cl order

9. First order reactions: some more details of the first order reactions are as follows;
a) Rate equation for a first order reaction: a first order reaction is an exponential process
and the concentration of the reactant decreases exponentially with time. Let us consider the
following reaction which is of first order.
A products
If, [A]
0

= initial concentration of A, and [A] = concentration of A after a time interval of t ,
we have
[A] =[A]
0
e
kt
..(i)
Where, k is the rate constant of the reaction.
The above equation can also be written as
K =
0
[ ] 2.303
log
[ ]
A
t A
(ii)
This equation represents the rate equation of a first order reaction.
If the initial concentration of A is a mol L
-1
and x moles of it change into products during
time interval t, we have [A]
0
= a mol L
-1
and [A] = a x mol L
-1
. Thus, the above equations
can also be written as
10
2.303
log
a
t a x
..(iii)
Eqs. (ii) and (iii) are also referred to as integrated rate law or integrated rate equations for a
first order reaction.
b) Graphical representation of a first order reaction: following are the different graphical
representations of a first order reaction: