3.

Integrated rate laws

(a) First-order reactions
A P
dA dP
 k  A
1
v 
dt dT

d  A
  kdt
 A
A
t
d  A t

A   A  k 0 dt
o
  At
ln  kt  At   Ao e kt
 Ao

where [A]o is the initial concentration of A (at t= 0).

The exponential decay of the

reactant in a first -order reaction. The
larger the rate constant. the more rapid
the decay:
here klarge = 3ksmall.
 The other equation is :

 t  o  ln  At  kt  ln  Ao

A  A e  kt

y= mx + C
Self-test 4. In a particular experiment, it was found that
the concentration of N205 in liquid bromine varied with
time as follows:

Confirm that the reaction is first-order in N205 and determine

the rate constant.
(b) Half-lives and time constants

the half-life, t I/2 , of a substance, the time taken for the

concentration of a reactant to fall to half its initial value. The time for
[A] to decrease from [A]o to 1/2[A]o in a first-order reaction is given
by eqn :

Hence
Another indication of the rate of a first -order reaction is the time
constant, '" (tau), the time required for the concentration of a
reactant to fall to lie 1/e of its initial value. From eqn above it
follows that

That is, the time constant of a first -order reaction is the reciprocal of
the rate constant:
(c) Second-order reactions

(22.15a)

To integrate eqn 22.15a we rearrange it into

Because the integral of 1/x2 is -1/x, we obtain eqn 22.15b by

substitution of the limits
Half-lives and time constants

t1/2 : [A]o  ½ [A]o

1 1
  kt
 At  Ao
1 1
  kt1/ 2
2  Ao  Ao
1

1
 kt1/ 2
 Ao
In general, for an nth-order reaction of the form A products, the half-life
is related to the rate constant and the initial concentration of A by

Another type of second-order reaction is one that is first-order in

each of two reactants A and B:

A+BP
 A + B  P

Initial : [A]o [B]o

Rx : -x -x +x
 : [A]o - x [B]o - x x

d  A d  B
v   k  A B 
dt dt
d  A x k

dt
o
  A o
x   B 
o
x 
dx
dt

 k  Ao  x   B o
x 
The initial condition is that x = 0 when t = 0; so the integration
required is
Table 1 Integrated rate laws
Latihan :
1. The rate of the reaction A + 3 B  C + 2 D was reported as 1.0 mol
dm-3 s-1. State the rates of formation and consumption of the participants.

2. At 400 K, the rate of decomposition of a gaseous compound initially

at a pressure of 12.6 kPa, was 9.71 Pa s-1 when 10.0 per cent had
reacted and 7.67 Pa s-1 when 20.0 per cent had reacted. Determine
the order of the reaction.

3. The data below apply to the reaction, (CH3)3CBr + H2O 

(CH3)3COH + HBr. Determine the order of the reaction. the rate
constant, and the molar concentration of (CH3)3CBr after 43.8 h.