752 20 PHYSICAL CHEMISTRY

and we have
1 1
k t1/ 2 = –
1 [A] 0
[A] 0
2
2 1
or k t1/ 2 = –
[A] 0 [A] 0
Solving for t1/2 we find that
1
t1/ 2 =
k [A] 0
As in case of a first order reaction, half-life for a second order reaction is inversely proportional
to rate constant k. While half-life of a first order reaction is independent of initial concentration,
half-life of a second order reaction depends on initial concentration. This fact can be used to distinguish
between a first order and a second order reaction.

[A]0
Concentration of A

[A]0 /2

[A]0 /4

[A]0 /8

0
0 1 2 3 4 5 6 7 8 9 10
Time
Figure 20.6
Second-order half-life. Concentration of a reactant A as a function of time for a
second-order reaction. Note that each half-life is twice as long as the preceding
one because t ½ = 1/k[A]0 and the concentration of A at the beginning of each
successive half-life is smaller by a factor of 2.

HOW TO DETERMINE THE ORDER OF A REACTION

There are at least four different methods to determine the order of a reaction.
(1) Using integrated rate equations
The reaction under study is performed by taking different initial concentrations of the reactant (a)
and noting the concentration (a – x) after regular time intervals (t). The experimental values of a,
 CHEMICAL KINETICS 753

(a – x) and t are then substituted into the integrated rate equations for the first, second and third order
reactions. The rate equation which yields a constant value of k corresponds to the correct order of the
reaction. This method of ascertaining the order of a reaction is essentially a method of hit-and-trial but
was the first to be employed. It is still used extensively to find the order of simple reactions.
(2) Graphical method
For reactions of the type A → products, we can determine the reaction order by seeing whether
a graph of the data fits one of the integrated rate equations.
In case of First order
We have already derived the integrated rate equation for first order as
a
1n = kt
a–x
Simplifying, it becomes
1n (a – x) = – kt + 1n a
↑ ↑ ↑
y = mx + b
Thus the two variables in the first order rate equation are :
a
1n and t
a–x
a
Hence, if 1n is plotted against t and straight line results (Fig. 20.7), the corresponding
a–x
reaction is of the first order. However, if a curve is obtained, the reaction is not first order.
log (a – x)

(a – x)
1

t t
Figure 20.7 Figure 20.8
Plot of log(a – x) against t for a first Plot of 1/(a – x) against t for a second
order reaction. order reaction.
In case of Second order
We have already shown that second order rate equation can be written as
1 1
= kt +
a−x a
↑ ↑ ↑
y = mx + b
This is the equation of a straight line, y = mx + b. Here the two variables are
1
and t
a−x
754 20 PHYSICAL CHEMISTRY

1
Thus when is plotted against t and we get a straight line (Fig. 20.8), the reaction is second
a−x
order. In case a curve is obtained, the reaction is not second order.
(3) Using half-life period
Two separate experiments are performed by taking different initial concentrations of a reactant.
The progress of the reaction in each case is recorded by analysis. When the initial concentration is
reduced to one-half, the time is noted. Let the initial concentrations in the two experiments be [A1] and
[A2], while times for completion of half change are t1 and t2 respectively.
Calculation of order of reaction. We know that half-life period for a first order reaction is
independent of the initial concentration, [A]. We also know :
1
half-life ∝ for 2nd order reaction
[A]
1
half-life ∝ for 3rd order reaction
[A] 2
1
half-life ∝ for nth order reaction
[A] n – 1
Substituting values of initial concentrations and half-life periods from the two experiments, we
have
1 1
t1 ∝ n –1
t2 ∝
[A1 ] [A 2 ] n – 1
n –1
t2 ⎡ A1 ⎤
and =
t1 ⎢⎣ A 2 ⎥⎦
⎡A ⎤ ⎡t ⎤
(n – 1) log ⎢ 2 ⎥ = log ⎢ 1 ⎥
⎣ A1 ⎦ ⎣ t2 ⎦
Solving for n, the order of reaction
log [t1 / t2 ]
n =1+
log [A 2 / A1 ]

SOLVED PROBLEM. In the reduction of nitric oxide, 50% of reaction was completed in 108 seconds
when initial pressure was 336 mm Hg and in 147 seconds initial pressure was 288 mm Hg. Find the
order of the reaction.
SOLUTION
We know that
n –1
t2 ⎡ A1 ⎤
= ...(1)
t1 ⎢⎣ A 2 ⎥⎦
where t1 and t2 are half-life periods and [A1] and [A2] are the corresponding initial concentrations,
while n is the order of the reaction.
Taking logs of the expression (1), we have
log [t2 / t1 ]
n =1+ ...(2)
log [A1 / A 2 ]
Substituting values in expression (2),
log 108 /147
n =1+
log 288 / 336
 CHEMICAL KINETICS 755

0.1339
=1+ =1+ 2 = 3
0.0669
Therefore, the reaction is of the third order.

(4) The Differential method

This method was suggested by van’t Hoff and, therefore, it is also called van’t Hoff’s differential
method. According to it, the rate of a reaction of the nth order is proportional to the nth power of
concentration.
dC
– = k Cn
dt
where C = concentration at any instant. In two experiments performed with different initial
concentrations, we can write
dC1
– = k C1n ...(1)
dt
dC2
– = k C2n ...(2)
dt
Taking logs of the expression (1) and (2)
⎛ dC ⎞
log ⎜ − 1 ⎟ = log k + n log C1 ...(3)
⎝ dt ⎠
⎛ dC ⎞
log ⎜ − 2 ⎟ = log k + n log C2 ...(4)
⎝ dt ⎠
On substracting (4) from (3), we get
⎛ dC1 ⎞ ⎛ dC2 ⎞
log ⎜ – ⎟ – ⎜– ⎟
n= ⎝ dt ⎠ ⎝ dt ⎠ ...(5)
log C1 – log C2
⎛ dC ⎞
To find n,⎜− ⎟ in the two experiments is determined by plotting concentrations against time (t).
⎝ dt ⎠
⎛ dC ⎞
The slope, ⎜ – ⎟ at a given time interval is measured by drawing tangents. Using the values of
⎝ dt ⎠
⎛ dC1 ⎞ ⎛ dC2 ⎞
slopes ⎜ – ⎟ and ⎜ – ⎟ in the equation (5), n can be calculated.
⎝ dt ⎠ ⎝ dt ⎠
(5) Ostwald’s Isolation method
This method is employed in determining the order of complicated reactions by ‘isolating’ one of
the reactants so far as its influence on the rate of reaction is concerned. Suppose the reaction under
consideration is :
A + B + C ⎯⎯ → products
The order of the reaction with respect to A, B and C is determined. For the determination of the
order of reaction with respect to A, B and C are taken in a large excess so that their concentrations are
not affected during the reaction. The order of the reaction is then determined by using any of the
methods described earlier. Likewise, the order of the reaction with respect to B and C is determined. If
nA, nB and nC are the orders of the reaction with respect to A, B and C respectively, the order of the
reaction n is given by the expression.
n = nA + nB + nC