Lecture 4: CHE 316

Second-Order Reactions
 The rate of a second-order reaction depends on two concentration terms; they may both refer
to the same reactant e.g. dissociation of HI or two different reactants.
 If the two reacting molecules are the same the equation may be represented as

2A  products and the rate law given by  d   k 2

dt
𝑑[𝐴]
Rearranging the equation; = −𝑘𝑑𝑡
[𝐴]2

Since we are interested in the change in concentration of A over a period of time, we integrate
between t = 0 and t = t;
[𝐴]𝑡 𝑡
𝑑[𝐴]
∫ ∫
= −𝑘 𝑑𝑡
[𝐴]𝑜 [𝐴]2 0
𝑑𝑥 1
To solve this, we use the following rule of integration (power rule): ∫ 𝑥 2 = 𝑥 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝒙𝒏+𝟏
Or (∫ 𝒙𝒏 = + 𝑪)
𝒏+𝟏

We then obtain the integrated rate equation.

1 1
− = 𝑘𝑡
[𝐴]𝑡 [𝐴]𝑂
Upon rearrangement of the integrated rate equation, we obtain an equation of the line:
1 1
= 𝑘𝑡 +
[𝐴]𝑡 [𝐴]𝑂
This equation has the form of a straight line (y = mx + b). If the reaction is second-order;
(i) A plot of 1 versus t will yield a straight line with a slope equal to k and y-intercept
[  ]t

equal to 1 .
[  ]o

1
(ii) One way to distinguish between first and second-order rate laws is to graph both In[A]t
and 1 against t. If the In[A]t plot is linear, the reaction is first-order; if the 1 plot is
[  ]t [  ]t

linear, the reaction is second-order.

(iii) The rate law, expressed as t  o allows us to predict concentration of A at any
1  kt o

given time after the start of the reaction. It shows that the concentration of A approaches
zero more slowly than in a first-order reaction.

The half-life of second order reaction

 We can find an expression for the half-life of a second order reaction by using the previously
derived integrated rate equation.
1 1
− = 𝑘𝑡
[𝐴]𝑡 [𝐴]𝑂

1
𝑆𝑖𝑛𝑐𝑒, [𝐴]𝑡1⁄ = [𝐴]𝑂
2 2
When t = t½
The integrated equation becomes;
1 1
− = 𝑘𝑡1⁄
1 [𝐴] 2
2 [𝐴] 𝑜
𝑂

2 1
− = 𝑘𝑡1⁄
[𝐴]𝑜 [𝐴]𝑂 2

1
= 𝑘𝑡1⁄
[𝐴]𝑂 2
1
𝑡1⁄ =
2 𝑘[𝐴]𝑂
The half-life of a second-order reaction is dependent on the initial concentration of reactant.

2
NB: Environmentally harmful substances that decay by second-order reactions may persist in low
concentration for long periods because their halve-lives are long when their concentrations are low.

Sample Exercise
The following data were obtained for the gas-phase decomposition of nitrogen dioxide at 300 oC,
2NO2(g)  2NO(g) + O2(g):
Time [NO2] (M)
0.0 0.0100
50.0 0.0079
100 0.0065
200 0.0048
300 0.0038

Is the reaction first or second-order with respect to NO2?

Solution:
To test whether the reaction is first or second order, we can construct plots of In[NO2] and
1
against time. In doing so, we will find it useful to prepare the following table from the
[ NO2 ]
data given.
Time (s) [NO2](M) ln [NO2] 1
[ NO2 ]
0.0 0.0100 - 4.61 100
50.0 0.0079 - 4.84 127
100.0 0.0065 - 5.04 154
200.0 0.0048 - 5.34 208
300.0 0.0038 - 5.57 263

300
250
ln[NO2]/ln 1/[NO2]

200
150 ln[NO2]
Series1
100 Series2
1/[NO2]
50 Linear (Series2)

0
0 100 200 300 400
-50
Time (s)

3
 -4.6
0 100 200 300 400
-4.8

-5
ln [NO2]

Series1
-5.2 Linear (Series1)

-5.4

-5.6
Time (s)

Plots of the kinetic data for the reaction 2NO2(g)  2NO(g) + O2(g) at 300 0C.
(a) Plot of ln[NO2] versus time is not linear and consequently, the reaction is not first
order in NO2.

(b) The plot of 1 versus time is linear: the reaction is second order in NO2.
[ NO2 ]
Therefore Rate = k[NO2]2. From the slope of the straight-line graph we have k =
0.543 M-1 s-1 for the disappearance of NO2.
Practice Exercise
1. Butadiene reacts to form its dimer according to the equation: 2C4H6(g) → C8H12(g). The
following data were collected for this reaction at a given temperature.
t (s) 0 1000 1800 2800 3600 4400 5200 6200
[C4H6] (mol/L) 0.01000 0.00625 0.00476 0.00370 0.00313 0.00270 0.00241 0.00208

(a) Is this reaction first order or second order? [ Ans: 2nd order].
(b) What is the value of the rate constant for the reaction? [ Ans: k = 6.14 × 10-2 L/mol.s].
(c) What is the half-life for the reaction under the conditions of this experiment? [ Ans. 1630 s].

Zero-order Rate Laws

Zero order reaction means that the rate of the reaction is proportional to zero power of the
concentration of reactants. Consider the reaction
A → products, to be of zero order,
𝑑[𝐴]
𝑅𝑎𝑡𝑒 = − = 𝑘[𝐴]0
𝑑𝑡

As any quantity raised to power zero is unity (1)

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 Therefore; d[A] = -kdt
Integrating both sides;
[𝐴]𝑡 𝑡
∫ 𝑑[𝐴] = −𝑘 ∫ 𝑑𝑡
[𝐴]0 0

[A] = – kt + C.....(i)
where, C is the constant of integration
(d) At t = 0, the concentration of the reactant A = [A] 0, where [A]0 is initial concentration of
Therefore; [A]t = -kt + [A]0 ….. (ii)
Comparing equation (ii) with equation of a straight line: y = mx + c
A plot of [A]t against t gives a straight line with slope = –k and intercept equal to [A]0.

Some photochemical reaction and a few heterogeneous reactions are zero-order reactants. Such
reactions are not common.

Half-life of a Zero Order Reaction

 For zero order reaction, we know that;
[A] = -kt + [A]0
[𝐴]0 − [𝐴]
𝑘=
𝑡
At half life of reaction,
[𝐴]0
t = t½ & [A] =
2

So;
[𝐴]0⁄
[𝐴]0 − 2 = [𝐴]0
𝑘=
𝑡 2𝑡1⁄
2

[𝐴]0
𝑡1⁄ =
2 2𝑘