𝑪𝑯𝑬𝑴𝑰𝑪𝑨𝑳 𝑲𝑰𝑵𝑬𝑻𝑰𝑪𝑺 (𝑫𝑨𝑻𝑨 & 𝑮𝑹𝑨𝑷𝑯𝑰𝑪𝑨𝑳 𝑰𝑵𝑻𝑬𝑹𝑷𝑹𝑬𝑻𝑨𝑰𝑶𝑵)

CHEMICAL KINETICS
Kinetics is the study of reaction rates, determining which products are formed fastest. Kinetics
also helps to predict how the rate will change if the reaction conditions are changed.

1. Rate of reaction;
Some reactions e.g. ionic reactions occur very fast like precipitation of silver chloride by
mixing aqueous solver nitrate with sodium chloride solution. On the other hand, some
reactions are very slow e.g. rusting of iron in the presence of air and moisture.
The rate/ speed of chemical reaction can be defined as the change in concentration of a
reactant or product per unit time. To be more specific, it can be expressed in terms of;
 The rate of decrease in concentration of any one of the reactants or
 The rate of increase in concentration of any one of the products.
2. Rate law: rate law is an expression which gives the relationship between rate of reaction
and concentration of the reactants.

Consider a general reaction

aA + bB cC + dD

Rate = k[A]x [B]y

The above equation is known as the rate law or expression. K is known as the rate constant.

NB: Rate law for any reaction cannot be predicted by merely looking at the balanced chemical
equation (it has nothing to do with stoichiometric ratios i.e. theoretically but it is determined
experimentally, for example consider the equation below;

CHCl3 + Cl2 CCl4 + HCl

1
Rate = k[𝐶𝐻𝐶𝑙3 ][𝐶𝑙2 ]2

3. Order of reaction is defined as the exponents of the concentration terms in the

experimental rate law of reaction. It can be 1, 2, 3 or fractional.

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 Or the power to which a concentration is raised in the experimentally determined rate
equation.
4. Overall order of reaction: the sum of all the individual orders in the experimentally
determined rate equation.

Classification of reaction orders.

1. Zero order.
The rate of reaction is proportional to zero power of the concentration of the reactants.
Consider the reaction: 𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠

−𝑑[[𝐴]
𝑅𝑎𝑡𝑒 = = 𝑘[𝐴]0
𝑑𝑡

−𝑑[[𝐴]
=𝑘 ⇒ 𝑑[𝐴] = −𝑘𝑑𝑡
𝑑𝑡
𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑛𝑔 𝑏𝑜𝑡ℎ 𝑠𝑖𝑑𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛;
[𝐴]𝑡 𝑡
∫ 𝑑[𝐴] = − 𝑘 ∫ 𝑑𝑡
[𝐴]𝑂 0

[𝐴]𝑡 − [𝐴]0 = −𝑘𝑡

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 … … … … … … … … … … … (𝑖)

𝑐𝑜𝑚𝑝𝑎𝑟𝑖𝑛𝑔 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (𝑖)𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑔𝑒𝑛𝑟𝑎𝑙 𝑙𝑖𝑛𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛;

𝑦 = 𝑚𝑥 + 𝑐; 𝑖𝑓 𝑤𝑒 𝑝𝑙𝑜𝑡 𝑎 𝑔𝑎𝑟𝑎𝑝ℎ 𝑜𝑓 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑎𝑟𝑖𝑜𝑛 𝑎𝑔𝑎𝑖𝑛𝑠𝑡 𝑡𝑖𝑚𝑒, 𝑎 𝑠𝑡𝑟𝑎𝑖𝑔ℎ𝑡 𝑙𝑖𝑛𝑒 𝑤𝑖𝑡ℎ 𝑠𝑙𝑜𝑝𝑒 =
−𝑘 𝑎𝑛d 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = [𝐴]0
Note; a plot of 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑎𝑟𝑖𝑜𝑛 𝑎𝑔𝑎𝑖𝑛𝑠𝑡 𝑡𝑖𝑚𝑒 gives a linear (straight) graph and if the graph is not linear,
then the reaction is not zero order.

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 2. First order.
The rate of reaction is proportional to zero power of the concentration of the reactants.
Consider the reaction: 𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠

−𝑑[[𝐴]
𝑅𝑎𝑡𝑒 = = 𝑘[𝐴]1
𝑑𝑡

−𝑑[[𝐴] 𝑑[𝐴]
= 𝑘]𝐴] ⇒ = −𝑘𝑑𝑡
𝑑𝑡 [𝐴]
𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑛𝑔 𝑏𝑜𝑡ℎ 𝑠𝑖𝑑𝑒𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛;
[𝐴]𝑡 𝑡
𝑑 [𝐴]
∫ = − 𝑘 ∫ 𝑑𝑡
[𝐴]𝑂 [𝐴] 0

𝐼𝑛[𝐴]𝑡 − 𝐼𝑛[𝐴]0 = −𝑘𝑡

𝐼𝑛[𝐴]𝑡 = −𝑘𝑡 + 𝐼𝑛[𝐴]0 … … … … … … … … … … … (𝑖𝑖)

𝑐𝑜𝑚𝑝𝑎𝑟𝑖𝑛𝑔 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (𝑖)𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑔𝑒𝑛𝑟𝑎𝑙 𝑙𝑖𝑛𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛;

𝑦 = 𝑚𝑥 + 𝑐; 𝑖𝑓 𝑤𝑒 𝑝𝑙𝑜𝑡 𝑎 𝑔𝑎𝑟𝑎𝑝ℎ 𝑜𝑓 In[A] 𝑎𝑔𝑎𝑖𝑛𝑠𝑡 𝑡𝑖𝑚𝑒(𝑡), 𝑎 𝑠𝑡𝑟𝑎𝑖𝑔ℎ𝑡 𝑙𝑖𝑛𝑒 𝑤𝑖𝑡ℎ 𝑠𝑙𝑜𝑝𝑒
= −𝑘 𝑎𝑛 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = [𝐴]0
Note; a plot of In[A] 𝑎𝑔𝑎𝑖𝑛𝑠𝑡 𝑡𝑖𝑚𝑒(𝑡) gives a linear (straight) graph and if the graph is not linear, then
the reaction is not first order.

Half-life of a reaction:
Is the time taken for the concentration of the reactant to reduce to one half of its
initial (original) 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛. It is denoted by 𝑡1 .
2

Half-life for first order reaction;

From; 𝐼𝑛[𝐴]𝑡 − 𝐼𝑛[𝐴]0 = −𝑘𝑡

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 [𝐴]𝑡
𝐼𝑛 ( ) = −𝑘𝑡
[𝐴]0

[𝐴]0
𝑇ℎ𝑖𝑠 𝑖𝑚𝑝𝑙𝑖𝑒𝑠 𝑡ℎ𝑎𝑡 𝐼𝑛 ( ) = 𝑘𝑡 … … … … … … … … … . . (𝑖𝑖𝑖)
[𝐴]𝑡

[𝐴]0
𝐴𝑡 ℎ𝑎𝑙𝑓 𝑙𝑖𝑓𝑒, 𝑡 = 𝑡1 , 𝑎𝑛𝑑 [𝐴]𝑡 = ; substituting these values into equation (ii)
2 2

gives;

[𝐴]0
𝐼𝑛 ( ) = 𝑘𝑡1 , 𝑠𝑖𝑚𝑝𝑙𝑖𝑓𝑦𝑖𝑛𝑔 𝑔𝑖𝑣𝑒𝑠 𝐼𝑛2 = 𝑘𝑡1
[𝐴]0 2 2
2

0.693
𝑖𝑚𝑝𝑙𝑦𝑖𝑛𝑔 𝑡ℎ𝑎𝑡 𝑡1 =
2 𝑘

Sample calculations.
1. For a general reaction “aA + bB →products,” the following initial rates are
determined experimentally when reactions are set up with the initial amounts
indicated in units of molarity, M.
Expt [A] (M) [B] (M) Initial Rate (MS-1)
1 1.44 0.35 5.37 × 10−3
2 1.44 0.70 2.15 × 10−2
3 2.89 0.35 2.69 × 10−3
Assuming the rate law is written as; 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑚 [𝐵]𝑛 , determine the value of m, n
and k. [Answer is m is -1, n is 2 and k is 6.31 × 10−2 𝑆 −1
2. Using the following data for the reaction illustrated in Equation (35.13), determine the
order of the reaction with respect to A and B, and the rate constant for the reaction:
Expt [A] (M) [B] (M) Initial Rate (MS-1)
1 2.30 × 10−4 3.10 × 10−5 5.25 × 10−4
2 4.60 × 10−4 6.20 × 10−5 4.20 × 10−3
3 9.20 × 10−4 6.20 × 10−5 1.68 × 10−2

[Answer is wrt A is 2 and wrt B is 1 and rate constant is 3.17 × 108 𝑀−2𝑆 −1]

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 3. In a reaction between A and B, the initial rate of reaction (𝑟0 ) was measured for different
initial concentrations of A and B as given below;
A (MolL-1) 0.20 0.20 0.40
B (MolL-1) 0.30 0.10 0.05
𝑟0 (MolL-1S-1) 5.07 × 10−5 5.07 × 10−5 1.43 × 10−4
What is the order of the reaction with respect to A and B?

Experimental determination of reaction rates

The rate of a chemical reaction can be obtained by following some property of the reaction e.g.
concentration of the reactant or product which changes with extent of this reaction, then
analyzing the reaction mixture at suitable intervals of time which makes it possible to determine
the concentration of both the reactants and products at different time hence obtain a suitable
measure of reaction rate.

Titrimetric analysis.

1. Experiment to show that iodination of propanone is zero order with respect to iodine.
𝐻+
𝐶𝐻3 𝐶𝑂𝐶𝐻3 (𝑎𝑞) + 𝐼2 (𝑎𝑞) ↔ 𝐶𝐻3 𝐶𝑂𝐶𝐻2 𝐼2 (𝑎𝑞) + 𝐻𝐼(𝑎𝑞)
𝑝𝑟𝑜𝑐𝑒𝑑𝑢𝑟𝑒
 A known volume of propanone and dilute sulphuric acid are placed in a beaker
and then a known volume of iodine is added to this beaker and the stop clock
simultaneously started.
 The beaker is shaken for some time and after a given time interval e.g. 5 minutes,
a known volume of the reaction mixture is pipetted and removed for analysis by
adding it into a conical flask that contains a reagent which quenches (stops) the
reaction e.g. sodium carbonate or sodium hydrogen carbonate to neutralize the
acid catalyst.

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  The quenched mixture is then analyzed by titrating it with a standard solution of
sodium thiosulphate using starch indicator. This procedure is repeated at
measured time intervals and since volume of
sodium thiosulphate gives a measure of amount
of iodine remaining in the reaction mixture at
given time interval, a graph of volume of
thiosulphate versus time is plotted.
 Or a graph of rate of reaction against
concentration of thiosulphate is plotted.
 From the graph, order of reaction with
respect to iodine is zero because it is a linear
graph.

2. Experiment to show that decomposition of hydrogen peroxide is first order.

𝐹𝑒 3+
2H2O2 (aq) 2H2O (l) + O2 (g)
−
𝑂𝐻
𝑃𝑟𝑜𝑐𝑒𝑑𝑢𝑟𝑒:

 A known volume of hydrogen peroxide is placed in a beaker followed by a known

volume of sodium hydroxide solution.
 A known volume of a catalyst of iron(iii) chloride is added and a stop clock is
simultaneously started.
 Samples of the reaction are pipetted and added to a conical flask containing excess dilute
sulphuric acid (to prevent further decomposition of hydrogen peroxide) at given time
intervals.
 These samples are then titrated with a standard solution of potassium permanganate from
the burette.
 The concentration of hydrogen peroxide at a given time interval is calculated by
backward calculation and a graph of concentration against time is plotted or a graph of
rate against time is plotted.
 The reaction is found to be first order with respect to hydrogen peroxide.

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 3. For esterification;

𝐻+
HCOOH (aq) + CH3OH HCOOCH3 (aq) + H2O (aq)
Heat
𝑝𝑟𝑜𝑐𝑒𝑑𝑢𝑟𝑒

 A given amount of the ester is added to a given amount of water in a beaker. The mixture
is heated to a given temperature i.e. above 40oc.
 A few drops of concentrated sulphuric acid are added and the stop clock is started
simultaneously.
 The beaker is shaken for some minutes and at measure time intervals, known volumes of
the reaction mixtures are pipetted into conical flask and cooled in ice cold water to
prevent the reaction.
 Then amount of carboxylic acid formed is then titrated with a standard solution of sodium
hydroxide using phenolphthalein indicator.
 A graph of concentration of sodium hydroxide is then plotted against time.

Graphical determination of orders of reaction

NOTE: If a graph of concentration is plotted against time,

 For first order, the half-life is constant each time the “initial” concentration is reduced to
half its previous value.
 For second order’ the half-life doubles each time the “initial” concentration is reduced to
half its previous value.
𝑬𝒙𝒂𝒎𝒑𝒍𝒆𝒔
1. The table below shows the kinetic data that were obtained for the hydrolysis of the
ester, methyl ethanoate in acid solution
Time (min) 0 3600 7200 10800 14400
Concentration of ester (moldm-3) 0.2405 0.1565 0.1045 0.0685 0.0455
(i) Plot a graph of concentration of the ester, methyl ethanoate against time.
(ii) Determine the half-life of the reaction.

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 Solution

A graph of cncentration of the ester against time

0.3

0.25

0.2
[Ester] moldm-3

0.15

0.1

0.05

0
0 2000 4000 6000 8000 10000 12000 14000 16000
time (min)

2. The experimental data for decomposition of N2O5; [𝑁2 05 ⟶ 4𝑁𝑂2 + 𝑂2 ] in gas phase
at 318K are given below;
t (s) 0 400 800 1200 1600 2000 2400 2800 3200
[𝑁2 05 ] 𝑚𝑜𝑙𝑑𝑚−3 163 136 114 93 78 64 53 43 35
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(See next page for solution)

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 A graph of [N2O5] against t
180

160

140

120
[N2O5] moldm-3

100

80

60

40

20

0
0 500 1000 1500 2000 2500 3000 3500
t (s)

163
From the graph, Time corresponding to the concentration, = 81.5 𝑚𝑜𝑙𝑑𝑚−3is the
2

half-life. From the graph, the half-life is 1450s also the successive half-lifes are
constant implying that the reaction is first order.

3. For the gas phase (Dimerization) reaction at 300Oc, 2𝐶2 𝐹4 → 𝐶4 𝐹8 , the following
concentration of C2F4 were obtained.
t (s) 0 250 750 1750 3750
[𝐶2 𝐹4 ] 𝑚𝑜𝑙𝑑𝑚−3 0.0500 0.0250 0.0125 0.00625 0.00312
Plot a graph of concentration against time, determine the half-life and order of reaction
giving a reason for your answer.

(See next page for solution)

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 A graph of concentration against time
0.06

0.05

0.04

0.03

0.02

0.01

0
0 500 1000 1500 2000 2500 3000 3500 4000
Time (min)

The half-life doubles each time the “initial” concentration is reduced to half its previous value.
This behavior indicates a second-order reaction.

END

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