LEECTURE NOTES CHM 4205 Prepared by Dr.

Kamal Suleiman Kabo

CHM 4205: Reaction Kinetics Lecture Notes

1. Review Of First Order, Second Order and Third Order Reactions
2. Rate Equations, Rate Constants and Equilibrium Constants
3. Collision Theory Section – A
4. Transition State Theory
5. Reaction Coordinates
6. Unimolecular Reaction Theory
7. Bimolecular Reaction Mechanisms
8. Chain Reaction Mechanisms Section – B
9. Catalysis And Heterogeneous Reactions
10. Photochemical Reaction Mechanisms
Section – A
Introduction
Reaction Kinetics concerns with the speed or rates of chemical reactions. The study of reaction rates
allows for the prediction of how fast it will take a reaction mixture to reach equilibrium. It also accounts
for how the reaction rate would be optimized by controlling certain factors such as temperature, pressure
and the presence of a catalyst. The study of rate often reveals the sequence of elementary steps that lead to
the product formation from the reactants, which is referred to as the reaction mechanism. Many reactions
of industrial and biological importance involve complex sequence of steps, or proceed at a useful rate only
in the presence of catalysts. Many gas reactions of industrial importance also occur only on the surface of
solids which act as catalysts. The mode of action of such surface reactions are discussed in this course.
Light is a form of energy and light energy can be used to initiate or sustain chemical reaction. All this will
also be discussed in this course.
Review Of First Order, Second Order and Third Order Rate Equations, Rate Constants and Equilibrium
Constants
Order of the Reaction
The order of a chemical reaction refers to the mathematical relationship between the rate of the reaction
and the concentrations of the reactants. It is determined by experimental data and is represented by an
exponent in the rate equation. For a general reaction of the form:

The rate equation can be expressed as:

where:

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

• k is the rate constant,

• [A] and [B] are the concentrations of the reactants A and B,
• m and n are the orders of the reaction with respect to A and B, respectively.
The overall order of the reaction (a+b) is the sum of the individual orders with respect to each reactant.
The order of a reaction can be zero, first, second, or even higher.
Experimental methods, such as the method of initial rates, are used to determine the orders of reaction by
varying the concentrations of the reactants and observing their effects on the rate of the reaction. The order
of a reaction provides insight into the reaction mechanism and influences the design and optimization of
chemical processes.
1. Zero Order Reaction:
Zero order reaction is a reaction in which the rate is independent of the concentration of the reactant.
In zero order reactions, increase the concentration of the reactant, does not change the rate of the reaction.
Since the reaction is independent on the concentration of reactants, the equation can be represented as;
0A P
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]0 = 𝑘 × 1 = 𝑘
𝑅𝑎𝑡𝑒 = 𝑘
Therefore, the rate equation for this zero-order reaction is:
Rate = k
where k is the rate constant. The unit of the rate constant (k) in a zero-order reaction is expressed as
concentration/time (e.g., moldm-3 s-1).
An example of a zero-order reaction is the decomposition of hydrogen peroxide
H2O2) in the presence of catalase enzyme:

The rate of this reaction is zero-order with respect to hydrogen peroxide. The rate is determined solely by
the concentration of the catalyst and is independent of the concentration of hydrogen peroxide.
2. First Order Reaction:
A first-order reaction can be defined as a chemical reaction for which the reaction rate is entirely
dependent on the concentration of only one reactant.
• The rate of the reaction is directly proportional to the concentration of a single reactant. E.g.
A P
• The rate equation is given by Rate = k[A]

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

where k is the rate constant and [A] is the concentration of the reactant.
An example is the decay of carbon-14 (14C isotope) in organic material used for radiocarbon dating. The
decay follows a first-order kinetics.

3. Second Order Reaction:

A second-order reaction can be defined as a chemical reaction for which the reaction rate is dependent on
the concentration of two reactants.
2A Products or A+B Products
• The rate of the reaction is proportional to the square of the concentration of a single reactant or to
the product of the concentrations of two reactants.
• The rate equation is given by
Rate=k[A]2, or Rate=k[A][B],
where k is the rate constant and [A] and [B] are the concentrations of the reactants.
Graph of concentration against time to obtain the plot of reactions order
4. Third Order Reaction:
A second-order reaction can be defined as a chemical reaction for which the reaction rate is dependent on
the concentration of two reactants.
3A Products or A+B+C Products
• The rate of the reaction is proportional to the concentration of a single reactant raised to the power
of 3 or to the product of the concentrations of two reactants.
• The rate equation is given by
Rate=k[A]3, or Rate = k[A] [B] [C],
where k is the rate constant and [A], [B] and [C] are the concentrations of the reactants.
Graph of concentration against time to obtain the plot of reactions order
Rates of Reaction:
The rate of a reaction simply means the decrease in concentration of the reactants or incr ease in the
concentration of the products per unit time. Thus;
𝑑[𝑅]
𝑅𝑎𝑡𝑒 = − or
𝑑𝑡
𝑑[𝑃]
𝑅𝑎𝑡𝑒 = 𝑑𝑡

Where, d means change. [R] the concentration of reactants, [P] concentration of products and t is time.
Example; Consider the equation below;

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

aA + bB cC + dD
A and B are reactants while C and D are products; a, b, c and d are the stoichiometric coefficients.
In order to determine the rate of he above equation, we can write;
1 𝑑[𝐴]
𝑅𝑎𝑡𝑒 = − 𝑎 [ ] or
𝑑𝑡

1 𝑑[𝐵]
𝑅𝑎𝑡𝑒 = − 𝑏 [ ] or
𝑑𝑡

1 𝑑[𝐶]
𝑅𝑎𝑡𝑒 = [ ] or
𝑐 𝑑𝑡

1 𝑑[𝐷]
𝑅𝑎𝑡𝑒 = − 𝑑 [ ]
𝑑𝑡

Instantaneous Rate
The rate of reaction at a specified time is also known as instantaneous rate of reaction; it can be generally
defined as the rate of change of concentration of a specified species at a particular instance.
Example;
Consider the reaction;
A P
𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴
Rate = or
𝑡𝑖𝑚𝑒
𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑃
Rate = 𝑡𝑖𝑚𝑒

Exercise:
10 g of CaCO3 was dissolved in 0.1 M HCl and after 20 mins only 2 g of the CaCO3 remains. Calculate
the rate of the reaction.
In laboratory, the rate of reaction is calculated by monitoring the concentration of the reaction species over
time interval. The results are carefully tabulated and a plot is drawn with concentration against time and
the slope of the plot is taken as the rate of reaction.

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

Rate Laws
Rate law is an expression that provides a relationship between the rate of reaction and the concentration of
the reactants participating in it.
Experimentally it is found that rates depend on the concentrations of the species involved in the reaction.
The relation between the rate and these concentrations is expressed mathematically in the form of an
equation called a rate law. Some rate laws are very simple and some are very complicated. A rate law may
be determined experimentally or may be the result of a theoretical prediction, or both.
Consider the reaction
aA + bB cC + dD
the rate law for the above equation is;

Zero Order Rate Law

A zero-order rate law is one in which the rate is not dependent on the concentration of the reactant.
𝑅𝑎𝑡𝑒 = 𝑘…………………………………………………………..1
Consider the reaction of the type
A P
In order to find solution for the zero-order integrated late law, we recall from the definition of rate.
𝑑[𝐴]
𝑅𝑎𝑡𝑒 = − [ ]……………………………………………………2
𝑑𝑡

Combining equations 1 and 2

𝑑[𝐴]
−[ ]=𝑘
𝑑𝑡

−𝑑[𝐴] = 𝑘𝑑𝑡
𝐴 𝑡
−𝑑 ∫ [𝐴] = 𝑘 ∫ 𝑑𝑡
𝐴𝑜 0

[𝐴] 𝑡
−[𝐴]] = 𝑘𝑡]
[𝐴]𝑜 𝑜
−([𝐴] − [𝐴]𝑜 ) = 𝑘(𝑡 − 0)
−[𝐴] + [𝐴]𝑜 = 𝑘𝑡
[𝑨] = [𝑨]𝒐 − 𝒌𝒕
In order to find the zero-order rate constant, a graph of concentration [𝐴] is plotted against time t and the
slope k is the rate constant

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

Half-life of Zero Order reactions

The half-life of a chemical reaction is the time taken for the concentration of the reactant to be reduced by
half its initial value. This implies that if the initial concentration of the reactant was ‘at’, at half-life, the
[𝐴]𝑜⁄
concentration will become, [𝐴] = 2.
Using this concept, the half-life for a zero-order reaction can be derived
[𝐴]𝑜 − [𝐴] = 𝑘𝑡
Therefore, at t1/2,
[𝐴]𝑜⁄
[𝐴]𝑜 − 2 = 𝑘𝑡1⁄2 multiply by 2
2[𝐴]𝑜 − [𝐴]𝑜 = 2𝑘𝑡1⁄
2

[𝐴]𝑜 = 2𝑘𝑡1⁄
2

[𝑨]𝒐
𝒕𝟏⁄ =
𝟐 𝟐𝒌
Example:
Calculate the half-life of a zero-order reaction if the concentration of A changes from 0.1 M to 0.025 M
after 30 minutes,
Solution;
[𝑨]𝒐
The equation = 𝒕𝟏⁄ =
𝟐 𝟐𝒌

Given;
[𝑨]𝒐 = 0.1 M
[𝐴] = 0.025 M

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

k =?
𝑡1⁄ = ?
2

First, we need to find the value of k using the integrated rate law, thus;

[𝐴]𝑜 − [𝐴] = 𝑘𝑡
0.1 – 0.025 = k × (30×60)
𝟎.𝟎𝟕𝟓
𝒌= = 4.16 × 10-5 Ms-1
𝟏𝟖𝟎𝟎

First Order Rate Law

A first-order rate law is one in which the rate is dependent on the concentration of a single reactant.
Consider the reaction of the type
A P
From the rate law
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]………………….,…………………………………..1
We recall from the definition of rate.
𝑑[𝐴]
𝑅𝑎𝑡𝑒 = − [ ]……………………………………………………2
𝑑𝑡

In order to find solution for the zero-order integrated late law, combining equations 1 and 2
𝑑[𝐴]
−[ ] = 𝑘[𝐴]
𝑑𝑡
𝑑[𝐴]
− = 𝑘𝑑𝑡
[𝐴]
𝐴 𝑡
𝑑[𝐴]
−𝑑 ∫ = 𝑘 ∫ 𝑑𝑡
𝐴𝑜 [𝐴] 0

[𝐴] 𝑡
−𝑙𝑛[𝐴]] = 𝑘𝑡]
[𝐴]𝑜 𝑜
−(𝑙𝑛[𝐴] − 𝑙𝑛[𝐴]𝑜 ) = 𝑘(𝑡 − 0)
−𝑙𝑛[𝐴] + 𝑙𝑛[𝐴]𝑜 = 𝑘𝑡
𝑙𝑛[𝐴]𝑜 − 𝑙𝑛[𝐴] = 𝑘𝑡
[𝑨]𝒐
𝒍𝒏 = 𝒌𝒕
[𝑨]
Also,

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

𝑙𝑛[𝐴]𝑜 − 𝑙𝑛[𝐴] = 𝑘𝑡
𝑙𝑛[𝐴] = 𝑙𝑛[𝐴]𝑜 − 𝑘𝑡
𝑙𝑛[𝐴] = 𝑙𝑛[𝐴]𝑜 − 𝑘𝑡
[𝑨] = [𝑨]𝒐 𝒆𝒙𝒑−𝒌𝒕
[𝑨]
In order to find the first-order rate constant, a graph of ln [𝑨]𝒐 is plotted against time t and the slope k is the
rate constant.

Half-life of First Order reactions

The half-life of a chemical reaction is the time taken for the concentration of the reactant to be reduced by
half its initial value. This implies that if the initial concentration of the reactant was ‘at’, at half-life, the
[𝐴]𝑜⁄
concentration will become, [𝐴] = 2.
Using this concept, the half-life for a first-order reaction can be derived
[𝐴]𝑜
𝑙𝑛 = 𝑘𝑡
[𝐴]
Therefore, at t1/2,
[𝐴]𝑜
𝑙𝑛 = 𝑘𝑡1⁄
[𝐴] 2
[ 2 𝑜]

𝑙𝑛2 = 𝑘𝑡1⁄
2

𝑙𝑛2
𝑡1⁄ =
2 𝑘

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

𝟎. 𝟔𝟗𝟑
𝒕𝟏⁄ =
𝟐 𝒌
Example1;
Radioactivity of a sample (z = 22) decreases 90 % after 20 years. What will be the half-life of the sample?
Solution
Radioactive decay follows first order reactions model, therefore,
𝟎.𝟔𝟗𝟑
𝒕𝟏⁄ =
𝟐 𝒌

Given:
At the beginning, the amount of the sample is 100%, so [𝐴]𝑜 = 100%
After 20 years, the amount decrease by 90%, so only 10% remain, so [𝐴] = 10%
t = 20 years
k =?, we have to find the value of k
[𝐴]
𝑙𝑛 [𝐴] = −𝑘𝑡
𝑜

10%𝑜
𝑙𝑛 = −𝑘 × 20 𝑦𝑒𝑎𝑟𝑠
100%
ln 0.1
−𝑘 = 20𝑦𝑒𝑎𝑟𝑠

−2.3059
−𝑘 = 20𝑦𝑒𝑎𝑟𝑠

𝑘 = 1.15 × 10−1 𝑦𝑒𝑎𝑟 −1

So, now we know the value of k, we can calculate the half-life, t1/2, thus;
0.693
𝑡1⁄ =
2 𝑘
0.693
𝑡1⁄ =
2 1.15 × 10−1 𝑦𝑒𝑎𝑟 −1
= 6.03 years
Example 2
Given that for a first order reaction, the concentration of the reactant changes from 0.1 M to 0.025 M in 60
minutes. Calculate;
i. the rate of reaction, when the concentration of A is 0.05 M
ii. the half-life of the reaction
Solution:

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

𝑟𝑎𝑡𝑒 = 𝑘[𝐴]
[𝐴]
𝑙𝑛 [𝐴] = −𝑘𝑡
𝑜

0.693
𝑡1⁄ =
2 𝑘

Given;
[𝐴] = 0.05 𝑀
[𝐴]𝑜 = 0.1 M
k=?
t = 60 minutes = (60 × 60) seconds = 3600 s
i. rate of the reaction
for first order reactions, 𝑟𝑎𝑡𝑒 = 𝑘[𝐴], we need to find the value of k, so;
[𝐴]
𝑙𝑛 [𝐴] = −𝑘𝑡
𝑜

0.025
𝑙𝑛 = −𝑘 × 3600 𝑠
0.1

-1.3863 = -k × 3600 s
1.3863
𝑘= = 3.85 × 10−4 𝑠 −1
3600𝑠

So, 𝑟𝑎𝑡𝑒 = 𝑘[𝐴]

𝑟𝑎𝑡𝑒 = 3.85 × 10−4 𝑠 −1 × 0.05 𝑀
𝑟𝑎𝑡𝑒 = 1.92 × 10−2 𝑀−1
half-life of the reaction
0.693
𝑡1⁄ =
2 𝑘
0.693
𝑡1⁄ = 3.85 × 10−4𝑠−1
2

𝑡1⁄ = 1,80 × 103 𝑠

2

Second Order Rate Law

The rate of the reaction is proportional to the square of the concentration of a single reactant or to the
product of the concentrations of two reactants.
Consider the reaction of the type
2A P or A+B Products
The rate equation is given by

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 or 𝑅𝑎𝑡𝑒 = 𝑘[𝐴][𝐵]……………………………………………………………..1

The, the rate equation takes the same form for a second order reaction, if the reaction is:
i) second order in a single reactant or
ii) the concentrations of the two are same (A = B) throughout the reaction.
In order to find solution for the second-order integrated late law, we recall from the definition of rate.
𝑑[𝐴]
𝑅𝑎𝑡𝑒 = − [ ]……………………………………………………2
𝑑𝑡

Combining equations 1 and 2

𝑑[𝐴]
−[ ] = 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2
𝑑𝑡
𝑑[𝐴]
− [𝐴]2 = 𝑘𝑑𝑡
𝐴 𝑡
𝑑[𝐴]
−𝑑 ∫ 2
= 𝑘 ∫ 𝑑𝑡
𝐴𝑜 [𝐴] 0

1 [𝐴] 𝑡 1 [𝐴] 𝑡
− − [𝐴]] = 𝑘𝑡] = [𝐴]] = 𝑘𝑡]
[𝐴]𝑜 𝑜 [𝐴]𝑜 𝑜
1 1
[ − ] = 𝑘(𝑡 − 0)
[𝐴] [𝐴]𝑜
1 1
[ − ] = 𝑘(𝑡 − 0)
[𝐴] [𝐴]𝑜
1 1
[ − ] = 𝑘𝑡
[𝐴] [𝐴]𝑜
𝟏 𝟏
= 𝒌𝒕 +
[𝑨] [𝑨]𝒐
𝟏
In order to find the second-order rate constant, a graph of concentration [𝑨] is plotted against time t and the
𝟏
slope k is the rate constant and the intercept is [𝑨]
𝒐

Half-life of Second Order reactions

The half-life of a chemical reaction is the time taken for the concentration of the reactant to be reduced by
half its initial value. This implies that if the initial concentration of the reactant was ‘at, at half-life, the
[𝐴]𝑜⁄
concentration will become, [𝐴] = 2.
Using this concept, the half-life for a second-order reaction can be derived
1 1
[ − ] = 𝑘𝑡
[𝐴] [𝐴]𝑜

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

[𝐴]𝑜⁄
𝑎𝑡 𝑡1⁄ , [𝐴] = 2
2

1 1
[ − ] = 𝑘𝑡1⁄
[𝐴]𝑜 [𝐴]𝑜 2
2
2 1
[ − ] = 𝑘𝑡1⁄
[𝐴]𝑜 [𝐴]𝑜 2

1
𝑘𝑡1⁄ =
2 [𝐴]𝑜
1
𝑡1⁄ =
2 𝑘[𝐴]𝑜
Consider the following reaction, 2Mg + O2 = 2MgO. If the rate equation can be written as,

The results of some three trial experiments generated the data given in the Table below;

Answer the following questions

i. What is the rate law for the reaction?
ii. What is the overall order, n of the reaction?
iii. Calculate the value of the rate constant, kn
Solution:
i. The expected rate law should take the form, 𝑅𝑎𝑡𝑒 = 𝑘𝑛 [𝑀𝑔]𝑥 [𝑂2]𝑦.
ii. From the data provided, when the concentration of O2 is held constant, then we can obtain the
order for Mg (using experiments 1 and 2) as follows,

This gives 2 = 21 which means that the order of the reaction with respect to Mg is 1.
Similarly, when the concentration of Mg is held constant in experiments 1 and 3, we have,

which gives, 2 = 22 hence the order of the reaction with respect to oxygen is 2.

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

The overall order is 1 + 2 =3, 3rd order, i.e. termolecular reaction.

iii. Using data obtained from experiment 1, we can obtain the value of the rate constant.
Thus, 0.002 = 𝑘𝑛 (0.01)1 (0.01)2,
which gives kn = 2.0 x 104.
This means that the rate equation can be re-written as 𝑅𝑎𝑡𝑒 = 20000[𝑀𝑔][𝑂2]2
Third Order Reaction
A third order reaction may be regarded as a termolecular reaction in which the rate of reaction depends on
three reactants concentration variables. Generally, a termolecular reaction can be represented as a reaction
in which three reactants combine to give a product as shown in equation;
2A P or A+B Products

If A = B = C, equation for the rate law becomes;

𝑑[𝐴]
𝑟𝑎𝑡𝑒 = −
𝑑𝑡
𝑟𝑎𝑡𝑒 = 𝑘[𝐴]3
𝑑[𝐴]
− = 𝑘[𝐴]3
𝑑𝑡
Integrating the above equation gives;
[𝐴] 𝑡
𝑑[𝐴]
∫ 3
= 𝑘 ∫ 𝑑𝑡
[𝐴]𝑜 [𝐴] 0

1 [𝐴]
[ ] = 𝑘[𝑡]𝑡0
2[𝐴]2 [𝐴]𝑜
1 1
− 2[𝐴]2 = 𝑘𝑡
2[𝐴]2 𝑜

Half-Life of Third Order Reactions

1 1
2
− = 𝑘𝑡
2[𝐴] 2[𝐴]2𝑜
[𝐴]𝑜⁄
At half-life, the concentration will become, [𝐴] = 2.
1 1
2− 2[𝐴]2𝑜
= 𝑘𝑡1⁄
2
[𝐴]
2 [ 2 𝑜]

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

1 1
2− 2[𝐴]2𝑜
= 𝑘𝑘𝑡1⁄
2
[𝐴]
2 [ 4 𝑜]

4 1
− = 𝑘𝑡1⁄
2[𝐴]𝑜 2[𝐴]2𝑜
2 2

3
= 𝑘𝑡1⁄
2[𝐴]2𝑜 2

3
𝑡1⁄ =
2 2𝑘[𝐴]2𝑜
From the above, it seen that the half-life of a third order reaction depends on the rate constant and on the
square of the initial concentration of the reactant.
Summary:

Relationship between Rate and Equilibrium Constants

Chemical equilibrium is a dynamic state in which all reaction the forward and back reactions continue to
occur in the same rate and no net change in concentration. The forward and backward rates are equal as a
result, there is no change in the concentration of any of the species, even though the reactions are still
going on.
Consider the reaction
𝑘𝑓
𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
𝑘𝑟
The rate constant for forward reaction can be written as;
𝑟𝑎𝑡𝑒 = 𝑘𝑓 [𝐴]𝑎 [𝐵]𝑏

The rate constant for reverse reaction can be written as;

𝑟𝑎𝑡𝑒 = 𝑘𝑟 [𝐶]𝑐 [𝐷]𝑑

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

At equilibrium,
the rate of forward reaction = equal to the rate of backward reaction,
𝑘𝑓 [𝐴]𝑎 [𝐵]𝑏 = 𝑘𝑟 [𝐶]𝑐 [𝐷]𝑑

𝑘𝑓 [𝐶]𝑐 [𝐷]𝑑
=
𝑘𝑟 [𝐴]𝑎 [𝐵]𝑏
Also, equilibrium constant for the above system is given as
[𝐶]𝑐 [𝐷]𝑑
𝐾𝑒𝑞 =
[𝐴]𝑎 [𝐵]𝑏
Therefore.
𝑘𝑓
𝐾𝑒𝑞 =
𝑘𝑟
Therefore, the rate and equilibrium constants are related in such a way that the ratio of the forward to that
of reverse rate constants is equal to the equilibrium constant.
Theories of Reaction Rates
Theories of reaction rates were proposed because it is necessary to consider internal processes that occurs
inside the molecules including collision and other molecular motions. This is because there is disparity in
reaction rate-temperature relationship. In most of reactions, the rate increases with increase in
temperature, but there are reactions in which the rate decreases with decrease in temperature. In order to
understand the cause of this disparity and explain the details about mechanisms and rates of reaction, some
theories of reaction have been proposed to explain how the internal molecular properties can affect the rate
of chemical reaction. Most accepted theories are Arrhenius theory, collision theory and transition state
theory, thus;
Arrhenius Theory
The Arrhenius theory of reaction rates, proposed by Swedish chemist Svante Arrhenius in the late 19th
century, provides a mathematical relationship between the rate constant of a reaction and temperature. The
theory is particularly important in understanding the temperature dependence of reaction rates. Thus;
Arrhenius suggested that;
Reaction occurs when molecules collide and that not all collision leads to chemical reaction. The collision
that leads to chemical reaction are called effective collision. According to the Arrhenius concept, collision
must produce energy equal to or higher than the minimum energy (activation energy) before it can be
effective. This implies that there is an energy barrier that must be overcome (i.e. the activation energy). In
order to overcome this barrier, the energy produce by collision must be equal to or higher than the
activation energy. According to Boltzmann equation, the fraction of molecules having energy, equal to or
greater than the activation energy (i.e., the fraction of molecules that have energy enough to be converted
to the product) can be expressed as

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

where 𝑛𝐸𝑎 is the number of molecules having energy equal to Ea and nT is the total number of molecules.
−𝐸𝑎
𝑛𝐸𝑎 = 𝑛𝑇 𝑒 𝑘𝑇

𝑛𝑇 is the total number of molecules of molecules = concentration of reactants

−𝐸𝑎
𝑛𝐸𝑎 = (concentration of reactants)𝑒 𝑘𝑇

Rate of reaction is proportional to 𝑛𝐸𝑎 i.e., the number of molecules having energy equal to Ea,

𝑅𝑎𝑡𝑒 ∝ 𝑛𝐸𝑎
−𝐸𝑎
𝑅𝑎𝑡𝑒 ∝ (concentration of reactants)𝑒 𝑘𝑇
By removing the sign of proportionality, it is replaced with an equality sign and constant A
−𝐸𝑎
𝑅𝑎𝑡𝑒 = 𝐴(concentration of reactants)𝑒 𝑘𝑇
where A is a constant known as the Arrhenius or pre-exponential factor.
Remember from the rate law
𝑅𝑎𝑡𝑒 = 𝑘(concentration of reactants)
𝑅𝑎𝑡𝑒
𝑘=
(concentration of reactants)
Therefore, upon substitution,
−𝐸𝑎
(concentration of reactants)𝐴𝑒 𝑘𝑇
𝑘=
(concentration of reactants)

𝐸𝑎
ln k = 𝑙𝑛𝐴 −
𝑅𝑇
Where:
• k is the rate constant of the reaction.
• A is the pre-exponential factor (also known as the frequency factor), representing the frequency of
collisions and the orientation factor of reacting molecules.
• Ea is the activation energy, the minimum energy required for a reaction to occur.
• R is the ideal gas constant (8.314 J/(mol·K)).

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

• T is the absolute temperature in Kelvin.

Key points related to the Arrhenius theory:
1. Effect of Temperature: The Arrhenius equation shows that the rate constant (k) of a reaction
−𝐸𝑎
increases exponentially with temperature. As the temperature rises, the exponential term 𝑒𝑥𝑝 ⁄𝑅𝑇
becomes smaller, resulting in a higher rate constant and, consequently, a faster reaction. The
Arrhenius theory emphasizes the strong temperature dependence of reaction rates. Even a small
increase in temperature can have a significant impact on the rate of a reaction due to the
exponential relationship between temperature and the rate constant.
2. Activation Energy: The activation energy (Ea) is a measure of the energy barrier that reactant
molecules must overcome for a reaction to occur. Higher activation energy corresponds to a slower
reaction, while lower activation energy corresponds to a faster reaction.
3. Frequency Factor (A): The frequency factor (A) is related to the frequency of collisions and the
orientation factor of reacting molecules. It represents the rate at which reactant molecules collide
in a way that leads to a successful reaction. However, A is not influenced by temperature and is
considered a constant for a specific reaction.
4. Arrhenius Plot: The Arrhenius equation can be rearranged to form a linear equation suitable for
plotting. Taking the natural logarithm of both sides, we get:

In order to determine the values of activation energy of Ea and pre-exponential factor A. A graph of ln(k)
1
vs 𝑇 is plotted to yield a straight line, allowing for the determination of Ea and A from the slope and
intercept, respectively.

The Arrhenius theory emphasizes the strong temperature dependence of reaction rates. Even a small
increase in temperature can have a significant impact on the rate of a reaction due to the exponential
relationship between temperature and the rate constant.
However, the following deviations are related to Arrhenius theory, thus;
i. the equation is most applicable to gaseous systems,

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

ii. it doesn’t explain how molecules becomes activated

iii. It is unable to explain the physical meaning of the frequency factor, A
In view of these and other problems, the collision theory was introduced.
The Collision Theory
Collision theory is a concept in chemical kinetics that helps explain how chemical reactions occur at the
molecular level. The collision theory applies the assumptions of the Arrhenius equation but in addition, it
has an additional assumption which requires that the molecule must be properly oriented at the point of
collision. This implies that even if there could be several bonds in a molecule, the collision must take
place at the appropriate bond. It was developed to provide insights into the other factors that influence
reaction rates.
In summary, there are three aspects to a successful reactive collision, thus;
✓ encounter rate, ZAB
✓ energy requirement, according to Maxwell-Boltzmann distribution Y and
✓ steric requirement P
for a bimolecular reaction, they are related with the rate of reaction in the following form.
k = (encounter rate) (energy requirement) (steric requirement)
k=ZAB × Y × P
We will now consider each of these factors in more detail.
1. Encounter rate, ZAB:
The rate of collisions between molecules A and B present at number densities nA and nB is;

2. Energy requirement, Y;
For a Maxwell-Boltzmann distribution of molecular speeds, the fraction of collisions for which the energy
is high enough to overcome the activation barrier is
−𝐸𝑎⁄
𝑌 = 𝑒𝑥𝑝 𝑅𝑇 .

S, according to the collision theory, the rate constant can be expressed as;
3. Steric requirement P;
Experimentally, measured rates are often found to be up to an order of magnitude smaller than those
calculated from simple collision theory, suggesting that features such as the relative orientation of the
colliding species is important in determining the reaction rate. We account for the disagreement between
experiment and theory by introducing a steric factor, P, into our expression for the reaction rate.
Alternatively, we can replace the collision cross section, σC, with a reaction cross section σR,
where σR = PσC.

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

Usually, P is considerably less than unity, but values greater than one are also possible.
Combining these three terms, the simple collision theory expression for the reaction rate is:
⁄
8𝑘𝑇 1 2 −𝐸𝑎
𝑘 = 𝑃𝜎𝐶 [ ] 𝑒 𝑅𝑇 𝑛𝐴 𝑛𝐵
𝜋𝜇
Where;
ν = rate of bimolecular reaction
P = stearic factor
k = Boltzmann Constant
T = temperature
𝑚𝐴 𝑚𝐵
𝜇 = reduced mass = 𝑚𝐴 +𝑚𝐴

σC = Collision cross section

Ea. = Activation energy
nA and nB are the number of densities of molecules A and B respectively
For example, in the molecule shown below, the collision that will be effective in overcoming the energy
barrier will be the one that takes place at the OH group. Therefore, even if the molecule has activation
energy, it will not collide to produce product until it is properly oriented.

3. Transition State Theory

Transition State Theory (TST) (also known as absolute reaction rate theory or activated complex theory) is
a theoretical framework that provides insights into the kinetics of chemical reactions used to explain the
rates of chemical reactions and the factors influencing these rates. TST was formulated independently by
Eyring, Evans, and Polanyi in the 1930s and is sometimes referred to as the Eyring equation.
According to the transition state theory, a reaction forming a product, first form an intermediate which is
in thermodynamic equilibrium with the molecules of the reactant. The only unique property of the
intermediate is that it has an energy that is higher than the energy of either the reactant or the molecule and
that it has a short life span. The intermediate is easily converted to the product.

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

This implies that the rate of the reaction depends on two major factors, which are,
(i) The concentration of the activation complex
(ii) The rate of dissociation of the activation complex into the product
According to this theory, the reactant molecules are first transformed into intermediate transition state
(also known as activated complex). The activated complex is formed by loose association or bonding of
reactant molecules or by redistribution of energy. The reactant molecules come into contact with each
other. In this process, a few bonds get distorted; some bonds start forming with the exchange or release of
atom or groups. The composite molecule so formed from the reactants prior to the formation of the
product is called the activated complex. The activated complex then decomposes to give the product. The
activated complex is unstable and breaks into the products at a definite rate as follows:

For a simple bimolecular reaction involving molecules A and B, then the reaction can be represented as
follows;
The activated complex [AB]++ is considered as a separate entity and there exists an equilibrium between
reactants and activated complex.

Energy of activation is the additional energy the reactants must have in order to form activated complex or
to reach at the peak of the energy barrier as shown in Fig below;

The rate of reaction can be expressed as the product of the concentration of the intermediate and the
frequency of decomposition of the activated complex

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

The concentration of activated complex can thus be obtained by applying the equilibrium conditions, i.e.

or

The constant, 𝑘++ can also be related to some changes in thermodynamic variables such as ∆𝐺++, ∆𝑆++ and
∆𝐻++. The equilibrium constant of the activated complex, 𝑘++ is related to ∆𝐺++ and can be written as;
∆𝐺++ = −𝑅𝑇𝑙𝑛𝑘++ indicating that

−Δ𝐺 ++
𝑘 ++ = 𝑒 𝑅𝑇

According to Eyring, the specific rate (k) of any reaction is proportional to 𝑘++
k ∝ k ++
k ∝ k ++
𝑅𝑇 ++
k= k
𝑁ℎ
where R is the universal gas constant, T is the temperature, N is the Avogadro’s number while h is the
Planck constant.
Remember,
−Δ𝐺 ++
++
𝑘 = 𝑒 𝑅𝑇
𝑅𝑇 −Δ𝐺++
k= 𝑒 𝑅𝑇
𝑁ℎ
Also, remember Δ𝐺 = Δ𝐻 − 𝑇Δ𝑆
𝑇ΔS++ ΔH++
𝑅𝑇 −
So, k = 𝑁ℎ 𝑒 𝑅𝑇 𝑒 𝑅𝑇

𝑇ΔS++ ΔH++ 𝑇ΔS++ ΔH++

𝑅𝑇
k = 𝑁ℎ 𝑒 𝑅 𝑒− 𝑅𝑇 [𝑘 ++ = 𝑒 𝑅 𝑒− 𝑅𝑇 ]

𝐸
Recall the Arrhenius equation, lnk = 𝑙𝑛𝐴 − 𝑅𝑇𝑎
𝐸𝑎
k = 𝐴𝑒 −𝑅𝑇

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

Upon comparison of the two equations;

𝑅𝑇 𝑇ΔS++ −ΔH++
k= 𝑒 𝑅 𝑒 𝑅𝑇
𝑁ℎ
𝐸𝑎
k = 𝐴𝑒 −𝑅𝑇
𝑅𝑇 𝑇ΔS++
A= 𝑒 𝑅
𝑁ℎ
𝐸𝑎 = ΔH ++
Example:
Given that the rate constants for a first order reaction at 25 and 60 C are 2 x 10-3 and 8 x 10-3 s/mol.
Calculate the activation energy for the reaction.
Solution;
The logarithm form of the Arrhenius equation can be used for the calculation. The equation is
𝑘1 𝐸𝑎 1 1
ln ( ) = ( − )
𝑘2 𝑅 𝑇1 𝑇2
Substituting the given values to the equation, we have

= 3,234 × 104kJmol-1
Summary of Theories of Reaction Rates
S/No. Name Main Concept Equation
1. Arrhenius Theory The rate of reaction depends largely Arrhenius equation;
depends on temperature and activation
energy.
2. Collision Theory The rate of reaction depends on the 1
8𝑘𝑇 ⁄2 −𝐸𝑎
encounter rate, energy requirement and 𝑘 = 𝑃𝜎𝐶 ( ) 𝑒 𝑅𝑇 𝑛𝐴 𝑛𝐵
𝜋𝜇
steric requirement
3. Transition State The rate of reaction depends on the Eyring equation;
Theory reactants passing through a high-energy, 𝑅𝑇 −Δ𝐺++
transitional state known as the transition k = 𝑒 𝑅𝑇
𝑁ℎ
state or activated complex (the
concentration of the activated complex) and
the frequency which the activated complex
is being converted into the product.

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

4. Reaction Coordinates
Reaction coordinate is the sequence of simultaneous changes in bond distances and bond angles. Such
changes result during the formation of the products from the reactants. Reaction coordinates are essential
concepts in the study of chemical reactions. The reaction coordinate is the collection of motions, such as
changes in interatomic distances and bond angles, that are directly involved in the formation of products
from reactants. (The reaction coordinate is essentially a geometrical concept and quite distinct from the
extent of reaction).
They provide a way to describe and understand the progress of a reaction by identifying the key structural
and energetic changes that occur as reactants transform into products.
As the reaction event proceeds, A and B come into contact, distort, and begin to exchange or discard
atoms. The potential energy rises to a maximum and the cluster of atoms that corresponds to the region
close to the maximum is called the activated complex. After the maximum, the potential energy falls as the
atoms rearrange in the cluster and reaches a value characteristic of the products. The climax of the reaction
is at the peak of the potential energy, which corresponds to the activation energy Ea. Here two reactant
molecules have come to such a degree of closeness and distortion that a small further distortion will send
them in the direction of products. This crucial configuration is called the transition state of the reaction.
Although some molecules entering the transition state might revert to reactants, if they pass through this
configuration then it is inevitable that products will emerge from the encounter.
Examples
Reaction progress leading to formation of activated complex

Exothermic Reactions;

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LEECTURE NOTES CHM 4205 Prepared by Dr. Kamal Suleiman Kabo

Endothermic Reactions

Catalyzed and Uncatalyzed Reaction;

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