CHE 450 Module 1 2014

MUKUBA UNIVERSITY
CHE 450: Physical Chemistry
MODULE 1
Mukuba University
Kitwe-Zambia
Natural Science Department
Copyright
© Mukuba University 2014.
No part of this module may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording or by any information storage
and retrieval system, without permission in writing from the publisher.
ii CHE 450; Physical Chemistry
Acknowledgements
The Mukuba College, Natural Science Department wishes to thank the following for their
contribution to this module:
EDITORS
Directorate of Distance Education (DODE)
AUTHORS
F.kayamba: Lecturer Mukuba University
Mbalushi.J; Lecturer Mukuba University
Mukuba University
Natural Science Department
P O Box 20382
Kitwe
Zambia
Contents
About this Module 5
How this module is structured ............................................................................. 5

Welcome to the module on foundation to chemistry ............................................ 6
Module outcomes ................................................................................................ 7
Timeframe ........................................................................................................... 7
Study skills .......................................................................................................... 7
Need help? .......................................................................................................... 9
Assignments........................................................................................................ 9
Assessments ....................................................................................................... 9
Getting around this Module 10
Margin icons ................................................................................................................ 10
Unit 1 12
1.0 Rate of chemical reaction ............................................................................. 12

1.1 Introduction ............................................................................................. 12
1.2 Recation rate and stoichiometry............................................................... 13
1.3 Order of recation ...................................................................................... 17
1.3.1. Intergrated Rate Law ....................................................................... 19
1.3.2. First order process ............................................................................ 20
1.3.3. Second order process....................................................................... 21
1.4 Half life ..................................................................................................... 24
1.4.1. Half life of second order recation ...................................................... 25
1.5. Temperature and rate ........................................................................... 27
1.5.1. Collision model ................................................................................. 28
1.5.2. Maxwell - Boltzman Distribution ........................................................ 29
1.6. Complex reaction ..................................................................................... 34
1.7. Reaction mechansim ............................................................................. 46
1.7.1. Multistep mechanism ...................................................................... 47
Unit summary ...................................................................................................... 50
Unit 2 51
2.0 Theories of rate of reaction .......................................................................... 51

2.1 Introduction ............................................................................................. 51
2.2. Collision theory ...................................................................................... 52
iv CHE 450; Physical Chemistry
2.2.1. Collision number ............................................................................... 54

2.2.2. Rate constant ................................................................................... 55
2.2.3. Energy consideration ........................................................................ 57
2.2.4. Steric requirement ............................................................................ 57
2.2.5. Reaction in the solution ................................................................... 59
2.3. Transtion state theory ............................................................................. 59
2.3.1. Thermodynamic aspect ................................................................... 61
2.3.2. Dynamics of molecular collision ........................................................ 64
2.4 Catalysis ................................................................................................. 65
2.4.1. Acid-base catalysis ........................................................................... 66
2.4.2.Homogeneous/Heterogeneous catalysis ........................................... 67
2.4.3.Enzymes ............................................................................................ 73
2.5 Kinetic slat effect ...................................................................................... 74
Unit summary ...................................................................................................... 78
Reading 79
Reference.......................................................................................................... 80
About this Module

CHE 450: Physical Chemistry Module 1 has been produced by
Error! No text of specified style in document.. All module produced
by Mukuba University are structured in the same way, as outlined
below.
How this module is structured
The module content

The module is broken down into units. Each unit comprises:
 An introduction to the unit content.
 Unit outcomes..
 Core content of the unit with a variety of learning activities.
 A unit summary.
 Assignments and/or assessments, as applicable.
Resources
For those interested in learning more on this subject, we provide
you with a list of additional resources at the end of this module;
these may be books, articles or web sites.
Your comments
After completing module 1 of CHE 450; Physical Chemistry we
would appreciate it if you would take a few moments to give us
your feedback on any aspect of this course. Your feedback might
include comments on:
 Course content and structure.
 Course reading materials and resources.
 Course assignments.
5
6 CHE 450; Physical Chemistry
 Course assessments.
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 Course support (assigned tutors, technical help, etc.)
Your constructive feedback will help us to improve and enhance

this course.
The module overview
Welcome to the module on foundation to chemistry
This module gives you the foundation to General Chemistry

Course. The module exposes you to measurement, the
composition of matter, and the basic atomic theory. These
concepts will help you to understand subsequent topics in
chemistry. If you are a secondary school teacher with a secondary
teacher’s diploma in science, then this is your module. It will help
you to lay a very strong foundation in chemistry as you pursue
your Bachelors of Education in Natural Sciences.
To complete this module successfully, you will need to spend three

(3) hours per week studying the module, and make sure you work
out all the activities in each unit. Don’t move to another unit before
you understand the previous unit. In case you need help contact
the course tutors.
You are expected to do all the self-marked activities and one tutor
marked assignment. You are required to submit the assignment to
the nearest resource centre in your district. This module has four
units.
We strongly recommend that you read the overview carefully

before starting your study.
6
Module outcomes
Upon completion of this module you will be able to:
 Determine the rate. order and half life of a chemical reaction
 Describe factors that affect the chemical reaction
Outcomes  Describe the mechanistic pathway and catalysis of chemical

reaction.
 Describe in details the condition needed for a chemical reaction

to take place
Timeframe
This module is expected to be covered within a period of 100

hours. The 100 hours will include studying the actual module
including all the activities.
How long?
Study skills
As an adult learner your approach to learning will be different to

that from your school days: you will choose what you want to
study, you will have professional and/or personal motivation for
doing so and you will most likely be fitting your study activities
around other professional or domestic responsibilities.
Essentially you will be taking control of your learning environment.

As a consequence, you will need to consider performance issues
related to time management, goal setting, stress management, etc.
Perhaps you will also need to reacquaint yourself in areas such as
essay planning, coping with exams and using the web as a
learning resource.
7
Your most significant considerations will be time and space i.e. the
time you dedicate to your learning and the environment in which
you engage in that learning.
We recommend that you take time now—before starting your self-

study—to familiarize yourself with these issues.
8
Need help?
Should you require help in the course of your studies, do not
hesitate to contact the following course tutors
Help Mbalushi. J Mobile; 0971507836 /0968487475
Email;
Mr Kayamba. F Mobile: 096/7 7370381 / 0954 013237
Email; francoiskay@live.com
Assignments
You will be expected to write at least two assignments in an

academic year. The first assignment will in module two
The assignments should be handed in to course tutors during the
Assignments residential sessions.
You will be required to submit the assignments in the order in

which they are given to you.
Assessments
You will be expected to write two tutor- marked test which will be
written during each residential session. You are also expected to
answer the self- marked assessments in each unit of this module.
Assessments
9
Getting around this Module
Margin icons
While working through this module you will notice the frequent
use of margin icons. These icons serve to “signpost” a particular
piece of text, a new task or change in activity; they have been
included to help you to find your way around the module.
A complete icon set is shown below. We suggest that you

familiarize yourself with the icons and their meaning before
starting your study.
Activity Assessment Assignment Case study
Discussion Group Help Note it!

activity
Outcomes Reading Reflection Study skills
Summary Terminology Time Tip
11
Unit 1
1.0. Rate chemical reaction
1.1. Introduction
Welcome to this unit. In this unit we will look at the following
aspect; review of rate law, integrated rate equations for zero, first,
second and third order and determination of order, half-life, order
and concentration pseudo order, experimental methods for
studying slow and fast reactions. You will discover that all the
aspects that we have outline falls under rate of the chemical
reaction. We will look at the study of the rate at which a chemical
process occurs. Besides information about the speed at which
reactions occur, kinetics also sheds light on the reaction
mechanism (exactly how the reaction occurs).
Chemical reaction outline that will look are summarised in the

table below
12
Upon completion of this module you will be able to:
 Determine the rate. order and half life of a chemical
Outcomes reaction
 Describe in details the condition needed for a chemical

reaction to take place
 Describe factors that affect the chemical reaction
 Describe the mechanistic pathway of chemical reaction
1.2. Reaction Rates and Stoichiometry

Rates of reactions can be determined by monitoring the change
in concentration of either reactants or products as a function of
time. [A] vs t . Let us look at the following reaction between
C H Cl (aq) and H2O (l).
4 9
C H Cl (aq) + H O (l) C H OH (aq) + HCl(aq)

4 9 2 4 9
The table below gives the various times taken for C H Cl (aq) to
4 9
be consumed in the reaction
In this reaction, the concentration of butyl chloride, C4H9Cl, was

measured at various times, t.
13
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)
From the definition of the rate of the reaction the average rate of
the reaction over each interval is the change in concentration
divided by the change in time:
For above reaction will be
And when you do the same for all the intervals, the following rate
swill obtained as shown in the table
 Note that the average rate decreases as the reaction

proceeds.
 This is because as the reaction goes forward, there are fewer

collisions between reactant molecules.
When you plot a graph for the concentration vs. time for this
reaction it will yield a curve like this. The slope of a line tangent to
the curve at any point is the instantaneous rate at that time.
14
The reaction slows down with time because the concentration of

the reactants decreases.
In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1.
C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl(aq)
Thus, the rate of disappearance of C4H9Cl is the same as the rate

of appearance of C4H9OH.
[ ] [ ]
Rate = =
And What if the ratio is not 1:1? Then the rate will be
H2 (g) + I2 (g)  2 HI (g)
From what we have looked at we can generalize the relation

between the rate of the reaction and stoichiometry. Let us
consider the following reaction and see how the rate will be
15
aA + bB → cC + dD
The rate of the reaction will be written as
Reactants (decrease) Products (increase)
The negative sign means the reactants are being consumed and
a positive sign that the products are being produced. The above
expression is driven from
[ ]
= rate, V =volume, =rate of conversion, = reaction
coefficient, n number of moles
Activity 1.1
1. The reaction H2 + Br2 =2HBr is carried out in a 0.250-L

reaction vessel. The change in the amount of Br2 in 0.01 s is -
0.001 mol. (a) what is the rate of conversion d / dt? (b) What
is the rate of reaction ? What are the values of d[H2]/dt,
d[Br2]/dt and d[HBr]/dt?
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Solution
(a)
(b) = = 0.40 mol L-1s-1

[ ]
(c) = - 0.04 mol L-1s-1
[ ]
=- 0.04 mol L-1s-1
[ ]
= 2(- 0.04 mol L-1s-1) = - 0.08 mol L-1s-1
2. In discussing the rate of a reaction, it is important to know

the stoichiometric equation is written because the rate may
depends on that different are obtained when the reaction is
written as
2A + B = 2C and A + B = C
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Solution
According to the first stoichiometric equation
[ ] [ ] [ ]
= =
According to the second stoichiometric equation
[ ] [ ] [ ]
= =
1.3. The order of the reaction
17
The reaction between Concentration and Rate

Each reaction has its own equation that gives its rate as a
function of reactant concentrationsthis is called its Rate Law
To determine the rate law we measure the rate at different

starting concentrations.
Compare Experiments 1 and 2: when [NH4+] doubles, the initial

rate doubles.
Likewise, compare Experiments 5 and 6: when [NO2-] doubles,

the initial rate doubles.
This equation is called the rate law, and k is the rate constant.
Rate Laws
18
A rate law shows the relationship between the reaction rate and
the concentrations of reactants.
 For gas-phase reactants use PA instead of [A].
 k is a constant that has a specific value for each reaction.
 The value of k is determined experimentally.
“Constant” is relative here- k is unique for each reaction. k

changes with T Exponents tell the order of the reaction with
respect to each reactant.
This reaction is
First-order in [NH4+]
First-order in [NO2−]
The overall reaction order can be found by adding the exponents

on the reactants in the rate law.
This reaction is second-order overall.
1.3.1. Integrated Rate Laws
Consider a simple 1st order reaction: A  B
Differential form:
How much A is left after time t? Integrate:
19
The integrated form of first order rate law:
Can be rearranged to give:
[A]0 is the initial concentration of A (t=0). [A]t is the concentration

of A at some time, t, during the course of the reaction.
Manipulating this equation produces…
When plotted the equation gives a straight line…which is in the

form;
y = mx + b
Where y = In[a]t , m= -K and b = in[A]0
1.3.2. First-Order Processes
If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight

line with a slope of -k. So, the graph can also be used to
determine reaction order.
Consider the process in which methyl isonitrile is converted to

acetonitrile
20
CN3N→CH3C
How do we know this is a first order reaction? This data was

collected for this reaction at 198.9°C.
Does rate=k[CH3NC] for all time intervals?
When ln[A]t is plotted as a function of time, a straight line results.
 The process is first-order.
 k is the negative slope: 5.1  10-5 s-1.
1.3.3. Second-Order Processes

Similarly, integrating the rate law for a process that is second-
order in reactant A:
21
Rearrange, integrate:
Also in the form; y = mx + b
So if a process is second-order in A, a plot of 1/[A] vs. t will yield a

straight line with a slope of k.
If a reaction is first-order, a plot of ln [A]t vs. t from the wquation

below will yield a straight line with a slope of -k.
Activity 1.2.
Try to solve the question before you look at the answer and see
what you will get
The decomposition of NO2 at 300°C is described by the equation.

Determining reaction order
NO2 → NO (g) + 1/2O2
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Solution
The plot is not a straight line, so the process is not first-order in

[A].i.e. do not fit in the equation below
Second-Order Processes
A graph of 1/[NO2] vs. t gives this plot.
When you plot the values in the table you get a straight line as
shown below and this therefore tells you that the process is
second-order in [NO2].
23
1.4. Half-Life
Half-life is defined as the time required for one-half of a reactant
to react. Because [A] at t1/2 is one-half of the original [A], [A]t = 0.5
[A]0. The trend in deposition due to half live is shown in the graph
below
For a first-order process, set [A]t=0.5 [A]0in integrated rate

equation:
NOTE: For a first-order process, the half-life does not depend on

[A]0.
24
1.4.1. Half-Life- second order

For a second-order process, set [A]t=0.5 [A]0in 2nd order
equation.
Activity 1.3.
1. The decomposition of A is first order, and [A] is monitored.
The following data are recorded:
t / min 0 2 4 8
[A]/[M] 0.100 0.0905 0.0819 0.0670
25
i. Calculate k (What is the rate constant? (k = 0.0499)

ii. Calculate the half life (What is the half life? Half life =
13.89)
iii. Calculate [A] when t = 5 min. (What is the concentration
when t = 5 min?)
iv. Calculate t when [A] = 0.0100. (Estimate the time required
for 90% of A to decompose.)
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2. N2O5 decomposes according to 1st order kinetics, and 10% of

it decomposed in 30 s. Estimate k, t½ and percent
decomposed in 500 s.
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3. Dimerization of butadiene is second order:
2 C4H6 (g) = C8H12 (g).
The rate constant k at some temperature is 0.100 /min. The initial

concentration of butadiene [B] is 2.0 M.
i. Calculate the time t required for [B] = 1.0 and 0.5 M

ii. Calculate concentration of butadiene when t = 1, 5, 10,
and 30.
26
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Solution
A2Solution
t= 1 5 10 15 30 35
[B] = 1.67 1.0 0.67 0.50 0.29 0.25
1.5. Temperature and Rate

Generally, as temperature increases, so does the reaction rate.
This is because k is temperature dependent.
27
1.5.1. The Collision Model

To explain the properties of temperature on the rate of the
reaction we use the collision model. In a chemical reaction,
bonds are broken and new bonds are formed. Molecules can only
react if they collide with each other. Furthermore, molecules must
collide with the correct orientation and with enough energy to
cause bond breakage and formation as shown below.
For a chemical reaction to take place the colliding particles should

have minimum amount of energy that is required for reaction to
take place. This energy is called the activation energy, Ea.
Reaction Coordinate Diagrams
28
It shows the energy of the reactants and products (and, therefore,

E). The high point on the diagram is the transition state. The
species present at the transition state is called the activated
complex. The energy gap between the reactants and the
activated complex is the activation energy barrier.
1.5.2. Maxwell–Boltzmann Distributions

Temperature is defined as a measure of the average kinetic
energy of the molecules in a sample. As the temperature
increases, the curve flattens and broadens. Thus at higher
temperatures, a larger population of molecules has higher
energy. In the diagram below, If the dotted line represents the
activation energy, as the temperature increases, so does the
fraction of molecules that can overcome the activation energy
barrier as a result, the reaction rate increases.
29
Molecular collisions lead to chemical reactions. Thus, the reaction

constant, k is determined by several factors.
k=Zfp
Z: collision frequency
p, the fraction of particles with proper orientation
f, fraction of collision having sufficient energy for reaction
f is related to the potential energy barrier called activation energy,

Ea.
or exp (– Ea/ R T)
– Ea / RT
Thus, the expression k = A e is called Arrhenius
equation that gives us mathematical relationship between k and
Ea the where A is a constant, R is the gas constant and T is the
temperature in Kelvin. A is the frequency factor, a number that
represents the likelihood that collisions would occur with the
proper orientation for reaction. According to Arrhenius, molecules
must acquire a certain critical energy Ea before they can react.
The Boltzmann factor given by is the fraction of molecules

that manages to obtain the necessary energy.
When you taking the natural logarithm of both sides, the equation
becomes
Y = mx +b
Where y =Ink, m = -Ea/RT and b = in A
When k is determined experimentally at several temperatures, Ea

can be calculated from the slope of a plot of lnk vs. 1/T as shown
in the figure below
30
The temperature dependence of the rate constant k is best

described by the Arrhenius equation:
k = A e – Ea / R T
or lnk = lnA – Ea / R T
If k1 and k2 are the rate constants at T1 and T2 respectively, then

then Arrhenius equation becomes
( )
Activity1.4.
From k = A e – Ea / R T, calculate A, Ea, k at a specific temperature

and T.The reaction:
2 NO2(g) -----> 2NO(g) + O2(g)
The rate constant k = 1.0 x10-10 s-1 at 300 K and the activation
energy Ea = 111 kJ mol-1. What are A, k at 273 K and T when k =
1 x 10-11?
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Solution
Method: derive various versions of the same formula
k =A e – Ea / R T
A = ke Ea / R T
A / k = e Ea / R T
ln(A / k) = Ea / R T
Using the formula derived earlier:
A = keEa / R T = 1x 10-10 s-1exp (111000 J mol-1 / (8.314 J mol-1 K –1

x 300 K)) = 2.13 x 109 s-1
k = 2.13 x 109 s-1exp (– 111000 J mol-1) / (8.314 J mol-1 K –1x 273

K) = 1.23x 10-12 s-1
T = Ea / [R* ln (A/k)] = 111000 J mol-1 / (8.314 x 46.8) J mol-1 K-1 =

285 K
Activity.1.5.
The rate constants from the first order reaction N2O5 = 2NO2 +
1/2O2 are as follows
T/K 273 298 308 318 328 338
k/10-5s-1 0.0787 3.46 13.5 49.8 150 487
What are the values of the activation energy and pre exponential
factor?
32
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Solution
Using the equation lnk = lnA – Ea / R T, the plot of ink vs 1/T is

given below.
1/T( x10-3) 3.66 3.36 3.25 3.15 3.05 2.96
InK -2.54 1.24 2.60 3.91 5.01 6.19
7
6
5
4
3
Ink
2
1
0
-1 2.96 3.16 3.36 3.56 3.76
-2
-3
K/T (x 10-3)
The plot of the points was fit by the least squares method,
which yielded a slope of 12 375 K-1 and an intercept of
31.27. Therefore, the activation energy Ea= (13 375 K -
1
)(8.314 JK-1 mol-1) = 103 x103 j mol-1. The pre exponential
factor is given by exp(31.27) =3.96 x 1013 s-1. Thus equation
18.66 becomes
33
( ) [ ]
( )
In summary the equation that we looked at are given below
1.6. Complex Reactions

A complex reaction occurs when a number of elementary
chemical reactions take place simultaneously, including
reversible reactions, consecutive reactions, and concurrent
or side reactions. In other words, complex reactions can be
explained in multiple elementary reaction steps.
A sample reaction coordinates of a complex reaction.

A sample reaction coordinates of an
Note: It involves an intermediate and multiple transition
34
elementary reaction. Note: There is one states. A complex reaction can be explained in terms of
transition state and no intermediates elementary reactions.
1.7.1. Elementary Reactions
Most reactions occur in a sequence of steps called

elementary reactions, each of which involves only a small
number of molecules or ions. Hence, molecularity of a
reaction refers to the number of reactant particles involved
in the elementary reaction. Molecularity can be described as
either unimolecular, bimolecular, or termolecular.
summary of three known types of elementary reactions:
Molecularity Elementary Step Rate Law Example
Unimolecular A → Products rate=k[A] N2O4(g)→2NO2(g)
Bimolecular A + A → Products rate=k[A]2 2NOCl → 2NO(g) + CO2(g)
A + B → Products rate=k[A][B] CO(g) + NO3(g) → NO2(g) +

CO2(g)
Termolecular A + A + A → Products rate=k[A]3
A + A + B → Products rate=k[A]2[B] 2NO(g) + O2(g) → 2NO2(g)
A + B + C → Products rate=k[A][B][C] H + O2(g) + M → HO2(g) + M
A unimolecular reaction occurs when a molecule

rearranges itself to produce one or more products.
Examples of this is include radioactive decay, in which
35
particles are emitted from an atom. Other examples include

cis-trans isomerization, thermal decomposition, ring
opening, and racemization. Unimolecular reactions are
often first-order reactions because rate at which a
substance decomposes is dependent on its concentration.
[ ]
A → Products, [ ]
A bimolecular reaction involves the collision of two

particles. A bimolecular reaction is second-order because its
rate is proportional to the rate at which the reactant species
meet, which in turn is proportional to their concentrations.
[ ]
A + B → Products, [ ][ ] First-order in A,
first-order in B, therefore is overall second-order.
A termolecular reaction requires the collision of three

particles at the same place and time. This type of reaction is
very uncommon as all three reactants must simultaneously
collide with each other, with sufficient energy and correct
orientation, in order to produce a reaction. There are three
ways termolecular reactions can react, and all are third
order.
Activity1.6.
1. Choose the correct 2. Which of the following is a

statements. termolecular reaction?
a. An elementary step has 0 a. A + 2B + C → D

intermediates. b. A + B + B → C
b. An elementary step has 1 c. all of the above
intermediate.
d. 2A + 2B + 2C → 2D
36
c. An elementary step has 2 e. b and d

intermediates.
d. An elementary step has 0

transition states.
e. An elementary step has 1

transition state.
f. An elementary step has 2

transition states.
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3. Discuss the following overall reactions with respect to

order of reaction
a. 2A → 4B + C, ( [ ]) [ ]
b. A + B → C, ( [ ]) [ ][ ]
c. 2A + B → 2C, ( [ ]) [ ] [ ]
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4. If a reaction is an elementary bimolecular process and

therefore has second order kinetics, are kinetics that are
second order bimolecular processes?
37
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Consecutive Unimolecular Elementary

Reactions
Some reaction proceed through the formation of an

intermediate (I), as in the consecutive unimolecular
reactions;
ka kb
A I P
An example is the decay of uraniam-239, with half-lives time

shown below;
23.5 min 239 2.35 day

239
U Np 239
Pu
Variation of Concentration with time
The rate of unimolecular decomposition of A is;
[ ]
[ ]
and A is not replenished. The intermediate I is formed from

A (at a rate ka[A]) but decays to P (at a rate kb[I]). The net
rate of formation of I is therefore;
[]
[ ] []
The product P is formed by the unimolecular decay of I;
38
[ ]
[]
We suppose that initially only A is present, and that its

concentration is [A]0. The first rate law is an ordinary first-
order decay, written as;
[ ] [ ]
When this equation is substituted in ( [ ]) [ ]

[ ], we obtain the rearrangement;
[]
[] [ ] ]
After setting [I]0, this differential equation has a standard

form;
[] ( )[ ]
At all times [A] + [I] + [P] = [A]0, so it follows that
[ ] { }[ ]
The concentration of I rises to a maximum and then falls to

zero (according to the equation ). The concentration
of the product P rises from zero towards [A]0.
Activity.1.7.
39
An industrial batch process occurs where substance A

produces an intermediate I which goes on to decay to
product C. Intermediate I is priceless whereas product C is
worthless. At what time in the reaction is the concentration
of I at its peak?
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Solution
The time dependence of the concentration of I is given by;
[] ( )[ ]
We can determine the time at which [I] passes through the

maximum, tmax, by calculating d[I]/dt and setting the resulting
rate equal to zero.
[] [ ] ( )
This rate is equal to zero when . Therefore,
For a given value of , as increases both the time at

which [I] is a maximum and the yield of I decrease.
The rate determining step
A rate in a reaction mechanism that is much slower than any

of the other steps is called the rate-determining step (RDS).
Therefore, The rate of the RDS determines the rate of the
overall reaction.
40
In these reaction schemes, The reaction profile for a

heavy arrows represent fast mechanism in which the first
steps and vice-versa. step (RDS) is rate-
determining.
(a) The first step is the RDS
(b) The second step is the

RDS
(c) Although one step is slow,

it is not the RDS, because
there is a fast route that
circumvents it.
The rate law of a reaction that has a RDS can often be

written down almost by inspection. If the first step in a
mechanism is rate-determining, then the rate of the overall
reaction is equal to the rate of the first step because all
subsequent steps are so fast that once the first intermediate
is formed, it results immediately in the formation of products.
Self test
Describe a case where the rate determining step might not

stem from a step with the highest activation barrier?
41
Parallel or Competitive Unimolecular Reactions
A parallel or competitive reaction takes place when a

substance reacts simultaneously to give two different
products.
k1 B
A
k2
C
The rate laws
A → B and A → C
so that; Integrated form
- d[A]
= k 1 [A] + k 2 [A] = ( k 1 + k 2 )[A] [ A ]  [ A ]o e  ( k1  k 2 )t
dt
[ ] [ ]
[ ] [ ]
A disappears with first order kinetics, with a rate constant k

= k1 + k2. The overall rate is determined by the fastest step.
At the completion of the reaction, the ratio of products is
shown below, which is one important relationship in this
case is;
[ ]
[ ]
Opposing Reactions
Composite reactions, occurring in forward and reverse

directions, like;
k1
A B
k-1
42
K = k1/k-1; which follows the principle of microscopic

reversibility (PMR). The reaction could take place as shown,
A B and B A by the same path(reversible unimolecular).
The PMR requires that a mechanism for a forward reaction
is also one for the reverse reaction.
Polymerization Kinetics and Chain Reactions
A reaction in which one or more reactive reaction

intermediates (frequently radicals) are continuously
regenerated, usually through a repetitive cycle of
elementary steps (the propagation steps).
In stepwise polymerization, any two monomers in the

reaction mixture can link together at anytime and the growth
of polymer is not confined to chains that are already
forming. The longer the stepwise polymerization proceeds,
the higher the average molar mass of the product.
Example: Condensation reaction (elimination of H2O in each

step) in the production of polyamides: nylon-66
H2N(CH2)6NH2 + HOOC(CH2)4COOH  H2N(CH2)6NHCO(CH2)4COOH + H2O
 H-[NH(CH2)6NHCO(CH2)4CO]n-OH
The rate law can be expressed as

[ ]
=-k[ ]
Assuming that the rate constant k is independent of the

chain length (remains constant throughout the reaction);
second order integrated rate law.
[ ]
[ ]= [ ]
Fraction of groups that have condensed;
43
[ ] [ ] [ ]
= [ ] [ ]
The degree of polymerization is calculated. This is the

average number of monomer residues per polymer
molecule. This quantity is the ratio of the initial concentration
of A, [A]0, to the concentration of end groups.
[ A ]0 1
N  
[ A] 1 p
The degree of polymerization in terms of the rate constant is
given by;
〈 〉 [ ]
The average length grows linearly with time. Therefore, the

longer the stepwise polymerization proceeds, the higher the
average molar mass of the product.
In chain polymerization an activated monomer, M, attacks

another monomer, links to it, then that unit attacks another
monomer, and so on. A series of subsequent intermediates
are formed, commonly referred to as chain carriers. High
polymers are rapidly formed and only the yield, not the
average molar mass, of the polymer is increased by
allowing long reaction times.
Example:
Addition polymerization with the formation of radicals as

chain carriers
-CH2CH2X· + CH2=CHX → -CH2CHXCH2CHX·
There are three basic types of reaction step in a chain

polymerization process, initiation, propagation and
termination:
44
(a) Initiation
[]
(fast)
where I = Initiator, R=radical formed from I and ·M1 =

monomer radical
(b) Propagation
[ ][ ]
Chain reactions propagate quickly, therefore, the rate at

which the total concentration of radicals grows is equal to
the rate of the rate-determining initiation step. it follows that;
[ ]
( ) []
where f is the fraction of radicals R· that successfully initiate

a chain
(c) Termination
(Mutual termination)
(Disproportionation)
(Chain transfer)
In mutual termination, two growing radical chains combine.

In termination by disproportionation, a hydrogen atom
transfers from one chain to another, corresponding to the
oxidation of the donor and the reduction of the acceptor. In
chain transfer, a new chain initiates at the expense of the
currently growing.
45
Supposing only mutual termination occurs, we assume that

the rate of termination is independent of the length of the
chain, the rate law for termination is;
[ ]
and the rate of change of radical concentration by this

process is;
[ ]
( ) [ ]
The kinetic chain length, ѵ, is the ratio of the number of

monomer units consumed per activated centre produced in
the initiation step;
The kinetic chain length can be expressed in terms of the

rate expressions, by recognizing that monomers are
consumed at the rate that chains propagate;
1.7. Reaction Mechanisms

The sequence of events that describes the actual process by
which reactants become products is called the reaction
mechanism. Reactions may occur all at once or through several
discrete steps. Each of these processes is known as an
elementary reaction or elementary process.
The molecularity of a process tells how many molecules are

involved in the process or total order of rate law in an elementary
reaction. The rate law of elementary reaction is derived from the
equation. The order is the number of reacting molecules because
they must collide to react.
46
 When a molecule decomposes by itself is a unimolecular

reaction
 when two molecules collide and react is a bimolecular
reaction
 when three molecules collide and react is a termolecular
reaction As shown in the table below

Specific examples
 O3 O2 + O rate = k [O3] unimolecular

 NO2 + NO2 NO3 + NO rate = k [NO2]2 bimolecular
 Br + Br + Ar Br2 + Ar* rate = k[Br]2[Ar] termolecular
Caution: Derive rate laws this way only for elementary reactions.
The rate law for an elementary step is written directly from that
step.
1.7.1. Multistep Mechanisms

In a multistep process, one of the steps will be slower than all
others. The overall reaction cannot occur faster than this slowest,
rate-determining step.
a. Slow Initial Step
NO2 (g) + CO (g)  NO (g) + CO2 (g)
The rate law for this reaction is found experimentally to be Rate =

k [NO2]2
CO is necessary for this reaction to occur, but the rate of the

reaction does not depend on its concentration. This suggests the
47
reaction occurs in two steps. A proposed mechanism for this

reaction is
Step 1: NO2 + NO2 NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
Add these two equations led to the overall reaction
NO2 + CO  NO + CO2 (overall reaction)
The NO3 intermediate is consumed in the second step. As CO is

not involved in the slow, rate-determining step, it does not appear
in the rate law therefore the rate law will be Rate = k [NO2]2.
Fast Initial Step
The rate law for this reaction is found (experimentally) to be
Because termolecular (= trimolecular) processes are rare, this

rate law suggests a two-step mechanism. A proposed mechanism
Step 1 ; NO + Br2 ↔ NOBr2 (fast)
Step 2; NOBr2 + NO → 2 NOBr (slow)
Step 1 is an equilibrium- it includes the forward and reverses

reactions
The rate of the overall reaction depends upon the rate of the slow
step. The rate law for that step would be
But how can we find [NOBr2]? NOBr2 can react two ways:
 With NO to form NOBr

 By decomposition to reform NO and Br2
The reactants and products of the first step are in equilibrium with
each other.
Therefore, Ratef = Rater
48
Because Ratef = Rater ,
k1 [NO] [Br2] = k−1 [NOBr2]
Solving for [NOBr2] gives us
[ ][ ] [ ]
Note that the rate law for slow step (step 2) is
When you make [ ] the subject of the formulae will get
[ ]
[ ]
Substituting this expression for [NOBr2] in the rate law for the
rate-determining step gives
[ ][ ] [ ]=
[ ]
[ ][ ]
[ ]
49
Unit summary
In this unit we explained how the various factors affect reaction

rates, define reaction rates, average rates, initial rates and rate
constants. Evaluate rate law from experiments. Properly apply 1st
Summary
and 2nd differential rate laws and integrated rate laws. Interpret
elementary reactions and mechanisms. Derive rate laws from a
given mechanism. Apply the steady-state method to derive the rate
law of a given mechanism, and discuss the results. Explain the
action of catalysts in terms of chemistry and in terms of energy of
activation.
50
Unit 2
2.0. Theories of Reaction Rates
2.1. Introduction
There are two basic theories that explain the rate of the
chemical reaction. These are called Collision theory and
activated complex theory (transition state theory). We will
look at each on in details. The simplest of the two is the
collision theory and this based on reaction in gas phase only
Both (collision and activated complex) theories say that:
molecular encounters make them excited making reactions.
Excitation can be through collisions (collision theory) or the
energy can be taken from surroundings (activated complex,
in solutions).
Upon completion of this unit you will be able to:
 Describe the theories of the rate of chemical reaction
 Describe the catalysis of chemical reaction
Outcomes
51
2.2. Collision Theory

Let us consider the following reaction
A + B →Products
Rate = k2[A][B]
k2 will be affected by
 Rate of encounter
 Energy
 Orientation
Where k2 α rate of collisions x energy requirement x steric
requirement
The basic assumptions
Molecules are hard spheres
For reactions to occur, molecules must collide
Reactions occur only if molecules are energetic
Collisions should transfer certain minimum energy
Number of Collisions
Number of molecules N in volume V
Number of collisions of one molecule per second is the

collision frequency, z
The average velocity of the molecule that will collide is

m/s. Collision of the molecule can only take place if
molecules are within the distance, d. Therefore, all the
molecules within the volume πd2V will collide with the other
molecule per second.
Encounter of A with B
This is the area within which centre of A has to enter around

the target molecule B for collisions to occur given by πd 2-
collision cross section. This is the volume that will be swept
by the molecule/sec. The solid line represents the average
52
velocity of the molecule. Area πd2, is the area covered by

the dotted lines.
Number of collisions of one molecule per second,
z = (N/V) (πd2)( s-1)
Where N/V is number of molecules in unit volume.
From Bohr equation, relative speed = ( ) and m is
replaced by μ = , reduced mass for particles that are
colliding. When two identical particles are colliding then, μ =

m/2
= (8kT/πm/2) ½
z11= √ N/V πd2(8kT/πm)½s-1
z11= √ N/V πd2(8RT/πM)½s-1
πd2= σ; Collision cross –section the equation becomes

z11= √ N/V σ(8kT/πm)½s-1
Activity 2.1.
What is the mean speed of Hydrogen molecule with respect

to oxygen molecules (n or oxygen molecules with respect to
hydrogen molecules) at 298 K?
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53
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Solution
m1 = =
m2 = =
( )( )
µ= =
µ=
= ( )
( )( )
=( )
( )
= 1824 ms-1
2.2.1. Collision number
Number of bimolecular collisions in 1 m3 per sec,
Z11(s-1m-3) = ½ (N/V) z11 ; ½ not to count collisions twice
=1/√ (N/V)2πd2
For biomolecules; different molecules,
Z12= (NA/V) (NB/V) π(rA+ rB)2(8kT/πμ)½
Where rA and rB are radius of particle A and B respectively

The collision Number is very large up to 1034 for N2 at STP
Activity 2.2.
For molecular oxygen at 25 , calculate the collision

frequency z11 and the collision density Z11 at the pressure of
54
1 bar. The collision diameter of oxygen is 0.361 nm or 3.61

x 10-10 m as determined
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Solution
( )( )
=( ) ( ) = 444 ms-1
( )
( )( )( )
( )( )
The collision frequency is given by

√
= ( )( ) ( )(444 ms-1)
The collision density
= ( )( ) ( )(444 ms-1)
( )( )
=
2.2.2. Rate constant
A + B →P
d[P]/dt = k[A][B]
If all collisions lead to reactions, then
d[P]/dt = ZAB/Nav Where Nav →Avogadro number
55
(Since rate is in moles/unit volume and not in molecules/unit

volume)
We know,
d[P]/dt = k (NA/V.Nav) (NB/V.Nav) …1
d[P]/dt = ZAB/Nav = [1/Nav] (NA/V) (NB/V) πd2 V …2
Compare 1 and 2
k/Nav = πd2
k = Nav πd2 mol-1m3s-1
Activity 2.3.
Calculate the bimolecular rate constant at 298 K for the

reaction of two different” average” small radicals with a
reduced mass µ of 30 x 10-3 Kg mol-1 /Na = 4.98 x 10-26 Kg
and a collision diameter d12 of 500 pm.
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Solution
k = Nav πd2 mol-1m3s-1 = Nav πd2 (8kT/πμ)½
( )
= (6.022 x 1023 mol-1)(3.14)(500 x 10-12 m)2[ ]
( )( )
= 2.17 x 108m3mol-1s-1
= 2.17 x 108m3mol-1s-1(103Lm-3)
= 2.17 x 1011mol-1s-1
56
2.2.3. Energy Considerations
We expect the rate constant for a bimolecular reaction to

depend on both frequency and energy of the collisions. The
above considerations do not take into account the role of
energy. The reaction of molecular pairs with energy above
Ea is given by= exp.–Ea/RT. These will be the fruitful
collisions leading to products.
ZAB(effective) = ZAB x exp-Ea/RT
The rate constant for a bimolecular reactions is
k’= NAVπd2AB(8kT/πm)½ exp–Ea/RT
This equation is similar to the Arrhenius law except for √T

term in AB of pre-experimental factor.
Kinetic data over a wide range of temperature range show

that the pre-experimental factor depends on √T (by about
2%) as predicted.
k = A’√T exp–Ea/RT
A’ = NAVπd2AB (8k/πm)½mol-1m3sec-1
2.2.4. Steric requirement
Collision energy is not the only criterion that contributes to the k.
The relative orientation of the molecules also plays an important
role. The A values disagree between theory and experiment
value. Therefore the rate constant can also be explained in terms
of a steric factor, P by
k11= P Z11e-Ea/RT
k12= P Z12e-Ea/RT
Where P = (Aexpt/Atheory)
Different equations used
For similar molecules
Rate = ZAA/NAV= 1/√2 (NA/V)2πd2 V (1/NAV)
57
Rate = k (NA/V NAV) (NA/ V NAV) = 1/√2

(NA/V)2 σ (1/NAV)
k/NAV= 1/√2 πd2
k = 1/√2 NAVπd2
= 1/√2 NAVπd2(8kT/πm)½
= 2 NAVd2(πkT/m) mol-1m3s-1
k = 2 NAVd2(πRT/M)½ e –Ea/RT
The steric factor is difficult to evaluate
k = Pσ(8kT/πμ)1/2NAe-Ea/RT
The effective σ can be considered as Pσ which is taken as
the reactive cross section σ*.
k = Pσ(8kT/πμ)1/2NAVe-Ea/RT
k = Ae-Ea/RT
A = Pσ(8kT/πμ)1/2NAV
This kind of evaluation shows that P is very small, of the
order of 10-6
One case where P is large is for the reaction,
K + Br2→KBr + Br
Here P = 4.8 (experimentally)
Suggested to follow Harpoon Mechanism
Harpoon extends the cross-section of reactive encounter.
The reaction need not occur as a result of simple
mechanical encounter
--------------------------------------------------------------------------------
Calculate P assuming harpoon mechanism
Net change in energy upon transfer of an electron from K to
Br2 to form K+ and Br2-is
E= I –Ea-e2/(4 πεoR), this will go to zero when harpoon will
transfer e2/4πεoR = I –Ea
So, P = σ*/σ= R2/d2= {e2/4 πεo(I-Ea)}2 d2
Value determined is 4.2, in agreement with experiment
(4.8).
58
2.2.5. Reactions in solution

Cage effect
Activation energy, Encounter pair
A + B →AB rate = kd[A][B]
AB ←A + B rate = kd’[AB]
AB →P rate = ka[AB]
d[AB]/dt = kd[A][B] - kd’[AB] - ka[AB] ~ 0
[AB] ~ kd[A][B]/[ka+ kd’]
d[P]/dt ~ ka[AB] = kakd[A][B]/[ka+ kd’] = k2[A][B]
kd’<<ka, d[P]/dt ~ kd[A][B] diffusion controlled

ka<<kd’, d[P]/dt ~ kakd/kd’[A][B] = kaK[A][B]
activation controlled
2.3. Transition State Theory
We have looked at the collision we can now deal with the

other names called Transition State Theory (Activated
complex theory and Absolute rate theory). The drawback of
collision theory is it is difficult to calculate the steric factor
from molecular geometry for complex molecules. The theory
is applicable essentially to gaseous reactions
Consider
A + B →P or A + BC = AB + C
A + B = [AB] * →P
A and B form an activated complex and are in equilibrium
with it. The reactions proceed through an activated or
transition state which has energy higher than the reactants
or the products.
59
The rate depends on two factors,

i. Concentration of [AB]
ii. The rate at which activated complex is
decomposed.
Rate of reaction = [AB*] x frequency of decomposition of
AB*
K*eq= [AB*] / [A] [B]
[AB*] = K*eq[A] [B]
The activated complex is an aggregate of atoms and
assumed to be an ordinary molecule. It breaks up into
products on a special vibration, along which it is unstable.
The frequency of such a vibration is equal to the rate at
which activated complex decompose.
-d[A]/dt = -d[B]/dt = k2[A][B]
Rate of reaction = [AB*] υ
= K*eq x υ[A] [B]
Activated complex is an unstable species and is held
together by loose bonds. Therefore the vibration of low
frequency will decompose the activated complex.
Energy of vibration E = hυ
υ= E/h = kBT/h
60
In a classical sense, the average energy of such a

vibrational degree of freedom, kBT (where kB= R/N).
Remember equipartition principle. If we know the energy
distribution of molecules clearly (statistical mechanics) we
can make a better description.
k = kBT/h K*eq(Co)1-m Eyring equation
C°is the standard –state concentration of 1 mol L-1, m is the
order.
The factor (C°)1-mis introduced because equilibrium
constant is dimensionless, but the units for rate constant
depend on the order of the reaction.
k = kB(J K-1) T (K)/h (J s) K*(C°)(1-m)
↑
Dimensionless
k is in s-1for 1st order for second order in L mol-1s-1= s-1(C°)-1
k2= K*eqkBT/h
K* for the formation of the transition state can be written in
terms of the molecular partition functions for the reactants
and the transition state.
2.3.1. Thermodynamic Aspects
The equilibrium constant K*eq can be interpreted in terms of
ΔG*, ΔS* and ΔH*. These quantities represent the
difference between the values of the respective
thermodynamic functions between activated complex and
reactants. All substances being in their standard states, is
activity of unity.
ΔG*= -RT ln K*eq
ΔG*= ΔH*-TΔS*
ΔH*-TΔS*= -RT ln K*eq
K*eq= exp (-ΔH*/RT) exp ΔS*/R
In the form of Arrhenius equation →
K2=kBT/h exp – ΔH*/RTexp ΔS* / R
61
This can be expressed in a form which involves

Ea(experimental) instead of ΔH*. We need to find relation
between ΔH*and Ea. The variation of Keq*with temperature
is given by, d (ln K*eq)/dT = ΔE*/RT2 (one form of Arrhenius
law). The assumption here is that K is actually, Kc. ΔE*
represents the increase in internal energy when reactants
go from the initial state to the activated state. k2= K*eqkBT/h
ln k2= ln T + ln K*eq+ ln kB/h
Differentiate with respect to temperature and rewrite.
d ln k2/dT = 1/T + dln K*eq/dT
d ln k2/dT = 1/T + ΔE*/RT2
d ln k2/dT = (RT+ ΔE*)/RT2
Compare this with Arrhenius equation
d ln k/dT = Ea/RT2 We get Ea= ΔE*+ RT
[ΔE*≡ΔU*]H = E + PV
Or Ea= ΔH*-PΔV* + RT
ΔE*= ΔH*- PΔV*or ΔU*= ΔH*-PΔV*at constant p
PΔV*= Δn*RT
For ideal gases, it becomes
Ea= ΔH*+ RT –Δn*RT
ΔV*is volume change and Δn*is the change in number of
moles from initial state to the activated state. For
bimolecular reaction
Δn*= -1
Ea= ΔH*+ RT –(-1)RT
= ΔH*+ 2RT
k2= kBT/h exp ΔS*/Rexp –(Ea-2RT)/RT
k2= kBT/h e2exp ΔS*/Rexp –Ea/RT
ΔS*can be calculated form k2 & Ea.
Can we show that A is the same by both the theories? For
reactions in solution and for unimolecular reactions,
ΔH*≈Ea(almost equal). ΔS*negative means activated
62
complex is more ordered than the reactants and A will have

smaller value
A = kBT/h expΔS*/Re (unimolecular)
A = kBT/h expΔS*/Re2(bimolecular)
And reaction will be slower.
Positive ΔS*means that entropy of the complex is greater
than the entropy of the reactants. A loosely bound complex
has higher entropy of activation than a tightly bound one.
Multiply rate constants with a factor (C°)1-m to take care of
the units of the rate constants (which depend on order).
Activity 2.4.
For the reaction CH3+ D2→CH3D + D, the rate constant is

given by k = 2 x 109exp–6389/TM-1s-1 over the temperature
range 300 to 626 K . Calculate enthalpy and entropy of
activation for this reaction at 300K.
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Solution
Since n = -1.
ΔH*= Ea–2RT
= e6389 x 8.314 –2 x 8.314 x 300
= 48.1 kJ/mol
exp ΔS*/R = AhCo/kBTe2
= ((2 x109M-1s-1) (6.63 x 10-34Js) (1M))/(1.38 x 10-23JK-1)
(300K) e2))
63
= 4.35 x 10-15
ΔS*= -83.50 JK-1mol-1
ΔS is negative; which means that the activated complex is
more restricted than the reactants. This suggests the
formation of a complex between CH3 and D2 with bond
energy ~48 kJ. Evidently, the structure of the complex is
rigid enough (vibrational frequencies are high.
2.3.2. Dynamics of molecular collisions
Reactions between species are better understood by
undertaking studies in the gas phase. Here molecular
beams can be used to study reactive collisions. Reactants
can be prepared in selected energy states and the products
can be studied as a function of their energy states. In the
case of a typical kinetics experiment, there is a distribution
of energy states. The study of factors governing collisions of
molecules constitute the area called reaction dynamics.
The results can be better understood in terms of potential
energy surfaces. For example, the collision between a
hydrogen molecule (H2) and a hydrogen atom (H) can be
represented in terms of a potential energy surface. In this
system, it is known that the lowest energy of interaction is
when the collision is along a line. The variation in the
potential energy of the system as a function of two distances
give the potential energy surface. This is depicted below.
The interaction can also be depicted in terms of a contour
diagram. There are also other approaches. A study of this
collision tells how the molecule HA-HB results in the
formation of HB-HC upon collision with an H atom and the
various factors which govern this reactive encounter. Such a
procedure can be extended to more complicated systems.
64
2.4. Catalysts
Catalysts increase the rate of a reaction by decreasing the
activation energy of the reaction. Catalysts change the
mechanism by which the process occurs.
 Let us look at the reaction, where NO is a catalyst
2 SO2 (g) + O2 — 2 SO3 (g)

via the mechanism
65
i 2 NO + O2 2 NO2 (3rdorder)

ii NO2 + SO2 SO3 + NO
 The best example is the catalyzed decomposition of

ozone.
R.J. Plunkett in DuPont discovered carbon fluorine chlorine

compounds CFC. The CFC decomposes in the atmosphere:
The CFC decomposes in the atmosphere as follows:
CFCl3 → CFCl2 + Cl
CF2Cl3 → CF2Cl + Cl.
The Cl decomposes the ozone layer via catalysis reaction

as shown in the following mechanism:
i. O3 + h v → O + O2,
ii. Cl + O → CIO
iii. ClO + O → Cl + O2
iv. O + O3 → O2 + O2.
The net result or reaction is

2 O3 → 3 O2
Scientists sound the alarm, and the CFC is banned now

because of the effect on the ozone layer
2.4.1. Acid-base Catalysis
Specific acid-base catalysis involves H+ or OH- from the solvent

that diffuses into the catalytic center. General acid-base catalysis
involves acids and bases other than H+ and OH-, which facilitate
transfer of H+ in the transition state. Specific and general acid-
base catalysis of simple reactions in solution may be
distinguished by determining the dependence of observed
reaction rate constants (kobs) on pH and buffer concentration.
66
 In specific acid-base catalysis, H+ or OH- concentration

affects the reaction rate, kobs is pH-dependent, but buffers
concentration has no effect.
 In general acid - base catalysis, in which an ionizable buffer
may donate or accept a proton in the transition state, kobs is
dependent on buffer concentration (dependent on all acids
and bases in solution).
In acid catalysis, the crucial step is the transfer of a proton to the

substrate;
Acid catalysis is the primary process in the solvolysis of esters

and keto-enol tautomerism.
In base catalysis, a proton is transfered from the substrate to a

base;
Base catalysis is the primary step in the isomerization and

halogenation of organic compounds.
2.4.2. Homogenous vs. heterogeneous catalysts
A catalyst in the same phase (gases and solutions) as the

reactants is a homogeneous catalyst. It is effective, but
recovery is difficult. When the catalyst is in a different phase
than reactants (and products), the process involve
heterogeneous catalysis. Chemisorption, absorption, and
adsorption cause reactions to take place via different
pathways.
Platinum is often used to catalyse hydrogenation
Catalytic converters reduce CO and NO emission.
i.e. Catalysed reactions:
67
CO + O2 → CO2
2 NO → N 2 + O2
Ceryx's vision is to design, produce, and commercialize

advanced systems that balance Cost, Performance,
Emissions Reduction, and Fuel Penalty to make the
economics of pollution control viable.
One way a catalyst can speed up a reaction is by holding

the reactants together and helping bonds to break as shown
below
Heterogeneous Catalysis
They is not much to be talked about on homogeneous

catalysis so we will base our focus Heterogeneous Catalysis
Heterogeneous catalysis refers to the form

of catalysis where the phase of the catalyst differs from that
of the reactants. The great majority of practical
heterogeneous catalysts are solids and the great majority of
reactants are gases or liquids. Heterogeneous catalysis is of
paramount importance in many areas of the chemical and
energy industries.
Adsorption
Adsorption is commonly an essential first step in

heterogeneous catalysis. Adsorption is when a molecule in
the gas phase or in solution binds to atoms on the solid or
liquid surface. The molecule that is binding is called the
adsorbate, and the surface to which it binds is the
adsorbent. The process of the adsorbate binding to the
adsorbent is called adsorption. The reverse of this process
(the adsorbate splitting from adsorbent) is called desorption.
In terms of catalyst support, the catalyst is the adsorbate
and the support is the adsorbent.
68
Hydrogenation of alkenes is enhanced by metal catalysts.

For example, hydrogenation of ethene on nickel as the
metal surface.
The table shows some example of large industrial

processes that requires heterogeneous catalysis.
Process Reactants, Catalyst

product
Sulphuric acid synthesis (Contact SO2 + O2, SO3 Vanadium oxides

process)
Ammonia synthesis (Haber process) N2 + H2, NH3 Iron oxides on alumina
Nitric acid synthesis NH3 + O2, HNO3 Pt-Rh gauze
Extent of adsorption
The extent of surface coverage is normally expressed as the

fractional coverage, θ;
69
The fractional coverage is often expressed in terms of the

volume of adsorbate adsorbed by θ = V/V∞, where V∞ is the
volume of adsorbate corresponding to complete monolayer
coverage. The rate of adsorption, dθ/dt, is the rate of
change of surface coverage with time.
The variation of θ with pressure at a chosen temperature is

called adsorption isotherm. Adsorption isotherm is based on
three assumptions;
 Adsorption cannot proceed beyond monolayer

coverage.
 All sites are equivalent and the surface is uniform
(i.e., the surface is perfectly flat on a microscopic scale).
 The ability of a molecule to adsorb at a given site is
independent of the occupation of neighbouring sites (i.e.,
there are no interactions between adsorbed molecules).
The dynamic equilibrium is;
( ) ( ) ( )
With the rate constants ka for adsorption and Kd desorption.

The rate of change of surface coverage due to adsorption is
proportional to the partial pressure p of A and the number of
vacant sites N(1-θ), where Nis the total number of sites;
( )
70
The rate of change of θ due to desorption is proportional to

the number of adsorbed species, Nθ;
At equilibrium, there is no net change (i.e., the sum of these

two rates is zero), and solving for θ gives the Langmuir
isotherm;
where
The fractional coverage increases with increasing pressure,

and approaches 1 only at very high pressure, when the gas
is forced on every available site of the surface. The
temperature dependence of K can be used to determine the
isosteric enthalpy of adsorption, ∆adHθ, the standard
enthalpy of adsorption at a fixed surface coverage. To
determine the quantity we recognize the K is equilibrium
constant, then use the van't Hoff euation to have;
( )
Rates of surface processes
The rate of adsorption at which a surface is covered by

adsorbate depends on the ability of the susbtrate to
dissipate the energy of the incoming particle as thermal
motion as it crashes on to the surface. The proportion of
collisions with the surface that successfully lead to
adsorption is called the sticking probability, s;
71
The rate of desorption is always activated because the

particles have to be lifted from the foot of a potential well. A
physisorbed particle vibrates in its shallow potential well,
and might shake itself off the surface after a short time. The
temperature dependence of the first-order rate of departure
can be expected to be Arrhenius-like, with an activation
energy for desorption, Ed, comparable to the enthalpy of
physisorption;
Therefore, the half-life for remaining on the surface has

temperature dependence
where
In the Langmuir-Hinshelwood mechanism (LH

mechanism) of surface-catalysed reactions, the reaction
takes place by encounters between molecular fragments
and atoms adsorbed on the surface. The rate law is second-
order in the extent of surface coverage;
A+B→P Rate = KrθAθB
Inserting the appropriate isotherms for A and B, gives the

reaction rate in terms of partial pressures of the reactants.
For example, if A and B follow Langmuir isotherms, and
adsorb without dissociation, we have;
72
Then it follows that the rate law is;
( )
In the Eley-Rideal mechanism (ER mechanism) of a

surface-catalysed reaction, a gas phase molecule collides
with another molecule already adsorbed on the surface. The
rate of formation of product is proportional to the partial
pressure, pB, of the non-adsorbed gas B and the extent of
surface coverage, θA, of the adsorbed gas A;
A+B→P Rate = KrpBθB
If the adsorption isotherm for A is known, we can express

the rate law in terms of its partial pressure, pA;
Almost all thermal surface-catalysed reactions are thought

to take place by LH mechanism, although a number of
reactions with an ER mechanism have been identified.
2.4.3. Enzymes; selective catalysts
Enzymes are catalysts in biological systems. Enzymes are

long protein molecules that fold into balls. They often have a
metal coordinated to the O and N sites. The substrate fits
into the active site of the enzyme much like a key fits into a
lock. A substrate is molecules catalysed by enzymes. They
are held by various sites (together called the active site) of
the enzyme molecules and just before and during the
73
reaction. After having reacted, the products P1& P2 are

released.
Enzyme + Substrate→ ES (activated complex)
ES → P1 + P2 + E
2.5. Kinetic Salt Effect
The kinetic Salt Effect is an effect on the rate of a reaction

by salts present in the solution. Salt molecules are able to
disassociate, and form cations and anions. An increase in
the charge(- or +) of a transition state or in an activated
complex results in an increase in solvation (more order),
and causes a decrease in the change of entropy (ΔS).
Whereas, a decrease in the charge of the transition state
causes an increase in ΔS.
I− + C+ Eo → Product
74
Kinetic Salt Effect affects the reaction through stabilization.

For example in the above reaction, both reactants have a
charge. The negatively charged reactant is stabilized by the
positive charges from the salt, while the positively charged
reactant is stabilized by the negative charges from the
salt. As a result the rate, at which the reactants come
together decreases, thus decreases the rate at which E
forms. Since a charged intermediate will be stabilized in the
solution as well, the half-life of the intermediate at
equilibrium will increase causing the reaction towards
product formation. Since the rate of the product formation
becomes higher because of increased amounts of the
intermediate present on the solution first order kinetics is
used to derive the rate constant equation:
logKTS = logKTSo + 2ZAZBI1/2
Where,
 Z is the charge on the cation and ion from the

salt. ZAZB is a product value.
 I is the ionic strength. I is also dependent on the
solubility of the salt in the reaction mixture. Ionic
strength is directly proportional to the solubility of the
salt. Changing the ionic strength manipulates the
solvation of the reactants and intermediates, thus
changing the ΔS, and affecting the reaction rate.
 logKTSo is the rate constant without the salt in the
reaction mixture.
 A is also a constant for the solvent the solution is in.
The A value for water is 0.509 at 298 K.
75
A hard concept to understand is the relationship

between ZAZB, I, and the rate of the reaction is presented in
tabular form to avoid confusion.
logKTS = logKTSo + 2ZAZBI1/2
ZAZB Rate of Reaction
+ Increases (salt present in the reaction mixture)
- Decreases (the ionic strength increases
Note: I=0 at very dilute salt concentrations or if salt is inert.

Reaction rate in this case is independent of salt.
Activity 2.5.
The rate constant of a reaction, consider

A+ and B2- →product
Is measured at 0.001 ionic strength and at 0.01 ionic
strength at 25 in water. What is the effective ratio of the
rate constant?
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
--------------------------------------------------------------------------------
Solution
To drive a general relation, consider
76
→ product
Log K0.001 =logKo + 2 (0.509)(0.001)1/2
Log K0.01 =logKo + 2 (0.509)(0.01)1/2
Log (0.509)(0.0011/2 -0.011/2)
= 2(1)(-2) (0.509)(0.0011/2 -0.011/2)
= 0.183
= 1.53
= 1.53
77
Unit summary
In this unit you have learnt that there are two types of theories that
explain the kinetic of a chemical reaction. These collision theory
and transition state theory. Collision theory explain kinetic
Summary
properties of the molecules and doesn’t account for a gaseous
state, How even the transition theories cater for the kinetics in
solution. In this unit we also look at the mechanistic pathway via
catalysis of molecular reaction. Any reaction to take place
molecules in the right orientation and with minimum energy called
activation energy. Catalysis speed up the process of a chemical
reaction by lowering the activation energy. And catalysis are of two
types homogeneous catalyst where the molecule catalyzed are in
the same state. This catalyst is difficult to retrieve after the reaction
and the other type of catalyst is heterogeneous where molecules
are catalyzed are in a different state from the catalyst.
78
Readings
Readings
There are a number of excellent resources on the web. A few

suggested links are:
 http://www.how-to-study.com/
The “How to study” web site is dedicated to study skills

resources. You will find links to study preparation (a list of
nine essentials for a good study place), taking notes,
strategies for reading text books, using reference sources,
test anxiety.
 http://www.ucc.vt.edu/stdysk/stdyhlp.html
This is the web site of the Virginia Tech, Division of

Student Affairs. You will find links to time scheduling
(including a “where does time go?” link), a study skill
checklist, basic concentration techniques, control of the
study environment, note taking, how to read essays for
analysis, memory skills (“remembering”).
 http://www.howtostudy.org/resources.php
Another “How to study” web site with useful links to time

management, efficient reading,
questioning/listening/observing skills, getting the most out
of doing (“hands-on” learning), memory building, tips for
staying motivated, developing a learning plan.
79
80 Unit 2
The above links are our suggestions to start you on your

way. At the time of writing these web links were active. If you
want to look for more go to www.google.com and type “self-
study basics”, “self-study tips”, “self-study skills” or similar.
There are also a few books you may refer to:
1. R.J. Silbery and R.A.Alberty (2001). “Physical

Chemistry,” (3rd Edition) , John Wiley and Sons,
Singapore.
2. Glyde R.Metz (1989)., “Theory and problems of physicl
chemistry," (2nd Edition), McGraw Hill. USA.
3. http://users.umassmed.edu/william.royer/Lecture_5a_Catal
ysis.ppt
4. http://www2.palomar.edu/users/ngeetha/115lecturestuff/
ch16_lecture_6e_final.ppt
5. http://www.chemistry.mtu.edu/pages/courses/files/ch112
0-sgreen/chapter_14_sg.ppt
6. http://people.virginia.edu/~cmg/slides/chapter_16.ppt
80

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MUKUBA UNIVERSITY

CHE 450: Physical Chemistry

© Mukuba University 2014.

Directorate of Distance Education (DODE)

F.kayamba: Lecturer Mukuba University

Mbalushi.J; Lecturer Mukuba University

About this Module 5

How this module is structured ............................................................................. 5

Getting around this Module 10

Margin icons ................................................................................................................ 10

1.0 Rate of chemical reaction ............................................................................. 12

2.0 Theories of rate of reaction .......................................................................... 51

2.2.1. Collision number ............................................................................... 54

About this Module

How this module is structured

The module content

 An introduction to the unit content.

 Core content of the unit with a variety of learning activities.

 Assignments and/or assessments, as applicable.

 Course content and structure.

 Course reading materials and resources.

 Course support (assigned tutors, technical help, etc.)

Your constructive feedback will help us to improve and enhance

The module overview

Welcome to the module on foundation to chemistry

This module gives you the foundation to General Chemistry

To complete this module successfully, you will need to spend three

We strongly recommend that you read the overview carefully

Upon completion of this module you will be able to:

 Determine the rate. order and half life of a chemical reaction

 Describe factors that affect the chemical reaction

Outcomes  Describe the mechanistic pathway and catalysis of chemical

 Describe in details the condition needed for a chemical reaction

This module is expected to be covered within a period of 100

As an adult learner your approach to learning will be different to

Essentially you will be taking control of your learning environment.

We recommend that you take time now—before starting your self-

Should you require help in the course of your studies, do not

hesitate to contact the following course tutors

Help Mbalushi. J Mobile; 0971507836 /0968487475

Mr Kayamba. F Mobile: 096/7 7370381 / 0954 013237

You will be expected to write at least two assignments in an

The assignments should be handed in to course tutors during the

Assignments residential sessions.

You will be required to submit the assignments in the order in

Getting around this Module

A complete icon set is shown below. We suggest that you

Activity Assessment Assignment Case study

Discussion Group Help Note it!

Outcomes Reading Reflection Study skills

Summary Terminology Time Tip

1.0. Rate chemical reaction

Chemical reaction outline that will look are summarised in the

Upon completion of this module you will be able to:

 Determine the rate. order and half life of a chemical

 Describe in details the condition needed for a chemical

 Describe factors that affect the chemical reaction

 Describe the mechanistic pathway of chemical reaction

1.2. Reaction Rates and Stoichiometry

C H Cl (aq) + H O (l) C H OH (aq) + HCl(aq)

be consumed in the reaction

In this reaction, the concentration of butyl chloride, C4H9Cl, was

C4H9Cl (aq) + H2O (l) C4H9OH (aq) + HCl (aq)

For above reaction will be