UNIVERSITY OF CAPE COAST

COLLEGE OF DISTANCE EDUCATION (CoDE).

COURSE CODE:

CHE203

COUERSE TITLE:

PHYSICAL CHEMISTRY

© COLLEGE OF DISTANCE EDUCATION, UNIVERSITY OF CAPE COAST (CoDEUCC)

CoDE PUBLICATIONS, 2019

 First printing in 2016 by Hampton Press, Cape Coast
Second printed in 2017 by Brenya Distribution Ltd., Accra
Printed in 2019 by Wilson Books & Stationery Ent. Ltd., Cape Coast

© COLLEGE OF DISTANCE EDUCATION, UNIVERSITY OF CAPE COAST

(CoDE UCC) 2016, 2017, 2019

CoDE PUBLICATIONS, 2019

All right reserved. No part of this publication should be reproduced, stored in a retrieval
system or transmitted by any form or means, electronic, mechanical, photocopying or
otherwise without the prior permission of the copyright holder.

Cover page illustrated by Nathaniel Ampah

ABOUT THIS BOOK

This Course Book “Physical Chemistry” has been exclusively written by experts in the
discipline to up-date your general knowledge of chemistry in order to equip you with
the basic tool you will require for your professional training as a teacher.

This two-credit course book of twenty-four (24) sessions has been structured to reflect
the weekly two-hour lecture for this course in the University. Thus, each session is
equivalent to a one-hour lecture on campus. As a distance learner, however, you are
expected to spend a minimum of three hours and a maximum of five hours on each
session.

To help you do this effectively, a Study Guide has been particularly designed to show
you how this book can be used. In this study guide, your weekly schedules are clearly
spelt out as well as dates for quizzes, assignments and examinations.

Also included in this book is a list of all symbols and their meanings. They are meant to
draw your attention to vital issues of concern and activities you are expected to perform.

Blank sheets have been also inserted for your comments on topics that you may find
difficult. Remember to bring these to the attention of your course tutor during your
face-to-face meetings.

We wish you a happy and successful study.

Dr. J. K. Bentum
Mr. E. J. Koranteng-Addo
Dr. J. P. K. Adotey
Prof. D. K. Essumang

CoDEUCC/Diploma in Maths & Science Education i

 ACKNOWLEDGEMENT

It has become a tradition in academic circles to acknowledge the assistance one

received from colleagues in the writing of an academic document. Those who
contributed in diverse ways toward the production of this particular course book merit
more than mere acknowledgement for two main reasons. First, they worked beyond
their normal limits in writing, editing and providing constant support and
encouragement without which the likelihood of giving up the task was very high.
Second, the time span for the writing and editing of this particular course book was so
short that their exceptional commitment and dedication were the major factors that
contributed to its accomplishment.

It is in the foregoing context that the names of Dr. J. K. Bentum, Mr. E. J.

Koranteng-Addo, Dr. J. P. K. Adotey and Prof. D. K. Essumang, University of Cape
Coast, who wrote and edited the content of this course book for CoDEUCC, will ever
remain in the annals of the College. This special remembrance also applies to those who
assisted me in the final editing of the document.

I wish to thank the Vice-Chancellor, Prof. Joseph Ghartey-Ampiah and the Pro-Vice-
Chancellor, Prof. Dora Edu-Buandoh and all the staff of the University’s
Administration without whose diverse support this course book would not have been
completed.

Finally, I am greatly indebted to the entire staff of CoDEUCC, especially Mrs. Christina
Hesse and Ms Alberta S.F Gogovi for typing and formatting the scripts.

Any limitations in this course book, however, are exclusively mine. But the good
comments must be shared among those named above.

Prof. Isaac Galyuon

(Provost)

ii CoDEUCC/Diploma in Maths & Science Education

 TABLE OF CONTENTS

About this Book … … … … … … … ... i

Acknowledgement … … … … … … ... ... ii
Table of Contents … … … … … … ... iii
Symbols and their Meanings … … … … … ... vi

UNIT 1: BASIC CALCULUS FOR CHEMISTRY STUDENTS … 1

Session 1: Introduction to Calculus … … … … … 3

Session 2: Introduction to Differentiation … … … … 9

Session 3: Introduction to Integration … … … … 13

Session 4: Differentiation of other Functions … … … … 19

Session 5: Integration of other Functions … … … … 25

Session 6: Application of Calculus in Physical Chemistry … … 31

UNIT 2: THERMOCHEMISTRY … … … … … 33

Session 1: Why Reactions Occur … … … … … 35

1.1 Terminologies Associated with the Course … … 35
1.2 Energy … … … … … … 36
1.3 The Law of Conservation of Energy … … … 36

Session 2: Thermodynamics [Heat/Energy Change] … … … 37

2.1 First Law of Thermodynamic … … … 37
2.2 State Function … … … … … 38
2.3 Reversibility … … … … … 38
2.4 Formulation of the First Law of Thermodynamics … 38

Session 3: Enthalpy … … … … … … … 41
3.1 Endothermic Reaction … … … … 41
3.2 Exothermic Reaction … … … … … 41
3.3 Standard Condition … … … … … 43

CoDEUCC/Diploma in Maths & Science Education iii

 TABLE OF CONTENTS

Session 4: Calorimetry and Heat Capacity … … … … 45

4.1 The Calorimeter … … … … … 45
4.2 Heat Capacity … … … … … 45
4.3 The Hess Law … … … … … 47

Session 5: Heat of Formation … … … … … … 51

Session 6: Entropy and Gibbs free Energy … … … … 55

6.1 Spontaneous Process … … … … 56
6.2 Non – Spontaneous Process … … … … 56
6.3 Factors that Determine Spontaneity … … … 56
6.4 Second Law of Thermodynamics … … … 58
6.5 Third Law of Thermodynamics … … … 58

UNIT 3: RATE OF CHEMICAL REACTION … … … 59

Session 1: Concept of the Terms in Chemical Kinetics … ... 61

1.1 Kinetic Explained … … … … … 61
1.2 Definition of Kinetic Terminologies … … … 61

Session 2: Rate of Reaction … … … … … … 67

Session 3: The Integrated Rate Law … … … … … 71

3.1 Derivation of the Integrated Rate Law … … 71
3.2 Half Life ( t 1 ) … … … … ... 72
2
3.3 Integrated Law for Zero Order … … … 73
3.4 Units for the rate Constant, K … … … 75
3.5 Half Life for 2nd Order Reaction … … … 76

Session 4: Factors that Affect Reaction Rate … … … … 79

4.1 Factors that affect Reaction Rate … … … 79

Session 5: Activation Energy and Transition State Theory … … 83

5.1 The Activation Energy of Chemical Reaction … 83
5.2 Determining the Activation Energy of a Reaction … 86
5.3 Transition State Theory (TST) … … … 88

Session 6: Catalysis … … … … … … … 91

iv CoDEUCC/Diploma in Maths & Science Education

 TABLE OF CONTENTS

UNIT 4: ELECTROCHEMISTRY … … … … … 95

Session 1: Electrochemistry Defined … … … … … 97

Session 2: Cell E.M.F. [Electromotive Force] … … … … 101

Session 3: Evaluating Standard Cell Potential De° of Galvanic Cells 105

Session 4: Using Standard Potential to Predict the Possibility of a

Reaction … … … … … … … 109

Session 5: Cell Potential and Composition of Reaction Mixture … 111

Session 6: Standard Cell Potential and Equilibrium Constant … 115

6.1 Corrosion … … … … … … 115
6.2 Prevention of Corrosion … … … … 116

References … … … … … … … … … 119

Answers to Self-Assessment Questions … … … … … 120

CoDEUCC/Diploma in Maths & Science Education v

 SYMBOLS AND THEIR MEANINGS

INTRODUCTION

OVERVIEW

UNIT OBJECTIVES

SESSION OBJECTIVES

DO AN ACTIVITY

NOTE AN IMPORTANT POINT

TIME TO THINK AND ANSWER QUESTION(S)

REFER TO

READ OR LOOK AT

SUMMARY

SELF- ASSESSMENT TEST

ASSIGNMENT

vi CoDEUCC/Diploma in Maths & Science Education

 SYMBOLS AND THEIR MEANINGS

OVE R E OVE R E

SUMMA RY SUMMA RY

CoDEUCC/Diploma in Maths & Science Education vii

 THIS MODULE FORMS PART OF CoDEUCC PACKAGE FOR THE
DIPLOMA IN MATHS AND SCIENCE EDUCATION PROGRAMME

FOR FURTHER DETAILS YOU MAY CONTACT

THE PROVOST
(CoDEUCC)
UNIVERSITY OF CAPE COAST
CAPE COAST
TEL/FAX O3321-35203, 36947

COLLEGE OF DISTANCE EDUCATION OF THE

UNIVERSITY OF CAPE COAST (CoDEUCC)

All rights reserved. No part of this publication should be reproduced,

stored in a retrieval system or transmitted by any form or means, electronic,
mechanical, photocopying or otherwise without the prior permission of the
copyright holder.
BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1

UNIT 1: BASIC CALCULUS FOR CHEMISTRY STUDENTS

Unit Outline

Session 1: Introduction to Calculus

Session 2: Introduction to Differentiation
Session 3: Introduction to Integration
Session 4: Differentiation of other Functions
Session 5: Integration of other Functions
Session 6: Application of Calculus in Physical chemistry

This unit will look at the basic calculus for chemistry students. In
physical chemistry, it is generally necessary to view certain quantities
(such as energy, enthalpy and entropy) as functions of several
variables. For example, if the energy of a single component system is thought of as a
function of the number of particles, N, the volume, V and the entropy, S; thus we may
write E = ƒ(N, V, S). The manipulation of such functions requires multivariate calculus.
Session 1 will focus attention on the introduction to calculus. Session 2 and 3 will also
elaborate on differentiation and integration respectively. With this, I hope you will
under the mathematics of slopes and areas. Session 4 and 5 will also further consider the
differentiation and integration of other functions such as cos, sine and logarithms
respectively. Finally, Session 6 will look at the application of calculus in physical
chemistry.

Unit Objectives
By the end of the unit, you should be able to;
(a) Find the derivatives for functions of cosine, sine and logarithms.
(b) Find the integral function of logarithms and other functions.
(c) Apply the concept of derivatives and integration in solving physical chemistry
questions.

CoDEUCC/Diploma in Maths & Science Education 1

 BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

2 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 1

SESSION 1: INTRODUCTION TO CALCULUS

Hello and welcome to Session 1 of unit 1. This session will introduce you
to the fundamental understanding of calculus; the concept of small
changes.

Objectives
By the end of the session, students should be able to;
(a) Appreciate the concept of calculus.
(b) Explain the types of calculus stated.

Now read on…

The word Calculus comes from Latin meaning "small stone". Because it is like
understanding something by looking at small pieces
Differential Calculus cuts something into small pieces to find how it changes.
Integral Calculus joins (integrates) the small pieces together to find how much there is.
And Differential Calculus and Integral Calculus are like inverses of each other, just like
multiplication and division are inverses

Calculus is all about changes.

Kofi and Ato are travelling in the car ... but the speedometer is
broken.

Kofi: "Hey Ato! How fast are we going now?"

Ato:
"Wait a minute ..."
"Well in the last minute we went 1.2 km, so we are going:"
1.2 km/minute x 60 minutes in an hour = 72 km/h

Kofi:
"No, Ato! Not our average for the last minute, or even the last second, I want
to know our speed RIGHT NOW."

CoDEUCC/Diploma in Maths & Science Education 3

 UNIT 1 INTRODUCTION TO CALCULUS
SESSION 1

Ato:
"OK, let us measure it up here ... at this road marker... NOW!"
"OK, we were AT the road marker for zero seconds, and the distance was
... zero meters!"
The speed is 0m / 0s = 0/0 = I Don't Know!
"I can't calculate it Ato! I need to know some distance over some time, and
you are saying the time should be zero? Can't be done."

That is pretty amazing ... you'd think it is easy to work out the speed of a car at any
point in time, but it isn't.
Even the speedometer of a car (when it works!) just shows us an average of how fast
we were going for the last short amount of time.
How About Getting Real Close
But our story is not finished yet!
Kofi and Ato got out of the car, because they have arrived on location. Kofi is about to
do a stunt:

Ato will perform a jump off a 20 m building.

Kofi, as photographer, asks:
"How fast will you be falling after 1 second?"

Ato uses this simplified formula to find the distance fallen:

d = 5t2
• d = distance fallen, in meters
• t = time from jump, in seconds
Example: at 1 second Kofi has fallen d = 5t2 = 5 × 12 = 5 m
But how fast is that? Speed is distance over time:
distance
Speed =
time
So at 1 second:
5m
Speed = = 5 m/s
1 second
"BUT", says Kofi, "again that is an average speed, since you started the jump, ... I want
to know the speed at exactly 1 second, so I can set up the camera properly."

4 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 1

Well ... at exactly 1 second the speed is:

5-5m 0m
Speed = = = ????
1-1s 0s

So again Ato has a problem.

Think about it ... how do we figure out a speed at an exact instant in time?
What is the distance? What is the time difference?
They are both zero, giving us nothing to calculate with!

But Ato has had an idea ... invent a time so short it won't matter.
Ato won't even give it a value, and will just call it "Δt" (called "delta t").
So Ato works out the difference in distance between t and t+Δt
At 1 second Ato has fallen d = 5t2 = 5 × (1)2 = 5 m
At (1+Δt) seconds Ato has fallen d = 5t2 = 5 × (1+Δt)2m
We can expand (1+Δt)2:
(1+Δt)2 = (1+Δt)(1+Δt) = 1 + 2Δt + (Δt)2
And we get:
d = 5× (1 + 2Δt + (Δt)2) m = 5 + 10Δt + 5(Δt)2 m

So between 1 second and (1+Δt) seconds the distance fallen is:

Change in d = (5 + 10Δt + 5(Δt)2) - 5 m = 10Δt + 5(Δt)2 m

Now divide that distance by time to get the speed:

10Δt +5(Δt)2 m
Speed = = 10 + 5Δt m/s
Δt s
So the speed is 10 + 5Δt m/s, and Ato thinks about that Δt value ... he wants Δt to be so
small it won't matter ... so he imagines it shrinking towards zero and he gets:
Speed = 10 m/s
Wow! Ato got an answer!
Ato: "I will be falling at exactly 10 m/s"
CoDEUCC/Diploma in Maths & Science Education 5
 UNIT 1 INTRODUCTION TO CALCULUS
SESSION 1

Kofi: "I thought you said you couldn't calculate it?"

Ato: "That was before I used Calculus!"
Yes, indeed, that was Calculus.
Ato used Differential calculus to cut time and distance into such small pieces that a
pure answer came out.
So ... was Ato's result just luck? Does it work for other things?

Let's try doing this for the function y = x3

This is going to be very similar to the previous example, but it will be just a slope on a
graph, no one has to jump for this one!

Example: What is the slope of the function y = x3 at x=1?

At x = 1, y = 13 = 1
At x = (1+Δx), y = (1+Δx)3
We can expand (1+Δx)3 to 1 + 3Δx + 3(Δx)2 + (Δx)3, and we get:
y = 1 + 3Δx + 3(Δx)2 + (Δx)3
And the difference between the y values from x = 1 to x = 1+Δx is:
Change in y =1+3Δx + 3(Δx)2+(Δx)3 - 1 = 3Δx + 3(Δx)2 + (Δx)3

Now we can calculate slope:

3Δx + 3(Δx)2 + (Δx)3
Slope = = 3 + 3Δx + (Δx)2
Δx
Once again, as Δx shrinks towards zero we are left with:
Slope = 3

And here we see the graph of y = x3

The slope is continually changing, but at the
point (1,1) we can draw a line tangent to the curve
and find the slope there really is 3.

What would the slope at the point (2,8) be?

Try It Yourself!
Go to the "Slope of a Function" page, put in the formula "x^3", then try to find the
slope at the point (1,1).

6 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 1

Zoom in closer and closer and see what value the slope is heading towards.

Conclusion
Calculus is about changes.

Self-Assessment Question
Exercise 1.1
What is the slope of the function y = x4 at x=1?

CoDEUCC/Diploma in Maths & Science Education 7

 UNIT 1 INTRODUCTION TO CALCULUS
SESSION 1

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

8 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 2

SESSION 2: INTRODUCTION TO DIFFERENTIATION

You are welcome to session 2 of unit 1. This session will introduce you to how to
determine the derivative of functions.
Objectives
By the end of the session, students should be able;
(a) Appreciate the concept of derivatives.
(b) Determine the derivatives of f(x) or f(y) functions.

Now read on……

It is all about slope!

Change in Y
Slope =
Change in X

You can find an average slope between two points.

But how do you find the slope at a point?

There is nothing to measure!

But with derivatives you use a small difference ...... then

have it shrink towards zero.

CoDEUCC/Diploma in Maths & Science Education 9

 UNIT 1 INTRODUCTION TO DIFFERENTIATION
SESSION 2

Let us Find a Derivative! We will use the slope formula:

Slope =

To find the derivative of a function y = f(x), follow these

steps:
Δy f(x+Δx) - f(x)
=
Δx Δx

Simplify it as best you can, and then make Δx shrink

towards zero.
Example: the function f(x) = x2
We know f(x) = x2, and can calculate f(x+Δx) :
Start f(x+Δx) =
with: (x+Δx)2
Expand
f(x+Δx) = x2 + 2x
(x +
Δx +(Δx)2
Δx) : 2

Fill in the
f(x+Δx) -f(x) x2 + 2x Δx + (Δx)2 - x2
slope =
Δx Δx
formula:
Simplify (x2
2x Δx + (Δx)2
2
and -x =
Δx
cancel):
Divide
through by = 2x + Δx
Δx:

10 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 2

And then as
Δx heads
= 2x
towards 0 we
get:

Result: the derivative of x2 is 2x

And we write dx instead of "Δx heads towards 0", so the

common notation for "the derivative of" is :
x2 = 2x

"The derivative of x2 equals 2x" or simply "d dx of x2 equals

2x"

Sometimes f’(x) is also used for "the derivative of":

f’(x) = 2x "The derivative of f(x) equals 2x"

What does x2 = 2x mean?

It means that, for the function

x2, the slope or "rate of change"
at any point is 2x.

So, when x=2, the slope will be

2x = 4, as shown here:

Or when x=5 the slope will be

2x = 10, and so on.

CoDEUCC/Diploma in Maths & Science Education 11

 UNIT 1 INTRODUCTION TO DIFFERENTIATION
SESSION 2

Let's try another example.

Example: What is x3?

We know f(x) = x3, and can calculate f(x+Δx) :

f(x+Δx) = (x+Δx)3
Start with:

Expand (x +
f(x+Δx) = x3 + 3x2 Δx + 3x (Δx)2 + (Δx)3
Δx) :3

f(x+Δx) - x3 + 3x2 Δx + 3x (Δx)2 + (Δx)3

3
Put it in the slope formula: f(x) = -x

Δx Δx

3x2 Δx + 3x (Δx)2 + (Δx)3

Simplify (x3 and -x3 cancel): =
Δx

Simplify more (divide through by

= 3x2 + 3x Δx + (Δx)2
Δx):

And then as Δx heads towards 0 we

x3 = 3x2
get:

Self-Assessment Question
Exercise 1.2

Example: What is x4?

12 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 3

SESSION 3: INTRODUCTION TO INTEGRATION

Hello and welcome to session 3 of unit 1. This session will introduce you to how to
determine integral functions.

Objectives
By the end of the session, students should be able;
(a) Appreciate the concept of integration.
(b) Determine the integration of f(x) or f(y) functions.

Now read on…

Integration is a way of adding slices to find the whole.

Integration can be used to find areas, volumes, central points and many useful things.
But it is easiest to start with finding the area under the curve of a function like this:

What is the area under y = f(x) ?

Slices

We could calculate the function at a few points and add

up slices of width Δx like this (but the answer won't be
very accurate):

CoDEUCC/Diploma in Maths & Science Education 13

 INTRODUCTION TO INTEGRATION
UNIT 1
SESSION 3

We can make Δx a lot smaller and add up many small

slices (answer is getting better):

And as the slices approach zero in width, the answer

approaches the true answer.

We now write dx to mean the Δx slices are approaching

zero in width.

Example: What is an integral of 2x?

We know that the derivative of x2 is 2x ...

... so an integral of 2x is x2

We will show you more examples later.

14 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 3

Notation

The symbol for "Integral" is a

stylish "S" (for "Sum", the idea
of summing slices):

After the Integral Symbol we put the function we want to find the integral of (called the
Integrand), and then finish with dx to mean the slices go in the x direction (and
approach zero in width).

And here is how we write the answer:

Plus C

We wrote the answer as x2 but why + C ?

It is the "Constant of Integration". It is there because of all the functions whose
derivative is 2x:

The derivative of a constant is zero, so when we reverse the operation (to find the
integral) there could have been a constant of any value.
So we wrap up the idea by just writing + C at the end.

CoDEUCC/Diploma in Maths & Science Education 15

 INTRODUCTION TO INTEGRATION
UNIT 1
SESSION 3

Tap and Tank

Integration is like filling a tank from a tap.

The input (before integration) is the flow rate from the tap.
Integrating the flow (adding up all the little bits of water)
gives us the volume of water in the tank.

Imagine the flow starts at 0 and gradually increases (maybe a motor is slowly opening
the tap).

As the flow rate increases, the tank

fills up faster and faster.

With a flow rate of 2x, the tank fills

up at x2.

We have integrated the flow to get

the volume.
Example: (assuming the flow is in litres per minute) after 3 minutes (x=3):
• the flow rate has reached 2x = 2×3 = 6 litres/min,
2 2
• and the volume has reached x = 3 = 9 litres.

We can do the reverse, too:

Imagine you don't know the flow
rate.
You only know the volume is
increasing by x2.
You can go in reverse (using the
derivative, which gives us the slope)
and find that the flow rate is 2x.

16 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 3

Example: at 2 minutes the slope of the volume is 4, meaning it is increasing at 4

litres/minute, which is the flow rate. Likewise at 3 minutes the slope will be 6, etc.

So Integral and Derivative are opposites.

We can write that down this way:

The integral of the flow rate 2x tells us the volume of water: ∫2x dx = x2 + C

And the slope of the volume increase x2+C gives us back the flow (x2 + C) =
rate: 2x

And hey, we even get a nice

explanation of that "C" value ...
maybe the tank already had water in
it!

• The flow would still

increase the volume by the
same amount
• And the increase in volume
can give us back the flow.

CoDEUCC/Diploma in Maths & Science Education 17

 INTRODUCTION TO INTEGRATION
UNIT 1
SESSION 3

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

18 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 4

SESSION 4: DIFFERENTIATION OF OTHER FUNCTIONS

You are welcome to session 4 of unit 1. This session will introduce you
to how to determine the derivative of other functions such as cos, sine
and logarithms.

Objectives
By the end of the session, students should be able;
(a) Appreciate the concept of derivatives of other functions.
(b) Determine the derivatives of sin, cos and logarithms.

Now read on…

We can use the same method to work out derivatives of other functions (like sine,
cosine, logarithms etc.) but in practice the usual way to find derivatives is to use
Derivative Rules.

Derivative Rules
The derivatives of many functions are well known. Here are some useful rules to help
you work out the derivatives of more complicated functions (with examples below).
Note: the little mark (’) means "Derivative of".

Common Functions Function Derivative

Constant c 0
x 1
Square x2 2x
Square Root √x (½)x-½
Exponential ex ex
ax ax(ln a)
Logarithms ln(x) 1/x
log a (x) 1 / (x ln(a))
Trigonometry (x is in radians) sin(x) cos(x)
cos(x) -sin(x)
tan(x) sec2(x)
sin-1(x) 1/√(1-x2)
tan-1(x) 1/(1+x2)

CoDEUCC/Diploma in Maths & Science Education 19

 UNIT 1 DIFFERENTIATION OF OTHER FUNCTIONS
SESSION 4

Rules Function Derivative

Multiplication by constant cf cf’
Power Rule xn nxn-1
Sum Rule f+g f’ + g’
Difference Rule f–g f’ - g’
Product Rule fg f g’ + f’ g
Quotient Rule f/g (f’ g - g’ f )/g2
Reciprocal Rule 1/f -f’/f2
Chain Rule (as "Composition of fog (f’ o g) × g’
Functions")
Chain Rule (in a different form) f(g(x)) f’(g(x))g’(x)

Example: what is the derivative of sin(x)?

From the table above it is listed as being cos(x)

It can be written as: sin(x) = cos(x) or sin(x)’ = cos(x)

Power Rule
Example: What is x3?
The question is asking "what is the derivative of x3?"
We can use the Power Rule, where n=3:
xn = nxn-1 therefore, x3 = 3x3-1 = 3x2

Example: What is (1/x)?

1/x is also x-1

We can use the Power Rule, where n=-1:
xn = nxn-1 therefore, x-1 = -1x-1-1 = -x-2

Multiplication by constant
Example: What is 5x3?

the derivative of cf = cf’; the derivative of 5f = 5f’

We know (from the Power Rule): x3 = 3x3-1 = 3x2

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BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 4

So:
5x3 = 5 x3 = 5 × 3x2 = 15x2

Sum Rule
Example: What is the derivative of x2+x3?
The Sum Rule says:
the derivative of f + g = f’ + g’
So we can work out each derivative separately and then add them.
Using the Power Rule:
• x2 = 2x ; x3 = 3x2

And so the derivative of x2 + x3 = 2x + 3x2

Difference Rule
It doesn't have to be x, we can differentiate with respect to, for example, v:
Example: What is (v3-v4)?

The Difference Rule says

the derivative of f - g = f’ - g’
So we can work out each derivative separately and then subtract them.
Using the Power Rule:
• v3 = 3v2 ; v4 = 4v3

And so the derivative of v3 - v4 = 3v2 - 4v3

Example: What is (5z2 + z3 - 7z4)?

Using the Power Rule:

• z2 = 2z ; z3 = 3z2 ; z4 = 4z3

And so: (5z2 + z3 - 7z4) = 5 × 2z + 3z2 - 7 × 4z3 = 10z + 3z2 - 28z3

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 UNIT 1 DIFFERENTIATION OF OTHER FUNCTIONS
SESSION 4

Product Rule
Example: What is the derivative of cos(x)sin(x) ?
The Product Rule says:
the derivative of fg = f g’ + f’ g
In our case: f = cos ; g = sin
We know (from the table above):
• cos(x) = -sin(x); sin(x) = cos(x)

So the derivative of cos(x)sin(x) = cos(x)cos(x) - sin(x)sin(x) = cos2(x) - sin2(x)

Reciprocal Rule
Example: What is (1/x)?

The Reciprocal Rule says the derivative of 1/f = -f’/f2

With f(x)= x, we know that f’(x) = 1
So the derivative of 1/x = -1/x2; which is the same result we got above using the Power
Rule.

Chain Rule
Example: What is sin(x2)?

Sin(x2) is made up of sin () and x2:

• f(g) = sin(g) and g(x) = x2
The Chain Rule says the derivative of f(g(x)) = f'(g(x))g'(x)
The individual derivatives are: f'(g) = cos(g) and g'(x) = 2x
So: sin(x2) = cos(g(x)) × 2x = 2x cos(x2)

Example: What is (1/sin(x)) ?

1/sin(x) is made up of 1/g and sin():

• f(g) = 1/g and g(x) = sin(x)
The Chain Rule says the derivative of f(g(x)) = f’(g(x))g’(x)

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BASIC CALCULUS FOR CHEMISTRY STUDENTS
UNIT 1
SESSION 4

The individual derivatives are: f'(g) = -1/(g2) and g'(x) = cos(x)

So: (1/sin(x))’ = -1/(g(x))2 × cos(x) = -cos(x)/sin2(x)

Example: What is (5x-2)3?

The Chain Rule says the derivative of f(g(x)) = f’(g(x))g’(x)

(5x-2)3 is made up of g3 and 5x-2:
• f(g) = g3 and g(x) = 5x-2
The individual derivatives are: f'(g) = 3g2 (by the Power Rule) and g'(x) = 5

So: (5x-2)3 = 3g(x)2 × 5 = 15(5x-2)2

Notation
"Shrink towards zero" is actually written as a limit like this:

"The derivative of f equals the limit as Δx goes to zero of f(x+Δx) - f(x) over Δx"
Or sometimes the derivative is written like this:

The process of finding a derivative is called "Differentiation".

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 UNIT 1 DIFFERENTIATION OF OTHER FUNCTIONS
SESSION 4

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

24 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 5

SESSION 5: INTEGRATION OF OTHER FUNCTIONS

You are welcome to session 5 of unit 1. This session will introduce you
to how to determine the integral functions such as cos, sine and
logarithms.

Objectives
By the end of the session, students should be able;
(a) Appreciate the concept of integration of other functions.
(b) Determine the integral functions of sin, cos and logarithms.

Now read on…

Well, we have played with y=2x enough now, so how do we integrate other functions?
If you are lucky enough to find the function on the result side of a derivative, then,
using your knowledge that derivatives and integrals are opposites, you have an answer
(but remember to add C).
Integration Rules

Integration can be used to find areas, volumes, central points

and many useful things. But it is often used to find the area
underneath the graph of a function like this:

The integral of many functions are well known, and there are also useful rules to work
out the integral of more complicated functions, many of which are shown here. There
are also many examples below to help you.
Common Functions Function Integral
Constant ∫a dx ax + C
Variable ∫x dx x2/2 + C
Square ∫x2 dx x3/3 + C
Reciprocal ∫(1/x) dx ln|x| + C
Exponential ∫e dx
x
ex + C
∫ax dx ax/ln(a) + C
∫ln(x) dx x ln(x) − x + C
Trigonometry (x in radians) ∫cos(x) dx sin(x) + C
∫sin(x) dx -cos(x) + C
∫sec (x) dx
2
tan(x) + C

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 UNIT 1 INTEGRATION OF OTHER FUNCTIONS
SESSION 5

Rules Function Integral

Multiplication by constant ∫cf(x) dx c∫f(x) dx
Power Rule (n≠-1) ∫xn dx n+1
x /(n+1) + C
Sum Rule ∫(f + g) dx ∫f dx + ∫g dx
Difference Rule ∫(f - g) dx ∫f dx - ∫g dx
Examples
Example: what is the integral of sin(x)?
From the table above it is listed as being -cos(x) + C
It is written as: ∫sin(x) dx = -cos(x) + C

Power Rule
Example: What is ∫x3 dx?
The question is asking "what is the integral of x3?"
We can use the Power Rule, where n=3: ∫xn dx = xn+1/(n+1) + C = ∫x3 dx = x4/4 + C
Example: What is ∫√x dx?
√x is also x0.5
We can use the Power Rule, where n=½: ∫xn dx = xn+1/(n+1) + C = ∫x0.5 dx = x1.5/1.5 + C

Multiplication by constant
Example: What is ∫6x2 dx?
We can move the 6 outside the integral: ∫6x2 dx = 6∫x2 dx
And now use the Power Rule on x2: = 6 x3/3 + C = 2x3 + C

Sum Rule
Example: What is ∫cos x + x dx?
Use the Sum Rule: ∫cos x + x dx = ∫cos x dx + ∫x dx
Work out the integral of each (using table above): = sin x + x2/2 + C

Difference Rule
Example: What is ∫ew - 3dw?
Use the Difference Rule: ∫ew - 3dw =∫ewdw - ∫3dw
Work out the integral of each (using table above): = ew - 3w + C
Example: What is ∫8z + 4z3 - 6z2 dz?
Use the Sum and Difference Rule: ∫8z + 4z3 - 6z2 dz =∫8z dz + ∫4z3 dz - ∫6z2 dz
Constant Multiplication: = 8∫z dz + 4∫z3 dz - 6∫z2 dz
Power Rule: = 8z2/2 + 4z4/4 - 6z3/3 + C
Simplify: = 4z2 + z4 - 2z3 + C

Definite vs Indefinite Integrals

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BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 5

We have been doing Indefinite Integrals so far. A Definite Integral has start and end
values: in other words there is an interval (a to b) which are put at the bottom and top
of the "S".

Indefinite Integral Definite Integral

We can find the Definite Integral by calculating the Indefinite Integral at points a and b,
then subtracting:
Example:

The Definite Integral, from 1 to 2, of 2x dx:

The Indefinite Integral is: ∫2x dx = x2 + C

• At x=1: ∫2x dx = 1 + C and At x=2: ∫2x dx = 2 + C
2 2
2 2 2 2
Subtract: (2 + C) - (1 + C) = 2 + C - 1 - C = 4 - 1 + C - C = 3
And "C" gets cancelled out ... so with Definite Integrals we can ignore C.
In fact we can give the answer directly like this:

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 UNIT 1 INTEGRATION OF OTHER FUNCTIONS
SESSION 5

We can check that, by calculating the area of the

shape:

Yes, it has an area of 3.

Let's try another example:

Example:

The Definite Integral, from 0.5 to 1.0, of cos(x) dx:

(Note: x must be in radians)

The Indefinite Integral is: ∫cos(x) dx = sin(x) + C

We can ignore C, and do the subtraction directly:

And another example to make an important point:

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BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 5

Example:
The Definite Integral, from 0 to 1, of sin(x) dx:

The Indefinite Integral is: ∫sin(x) dx = -cos(x) + C

Since we are going from 0, can we just calculate the area at x=1?
-cos(1) = -0.540...
What? The Area at x=1 is negative? No, because we forgot the "+ C", which is
important ....We can only ignore C when it gets cancelled by subtraction
So let us do it properly, subtracting one from the other:

And that is correct ... but you can have negative areas, when the curve is below the axis:

Example:

The Definite Integral, from 1 to 3, of cos(x) dx:

Notice that some of it is positive, and some

negative.
The definite integral will work out the net area.

The Indefinite Integral is:∫cos(x) dx = sin(x) + C

So let us do the calculations:

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 UNIT 1 INTEGRATION OF OTHER FUNCTIONS
SESSION 5

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

30 CoDEUCC/Diploma in Maths & Science Education

BASIC CALCULUS FOR CHEMISTRY STUDENTS UNIT 1
SESSION 6

SESSION 6: APPLICATION OF CALCULUS IN PHYSICAL CHEMISTRY

You are welcome to session 6 of unit 1. This session will look at the
application of derivatives and integration in physical chemistry.

Objectives
By the end of the session, students should be able;
(a) Apply derivatives in solving physical chemistry questions.
(b) Apply integration in solving physical chemistry questions.

Now read on…

(1) Find the half-life of a first-order reaction if the reaction constant, k , is 2.0 x 10-3
s-1.

Answer: Because it is a first-order reaction, the half-life equation is ln2 / k.

ln2/ (2.0 x 10-3) = 350 seconds.
I know the unit is seconds because the unit of my reaction constant is s-1.

NB: If the unit is minute-1, the half-life would be 350 minutes.

(2) Find the time when only 1% of reactant remains.

Answer: The integrated rate law of a first order-reaction is: ln[A]=-kt+ln[A] 0

(3) Find the 2nd order reaction’s activation energy with the given information.

K 1 =4.0L/mol*s at 37C° K 2 =8.0L/mol*s at 87C°

Hint: Use the activation energy equation

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 UNIT 1
APPLICATION OF CALCULUS IN PHYSICAL
SESSION 6 CHEMISTRY

Answer: Make sure you change the temperature to kelvin; 37C° =300k and 87C° =360k

R= 8.3145 J

The answer is 1.1x10^4 J/mol.

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THERMOCHEMISTRY
UNIT 2

UNIT 2: THERMOCHEMISTRY
Unit 2 Outline
Session 1: Why reaction occurs
Session 2: Thermodynamics (Heat/Energy change)
Session 3: Enthalpy
Session 4: Calorimetry & Heat capacity
Session 5: Heat of Formation
Session 6: Entropy& Gibbs free energy

This unit will focus attention on thermochemistry, a branch of

chemistry concerned with the heat effects that accompany chemical
reactions. To understand the relationship between heat and chemical and physical
changes, we must start with some basic definitions. We will then explore the concept of
heat and the methods used to measure the transfer of energy across boundaries. Another
form of energy transfer is work, and, in combination with heat, we will define the three
laws of thermodynamics. At this point, we will establish the relationship between heats
of reaction and changes in internal energy and enthalpy. We will see that the tabulation
of the change in internal energy and change in enthalpy can be used to calculate,
directly or indirectly, energy changes during chemical and physical changes. Session 1
will elaborate on why reactions occur and Session 2 will also look at Calorimetry and
heat capacity.

To conclude this unit, we will further consider three main ideas: spontaneity-whether or
not a process can take place unassisted; entropy-a measure of the degree of randomness
among the atoms and molecules of a system; and free energy-a thermodynamic function
that relates enthalpy and entropy to spontaneity.

Unit Objectives
After studying this unit, you should be able to;
1. Define thermodynamic system and surroundings.
2. Describe the three types of thermodynamic systems and give an example each.
3. Define thermodynamic equilibrium and describe the transfer of heat between a
system and its surroundings.
4. Define the terms exothermic and endothermic reactions, giving an example each
and indicating the signs of ∆H.
5. Explain why we indicate the physical state of all reactants and products when
designating the enthalpy change for a reaction.
6. Explain how the enthalpy of a system is related to its internal energy.
7. Define Calorimetry and describe how a calorimeter works.
8. Define heat capacity and specific heat and give specific their units.
9. Explain the terms spontaneity, entropy and free energy.
CoDEUCC/Diploma in Maths and Science 33
 THERMOCHEMISTRY
UNIT 2

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

34 CoDEUCC/Diploma in Maths & Science Education

 THERMOCHEMISTRY
UNIT 2
SESSION 1

SESSION 1: WHY REACTIONS OCCUR

You are welcome to session 1 of unit 2. This session will look at why reaction occurs.
For a reaction to take place spontaneously, the product of the reaction must be more
stable than the starting reactants. The most important factor in determining the stability
of a substance is the amount of energy contained in the substance. Highly energetic
substances are generally less stable and more reactive whilst less energetic substances
are generally more stable and less reactive.

Objectives
By the end of this session you should be able to:
1. Define key concepts in thermochemistry.
2. State the three types of energy.
3. Explain with examples, the types of system

Now read on…

1.1 Terminologies Associated with the Course

1. The Universe: It may be regarded as composed of two parts; a system and its
surroundings. The surroundings are the rests of the universe in which the system is in
contacts either directly or indirectly.
2. The Surroundings: The rest of the universe in which the system is in contact, either
directly or indirectly.
3. The System: It is that part of the universe in which we are particularly interested. OR
The part of the universe of interest.

When keeping track of the energy changes that occur in a chemical reaction, it is
helpful to think of the reaction as a separate entity from the world around it. The
substance we focused on in an experiment i.e. the starting reactants and the final
products are collectively called The System, whilst everything else, i.e. the
reaction flask, the room, the building etc are referred to as The Surroundings. A
typical example is the reaction vessel. There are three (3) types of system. They
are;
Open System, Closed System and Isolated System.

 Open System
In an Open System, there is an exchange of matter and energy with the surroundings.
Example: The beaker of hot coffee transfers energy to the surroundings-it loses heat as
it cools. Matter is also transferred in the form of water vapour.

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 UNIT 2 WHY REACTIONS OCCUR
SESSION 1

 Closed System
A closed system does not exchange matter, but can exchange energy with the
surroundings. Thus, the composition of a closed system is always constant. Example:
The flask of hot coffee transfers energy (heat) to the surroundings as it cools. Because
the flask is stoppered, no water vapour escapes and no matter is transferred.

 Isolated System
An isolated system does not exchange matter and energy with the surroundings.
Example: Thermo flask. OR Hot coffee in an insulated container approximates an
isolated system. No water vapour escapes, and, for a time at least, little heat is
transferred to the surroundings. (Eventually, though, the coffee in the container cools to
room temperature.)

NB: There cannot be any perfect isolated system.

1.2 Energy
Energy is the capacity to supply heat or to do work.
i.e. Energy = Heat + Work .
Energy can be classified as either Kinetic or Potential
1.2.1 Kinetic Energy
It is the energy of a body in motion. The amount of kinetic energy in a moving object
with mass, m and velocity, v is given by the expression;
1
K .E = mv 2
2
1.2.2 Potential Energy
This is the energy referred to as stored energy. Perhaps, energy stored in an object
because of its position or perhaps in a molecule, because of its Chemical Bond.

1.3 The Law of Conservation of Energy

It states that, energy cannot be created or destroyed; it can only be converted from one
form or state to another.

Self-Assessment Questions
Exercise 2.1
(1) Define the following terms as used in thermochemistry:
a) Universe
b) System
c) Surroundings
(2) State and explain the types of systems
(3) State the law of conservation of matter
(4) Distinguish between kinetic and potential energy

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THERMOCHEMISTRY
UNIT 2
SESSION 2

SESSION 2: THERMODYNAMICS [HEAT/ENERGY CHANGE]

Hello and welcome to session 2 of unit 2. This session will look at state
functions and how energy in thermodynamics manifests itself in three
forms. Work done as a result of volume change called PV work, will further be
considered.

Objectives
At the end of reading this session one would be able to:
1. Explain the forms of energy in thermodynamics
2. Show how formulated the first law of thermodynamics
3. Explain with illustration, the term PV work

Now read on…

2.0 Energy in thermodynamics manifest itself in three forms; they are:

1. Heat
2. Work
3. Internal Energy
 Heat: It is the energy in motion due to temperature gradient or difference.
The symbol of heat is Q or q.
 Work: It is the energy resulting from the translation of a force through a
distance. Work can be Mechanical or Electrical.

Mechanical Work or Energy

It can be derived from δw or ∆w .

∫ ∆w = ∫ F .∆x
w
⇒ ∫ 0
∆w = ∫ F .∆x ⇒ W = F .l

 Internal Energy: It is the energy possessed by a system by virtue of its state at a

particular time. In other words, it is the energy possessed by each particle in an
isolated system. The total internal energy of a system is the sum of al Kinetic energy
and Potential energy for each particle in a system. Symbol of Internal Energy is µ .

2.1 First Law of Thermodynamic

It states that, the total internal energy of an isolated system is constant. ⇒ µ=
Constant
δµ = 0

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 UNIT 2 THERMODYNAMICS [HEAT/ENERGY CHANGE]
SESSION 2

NB: Whenever you differentiate any constant, the answer is zero.

2.2 State Function

It is the function or property whose value depends only on the present state or condition
of the system, but not on the path taken to arrived at that condition.

Examples of state function are; Pressure, Volume, Temperature etc. But Work and Heat
are not state function.

For example, if we defined our system as 50 g of water at 25°C , our system could have
arrived at that stage by the cooling of 50 g of water from 100°C or by melting 50 g of
ice from 0°C to water at 25°C .

In all these cases, the internal energy of the water is the same. This means that, the
internal energy of the system is a state function.

The value of a state function does not depend on a particular path (previous history of
the system), but depends only on its present conditions.

Thus; ∆E = E fenal − Einitial or ∆E depends only on the initial and final states of the
system, but not how the changes occurs.

2.3 Reversibility
Imagine that, after melting ice at 0°C to water 25°C and without stopping, the water
freezes back to ice. Since the final position or state is now identical to the initial state,
the value of the change in state or position is 0°C . The overall change in a state
function is zero, when the system returns to its original position. But for a non-state
function, the overall change is not zero, even if the path returns the system to its original
condition. i.e. Any work you do in melting the ice is not recovered

2.4 Formulation of the First Law of Thermodynamics

Suppose any closed system undergoes a process by which it passes from one stage A to
stage B, if the only interaction with its surroundings is in the form of transfer of heat,
“q” to the system or the performance of work, “w” on the system, then the change in
internal energy, µ will be µ B − µ A = q + w i.e. ∆µ = µb − µ A = q + w .

Therefore a mathematical expression of the first law for a differential change becomes;
∆µ = ∆q + ∆w .

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 THERMOCHEMISTRY
UNIT 2
SESSION 2

The most common type of work on countered in chemical system is the Expansion
Work also called PV WORK (Pressure – Volume Work), as a result of volume change
in the system.

Example 1:
C3 H 3( g ) + 502 ( g ) → 3CO2 ( g ) + 4 H 2O( g )
6 moles 7 moles

If the reaction takes place inside a container which is fitted with a movable piston
F F
P= P =
A A

C3 H 2 ( g )` + 50 2 ( g
dx

3CO2 ( g ) + 4 H 2O( g )

δw = f .δx
w x
∫ 0
δw = ∫ F .δx ⇒ w = FX
0

F
But from P=
⇒ F = PA
A
⇒ W = PA. X
⇒ W = P. AX Where; A = Area
X = Distance
⇒ W = PV AX = Volume, V

∴ W = pdV This is the first law of thermo dynamic

The expansion in volume that occur during a reaction, forces the piston outwards
against atmospheric pressure P. The amount of work done is equal to the pressure
exerted in moving the piston (in the opposite direction of the atmospheric pressure -
P), times the volume change, ∆V .
i.e. Work done, W = − Px∆V .

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 UNIT 2 THERMODYNAMICS [HEAT/ENERGY CHANGE]
SESSION 2

- P implies or means, the work is been done by the system. Because the expanding gas
does work on its surroundings, in pushing back the atmospheric pressure, the work has a
negative sign.

Example 2:

3H 2 ( g ) + N 2 ( g ) → 2 NH 3( g )
(4moles or 4L) (2moles or 2L)

NB: moles (n) in this case, is directly proportional to the volume (v) therefore, they can
be used interchangeably.

When a reaction takes place with the contraction in volume rather than expansion, the
work has a positive sign. If there is no expansion, work done is zero, because ∆V will
be zero.

Example3:
CH 4 ( g ) + 20 2 ( g ) → CO2 ( g ) + 2 H 2 O( g )
3 moles 3 moles

Here, work done is zero, since ∆V is zero.

Self-Assessment Questions
Exercise 2.2

1. Calculate the work in kilojoules during a reaction in which the volume expands
from 12 liters to 14.5 litres, against an external pressure of 5 atmosphere.
2. Calculate the work done in kilojoules during the synthesis of NH 3 in which, the
volume contract from 8.6 litres to 4.3 litres at a constant external pressure of 44
atmosphere.
(i) In which direction does the work energy flow
(ii) What is the sign of the energy flow.

40 CoDEUCC/Diploma in Maths & Science Education

THERMOCHEMISTRY
UNIT 2
SESSION 3

SESSION 3: ENTHALPY
Hello and welcome to session 3 of unit 2. This session will look at a
thermodynamic potential called enthalpy, that consists of the internal
energy of the system (U) plus the product of pressure (P) and volume (V) of the system
will also be considered.

Objectives
At the end of reading this session one would be able to:
(1) Explain the term enthalpy.
(2) Calculate for the enthalpy change of a given chemical reaction.
(3) State the thermodynamic standard conditions of a pure substance.

Now read on…

We have seen up to this point that, a system can exchange energy with its surroundings,
either by transferring heats or doing work. Using the symbol q to represent transferred
heat, we can write the total energy change of a system as
∆E = q + w
But w = − P∆V
⇒ ∆E = q − P∆V
q has a positive sign, if the system g aims heat. i.e. Endothermic Reaction.

3.1 Endothermic Reaction

It is the reaction in which the system absorbs heat from the surroundings. The
surroundings having lost heat, becomes cold. This water freezes around the outside of
the container. Example: Melting of ice.

Ba(OH ) 2 .8 H 2O( g ) + 2 NH 4Cl( g ) → BaCl2 (9 q ) + 2nh3(9 q ) + 10 H 2O(l ) q° = +80.3KJ

q has a negative sign, if the system loses heat to the surroundings. i.e. Exothermic
Reaction.

3.2 Exothermic Reaction

This is when the system loses heat to the surroundings. The surroundings having gain
heat get so hot and can even be used in melting ice.
∆E = q − P∆V
⇒ q = ∆E + P∆V

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 UNIT 2
ENTHALPY
SESSION 3

The constant-pressure lose is important in chemistry, because most chemical reactions,

including those in living systems take place under constant pressure of the earth
atmosphere.

Thus q p = ∆E + P∆V
⇒ q p = E final − Einst + PV fial − PVrush
= ( E final + PV final − ( Eins tan t + PVrush )

Thus q p = ∆E + P∆V = ∆H

1. Enthalpy like internal energy is a state function.

2. Enthalpy is an extensive property
3. The enthalpy for a reaction is equal in magnitude but opposite in sign to ∆H for the
reverse reaction
4. The enthalpy change for a reaction depends in the state of the reactant and products.
2 H 2O( g ) → 2 H 2O(l ) ∆H = −88 KJ
q = ∆E + P∆V
At constant volume, ∆V = 0 qv = ∆E ; and
At constant a pressure, P• = P11
q p = ∆E + PV But ∆E + P∆V = ∆H .
⇒ q p = ∆E + P∆V = ∆H ⇒ q p = ∆H
q p = ∆E + P∆V
⇒ ∆H = ∆E + P∆V

∆H Simply means H final − H initial OR H product − H reac tan t

i.e. ∆H = H product − H reac tan t

NB: The Enthalpy change is reported at the end of a balanced equation.

Example 1:
The reaction of Nitrogen with hydrogen to produce
NH 3 has ∆H = −92.2 KJ
N 2 ( g ) + 3H 2 ( g ) → 2 NH 3( g ) ∆H = −92.2 KJ
What is the value of ∆E in KJ, if the reaction of 40 atmospheres (atm) and the volume
change is − 1.12 litres.

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THERMOCHEMISTRY
UNIT 2
SESSION 3

Answer
From the equation: ∆H = ∆E + P∆V
∆E = ∆H − P∆V
∆E = − 92.2 KJ − (40atm x -1.12L)
∆E = − 92.2 KJ + (44.8J)
∆E = − 92.2 KJ + (44.8 x 10-3KJ)
∆E = − 92.1552 KJ
∆E = − 92.16 KJ

3.3 Standard Condition

Thermodynamic standard state for a pure substance in a specified state, usually its most
stable state at 1 atmospheric pressure and at a specified temperature (25°C ) , one molar
(1M) concentration for all substances in a solution is referred to as the standard
condition.

A measurement made under this condition is indicated by the addition of the superscript
[  ] to the symbol of the quantity reported. Thus, the enthalpy change measured under
standard condition [P = 1 atmosphere, T = 25°C and 1M concentration of reactants] is
called a standard enthalpy of reaction and is indicated by the symbol ∆H ° .

Self-Assessment Questions

The reaction of Nitrogen with hydrogen to produce NH 3 has ∆H = −92.2 KJ

N 2 ( g ) + 3H 2 ( g ) → 2 NH 3( g ) ∆H = −92.2 KJ

(1) The reaction between Hydrogen and Oxygen to yield water vapour
has ∆H = −484 KJ .
1
H 2 ( g ) + O2 ( g ) → H 2 O( g ) ∆H = −484 KJ
2
(i) How much PV work is done?
(ii) What is the value of ∆E in KJ for the reaction of 0.5 moles of Hydrogen with
0.25 moles of O2 , at an atmospheric pressure if the value of change in volume is
− 5.6 litres?
(2) How much heat of KJ is evolved when 5g of Aluminum reacts with a stoichiometric
amount of Fe2O3 .
2 Al( s ) + Fe2O3( s ) → 2 Fe( s ) + Al2O3( s ) ∆H = −852 KJ

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 UNIT 2
ENTHALPY
SESSION 3

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• Issues that are not clear: and
• Difficult topics if any

44 CoDEUCC/Diploma in Maths & Science Education

THERMOCHEMISTRY UNIT 2
SESSION 4

SESSION 4: CALORIMETRY AND HEAT CAPACITY

Hello and welcome to session 4 of unit 2. This session will look at how
heat energy during a reaction is measured and how to raise the
temperature of a substance by one degree Celsius.

Objectives
At the end of reading this session one would be able to:
(1) Define the terminologies under heat capacity.
(2) Calculate heat, specific heat and molar heat capacities of substances.
(3) State the Hess law and use it to calculate enthalpy change.

Now read on…

4.1 The Calorimeter

The amount of heat transfer during a reaction can be measured experimentally; by
measuring the heat flow accompanied a reaction at constant pressure with the device
called calorimeter.

A calorimeter is just an insulated vessel with a stirrer, a thermometer and a loose cover.

The pressure inside the calorimeter is constant (ie. Atmospheric pressure). The
temperature measurement makes it possible to calculate the enthalpy change during a
reaction.

4.2 Heat Capacity

Heat capacity, C is the amount of Heat or energy required to raise the temperature of an
object or substance by one degree Celsius ( 1°C ).

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 UNIT 2 CALORIMETRY AND HEAT CAPACITY
SESSION 4

q
C= ⇒ q = C∆T
∆T

4.2.1 Specific Heat Capacity

Specific heat capacity, c is the amount of heat required to raise the temperature of 1
gram of a substance by 1°C .
q = C∆T , but C = m × c
⇒ q = mC∆T .

4.2.2 Molar Heat Capacity

Molar heat capacity, Cm is the amount of heat required to raise the temperature of 1
mole of a substance by 1°C .
q = Cm × (moles of a substance)∆T
⇒ q = Cm × n × ∆T
q = Cm n∆T

The specific heat of liquid water is considerably higher than that of most other
substances and a large transfer of heat is therefore necessary to either cool or warm a
given amount of water. One consequence of this is that, large lake or other bodies of
water tends to moderate the air and temperature in the surrounding area.

Another consequence is that, human body is about 60% water and is able to maintain a
steady internal temperature under change in outside conditions.

Examples:
1. What is the specific heat of silicon, if it takes 192 Joules to raise the temperature of
 0.71J 
45 gram of silicon by 6°C . Answer = 
 g°C 
2. When 1.25 gram of Iron reacts with sulphur to form Fe(11) sulphide, 1.24KJ of heat
is released. Calculate the enthalpy of the reaction in KJ per mole. Molar Mass =
55.85glmol for Fe.
3. Aqueous silver ion reacts with aqueous chloride ion to yield a white precipitate of
solid silver chloride.

Ag (+aq ) + Cl(−aq ) → AgCl( s )

When 10.0ml of 1.0M silver nitrate solution is added to 10.0ml of 1.0m NaCl solution
at 25°C in a calorimeter, a white precipitate of AgCl formed and the temperature of

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THERMOCHEMISTRY UNIT 2
SESSION 4

the aqueous mixture increase to 32.6°C . Assuming that, the specific heat of the mixture
is 4.18 JKg .o C . The density of the mixture is | g | ml and that of the calorimeter itself
absorbs a negligible amount of heat. Calculate ∆H in KJ/mol for the reaction.

Because enthalpy is a state function, the enthalpy change associated with any chemical
process depends on only the amount of matter that undergoes change and on the nature
of the final stage of the product as well as the initial state of the reactant. This means
that, step or a series of steps, the sum of the enthalpy changes associated with the
individual steps must be the same as the enthalpy change associated with the one step
process.

Example:
1. CH y ( g ) + 202 ( g ) → CO2 ( g ) + 2 H 2O( g ) ∆H = −802 KJ
2. 2 H 2O( g ) → 2 H 2O(l ) ∆H = −88 KJ
3. CH 4 ( g ) + 202 ( g ) → CO2 ( g ) + 2 H 2O(l ) ∆H = −890 KJ

To obtain a net equation, the sum of the reactant(s) of the equation is placed on one side
of the arrow and the sum of product on the other side. Because water in the gaseous
form occurs at both sides of the equation, they conceal out. It can conceal out like an
algebraic quantity that appears on both sides of an equal sign.

4.3 The Hess Law

The law states that, if a reaction is carried out in a series of steps, enthalpy change for
the reaction will be equal to the sum of the enthalpy changes for each step.

Question
1. Calculate the ∆H for the reaction 2C( g ) + H 2 ( g ) → C2 H 2 ( g )
given the following reactions and their respective
5
(a) C2 H 2 ( g ) + O2 ( g ) → 2CO2 ( g ) H 2O(l ) ∆H = −1299.6 KJ
2
(b) C( g ) + O2 ( g ) → CO2 ( g ) ∆H = −393.5 KJ
1
(c) H 2 ( g ) + O2 ( g ) → H 2O(l ) ∆H = −285.9 KJ
2

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 UNIT 2 CALORIMETRY AND HEAT CAPACITY
SESSION 4

Solution:
Reverse equation (a), multiply equation (b) by 2 and maintain equation
5
2CO2 ( g ) + H 2O(l ) → C2 H 2 ( g ) + O2 ( g ) ∆H = + 1299.6 KJ
2

2C( g ) + 2O2 ( g ) → 2CO2 ( g ) ∆H = − 393.5 KJ × 2

1
H 2 ( g ) + O2 ( g ) → H 2O(l ) ∆H = − 285.9 KJ
2

2C( g ) + H 2 ( g ) → C2 H 2 ( g ) ∆H = + 226.7 KJ

2. Water gas is the name for the industrially important mixture of CO( g ) and H 2 ( g ) ,
prepared by passing steam over hot charcoal at 1000°C
°C
i.e. C( s ) + H 2O( g ) 1000
 → CO( g ) + H 2 ( g ) (Water gas)

The hydrogen is then purified and used as a starting material for preparing ammonia.
Use the following information to calculate the ∆H for the water gas.
1. 2CO( g ) + O2 ( g ) → 2CO2 ( g ) ∆H = −566.0 KJ
2. C( g ) + O2 ( g ) → CO2 ( g ) ∆H = −393.5 KJ
3. 2 H ( g ) + O2 ( g ) → 2 HO2 ( g ) ∆H = −483.6 KJ

Solution:
Reverse equation (3) and divide by 2
Reverse equation (1) and divide by 2
Maintain equation (2)

2 2 1 1483.6
H 2 O( g ) → H 2 ( g ) + O2 ( g ) ∆H = = 241.8r
2 2 2 2

2 2 1 1566
C( g ) → CO2 ( g ) + O2 ( g ) ∆H = = +283KJ
2 2 2 2

C ( s ) + H 2 O( g ) → CO(l ) + H 2 ( g ) ∆H = + 131.3KJ

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THERMOCHEMISTRY UNIT 2
SESSION 4

Self-Assessment Questions
Exercise 2.4
(1) Calculate the heat needed to raise 27.0 g of water from 10.0 °C to 90.0 °C.

(2) What is the final temperature when 150.0mL of water at 90.0°C is added to
100.0mL of water at 30.0°C?
(3) Use Hess’s law to determine ∆H  for the reaction
C 3 H 4 (g) + 2 H 2 (g) C 3 H 8 (g), given that
1
(a) H 2 (g) + O 2 (g) H 2 O(l), ∆H  = -285.8 kJ
2
(b) C 3 H 4 (g) + 4 O 2 (g) 3 CO 2 (g) + 2 H 2 O(l), ∆H  = -1937 kJ
(c) C 3 H 8 (g) + 5 O 2 (g) 3 CO 2 (g) + 4 H 2 O(l), ∆H  = -2219.1 KJ

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 UNIT 2 CALORIMETRY AND HEAT CAPACITY
SESSION 4

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• Difficult topics if any

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THERMOCHEMISTRY UNIT 2
SESSION 5

SESSION 5: HEAT OF FORMATION

Hello and welcome to session 5 of unit 2. This session will focus
attention on the enthalpy change for the formation of substances.

Objectives
At the end of reading this session one would be able to:
(1) Define the term heat of formation of a substance.
(2) Calculate the heat of formation for a given reaction.

Now read on…

Heat of Formation is defined as the enthalpy change (∆H f ) for the formation of 1 mole
of a substance in its standard state from its constituent element in their standard state.
By conversion, the stable form of any element is zero.
Standard states are as follows:
1. For a gas: the standard state is a pressure of exactly 1 atm
2. For a solute present in an ideal solution: a concentration of exactly 1 M at a
pressure of 1 atm
3. For a pure substance or a solvent in a condensed state (a liquid or a solid): the
standard state is the pure liquid or solid under a pressure of 1 atm
4. For an element: the form in which the element is most stable under 1 atm of
pressure. One exception is phosphorus, for which the most stable form at 1 atm
is black phosphorus, but white phosphorus is chosen as the standard reference
state for zero enthalpy of formation.

For example, the standard enthalpy of formation of carbon dioxide would be the
enthalpy of the following reaction under the conditions above:
C (s,graphite) + O 2(g) → CO 2(g)

Note that all elements are written in their standard states, and one mole of product is
formed. This is true for all enthalpies of formation.

The standard enthalpy of formation is measured in units of energy per amount of

substance. Most are defined in kilojoules per mole (kJ mol−1), but can also be measured
in calories per mole, joules per mole or kilocalories per gram (any combination of these
units conforming to the energy per mass or amount guideline). In physics the energy per
particle is often expressed in electronvolts which corresponds to about 100 kJ mol−1.
All elements in their standard states (oxygen gas, solid carbon in the form of graphite,
etc.) have a standard enthalpy of formation of zero, as there is no change involved in
their formation.

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 UNIT 2 HEAT OF FORMATION
SESSION 5

The formation reaction is a constant pressure and constant temperature process. Since
the pressure of the standard formation reaction is fixed at 1 atm, the standard formation
enthalpy or reaction heat is a function of temperature.

Standard enthalpies of formation are used in thermochemistry to find the standard

enthalpy change of any reaction. This is done by subtracting the sum of the standard
enthalpies of formation of the reactants (each being multiplied by its respective
stoichiometric coefficient, ν) from the sum of the standard enthalpies of formation of
the products (each also multiplied by its respective stoichiometric coefficient), as shown
in the equation below:

ΔH° = Σ(ν × ΔH f °) (products) - Σ(ν × ΔH f °) (reactants)

For example, for the reaction CH 4 + 2 O 2 → CO 2 + 2 H 2 O:

ΔH f ° = [(1 × ΔH f ° (CO2) ) + (2 × ΔH f ° (H2O) )] - [(1 × ΔH f ° (CH4) ) + (2 × ΔH f ° (O2) )]

If the standard enthalpy of the products is less than the standard enthalpy of the
reactants, the standard enthalpy of reaction will be negative. This implies that the
reaction is exothermic. The converse is also true; the standard enthalpy of reaction will
be positive for an endothermic reaction.
Key concepts for doing enthalpy calculations
1. When a reaction is reversed, the magnitude of ΔH stays the same, but the sign
changes.
2. When the balanced equation for a reaction is multiplied by an integer, the
corresponding value of ΔH must be multiplied by that integer as well.
3. The change in enthalpy for a reaction can be calculated from the enthalpies of
formation of the reactants and the products
4. Elements in their standard states are not included in the enthalpy calculations for
the reaction since the enthalpy of an element in its standard state is zero

Examples:
Calculate the ∆H f for the synthesis of lime, CaO from lime stone CaCO3 , an
important step in the manufacturing of cement.

∆
CaCO3( s ) 
→ CaO( s ) + CO2 ( g )
∆H of (C a CO3( s ) = − 1206.9 KJmol −1
∆H of (C a O( s ) = − 635.1KJmol −1
∆H of (CO2 ( s ) = − 393.5 KJmol −1
∆H of ( reaction ) = ∆H of ( product ) − ∆H of ( reactnt )

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THERMOCHEMISTRY UNIT 2
SESSION 5

∆H of ( product ) = [1mol (−635.1KJmol −1 )] + [1mol ( − 393.5 KJmol −1 )] = −1028.6 KJ

∆H of ( reactnt ) = [1mol (−1206.9 KJmol −1 ) ] = −1206.9 KJ .
∴ ∆H of ( reaction = −1028.6 − (−1206.9)
= −1028.6 + 1206.9
= 178.3KJ

Self-Assessment Questions
Exercise 2.5
(1) Ammonium dichromate decomposes in a reaction when heated.
Calculate the heat transferred for the decomposition of 53.0 g of ammonium
dichromate according to
(NH 4 ) 2 Cr 2 O 7 (s) ⟶ Cr 2 O 3 (s) + N 2 (g) + 4H 2 O(g) ΔH° = -315 kJ
(2) The standard heat of formation ΔH f for C 2 H 4 is +52.3 kJ/mol. If C 2 H 4 (ethene)
reacts with H 2 (g) to produce C 2 H 6 (g) (ethane) ΔH = -137 kJ. What is the heat
formation of ethane?

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 UNIT 2 HEAT OF FORMATION
SESSION 5

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• Issues that are not clear: and
• Difficult topics if any

54 CoDEUCC/Diploma in Maths & Science Education

THERMOCHEMISTRY
UNIT 2
SESSION 6

SESSION 6: ENTROPY AND GIBBS FREE ENERGY

Hello and welcome to session 6 of unit 2. This session will focus
attention on entropy and Gibbs free energy. It will further explain how
energy together with enthalpy is used to determine spontaneity of a
given reaction.

Objectives
At the end of reading this session one would be able to:
(1) Define entropy and use it together with enthalpy change to determine
spontaneity of a reaction.
(2) State the second and third laws of thermodynamics.

Now read on…

Entropy is defined as the amount of randomness or molecular disorder in a system. It

has the unit JK −1

Gases have more randomness and higher entropy than liquids and liquids have more
randomness than solids and thus a higher entropy than solids. A change in entropy is
represented by ∆S .

∆S ° = S final − Sinitial

∆S ° is positive when randomness increase ∆S ° = +22.0 JK −1 is the entropy for melting

ice entropy has a negative sign when it decreases. Example, freezing of water which
has ∆S ° = +22.0 JK −1 .

If ∆S is positive, the system becomes more random and if that is negative the system
becomes less random.

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 UNIT 2
ENTROPY AND GIBBS FREE ENERGY
SESSION 6

6.1 Spontaneous Process

It is a process that proceeds on its own without any continuous external influence. The
change need not happen quickly but slowly like the gradual rusting of an iron.

6.2 Non – Spontaneous Process

A non – spontaneous process by contrast takes place only in the presence of a
continuous external influence. The reverse of any spontaneous process is always non –
spontaneous.

6.3 Factors that Determine Spontaneity

The two features that determine the spontaneity of a chemical or physical process in a
system are;
(i) A release or absorption of heat, ∆H .
(ii) An increase or decrease in molecular randomness, ∆S .

To decide whether a process is spontaneous, both enthalpy and entropy change must be
taken into account. Spontaneous process is favoured by decreased in enthalpy change.
What it means is that H final 〈 H initial → − ∆H . It is also favoured by increased in
entropy change. i.e S final 〉 S initial → + ∆S .

The non-spontaneous process is disfavoured by decreased in enthalpy and favoured by

increased in entropy change.

The two factors do not have to operate in the same direction. It is possible for a process
to be disfavoured by enthalpy, yet the process can be spontaneous, because it is strongly
favoured by entropy change.

∆G = ∆H − T∆S

For a process to be spontaneous, one of the ∆H or T∆S should be positive and the
other negative.

i.e. for spontaneous process, ∆G = negative. Again its also possible for a process to be
favoured by enthalpy (−∆H ) , yet the process becomes non-spontaneous. This is
because it is strongly disfavoured by entropy change. To take both factors to account
when deciding the spontaneity of a chemical reaction or other Process, we defined
another quantity called The Gibbs Free Energy; ∆G . The value of the free energy
change; ∆G is a general measure for the spontaneity of a physical or chemical process.
If ∆G has a negative value, the process is said to be spontaneous. If ∆G has a value of

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UNIT 2
SESSION 6

zero, the process is neither spontaneous nor non-spontaneous but instead the process is
at equilibrium and ∆G is zero. If ∆G has a positive value, the process is non-
spontaneous.

The fact that, the T∆S term in the Gibbs free energy equation is temperature dependent
implies that, some process might either be spontaneous or non-spontaneous depending
on the temperature of the system. At low temperature, + ∆H is less than + T∆S which
also implies that, ∆G is negative.

Thus an endothermic process that is non-spontaneous at low temperature can become

spontaneous at high temperature.

Examples:
1. Predict whether ∆S is rightly to be positive or negative for each of the following
reactions.
(a) CH 2 = CH 2 ( g ) + Br2 (l ) → CH 2 Br CH 2 Br (l )
Answer: ∆S = Negative

(b) 2C2 H 6 ( g ) + 702 ( g ) → 4CO2 ( g ) + 6 H 2O( g )

Answer: ∆S = Positive

2. Quickline CaO is produced by heating limestone, CaCO3 to drive out CO2 gas.
(i) Is the reaction spontaneous at standard condition at 25°C
(ii) Calculate the temperature at which the reaction becomes spontaneous
∆H = 178.3KJ and ∆S = 160.0 JK −1

Answers:
(i) ∆G = +130.62 KJ ⇒ Reaction is non-spontaneous.

(ii)Temperature, T = 1114.4 K OR 841.4°C

3. Is the Heber process for the industrial synthesis of NH 3 , spontaneous or non-

spontaneous at standard condition. At what temperature in degree al sin s does the
change ever occur?
∆H = −92.2 KJ , ∆S = −199 JK −1

Answer: ∆H = −151.502 KJ
∴ Reaction is spontaneous.
Temperature, T = 190.3°C

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 UNIT 2
ENTROPY AND GIBBS FREE ENERGY
SESSION 6

6.4 Second Law of Thermodynamics

It states that, in any spontaneous process the entropy of the universe increase, the
entropy of the universe increases, ie. ∆S system + ∆S surroundings 〉 O .

6.5 Third Law of Thermodynamics

It states that, the entropy of a pure crystalline solid at zero Kelvin is zero.

Self-Assessment Questions
Exercise 2.6

Calculate the free energy change for the complete combustion of one mole of
methane,CH 4 (g), the main component of natural gas. Is this reaction spontaneous?

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RATE OF CHEMICAL REACTION
UNIT 3

UNIT 3: RATE OF CHEMICAL REACTION

Unit Outline
Session 1: The Concept of Chemical kinetic Terminologies
Session 2: Rate of Reaction
Session 3: Integrated Rate Law
Session 4: Factors that affect Reaction Rate
Session 5: Arrhenius Equation
Session 6: Catalysis

This unit will consider rate of chemical reaction. Rocket fuel is

designed to give a rapid release of gaseous products and energy to
provide a rocket maximum thrust. Milk is stored in a refrigerator to slow down the
chemical reactions that cause it to spoil. Current strategies to reduce the rate of
deterioration of the ozone layer try to deprive the ozone-consuming reaction cycle of
key intermediates that come from chlorofluorocarbons (CFCs). Catalysts are used to
reduce the harmful emissions from internal combustion engines that contribute to smog.
These examples illustrate the importance of the rates of chemical reactions. Moreover,
how fast a reaction occurs depends on the reaction mechanism-the step-by-step
molecular pathway leading from reactants to products. Thus, chemical kinetics concerns
how rates of chemical reactions are measured, how they can be predicted, and how
reaction rate data are used to deduce probable reaction mechanisms. The unit begins
with a discussion of the meaning of a rate of reaction and some ideas about measuring
rates of reaction. This is followed by the introduction of mathematical equations, called
rate laws that relate the rates of reactions to the concentrations of the reactants. Finally,
with this information as background, rate laws are related to plausible reaction
mechanisms, which are a central focus of this unit.

Unit Objectives
By the end of this unit, you should be able to;
1. State two quantities that must be measured to establish the rate of a
chemical reaction.
2. Cite the factors that affect the rate of a chemical reaction.
3. Explain the terms rate, rate constant, and rate law.
4. Define half-life and explain whether it is constant for zero-order, first-order and
second-order reactions.
5. State the variables that Arrhenius equation relates? Explain each of the terms in
the equation.
6. Define elementary reaction and state the three types.
7. State the difference between homogeneous and heterogeneous catalysis.
8. Define rate-determining step.

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 RATE OF CHEMICAL REACTION
UNIT 3

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• Issues that are not clear: and
• Difficult topics if any

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 1

SESSION 1: CONCEPT OF THE TERMS IN CHEMICAL

KINETICS
Hello and welcome to session 1 of unit 3.This session would look at some definitions of
kinetic terminologies and develop the concept of calculating how fast of given reaction
could proceed. This session also attempt to derive the general rate law of given
chemical reaction.

Objectives
By the end of reading this session one would be able to:
(1) Define the terminologies as applied in chemical Kinetics
(2) Derive the general rate law
(3) Determine the rate law from a given data.

Now read on…

1.1 Kinetic Explained

Kinetic is the part of the science of motion. In Physics, the size of motion is termed
Dynamics and sub-divided into Kinematics which treat the motion of bodies and
Kinetics which deals with the effect of forces on motions.

In Chemistry, no such distinction is made. Kinetics in Chemistry, deals with the rate of
a chemical reaction, with all the factors which influence the rate of the reaction and with
the explanation of the rate in terms of the reaction mechanism.

Kinetics is concerned fundamentally with the details of a process whereby a system

moves from one state to another and with the time required for the transition. Kinetics
provides the most general method for determining the mechanism of a reaction.

1.2 Definition of Kinetic Terminologies

 Mechanism of a Reaction: Is a sequence of elementary reactions or
elementary reactions or elementary steps that defines the pathway from
reactants to products.
 Elementary Reaction: It describes the behavior of individual molecules. It
is a single step, unimolecular, Bimolecular and Trimolecular steps.

Example of an elementary step;

NO2 ( g ) + NO2 ( g ) → NO( g ) + NO3( g ) OR
2 NO2 ( g ) → NO( g ) + NO3( g ) .

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 CONCEPT OF THE TERMS IN CHEMICAL
UNIT 3
KINETICS
SESSION 1

 Rate Determining Step: The rate determining step in a chemical reaction is

the slowest step in a reaction that proceeds via a series of elementary steps
from reactants to products.

 Rate of Reaction: The rate of change of concentration of a substance

involved in the reaction. In other words, it is the decrease in concentration of
the reactant molecule or the increase in the concentration of the product
molecule with time.

 Rate Law: The rate law is an equation in which the reaction rate is set equal
to a mathematical expression involving the concentration of reactants and
sometimes of products. For a reaction A → C Rate, R = K [ A]n ; n =
order of reaction. The rate law of any chemical reaction must be determined
experimentally, it cannot be predicted by merely looking at the chemical
equation.

 Molecularity of a Reaction: It is defined as the number of molecules that

participate as reactants in an elementary reaction. The terms Unimolecular,
Bimolecular, and Trimolecular are used to denote the reaction of 1st, 2nd and
3rd orders respectively.

 Order of a Reaction: It is defined as the sum of the powers to which all the
reactants appearing in the rate law expression are raised. R = K [ A]n for
A → C n = order
Also, for A + B → C + D , Rate, R = K [ A]m [ B]n
R = K [reactant]m [reactant]n ; m + n = order .
The exponents “m” and “n” are the reaction order with respect to the
individual molecules and their sum is the overall order.
If n = 1 , the reaction is 1st order
n = 2 , the reaction is 2nd order etc.
 Half-Life: Half-life of a reaction is denoted by t 1 is the time required for the
2

reactant concentration to drop to a half of its initial value.

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 1

Example 1:
The initial rate of a reaction A + B → C was measured for several different starting
concentrations for A and B.

Experiment No. [ A] M [ B] M Initial Rate / m5′

1 0.100 0.100 4.0 × 10−5
2 0.100 0.200 4.0 × 10−5
3 0.200 0.100 16 ×10 −5

Using the data above; Determine;

(a) the rate law of the reaction
(b) the magnitude of the rate constant, K.
(c) the rate of reaction, R when concentration is o.o500M and concentration of [A] is
0.0500M.

Solution:
(a) R = K [ A]n [ B ]m
Develop three equation form the table

4.0 × 10−5 = K [0.100]n [0.100]m (1)

4.0 × 10− 5 = K [0.100]n [0.200]m ( 2)

16.0 × 10− 5 = K [0.100]n [0.100]m (3)

Dividing equation (3) by equation (1)

16.0 × 10 −5 K [0.200]n [0.100]m (3)

=
4.0 × 10 − 5 K [0.100]n [0.100]m (1)

n
[0.200]n  0.2 
⇒4= ⇒4= 
 0.1 
n
[0.100]

⇒ 4 = [2]n

22 = 2n ; ∴n = 2

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UNIT 3
KINETICS
SESSION 1

Dividing equation 2 by equation (1)

4.0 × 10 −5 K [0.200]n [0.200]m

=
4.0 × 10 − 5 K [0.100]n [0.100]m

n
[0.200]n  0.2 
⇒1= ⇒1=  0.1 
[0.100]n  

⇒ 2° = 2n ; m=0

∴ Rate Law, R = K [ A]2 [ B]° But [ B]o = 1

⇒ R = K [ A]2

(b) R = K [ A]2
R
⇒K= from equation 3
[ A]2

16.0 × 10−5 MS −1 16.0 × 10−5 MS −1

K= =
[0.2M ]2 0.04M 2

∴ K = 4 × 10−3 M −1S −5

Self-Assessment Questions
Exercise 3.1

1. The combustion of ethane (C 2 H 6 ) is represented by the equation:

2C 2 H 6 (g) + 7O 2 (g) 4CO 2 (g) + 6H 2 O(l)
In this reaction:
(a) the rate of consumption of ethane is seven times faster than the rate of
consumption of oxygen.
(b) the rate of formation of CO 2 equals the rate of formation of water.
(c) water is formed at a rate equal to two-thirds the rate of formation of CO 2 .
(d) the rate of consumption of oxygen equals the rate of consumption of water.
(e) CO 2 is formed twice as fast as ethane is consumed.
2. The speed of a chemical reaction
(a) is constant no matter what the temperature is.
(b) is independent of the amount of contact surface of a solid involved.

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UNIT 3
SESSION 1

(c) between gases should in all cases be extremely rapid because the average
kinetic energy of the molecules is great.
(d) between ions in aqueous solution is extremely rapid because there are no
bonds that need to be broken.
(e) varies inversely with the absolute temperature.
3. For a reaction 2A + B 2C, with the rate equation: Rate = k[A]2[B]
(a) the order with respect to A is 1 and the order overall is 1.
(b) the order with respect to A is 2 and the order overall is 2.
(c) the order with respect to A is 2 and the order overall is 3.
(d) the order with respect to B is 2 and the order overall is 2.
(e) the order with respect to B is 2 and the order overall is 3.
4. Given the following data for this reaction:
NH 4 +(aq) + NO 2 -(aq) N 2 (g) + 2H 2 O(l)
EXPT [NH 4 +] [NO 2 -] RATE
1 0.010 M 0.020 M 0.020 M/s
2 0.015 M 0.020 M 0.030 M/s
3 0.010 M 0.010 M 0.005 M/s
The rate law for the reaction is:
(a) Rate = k[NH 4 +][NO 2 -]
(b) Rate = k[NH 4 +]2[NO 2 -]2
(c) Rate = k[NH 4 +]2[NO 2 -]
(d) Rate = k[NH 4 +][NO 2 -]2
(e) none of the above
5. What are the units of k for the rate law: Rate = k[A][B]2, when the concentration
unit is mol/L?
(a) s-1
(b) s
(c) L mol-1 s-1
(d) L2 mol-2 s-1
(e) L2 s2 mol-2

6. Given: A + 3B 2C + D
This reaction is first order with respect to reactant A and second order with
respect to reactant B. If the concentration of A is doubled and the concentration
of B is halved, the rate of the reaction would _____ by a factor of _____.
(a) increase, 2
(b) decrease, 2
(c) increase, 4
(d) decrease, 4
(e) not change

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UNIT 3
KINETICS
SESSION 1

7. The decomposition of carbon disulfide, CS 2 , to carbon monosulfide, CS, and

sulfur is first order with k = 2.8 x 10-7 s-1 at 1000oC.
CS 2 CS + S
What is the half-life of this reaction at 1000oC?
(a) 5.0 x 107 s
(b) 4.7 x 10-6 s
(c) 3.8 x 105 s
(d) 6.1 x 104 s
(e) 2.5 x 106 s

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 2

SESSION 2: RATE OF REACTION

Hello and welcome to session 2 of unit 3.This session will look at rate of reaction and
how it depends on the concentrations of the reactants.

Objectives
By the end of reading this session one would be able to:
(1) Derive the general rate law
(2) Determine the rate law from a given data.
(3) Determine the reaction order of a rate law equation.

Now read on…

The rate of a reaction is defined as the increase in concentration of product per unit time
or as the decrease in concentration of reactant per unit time. One example of a reaction
that has been studied in detail is the thermal decomposition of gaseous dinitrogen
pentoxide ( N 2O5( g ) ) to give the brown gas Nitrogen dioxide, NO2 ( g ) and molecular
oxygen, O2 ( g ) .
i.e. 2 N 2OS ( g ) → 4 NO2 ( g ) + O2 ( g )

Time/s [ N 2O5( g ) ] NO2 [O5 ]

0 0.0200 0 0
100 0.0169 0.0063 0.0016
200 0.0142 0.0115 0.0029
300 0.0120 0.0160 0.0040
400 0.0101 0.0197 0.0049
500 0.0086 0.0229 0.0057
600 0.0072 0.0256 0.0064
700 0.0061 0.0278 0.0070

Reactants and products concentration as a function of time at 55°C are listed in the
table above.
[N O ] [ NO2 ] [O ]
−δ 2 5 = δ =δ 2
δt δt δt

[ N O ] − [ N 2O5 ]initial 
Rate = −  2 5 final 
 Timefinal − Timeinitial 

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 UNIT 3 RATE OF REACTION
SESSION 2

2 N 2OS ( g ) → 4 NO2 ( g ) + O2 ( g )

1 [ N O ] 1 [ NO2 ] [O ]
Rate, − δ 2 5 = δ =δ 2
2 δt 4 δt δt
i.e The average rate.

 Rate Law and Reaction Order: Considering the general reaction; a A+ b B →

Product, where “A” and “B” are the reactants and “a” and “b” are
stoichiometric coefficient in the balanced chemical equation.

The dependence of the reaction rates on the concentration of each reactant is given by an
equation called the Rate Law. The rate law is generally in the form:

[ A] [ B]
Rate = −∆ = K [ A]n [ B]m = −∆
∆t ∆t

Where, K is the rate constant. The exponents n and m in the rate law indicate how
sensitive the rate is to changes in “A” and “B” and they are usually unrelated to the
coefficient of “a” and “b” in the balanced chemical equation.

“n” and “m” is referred to as the Reaction Order.

Examples:

Rate Law Reaction Order Units (K)

R = K [ A]° 0 -
R = K [ A]′ 1st Order 1
or s -1
s

R = K [ A][ B ] 2nd Order 1

or M -1S-1
M.S

R = K [ A][ B]2 3rd Order 1

2
or M - 2S-1
M .S

The values of the exponents in the rate law must be determined experimentally, they
cannot be deduced from the stoichiometry of the reaction.

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UNIT 3
SESSION 2

Self-Assessment Questions
Exercise 3.2
1. The decomposition of dimethylether at 504 oC is first order with a
half-life of 1570 seconds. What fraction of an initial amount of dimethylether
remains after 4710 seconds?
(a) 1/3
(b) 1/6
(c) 1/8
(d) 1/16
(e) 1/32
2. The half-life for a first-order reaction is 32 s. What was the original
concentration if, after 2.0 minutes, the reactant concentration is 0.062 M?
(a) 0.84 M
(b) 0.069 M
(c) 0.091 M
(d) 0.075 M
(e) 0.13 M
3. Given that a reaction absorbs energy and has an activation energy of 50 kJ/mol,
which of the following statements are correct? (Hint: Draw the potential energy
diagram.)
(1) The reverse reaction has an activation energy equal to 50 kJ/mol.
(2) The reverse reaction has an activation energy less than 50 kJ/mol.
(3) The reverse reaction has an activation energy greater than 50 kJ/mol.
(4) The change in internal energy is less than zero.
(5) The change in internal energy is greater than zero.
(a) (1) and (4)
(b) (2) and (4)
(c) (3) and (4)
(d) (2) and (5)
(e) (3) and (5)
4. If reaction A has an activation energy of 250 kJ and reaction B has an activation
energy of 100 kJ, which of the following statements must be correct?
(a) If reaction A is exothermic and reaction B is endothermic then reaction A is
favored kinetically.
(b) At the same temperature the rate of reaction B is greater than the rate of
reaction A.
(c) The energy of reaction A must be greater than the energy of reaction B.
(d) The energy of reaction B must be greater than the energy of reaction A.
(e) The rate of reaction A at 25 oC equals the rate of reaction B at 100 oC.
5. If the activation energy in the forward direction of an elementary step is 52 kJ
and the activation energy in the reverse direction is 74 kJ, what is the energy of
reaction E for this step?

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 UNIT 3 RATE OF REACTION
SESSION 2

(a) 22 kJ
(b) -22 kJ
(c) 52 kJ
(d) -52 kJ
(e) 126 kJ
6. Suppose the reaction: A + 2B AB 2 occurs by the following mechanism:
Step 1 A + B AB slow
Step 2 AB + B AB 2 fast
Overall A + 2B AB 2
The rate law expression must be Rate = _________.
(a) k[A]
(b) k[B]
(c) k[A][B]
(d) k[B]2
(e) k[A][B]2
7. A possible mechanism for the reaction, 2A + B C + D, is:
(1) A + A 2A fast, equilibrium
(2) 2A + A 3A slow
(3) 3A + B A + C + D fast
According to the mechanism, the rate law will be:
(a) Rate = k[A]2
(b) Rate = k[A][B]
(c) Rate = k[A]2[B]
(d) Rate = k[A]
(e) Rate = k[A]3
8. Which of the following statements are true?
(1) Reactions with more negative values of Go are spontaneous and proceed at
a higher rate than those with less negative values of Go.
(2) The activation energy, E a , is usually about the same as E for a reaction.
(3) The activation energy for a reaction does not change significantly as
temperature changes.
(4) Reactions usually occur at faster rates at higher temperatures.
(a) 1, 2, 4
(b) 3, 4
(c) 1, 2, 3
(d) 2, 3, 4
(e) 1, 2, 3, 4

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 3

SESSION 3: THE INTEGRATED RATE LAW

Hello and welcome to session 3 of unit 3. Session 3 continues with
the rate law. It would look at the integrated form of the rate law for
zero, first and second order. It would also look how they could determine reaction
order from a given data.

Objectives
By the end of reading this session one would be able to:
(a) derive the integrated rat law for zero, first and second order
(b) plot a curve and deduce the order of a given data
(c) derive the half-life of zero, first and second order

Now read on…

3.1 Derivation of the Integrated Rate Law

Consider a simple first order reaction, aA → Product.

A first order reaction is a reaction whereby the rate depends on the concentration of a
single reactant raised to the power one.

Rate, R = K [ A]−1

∆[ A]
⇒− = K [ A]1
∆t

∆[ A]
⇒− = K∆t
[ A]

∆[ A]
⇒ = − K∆t
[ A]

∆[ A] ∆[ A]
⇒ ∫ [ A]
= − ∫ K∆ t ⇒ ∫
[ A]
= − K ∫ ∆t

t
[ A]t
⇒ ln[ A] = − Kt
[ A]0 0

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 UNIT 3 THE INTEGRATED RATE LAW
SESSION 3

⇒ ln[ A]t − ln[ A]0 = − K [t − 0]

⇒ ln[ A]t − ln[ A]0 = − K t

[ A]t
⇒ ln = −K t
[ A]0

[ A]t
⇒ = e−K t
[ A]0

⇒ [ A]t = [ A]0 e − K t

3.2 Half Life ( t 1 ):

2
The time taken for half the concentration of the original substance to drop to half its
original value

Consider the reaction aA → Product. Half – Life for 1st Order Reaction:
[ A]t
⇒ ln = −K t
[ A]0

At time t = t0 ⇒ [ A]0

[ A]0
At time t = t 1 ⇒ [ A]t =
2
2

From the integrated 1st Order Reaction:

 [ A]0 
 
− Kt1 =  2 
2  [ A]0 
 

[ A] 1 
− K t 1 = ln  0 × 
2 [ A]0 2 

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 3

1
ln
1
⇒ − K t 1 = ln ⇒ t 1 = − 2
2
2 2
K

ln 2
⇒ t1 = −
2 K

0.693
∴ t1 = −
2
K

3.3 Integrated Law for Zero Order

Considering the reaction; aA → Product

∆[ A]
− = K [ A]0 , But [ A]01
∆t

⇒ ∆[ A] = − K∆t

∫ ∆[ A] = −∫ K∆t
t
[ A]t
⇒ [ A] = − Kt
[ A]0 0

⇒ [ A]t − [ A]0 = − K t .

Half Life for zero order reaction:

[ A]t = − K t + [ A]0

y = mx + c

A graph of [A] at time t will give a negative slope.

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 UNIT 3 THE INTEGRATED RATE LAW
SESSION 3

Fig. 1: Concentration vs. time of a zero-order reaction.

With 1st order;

[ A]t
ln = Kt .
[ A]0

This is also the same as;

ln[ A]t − ln[ A]0 = − K t .

ln[ A]t = − K t + ln[ A]0

y = mx + c

NB: When you plot a graph of ln[ A]t against time t you’ll get a negative slope:

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UNIT 3
SESSION 3

Fig. 2: ln (concentration) vs. time of a first-order reaction.

If plotted ln[ A]t against time t we’ll obtain a straight line having a negative slope which
is equal to − K and an interception, c which is equal to [ A]0 .

3.4 Units for the rate Constant, K

1. For 1 Order; aA → Product
st

R = K [ A]
R moldm −3 S −1
⇒K= = −3
= S −1 OR
[ A] moldm

MS −1
= S −1 .
M

2. For 2nd Order; aA → Product

R = K [ A]2

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 UNIT 3 THE INTEGRATED RATE LAW
SESSION 3

R mol/dm 3 S −1
K= =
[ A] 2 (mol / dm 3 )2

S −1
= OR
mol / dm3

= S −1mol −1dm 3

MS −1 S −1
2
= = M −1S −1
M M

3.5 Half Life for 2nd Order Reaction:

∆[ A]
R=− = K [ A]2
∆t

∆[ A]
⇒ = − K∆ t
[ A]2

∆[ A]
⇒ ∫ [ A] 2
= − K ∫ ∆t

⇒ ∫ [ A]−2 ∆[ A] = − K ∫ ∆t

t
− 2 +1
[ A]t
[ A]
⇒ = − Kt
− 2 +1
[ A]0 0

t
−1
[ A]t
[ A]
⇒ = − Kt
−1
[ A]0 0
t
[ A]t
1
⇒ = + Kt
[ A]
[ A]0 0

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 RATE OF CHEMICAL REACTION
UNIT 3
SESSION 3

1 1
⇒ − = Kt
[ A]t [ A]0

1 1
⇒ = Kt +
[ A]t [ A]0

y = mx + c
1
Plotting a graph of against time t, will give a straight line with a positive slope.
[ A]t

Fig. 3: 1/concentration vs. time of a second-order reaction

1 1
− = Kt
[ A]t [ A] 0

At time t = t0 ⇒ [ A]0

[ A]0
At time t = t 1 ⇒ [ A]t =
2
2

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 UNIT 3 THE INTEGRATED RATE LAW
SESSION 3

1 1
− = Kt1
[ A]t [ A] 0 2
2

2 1
− − K t1
[ A]0 [ A]0 2

2 −1 1
= K t1 = = K t1
[ A]0 2
[ A]0 2

1
∴t 1 =
2
K [ A]0

Self-Assessment Questions
Exercise 3.3

The decomposition of A is first order, and [A] is monitored. The following data are
recorded:
t / min 0 1 2 4
[A]/[M] 0.100 0.0905 0.0819 0.0670

(a) Calculate the rate constant, K

(b) Calculate the half-life, t 1

2

(c) Calculate [A] when t = 5 min.

(d) Calculate t when [A] = 0.0500.

(e) Estimate the time required for 90% of A to decompose.

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 4

SESSION 4: FACTORS THAT AFFECT REACTION RATE

Welcome to session 4 of unit 3. Session 3 would look at the various
factors that affect reaction rate. This includes nature of reactions,
concentration of reactants, temperature and catalyst. It would also give the various
steps of the mechanism of heterogeneous catalysis.

Objectives
By the end of reading this session you would be able to:
(a) State and explain how the following affect reaction rate
 nature of reactant,
 concentration of reactant,
 temperature
 catalyst
(b) State and explain the collision theory.

Now read on…

4.1 Factors that affect Reaction Rate

Experiment shows that, four important factors affect reaction rates. These are;
1. nature of the reactants
2. concentration of the reactants
3. temperature
4. catalyst

 Nature of the Reactants

In chemical reactions, bonds are broken. The rate should therefore depend on the
specific bond involved. Eg. The reduction of permanganate ( M nO4− ) in acidic solution
by ferrous ion is practically instantaneous, the permanganate colour disappears as fast
as ferrous solution is added.

This is not so with the reduction of M nO4− ion in acidic solution by oxalic acid [this
process to heat the mixture before the reaction proceeds, because the oxalic acid is an
organic compound and thus its bonds cannot be broken down easily and that limits the
reaction rates.

 Concentration
It is found that, the rate of a homogenous chemical reaction depends on the
concentration of the reactants. A homogenous reaction is one of which the reactants are
in one phase; whiles a heterogeneous reaction involves more than one phase. It is found

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 UNIT 3
FACTORS THAT AFFECT REACTION RATE
SESSION 4

for a heterogeneous reaction that, the rate is proportional to the area of contact between
the two phases.

Examples: Rusting of iron, the process is slow when surface of contact is small as with
a bar of iron, however if the bar is made into powder, the rusting is very fast because of
the greater area of contact.

Quantitatively, the reaction is proportional to concentration. And therefore any change

in concentration affect the reaction rate.

 Temperature:
Everyday experience tells us that the rate of a chemical reaction increases with
increasing temperature. For example, most foods last longer when stored in a freezer
but spoils quickly at room temperature.

According to the collision theory model, a bimolecular reaction occurs when two
properly oriented reactant molecules come together in sufficiently energetic collision.
According to the theory, the rate of any step in a reaction is directly proportional to;
1. the number of collisions per second between the reacting particles involved in
that step;
2. the fraction of these collisions that are effective greater than the activation
energy, Ea is approximately given by the equation;

Fig.

The fraction that has acquired enough energy to overcome the Ea A plot of the fraction
of collision with particular energy at two different temperatures. For each plot, the total

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 4

area under the curve is unity and the area to the right of Ea is the fraction, f of the
collisions with an energy greater than or equal to Ea . The fraction of collision, f that
are sufficiently energetic to result in a reaction (product) increases rapidly with
increasing temperature.
Ea Ea
− −
1 1
= e RT0 , = e RT1 , where T0 = low temperature and T1 = high temperature.
8 5

Self-Assessment Questions
Exercise 3.4
(1) Aluminium reacts with warm dilute hydrochloric acid to give
aluminium chloride solution and hydrogen. Explain why the reaction of dilute
hydrochloric acid with aluminium foil is fairly slow whereas the reaction with
the same mass of aluminium powder can be extremely vigorous.

(2) Explain the effects of the following on the reaction rate:

 Nature of reactant
 Concentration
 Temperature
 Catalyst

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 UNIT 3
FACTORS THAT AFFECT REACTION RATE
SESSION 4

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

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RATE OF CHEMICAL REACTION
UNIT 3
SESSION 5

SESSION 5: ACTIVATION ENERGY AND TRANSITION STATE

THEORY
Welcome to session 5 of unit 3. Session 5 will focus attention on the activation energy
of a chemical reaction. For reactants to be converted into products, the free energy of
the system must overcome the activation energy.
Transition state theory will also be treated.

Objectives
By the end of reading this session you would be able to:
(a) Explain the term Activation energy
(b) State the ideas behind the Transition state theory
(c) Use the Arrhenius equation to calculate for the activation energy and rate constant
of a chemical reaction.

Now read on…

5.1 The Activation Energy of Chemical Reaction

Only a small fraction of the collisions between reactant molecules convert the reactants
into the products of the reaction. This can be understood by considering the reaction
between ClNO 2 and NO.
ClNO 2 (g) + NO(g) NO 2 (g) + ClNO(g)

In the course of this reaction, a chlorine atom is transferred from one nitrogen atom to
another. In order for the reaction to occur, the nitrogen atom in NO must collide with
the chlorine atom in ClNO 2 .

Reaction won't occur if the oxygen end of the NO molecule collides with the chlorine
atom on ClNO 2 .

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ACTIVATION ENERGY AND TRANSITION STATE
SESSION 5 THEORY

Nor will it occur if one of the oxygen atoms on ClNO 2 collides with the nitrogen atom
on NO.

Another factor that influences whether reaction will occur is the energy the molecules
carry when they collide. Not all of the molecules have the same kinetic energy, as
shown in the figure below. This is important because the kinetic energy molecules carry
when they collide is the principal source of the energy that must be invested in a
reaction to get it started.

The overall standard free energy for the reaction between ClNO 2 and NO is favorable.
ClNO 2 (g) + NO(g) NO 2 (g) + ClNO(g) Go = -23.6 kJ/mol

But, before the reactants can be converted into products, the free energy of the system
must overcome the activation energy for the reaction, as shown in the figure below.
The vertical axis in this diagram represents the free energy of a pair of molecules as a
chlorine atom is transferred from one to the other. The horizontal axis represents the

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UNIT 3
SESSION 5

sequence of infinitesimally small changes that must occur to convert the reactants into
the products of this reaction.

To understand why reactions have an activation energy, consider what has to happen in
order for ClNO 2 to react with NO. First, and foremost, these two molecules have to
collide, thereby organizing the system. Not only do they have to be brought together,
they have to be held in exactly the right orientation relative to each other to ensure that
reaction can occur. Both of these factors raise the free energy of the system by lowering
the entropy. Some energy also must be invested to begin breaking the Cl-NO 2 bond so
that the Cl-NO bond can form.

NO and ClNO 2 molecules that collide in the correct orientation, with enough kinetic
energy to climb the activation energy barrier, can react to form NO 2 and ClNO. As the
temperature of the system increases, the number of molecules that carry enough energy
to react when they collide also increases. The rate of reaction therefore increases with
temperature. As a rule, the rate of a reaction doubles for every 10oC increase in the
temperature of the system.

Purists might note that the symbol used to represent the difference between the free
energies of the products and the reactants in the above figure is Go, not Go. A small
capital "G" is used to remind us that this diagram plots the free energy of a pair of
molecules as they react, not the free energy of a system that contains many pairs of
molecules undergoing collision. If we averaged the results of this calculation over the
entire array of molecules in the system, we would get the change in the free energy of
the system, Go.

Purists might also note that the symbol used to represent the activation energy is written
with a capital "E". This is unfortunate, because it leads students to believe the activation
energy is the change in the internal energy of the system, which is not quite true. E a
measures the change in the potential energy of a pair of molecules that is required to
begin the process of converting a pair of reactant molecules into a pair of product
molecules.

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SESSION 5 THEORY

5.2 Determining the Activation Energy of a Reaction

The rate of a reaction depends on the temperature at which it is run. As the temperature
increases, the molecules move faster and therefore collide more frequently. The
molecules also carry more kinetic energy. Thus, the proportion of collisions that can
overcome the activation energy for the reaction increases with temperature.

The only way to explain the relationship between temperature and the rate of a reaction
is to assume that the rate constant depends on the temperature at which the reaction is
run. In 1889, Svante Arrhenius showed that the relationship between temperature and
the rate constant for a reaction obeyed the following equation.

In this equation, k is the rate constant for the reaction, Z is a proportionality constant
that varies from one reaction to another, E a is the activation energy for the reaction, R is
the ideal gas constant in joules per mole kelvin, and T is the temperature in kelvin.
The Arrhenius equation can be used to determine the activation energy for a reaction.
We start by taking the natural logarithm of both sides of the equation.

We then rearrange this equation to fit the equation for a straight line.
y = mx + b

According to this equation, a plot of ln k versus 1/T should give a straight line with a
slope of - E a /R, as shown in the figure below.

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SESSION 5

Another form of Arrhenius equation can be derived and that allows for the estimation of
the Ea from rate constant at just two temperatures.
E
ln K = ln A = a
RT
at T = T1

Ea
⇒ ln K1 = ln A − (1)
RT1

at T = T2

Ea
⇒ ln K 2 = ln A − (2)
RT2
Equation (2) – equation (1)

 E  1 1
ln K 2 − ln K1 = ln A − ln A −  a   − 
 RT   T2 T1 

K  E 1 1
⇒ ln  2  = − a  −  .
 K1  R  T2 T1 

Example:

Use the following data to determine the activation energy for the decomposition of HI:
Temperature, T (K) Rate Constant, K (M/s)
573 2.91 x 10-6
673 8.38 x 10-4
773 7.65 x 10-2

Answer:
We can determine the activation energy for a reaction from a plot of the natural log of
the rate constants versus the reciprocal of the absolute temperature. We therefore start
by calculating 1/T and the natural logarithm of the rate constants:
ln k 1/T (K-1)
-12.75 0.00175
-7.08 0.00149
-2.57 0.00129

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SESSION 5 THEORY

When we construct a graph of these data, we get a straight line with a slope of -22,200
K, as seen in Figure 1.

Figure 1. A plot of the natural

log of the rate constant for the
reaction at different temperatures
versus the inverse of the
temperature in kelvin is a straight
line with a slope equal to -E a /R.

According to the Arrhenius equation, the slope of this line is equal to -E a /R:

When this equation is solved, we get the following value for the activation energy for
this reaction:
E a = 183 kJ/mol
5.3 Transition State Theory (TST)
(TST) explains the reaction rates of elementary chemical reactions. The theory assumes
a special type of chemical equilibrium (quasi-equilibrium) between reactants and
activated transition state complexes.
TST is used primarily to understand qualitatively how chemical reactions take place.
TST has been less successful in its original goal of calculating absolute reaction rate
constants because the calculation of absolute reaction rates requires precise knowledge
of potential energy surfaces, but it has been successful in calculating the standard
enthalpy of activation (Δ‡Hɵ), the standard entropy of activation (Δ‡Sɵ), and the standard
Gibbs energy of activation (Δ‡Gɵ) for a particular reaction if its rate constant has been
experimentally determined. (The ‡ notation refers to the value of interest at the
transition state)
TST is also referred to as "activated-complex theory," "absolute-rate theory," and
"theory of absolute reaction rates." Before the development of TST, the Arrhenius rate
law was widely used to determine energies for the reaction barrier. The Arrhenius
equation derives from empirical observations and ignores any mechanistic
considerations, such as whether one or more reactive intermediates are involved in the
conversion of a reactant to a product. Therefore, further development was necessary to
understand the two parameters associated with this law, the pre-exponential factor (A)
and the activation energy (E a ).
The basic ideas behind transition state theory are as follows:

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SESSION 5

1. Rates of reaction can be studied by examining activated complexes which lie

near the saddle point of a potential energy surface. The details of how these
complexes are formed are not important. The saddle point itself is called the
transition state.
2. The activated complexes are in a special equilibrium (quasi-equilibrium) with
the reactant molecules.
3. The activated complexes can convert into products, and kinetic theory can be
used to calculate the rate of this conversion.

Self-Assessment Questions
Exercise 3.5
The Rate Constant for gas phase decomposition of hydrogen iodide;

2 HI ( g ) → H 2( g ) + I ( g )

are listed in the following table

Temp. / °C  1 
K 
 M .S 
283 3.52 × 10−7
356 3.02 ×10 −5
293 1.19 × 10−4
427 1.16 ×10 −3
508 3.95 × 10−2

(a) Find the Ea in KJ / mol

(b) Calculate the activation energy from the rate constants at temperatures
283°C and 508°C .
(c) Given the rate constant at 283°C , and the value of Ea obtained in part “b”,
what is the rate constant at 293°C ?
(d) State the basic ideas behind the transition theory.

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• Issues that are not clear: and
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RATE OF CHEMICAL REACTION UNIT 3
SESSION 6

SESSION 6: CATALYSIS
Welcome to session 6 of unit 3. Session 6 will focus attention on the
effects of a catalyst on reaction rate.

Objectives
By the end of reading this session you would be able to:
(a) Define a catalyst
(b) State the criteria by which a substance is classified as a catalyst
(c) Explain with illustration, the effect of catalyst on a reaction rate.

Now read on…

A catalyst is a substance that increases the rate of a reaction without been consumed in
the reaction. In the presence of a catalyst, the reaction is appreciably faster because it
can proceed by a different lower energy pathway. Note that, the catalyst does not appear
in the overall reaction, because it is consumed in one step and regenerated in a later
step. A catalyst accelerates the rate of a reaction by making available a new and a more
efficient mechanism for the convection of reactants to products. The catalyzed pathway
for a reaction might have a faster rate than the uncatalyzed pathway either because of a
larger frequency factor “A” or a smaller activation energy, Ea in the Arrhenius
equation. Usually, catalyst functions by making available a reaction pathway with a
lower Ea .

Aqueous solutions of hydrogen peroxide are stable until we add a small quantity of the
I- ion, a piece of platinum metal, a few drops of blood, or a freshly cut slice of turnip, at
which point the hydrogen peroxide rapidly decomposes.
2 H 2 O 2 (aq) 2 H 2 O(aq) + O 2 (g)

This reaction therefore provides the basis for understanding the effect of a catalyst on
the rate of a chemical reaction. Four criteria must be satisfied in order for something to
be classified as catalyst.
• Catalysts increase the rate of reaction.
• Catalysts are not consumed by the reaction.
• A small quantity of catalyst should be able to affect the rate of reaction for a
large amount of reactant.
• Catalysts do not change the equilibrium constant for the reaction.

The first criterion provides the basis for defining a catalyst as something that increases
the rate of a reaction. The second reflects the fact that anything consumed in the
reaction is a reactant, not a catalyst. The third criterion is a consequence of the second;

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because catalysts are not consumed in the reaction, they can catalyze the reaction over
and over again. The fourth criterion results from the fact that catalysts speed up the rates
of the forward and reverse reactions equally, so the equilibrium constant for the reaction
remains the same.

Catalysts increase the rates of reactions by providing a new mechanism that has smaller
activation energy, as shown in the figure below. A larger proportion of the collisions
that occur between reactants now have enough energy to overcome the activation
energy for the reaction. As a result, the rate of reaction increases.

To illustrate how a catalyst can decrease the activation energy for a reaction by
providing another pathway for the reaction, let's look at the mechanism for the
decomposition of hydrogen peroxide catalyzed by the I- ion. In the presence of this ion,
the decomposition of H 2 O 2 doesn't have to occur in a single step. It can occur in two
steps, both of which are easier and therefore faster. In the first step, the I- ion is oxidized
by H 2 O 2 to form the hypoiodite ion, OI-.
H 2 O 2 (aq) + I-(aq) H 2 O(aq) + OI-(aq)

In the second step, the OI- ion is reduced to I- by H 2 O 2 .

OI-(aq) + H 2 O 2 (aq) H 2 O(aq) + O 2 (g) + I-(aq)

Because there is no net change in the concentration of the I- ion as a result of these
reactions, the I- ion satisfies the criteria for a catalyst. Because H 2 O 2 and I- are both
involved in the first step in this reaction, and the first step in this reaction is the rate-
limiting step, the overall rate of reaction is first-order in both reagents.

Types of Catalyst:
1. Homogenous Catalyst: It is the one that exist in the same phase as the reactants.
Example: Iodide ions in the decomposition of Peroxide H 2O2 and H 2O2 are
present in the same aqueous solution phase

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2. Heterogeneous Catalyst: It is the one that exist in a different phase from that of
the reactants. Example: the catalyst is solid and the reactants are either liquids or
gas. In the manufacturing of synthetic gasoline, tiny particles of a metal such as
Fe or Co coated on Alumina catalyzed the conversion of gaseous CO( g ) and
hydrogen to produce hydrocarbons such as Octane. i.e.
8.CO( g ) + 17 H 2 ( g )Co / H 2O3C2 H18 + 8 H 2O(l ) .

The mechanism of heterogeneous catalysis is often complex and not will

understand. However, the important steps that involve are;
• adsorption of reactants unto the surface of the catalyst
• Conversion of the reactants to products on the surface of the catalyst.
• Desorption of products from the surface of the catalyst

The adsorption step is through to involve chemical bonding of the reactants to

highly reactive metal atoms of the catalyst on the surface with the accompanying
breaking or at least weakening of bonds in the reactant.

Self-Assessment Questions
Exercise 3.6
(1) Define the word catalyst.
(2) Explain with diagram, the effect of catalyst on reaction rate.
(3) State and define two types of catalyst

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This is a blank sheet for your short notes no:

• Difficult topics if any.
• Issues that are not clear;

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ELECTROCHEMISTRY
UNIT 4

UNIT 4: ELECTROCHEMISTRY

Unit Outline
Session 1: Introduction to Electrochemistry
Session 2: Cell E.M.F. [Electromotive Force]
Session 3: Standard Electrode Potential
Session 4: Using Standard Potential to predict the possibility of a reaction
Session 5: Cell Potential and Composition of reaction mixture
Session 6: Standard Cell Potential and Equilibrium constant

The conversion of chemical energy into electrical energy is one of the

main subjects of this unit.
A conventional gasoline-powered automobile is only about 25%
efficient in converting chemical energy into kinetic energy (energy of motion). An
electric-powered auto is about three times as efficient. Unfortunately, when automotive
technology was first being developed, devices for converting chemical energy to
electrical energy did not perform at their intrinsic efficiencies. This fact, together with
the availability of high-quality gasoline at a low cost, resulted in the pre-eminence of
the internal combustion automobile. Now, with concern about long-term energy
supplies and environmental pollution, there is a renewed interest in electric-powered
buses and automobiles. In this unit, we will see how chemical reactions can be used to
produce electricity and how electricity can be used to cause chemical reactions. The
practical applications of electrochemistry are countless, ranging from batteries and fuel
cells as electric power sources to the manufacture of key chemicals, the refining of
metals, and methods for controlling corrosion. Also important, however, are the
theoretical implications. Because electricity involves a flow of electric charge, a study
of the relationship between chemistry and electricity gives us additional insight into
reactions in which electrons are transferred-oxidation-reduction reactions.

Unit Objectives
By the end of reading this session five one would be able to:
(i) Define electrochemistry and the terminologies associated with it.
(ii) Draw electrochemical and electrolytic cell
(iii) Calculate cell E.M.F of a given reaction
(iv) State and explain corrosion and corrosion prevention using electrochemistry.

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ELECTROCHEMISTRY
UNIT 4
SESSION 1

SESSION 1: ELECTROCHEMISTRY DEFINED

Hello and welcome to session 1 of unit 4.This session will elaborate on
electrochemistry, an area of chemistry concern with the interconversion of
chemical and electrical energy.

Objectives
By the end of reading this session you would be able to:
(a) Define Electrochemistry
(b) Define Electrochemical cell
(c) Distinguish between Galvanic cells and Electrolytic cells

Now read on…

Electrochemistry is the area of chemistry concern with the interconversion of chemical

and electrical energy. Batteries provide the electrical current needed to start our
automobile and to power a host of products such as Pocket Calculators, Radios, and
T.V. etc. A battery is an example of electrochemical cell. Electrochemical cell is a
device for interconverting chemical and electrical energy. A battery takes the energy
released by a spontaneous chemical reaction and uses it to produce electricity.

Electrochemical cells are of two basic types; Galvanic Cells, also known or called
Voltage cells and Electrolytic cells. The Galvanic or voltage cell is a device in which a
spontaneous redox reaction is used to produce an electrical current.

In principle, the energy released in any spontaneous reaction can be directly harnessed
to perform electrical work. This task is accomplished through a Galvanic cell in which
electron transfer is forced to take place through an external pathway rather than directly
between, reactants.
One such spontaneous reaction occurs when a piece of Z n metal is placed in contact
with the solution containing Cu 2 + , as the reaction proceeds, the blue colour, that is
characteristic of Cu 2 + aqueous ion fades and copper metal begins to deposits on the Z n
metal. At the same time, the Z n begins to dissolve.
Z n Z n2 + // Cu2 + / Cu ⇒ Short-hand notation

Cu2 + + Z n → Z n2 + + Cu [Overall Redox Equation]

Half reactions;

Cu2(+aq ) + 2e − → Cu ( s ) Cu is being reduced.

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SESSION 1

Z n( s) → Z n2 + + 2e − Z n is being oxidized.

Fig.1: Electrochemical cell

The metal plate is called an electrode. An electrode is a metal stripe partly immersed in
a solution which contains ions and the solution where oxidation occurs is called
ANODE, by convention, we say it is the positive electrode. And the electrode where the
reduction occurs is also called the CATHODE, and is also given a negative sign by
convention. In the example above;

We may regard the galvanic cell as two half cells, one corresponding to the oxidation
process and the other, the Reduction process as shown above. Electrons become
available as Z n metal is oxidized at the anode. The electrons released at the anode flows
through an external circuit to the cathode, where they are consumed as Cu2 + reduces to
Cu (3) . The salt bridge is a U – tube that contains an electrolyte, its ions moves to such
equilibrium in the cell. The ends of the U – tube are plucked with glass rod. The salt
bridge brings about electrical neutrality as oxidation – reduction proceeds at the
electrodes. Ions on the salt bridge migrates to neutralize charges on the anode and
Cathode compartments.

Anions move to the anode and cautions move to the cathode. No measurable electron
flow will occur through the external circuit unless, a means is provided for ions to
migrate through the solution from one electrode compartment to another, thereby
completing the circuit. The half-cell reactions must be added up to give the overall order
reaction. Eg.

Z n Z n2 + // Cu2 + / Cu ,

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SESSION 1

At the anode, oxidation occurs i.e.

Z n ( s ) → Z n2(+aq ) + 2e − and at the cathode; reduction occurs; i.e.

Cn2(+aq ) + 2e − → Cu ( s ) . Hence the overall reaction is given by;

Z n ( s ) + Cu2(+aq ) → Z n2(+aq ) + Cu ( s )

Self-Assessment Question
Exercise 4.1
(1) Define the following;
(a) Electrochemistry
(b) Electrochemical cell

(2) Deduce the overall reaction equation for the short-hand notation equation: Ag /
Ag+// Cu2+ / Cu

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SESSION 1

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UNIT 4
SESSION 2

SESSION 2: CELL E.M.F. [ELECTROMOTIVE FORCE]

Hello and welcome to session 2 of unit 4.This session will look at the
electromotive force -voltage developed by a source of electrical energy
such as a battery or dynamo.

Objectives
By the end of reading this session you would be able to:
(a) Define Electromotive force
(b) Define Standard Cell Potential
(c) Define Standard Hydrogen Electrode

Now read on…

Electromotive force, also called emf (denoted and measured in volts), is the voltage
developed by any source of electrical energy such as a battery or dynamo.
The word "force" in this case is not used to mean mechanical force, measured in
newtons, but a potential, or energy per unit of charge, measured in volts.
In electromagnetic induction, emf can be defined around a closed loop as the
electromagnetic work that would be transferred to a unit of charge if it travels once
around that loop. (While the charge travels around the loop, it can simultaneously lose
the energy via resistance into thermal energy.) For a time-varying magnetic flux
impinging a loop, the electric potential scalar field is not defined due to circulating
electric vector field, but nevertheless an emf does work that can be measured as a
virtual electric potential around that loop.
In a two-terminal device (such as an electrochemical cell or electromagnetic generator),
the emf can be measured as the open-circuit potential difference across the two
terminals. The potential difference thus created drives current flow if an external circuit
is attached to the source of emf. When current flows, however, the potential difference
across the terminals is no longer equal to the emf, but will be smaller because of the
voltage drop within the device due to its internal resistance.
Devices that can provide emf include electrochemical cells, thermoelectric devices,
solar cells and photodiodes, electrical generators, transformers, and even Van de
Graaff generators. In nature, emf is generated whenever magnetic field fluctuations
occur through a surface. An example for this is the variation in the Earth's magnetic
field during a geomagnetic storm, acting on anything on the surface of the planet, like
an extended electrical grid.
In the case of a battery, charge separation that gives rise to a voltage difference is
accomplished by chemical reactions at the electrodes. Chemically, by separating
positive and negative charges, an electric field can be produced, leading to an electric

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 UNIT 4 CELL E.M.F. [ELECTROMOTIVE FORCE]
SESSION 2

potential difference. A voltaic cell can be thought of as having a "charge pump" of

atomic dimensions at each electrode, that is:
A source of emf can be thought of as a kind of charge pump that acts to move positive
charge from a point of low potential through its interior to a point of high potential. …
By chemical, mechanical or other means, the source of emf performs work dW on that
charge to move it to the high potential terminal. The emf ℰ of the source is defined as
the work dW done per charge dq: ℰ = dW/dq.

The electromotive force (EMF) is the maximum

potential difference between two electrodes of a
galvanic or voltaic cell. This quantity is related to the
tendency for an element, a compound or an ion to
acquire (i.e. gain) or release (loss) electrons. For
example, the maximum potential between Zn and Cu of
a well-known cell
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
has been measured to be 1.100 V. A concentration of 1
M in an ideal solution is defined as the standard condition, and 1.100 V is thus the
standard electromotive force, DEo, or standard cell potential for the Zn-Cu galvanic
cell.

The standard cell potential, DEo, of the a galvanic cell can be evaluated from the
standard reduction potentials of the two half cells Eo. The reduction potentials are
measured against the standard hydrogen electrode (SHE):
Pt (s) | H 2 (g, 1.0 atm) | H+ (1.0 M).

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UNIT 4
SESSION 2

Its reduction potential or oxidation potential is defined to be exactly

zero.
The reduction potentials of all other half-cells measured in volts against the SHE are the
difference in electrical potential energy per coulomb of charge.
Note that the unit for energy J = Coulomb volt, and the Gibbs free energy G is the
product of charge q and potential difference E:
G in J = q E in C V
for electric energy calculations.

Self-Assessment Question
Exercise 4.2
Define the following;
(1) Electromotive force
(2) Standard Cell Potential
(3) Standard Hydrogen Electrode

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SESSION 2

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UNIT 4
SESSION 3

SESSION 3: EVALUATING STANDARD CELL POTENTIAL DE°

OF GALVANIC CELLS
Hello and welcome to session 3 of unit 4.This session will further elaborate on
evaluating the standard cell potential of galvanic cells.

Objectives
By the end of reading this session you would be able to:
(a) Write an oxidation half-cell equation
(b) Write a reduction half-cell equation
(c) Calculate the overall standard cell potential of a cell and state the significance of
its sign.

Now read on…

To make possible a consistent table of values of half-cell E.M.F, it is internationally

accepted that the EMF of the hydrogen half-cell.
H 2 ( g ) → 2 H + + 2e − E ° = 0.00V ;
shall be taken as 0.00V, i.e. the reference electrode. The EMF of any other half cell can
then be measured relative to that of the EMF of the hydrogen cell. When these
measurements are done at standard condition [at temperature 25°C and with effective
ion concentration of 1.0M]. The value obtained is called standard electrode potential
and the symbol is E ° .

o
Ecell = Eoxidation + Ereduction .

A galvanic cell consists of two half-cells. The convention in writing such a cell is to put
the (reduction) cathode on the right-hand side, and the (oxidation) anode on the left-
hand side. For example, the cell
Pt | H 2 | H+ || Zn2+ | Zn

consists of the oxidation and reduction reactions:

H 2 => 2 e + 2 H+ . . . . anode (oxidation) reaction

Zn2+ + 2 e => Zn . . . . cathode (reduction) reaction

If the concentrations of H+ and Zn2+ ions are 1.0 M and the pressure of H 2 is 1.0 atm,
the voltage difference between the two electrodes would be -0.763 V (the Zn electrode
being the negative electrode). The conditions specified above are called the standard
conditions and the EMF so obtained is the standard reduction potential.

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SESSION 3 DE° OF GALVANIC CELLS

Note that the above cell is in reverse order compared to that given in many
textbooks, but this arrangement gives the standard reduction potentials directly,
because the Zn half-cell is a reduction half-cell. The negative voltage indicates
that the reverse chemical reaction is spontaneous. This corresponds to the fact that Zn
metal reacts with an acid to produce H 2 gas.

As another example, the cell

Pt | H 2 | H+ || Cu+ | Cu

consists of an oxidation and a reduction reaction:

H 2 => 2 e + 2 H+ . . . . anode reaction
Cu2+ + 2 e => Cu . . . . cathode reaction

and the standard cell potential is 0.337 V. The positive potential indicates a spontaneous
reaction,
Cu2+ + H 2 => Cu + 2 H+

but the potential is so small that the reaction is too slow to be observed.

Example 1
What is the potential for the cell
Zn | Zn2+(1.0 M) || Cu2+(1.0 M) | Cu

Solution
From a table of standard reduction potentials we have the following values
(Reduction): Cu2+ + 2 e => Cu . . . E° = 0.337 - - - (1)
(Oxidation): Zn => Zn2+ + 2 e . . . E° = 0.763 - - - (2)

Add (1) and (2) to yield

Zn + Cu2+ => Zn2+ + Cu . . . DE° = E° (red) + E° (oxid) = 1.100 V

The standard cell potential is represented by dE°.

Discussion
The positive potential confirms your observations that zinc metal reacts with
cupric ions in solution to produce copper metal.

Example 2
What is the potential for the cell
Ag | Ag+(1.0 M) || Li+(1.0 M) | Li

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SESSION 3

Solution
From the table of standard reduction potentials, you find
(Reduction): Li+ + e => Li . . . E° = -3.045, - - - (3)
(Oxidation): Ag => Ag+ + e . . . E° = -0.799, - - - (4)

According to the convention of the cell, the reduction reaction is on the right. The cell
on your left-hand side is an oxidation process. Thus, you add (4) and (3) to obtain
Li+ + Ag => Ag+ + Li . . . dE° = -3.844 V

Discussion
The negative potential indicates that the reverse reaction should be spontaneous.

NB: Some calculators use a lithium battery. The atomic weight of Li is 6.94,
much lighter than Zn (65.4).

Self-Assessment Questions
(1) In which cell does reduction takes place? The right-hand cell or the left-hand
cell in the notation:
| left | left+ || right+ | right |?

(2) Reduction potentials of half cells are measured against what?

(A) The zinc half-cell: Zn | Zn2+ 1 M.

(B) The hydrogen half-cell: Pt | H 2 | H+ 1 M.
(C) The hydrogen half-cell: H+ 1 M | H 2 | Pt.
(D) The copper half-cell: Cu2+ 1 M | Cu.
(E) The hydrogen half-cell: Pt | H 2 | H+ 10-7 M.

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UNIT 4
SESSION 3 DE° OF GALVANIC CELLS

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UNIT 4
SESSION 4

SESSION 4: USING STANDARD POTENTIAL TO PREDICT

THE POSSIBILITY OF A REACTION
Hello and welcome to session 4 of unit 4.This session will also focus
attention on how to predict the possibility or feasibility of a reaction using
the standard potential value.

Objectives
By the end of reading this session you would be able to:
(a) Identify an oxidation half-cell equation
(b) Identify a reduction half-cell equation
(c) Predict the feasibility of a reaction

Now read on…

Electrode potential values from half equations give a quantitative measure of the
likelihood of a redox reaction taking place or not. In predicting whether a reaction will
occur, it is important to remember that, the electrode potential, E ° values relates to the
probability of a reaction occurring or not to the quantity of materials reacting. An
overall positive Eo value for the reaction suggests the reaction is energetically feasible
however, the negative value indicates that the reaction is unlikely to occur.
∆G° = −nFE ° , whenever ∆G = negative, it means reaction is feasible and when
∆G = positive, it indicates that the reaction is unlikely to occur.

NB: “n” and “F” are constants.

Example
Consider the reaction
Z n2(+aq ) + Cu ( s ) → Z n ( s ) + Cu2(+aq ) , E ° = −1.10V
Where,
Z n2+ + 2e − → Z u ( s ) , E ° = −0.76V

Cu2+ + 2e − → Cu ( s ) , E ° = +0.34V

Solution
(a) (Reduction): Z n2+ + 2e − → Z n ( s ) , E ° = − 0.76V
(Oxidation) : Cu ( s ) → Cu ( aq ) + 2e − E ° = −0.34V
Z n2(+aq ) + Cu ( s ) → Z n ( s ) + Cu2(+aq ) E ° = −1.10V

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 USING STANDARD POTENTIAL TO PREDICT
UNIT 4
SESSION 4
THE POSSIBILITY OF A REACTION

Since E ° = negative, the reaction will not be feasible. The reaction is not feasible, so a
zinc solution could be stored in a copper container.

However, if the process is reversed, we shall have:

Z n ( s ) + Cu2(+aq ) → Z n2(+aq ) + Cu ( s )

(b) (Oxidation): Z n → Z n2 + + 2e − , E ° = +0.76V

(Re duction) : Cu2+ + 2e − → Cu ( s ) E ° = +0.34V

Z n ( s ) + Cu2(+aq ) → Z n2(+aq ) + Cu ( s ) E ° = 1.10V
The overall positive potential, suggests that, the reaction is energetically feasible.
Therefore, copper ions in solution will react with a zinc metal container.

Self-Assessment Questions
Exercise 4.4
Is the potential for the battery positive or negative considering the cell below?

Pt | H 2 | H+ || Cl 2 | Cl- | Pt

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ELECTROCHEMISTRY
UNIT 4
SESSION 5

SESSION 5: CELL POTENTIAL AND COMPOSITION OF

REACTION MIXTURE
Hello and welcome to session 5 of unit 4.This session will also focus
attention on cell potential and composition of a reaction mixture.

Objectives
By the end of reading this session you would be able to:
(a) Deduce the Nernst equation
(b) Calculate the reaction quotient
(c) Use the Nernst equation to determine the initial voltage of a cell

Now read on…

 Nernst Equation
Cell potentials like free energy changes depend on the temperature and composition of
the reaction mixture, ie on the concentration of solutes or the partial pressures of gases.
The dependence can be derived from the equation below;
∆G = ∆G° + RT ln ϕ . But

∆G = −nFE and

∆G° = −nFE °

⇒ − nFE = −nFE ° + RT ln ϕ .

Dividing through by − nF

RT ln ϕ
⇒ E = E° −
nF

RT ln ϕ
⇒ Ecell − E °cell = − =>This equation is the Nernst Equation;
nF

E cell = cell potential under nonstandard conditions (V)

E0 cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)

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 CELL POTENTIAL AND COMPOSITION OF
UNIT 4
REACTION MIXTURE
SESSION 5

n = number of moles of electrons exchanged in the electrochemical reaction (mol)

F = Faraday's constant, 96500 coulombs/mol
ϕ = reaction quotient, which is the equilibrium expression with initial concentrations
rather than equilibrium concentrations

In writing this equation in logarithms instead of natural logarithm, we have;

2.303RT
E − E° = − log ϕ
nF

At standard temperature (25°C ), we assume that n = 1mole, R and F as well as 2.303

and T are constants.

2.303RT
⇒ = 0.0592.V
F

0.0592V
⇒ E = E° − log ϕ
n

Example
Z n ( s ) + 2 H (+aq ) → 2 H 2 ( g ) + Z n2(+aq )

Deducing ϕ from this relation;

[ Z n2+ ]
ϕ= ,
[ H + ]2
0.0592 [ Z n2+ ]
⇒ E = E° − log + 2
n [H ]
This is the overall Nernst Equation:

Example:
A zinc electrode is submerged in an acidic 0.80 M Zn2+ solution which is connected by
a salt bridge to a 1.30 M Ag+ solution containing a silver electrode. Determine the initial
voltage of the cell at 298K.

Solution
Unless you've done some serious memorizing, you'll need to consult the standard
reduction potential table, which will give you the following information:
E0 red : Zn2+ (aq) + 2e- → Zn (s) = -0.76 V

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ELECTROCHEMISTRY
UNIT 4
SESSION 5

E0 red : Ag+ (aq) + e- → Ag (s) = +0.80 V

E cell = E0 cell - (0.0591 V/n)log Q

The reaction proceeds spontaneously so E0 is positive. The only way for that to occur is
if Zn is oxidized (+0.76 V) and silver is reduced (+0.80 V). Once you realize that, you
can write the balanced chemical equation for the cell reaction and can calculate E0:
(oxidation): Zn (s) → Zn2+ (aq) + 2e- and E0 ox = +0.76 V
(reduction): 2Ag+ (aq) + 2e- → 2Ag (s) and E0 red = +0.80 V
which are added together to yield:
Zn (s) + 2Ag+ (aq) → Zn2+ (aq) + 2Ag (s) with E0 = 1.56 V
Q = [Zn2+]/[Ag+]2
Now, applying the Nernst equation:
Q = (0.80)/(1.30)2
Q = (0.80)/(1.69)
Q = 0.47
E = 1.56 V - (0.0591 / 2)log(0.47)
E = 1.57 V

Self-Assessment Question
Exercise 4.5

Consider a galvanic cell that uses the reaction:

Z n ( s ) + 2 H (+aq ) → H 2 ( g ) + Z n2(+aq )

Calculate the cell potential at 25°C ,

where [ H + ] = 1M , [ Z n2 + ] = 0.001M and R = 8.314 Jmol −1K −1

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 CELL POTENTIAL AND COMPOSITION OF
UNIT 4
REACTION MIXTURE
SESSION 5

This is blank sheet for your short note on:

• Issues that are not clear: and
• Difficult topics if any

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ELECTROCHEMISTRY
UNIT 4
SESSION 6

SESSION 6: STANDARD CELL POTENTIAL AND

EQUILIBRIUM CONSTANT
Hello and welcome to session 3 of unit 4.This session will also focus
attention on standard cell potential and equilibrium. Corrosion and
mechanisms of rust will further be looked at.

Objectives
By the end of reading this session you would be able to:
(a) Deduce the equation that relates standard cell potential to equilibrium constant
(b) Define the term, corrosion
(c) Explain the mechanism of rust

Now read on…

Standard free energy change for a reaction is related to the standard cell potential.

∆G° = −nFE ° (1)

Also ∆G° = − RT ln K (2)

Combining these two equations (1) and (2)

⇒ −nFE ° = − RT ln K

RT ln K 2.303RT
⇒ E° = = log K
nF nF
0.0592
⇒ E° = log K at 25°C
n

6.1 Corrosion
Corrosion is the Oxidative deterioration of a metal such as the conversion of Iron to
Rust, a hydrated Iron (lll) oxide of composition of Fe 2O3 . H 2O (Approximation).

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 STANDARD CELL POTENTIAL AND
UNIT 4 EQUILIBRIUM CONSTANT
SESSION 6

Mechanism of Rust:

Fig. 6: An electrochemical mechanism for corrosion of Iron.

The metal and a surface water droplet constitute a tiny galvanic cell in which Iron is
oxidized to Fe22 + in a region of the surface (Anode Region) far off from atmospheric
oxygen and the oxygen is reduced near the edge of the droplet at another region of the
surface (cathode Region). Dissolved oxygen from the atmosphere oxidizes Fe22 + further
to Fe32 + before it is deposited as rust. The actual potential for the reduction is less than
the standard potential [1.2303V]. This is because the water droplet is not 1M in H +
concentration [In fact the water is only slightly acidic because the main source of H +
ion is the reaction of water with dissolved atmosphere CO2 ].

Even at pH = 7, the potential for the reduction half reaction is 0.81V, which means that
the cell potential is highly positive, and indication of a spontaneous reaction.

6.2 Prevention of Corrosion

Corrosion of Iron metal can be prevented or minimized by shielding the iron surface
from moisture or Oxygen. A cost of paint is effective for a while, but nest begins to
form as soon as it scratched off. Metals such as chromium, Tin and Zinc afford a more
durable surface coating for Iron by a process called GALVANIZING.

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ELECTROCHEMISTRY
UNIT 4
SESSION 6

Fig. 7: Surface coating for Iron

A layer of zinc protects iron from oxidation, even when the zinc layer becomes
scratched. The zinc (Anode), iron (cathode), H 2O droplet constitute the tiny galvanic
cell.

Oxygen is reduced at the cathode and zinc is being oxidized at the Anode. Thus,
protecting the iron from oxidation.

+ −
Fe2( aq ) + 2e → Fu ( s ) , E ° = −0.45V

Z n2(+aq ) + 2e − → Z u ( s ) , E1o = −0.76V

As a potential indicates, zinc is oxidized more easily than iron and therefore when the
metal is oxidized, zinc is oxidized instead of iron.

Any recipient oxidation of iron will be reversed immediately because zinc can reduce
2+
Fe(aq ) to Fe(s ) .

1. Oxidation of Z n , Reduction of Fe
Fe 2+ + 2e − → Fe( s ) E ° = −0.45V

2. Oxidation of Fe , Reduction of Z n
Fe2( +s ) → Fe2+ + 2e − E ° = +0.45V

Z n2 + + 2e − → Z u ( s ) , E1 = −0.76V
2+ 2+
Fe2 + + Z n → Fe + Z n ( s ) E ° = −0.31V

⇒ Reaction is unlikely to occur.

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 STANDARD CELL POTENTIAL AND
UNIT 4 EQUILIBRIUM CONSTANT
SESSION 6

Self-Assessment Questions
Exercise 4.6
(a) Define oxidation in terms of electron transfer.

(b) What is the oxidation number of iodine in IO 3 ‾ ?

(c) What is the algebraic sum of the oxidation numbers of all the atoms in aluminium
sulphate, Al 2 (SO 4 ) 3 ?

(d) Will a reaction take place if a strip of zinc metal is placed in a solution of lead (II)
sulfate? Justify your answer

(e) Calculate for the following equation:

3Br 2(l) + 2Cr3+ (aq) + 7H 2 O (l) → Cr 2 O 7 2- (aq) + 14H+ (aq) + 6Br‾ (aq)
Decide whether the equation represents a spontaneous or a nonspontaneous reaction
at standard conditions.

(f) Distinguish between a primary cell and a secondary cell and give an example of
each.

(g) Explain why aluminum metal does not corrode as rapidly as a less active metal such
as iron.

(h) Explain why many new cars have galvanized body parts?

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UNIT 1: SESSION 1

At x = 1, y = 14 = 1

At x = (1+Δx), y = (1+Δx)4

We can expand (1+Δx)4 to 1 + 4Δx + 6(Δx)2 + 4(Δx)3+ (Δx)4, and we get:

y = 1 + 4Δx + 6(Δx)2 + 4(Δx)3+ (Δx)4

And the difference between the y values from x = 1 to x = 1+Δx is:

Change in y = (1+ 4Δx + 6(Δx)2 + 4(Δx)3+ (Δx)4)- 1 = 4Δx + 6(Δx)2 + 4(Δx)3+ (Δx)4

Now we can calculate slope:

4Δx + 6(Δx)2 + 4(Δx)3+ (Δx)4

Slope = = 4 + 6(Δx) + 4(Δx)2+ (Δx)3
Δx

Once again, as Δx shrinks towards zero we are left with:

Slope = 4

UNIT 1, SESSION 2

UNIT 1, SESSION 3

UNIT 1, SESSION 4

UNIT 1, SESSION 5

UNIT 1, SESSION 6

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UNIT2, SESSION 1
Refer to notes
UNIT 2, SESSION 2
(1) Given P = 5 atm, V i = 12.0L and V f = 14.5L
∆V = V f − V i = (14.5 − 12.0)L = 2.5L
W = − P∆V
W = − (5atm x 2.5L) = − 12.5J
W = − 1.25 x 10-2kJ

(2) Given P = 44 atm, V i = 8.6L and V f = 4.3L

∆V = V f − V i = (4.3 − 8.6)L = − 4.6L
W = − P∆V
W = − (44atm x − 4.6L) = 202.4J
W = 2.024 x 10-1kJ
(i) Work is done on the system. Therefore, the work energy flow is in the direction
of the external pressure.

(ii) The sign of the energy flow is positive (+)

UNIT2, SESSION 3
Refer to notes and other literature.

UNIT 2, SESSION 4
(1) q = (mass) (Δt) (C p )
Δt = 80.0 °C, the mass = 27.0 g, C p = 4.184 J g¯1 °C¯1
q = (27.0 g) (80.0 °C) (4.184 J g¯1 °C¯1)
q = 9037.44J

(2) -q HOT = q COLD

-(M HOT C H2O ΔT HOT ) = (M COLD C H2O ΔT COLD ), but C H2O cancels out

-(150.0g)(T f − 90.0°C) = (100.0g)(T f − 30.0°C),

T f = 66.0°C
NB: The density of water is 1.00g/mL => 1.00mL = 1.00g

(3) multiply (a) by 2; maintain (b) and reverse (c)

(a) becomes: 2 H 2 (g) + O 2 (g) 2 H 2 O(l), ∆H  = (-285.8 x 2)kJ

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 ANSWERS TO SELF-ASSESSMENT QUESTIONS

(b) remains: C 3 H 4 (g) + 4 O 2 (g) 3 CO 2 (g) + 2 H 2 O(l), ∆H  = -1937 kJ

(c) becomes: 3 CO 2 (g) + 4 H 2 O (l) C 3 H 8 (g) + 5 O 2 (g), ∆H  =
22191.1kJ
cancelling out all like-terms and summing-up all ∆H  gives the overall equation:

C 3 H 4 (g) + 2 H 2 (g) C 3 H 8 (g), and ∆H  = − 289.5 kJ

UNIT 2, SESSION 5
(1) The decomposition of ammonium dichromate has a standard enthalpy change of
−315kJ/mol. So you have a figure that relates the heat to moles. You need to
find out how many moles correspond to 53.0 g of the ammonium dichromate.
We use molar mass for this.
Molar mass(M) for (NH 4 ) 2 Cr 2 O 7 = 252.06gmol-1

Mass(g)/M(gmol-1) = moles (n)

⇓
53.0g/252.06gmol = 0.21mol
So far so good. Our figure of enthalpy change is per mole, thus you simply multiply the
two:
kJmol-1 x mol=kJ
⇓
Θ
ΔH = −315kJmol x 0.21mol = −66.15kJ
-1

(2) To solve this exercise you need to apply Hess' law:

ΔHΘreaction = ∑ΔHΘ f (products) − ∑ΔHΘ f (reactants)

But ΔHΘ f (H 2 )=0kJmol-1.

We now use Hess' law. We have the enthalpy of the reaction, and we have the formation
enthalpies of the reactants. So we rearrange the equation to find the formation enthalpy
for the single product.
ΔHΘreaction = ΔHΘ f (ethane) − ΔHΘ f (ethene)
⇓
ΔHΘ f (ethane) = ΔHΘreaction + ΔHΘ f (ethene)

ΔHΘ f (ethane) = −137kJmol + 53.3kJmol = −83.7kJmol

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UNIT 2, SESSION 6

We begin by writing the equation that represents this reaction. Recall that "complete
combustion," or burning, is a reaction with oxygen from the atmosphere, forming
carbon dioxide and water:

CH 4 (g) + 2 O 2 (g) → CO 2 (g) + 2 H 2 O(l)

ΔG° = (1 mol)[ΔG f ° for CO2(g)] + (2 mol)[ΔG f ° for H2O(l)] – (1 mol)[ΔG f ° for

CH4(g)]

– (2 mol)[ΔG f ° for O2(g)] =(1 mol) (–394.4 kJ/mol) + (2 mol) (–237.0 kJ/mol) – (1
mol)

(–50.8 kJ/mol) – (2 mol) (0) = –817.6 kJ

The negative value of ΔG° indicates that the reaction is spontaneous. This matches our
experiences in everyday life, where we have seen that natural gas burns spontaneously.

UNIT 3, SESSION 1
1. E 2. D 3. C 4. D 5. D 6. B 7. E

UNIT 3, SESSION 2
1. C 2. A 3. D 4. B 5. B 6. C 7. E 8. B

UNIT 3, SESSION 3
(a) We can calculate K from any two data points
(- Kt)
The integrated rate law for 1st order is [A] = [A] o

Using the point when t = 1

0.0905 = 0.100(- K* 1)
Applying ‘ln’ to both sides gives,

-K = ln (0.0905/0.100)
= ln(0.905)
K = 0.0998 min-1 ≈ 0.100 min-1 OR

Using the point when t = 2

0.0819 = 0.100 (-K * 2)

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 ANSWERS TO SELF-ASSESSMENT QUESTIONS

- 2K = ln (0.0819/0.100)
= ln (0.819)
= -0.200
K= 0.100 min-1

(b) half-life * K = ln 2

t 1 * 0.1= 0.693
2

t 1 = 0.693 / 0.1 = 6.93 min

2

(c) When t = 5 min

[A] = 0.100(-0.100 *5)
= 0.100(-0.5)
[A] = 3.162M

(d) Calculate the time t when [A] = 0.0500

0.0500 = 0.100(-0.100 t)
0.100 * t = ln (0.100/0.0500)
t = 6.93 min

(e) When [A] is reduced by 90%, we have [A] o = 100% = 1.0 and [A] = 10% = 0.1
0.1 =1.0(-0.100 * t)
0.100 * t = ln (10)
t = 2.303/0.100 = 23.03 min

UNIT 3, SESSION 4
(1) The reaction takes place on the surface of the metal. Aluminium powder will
have a huge surface area compared with the foil, and so there will be far more
hydrogen ions hitting the aluminium every second, and therefore a much faster
reaction with the powder.

(2) Refer to notes

UNIT3, SESSION 5
(a) (i) We can determine the activation energy for a reaction from a plot of the
natural log of the rate constants(InK) versus the reciprocal of the absolute

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 ANSWERS TO SELF-ASSESSMENT QUESTIONS

temperature(1/T). We therefore start by calculating 1/T and the natural

logarithm of the rate constants(InK)
(ii) Construct a straight line graph of InK against 1/T and equate the slope (the value
is negative) of the graph to –Ea/R. Using R=8.314Jmol-1K-1, compute the value of
Ea.

(b) Use the T values (T 1 and T 2 ) given to determine their respective K values (K 1
K  E 1 1
and K 2 ) and use the formula ln  2  = − a  −  to determine Ea.
 K1  R  T2 T1 
(c) Similar approach to (b)

(d) Refer to notes

NB: Temperature should be converted to Kelvin(K) before use.

UNIT 3, SESSION 6
Refer to notes

UNIT4 SESSION 1
(1) Refer to notes for both (a) and (b)
(2) The overall equation: 2Ag (s) + Cu2+ (aq) => 2Ag+ (aq) + Cu (s)

UNIT4 SESSION 2
Refer to notes

UNIT4 SESSION 3
(1) Right
Reasons: Oxidation takes place in the left hand cell (anode) and Reduction at
the right hand cell or cathode.
(2) B.

UNIT4 SESSION 4
Consider...
Cl 2 + 2 e => 2 Cl- . . .E° = 1.36
H 2 => 2 H+ + 2 e . . . E° = 0.00
----------------------------------
Cl 2 + H 2 => 2 HCl . . . ∆E° = 1.36 V

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 ANSWERS TO SELF-ASSESSMENT QUESTIONS

The potential is positive therefore, the reaction is spontaneous.

UNIT 4, SESSION 5
[Answer ⇒ E = 0.88V ]

UNIT 4, SESSION 6
(1) (a) Oxidation is the process in which an atom or ion loses electrons.
(b) +5
(c) Zero
(d) Oxidation half-reaction: Zn → Zn2+ + 2e‾ Eo = +0.76v
Reduction half-reaction: Pb + 2e‾ → Pb
2+
Eo = -0.13v
Overall reaction: Zn + Pb2+ → Zn2+ + Pb Eo = +0.63v
(e) Reduction half-reaction: 3Br 2(l) + 6e‾ → 6Br‾ (aq) Eo =
+1.06v
Oxidation half-reaction: 2Cr3+ (aq) → Cr 2 O 7 2‾ (aq) +14H+ (aq) +6e‾ Eo =-
1.33v
Overall reaction: 3Br 2(l) +2Cr3+ (aq) → 6Br‾ (aq) +Cr 2 O 7 2‾ (aq) +14H+ (aq) Eo =-
0.27v

(f) A primary cell cannot be recharged while a secondary cell can be recharged. The
1.5-V dry cell is an example of a primary cell and the nickel-cadmium cell is an
example of a secondary cell.

(g) Aluminum metal does not corrode as rapidly as iron because the aluminum
forms a protective layer of aluminum oxide which adheres tightly to the surface
of the metal. This prevents corrosion by effectively sealing any exposed
surfaces. Iron oxide is porous and thus allows the passage of O 2(g) and H 2 O (l).

(h) One way to protect iron from rusting is to coat it with zinc. Iron so treated is
called galvanized iron. If the zinc coating is scratched, the zinc will corrode
rather than the iron since zinc is a more reactive metal than iron. Galvanized
parts of a car are thus protected from excessive corrosion.

126 CoDEUCC/Diploma in Maths and Science Education

 REFERENCES

Truhlar, D. G.; Garrett, B. C.; Klippenstein, S. J. (1996). "Current Status of Transition-

State Theory". J. Phys. Chem. 100 (31): 12771–12800.
Laidler, K.; King, C. (1983). "Development of transition-state theory". J. Phys. Chem.
87 (15): 2657.
Laidler, K.; King, C. (1998). "A lifetime of transition-state theory". The Chemical
Intelligencer 4 (3): 39.
Laidler, K. J. (1969). Theories of Chemical Reaction Rates. McGraw-Hill.
Anslyn, E. V.; Dougherty, D. A. (2006). "Transition State Theory and Related Topics".
Modern Physical Organic Chemistry. University Science Books. pp. 365–373.
Eyring, H. (1935). "The Activated Complex in Chemical Reactions". J. Chem. Phys. 3
(2): 107–115.
Masel, R. (1996). Principles of Adsorption and Reactions on Solid Surfaces. New York:
Wiley.
Pineda, J. R.; Schwartz, S. D. (2006). "Protein dynamics and catalysis: The problems
of transition state theory and the subtlety of dynamic control". Phil. Trans. R. Soc. B
361 (1472): 1433–1438.

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