MACMILLAN COLLEGE WORK OUT SERIES

Heat and
Thermodynamics
Titles in this Series

Dynamics Heat and Thermodynamics

Electric Circuits Mathematics for Economists
Electromagnetic Fields Molecular Genetics
Electronics Operational Research
Elements of Banking Organic Chemistry
Engineering Materials Physical Chemistry
Engineering Thermodynamics Structural Mechanics
Fluid Mechanics Waves and Optics
MACMILLAN COLLEGE WORK OUT SERIES

Heat
and
Thermodynamics
Michael Sprackling

M
150th YEAR

MACMILLAN
© Michael Sprackling 1993
All rights reserved. No reproduction, copy or transmission of
this publication may be made without written permission.
No paragraph of this publication may be reproduced, copied or
transmitted save with written permission or in accordance with
the provisions of the Copyright, Designs and Patents Act 1988,
or under the terms of any licence permitting limited copying
issued by the Copyright Licensing Agency, 90 Tottenham Court
Road, London W1P 9HE.

Any person who does any unauthorised act in relation to this

publication may be liable to criminal prosecution and civil
claims for damages.
First published 1993 by
THE MACMILLAN PRESS LTD
Houndmills, Basingstoke, Hampshire RG21 2XS
and London
Companies and representatives
throughout the world

ISBN 978-0-333-56513-1 ISBN 978-1-349-12690-3 (eBook)

DOI 10.1007/978-1-349-12690-3
A catalogue record for this book is available
from the British Library
Contents

Preface viii

1 Basic Concepts in Thermodynamics

1.1 Introduction 1
1.2 Some Definitions 1
1.3 The First Stages in Problem-Solving With Closed Systems 3
1.4 Worked Example 4

2 Work
2.1 Definition of Work 5
2.2 Problem-Solving 6
2.3 Electrical Work 6
2.4 Worked Examples on Electrical Work 6
2.5 Work to Change the Volume of a Closed Hydrostatic System 8
2.6 Worked Examples on Pressure-Volume Work 8
2.7 Work to Change the Length of an Elastic Rod 12
2.8 Worked Examples on Work and Elastic Deformation 12
2.9 Exercises 14

3 Gases and the Ideal Gas Scale of Temperature

3.1 Boyle's Law 15
3.2 Ideal Gases 16
3.3 Problem-Solving 16
3.4 Worked Examples on Boyle's Law 16
3.5 The Ideal Gas Scale of Temperature and the Ideal Gas Equation 20
3.6 Worked Examples on the Ideal Gas Equation 21
3. 7 Exercises 25

4 The First Law of Thermodynamics

4.1 Internal Energy 26
4.2 The First Law of Thermodynamics 27
4.3 Problem-Solving 27
4.4 Worked Examples on the First Law of Thermodynamics 27
4.5 Reversible Processes 29
4.6 Worked Examples on Reversible Processes 30
4. 7 Heat Capacities 31
4.8 Worked Examples on Heat Capacities 33
4.9 Exercises 42

5 The Second Law of Thermodynamics

5.1 The Clausius Statement of the Second Law 43
5.2 Heat Engines 43
5.3 Worked Examples on Heat Engines 44
5.4 Kelvin's Statement of The Second Law 48

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 5.5 Carnot's Theorem and its Corollary 48
5.6 Universal Temperatures 49
5.7 Thermodynamic Temperature 49
5.8 Worked Examples on Heat Engines and Thermodynamic Temperature 50
5.9 Celsius Temperature 53
5.10 Problem-Solving 53
5.11 Worked Examples on Heat Engines and the Second Law of Thermodynamics 53
5 .12 Exercises 60

6 Entropy
6.1 The Inequality of Clausius 61
6.2 Entropy 61
6.3 Worked Examples on Entropy 62
6.4 Entropy and Work 66
6.5 Worked Examples on Entropy and Work 67
6.6 The Entropy Form of the First Law 68
6.7 Worked Examples on the Entropy Form of the First Law 69
6.8 Entropy and Irreversible Processes 71
6.9 Worked Examples on the Law of the Increase of Entropy 71
6.10 Maxwell's Relations 75
6.11 Some Useful Mathematical Relations 75
6.12 Problem-Solving 75
6.13 Worked Examples on Entropy 76
6.14 Exercises 81

7 Thermodynamic Potential Functions

7.1 The Helmholtz Function (Helmholtz Free Energy) 82
7.2 Worked Examples on the Helmholtz Function 83
7.3 The Gibbs Function (Gibbs Free Energy) 86
7.4 Worked Examples on the Gibbs Function 87
7.5 Useful Work and Availability 90
7.6 Worked Examples on Availability 91
7. 7 Exercises 100

8 Some Simple Thermodynamic Systems

8.1 Closed Hydrostatic Systems 101
8.2 Worked Examples on Closed Hydrostatic Systems 102
8.3 Ideal Gases 111
8.4 Worked Examples on Ideal Gases 112
8.5 Perfectly Elastic Solids 119
8.6 Worked Examples on Perfectly Elastic Solids 120
8.7 Voltaic Cells 126
8.8 Worked Example on Voltaic Cells 127
8.9 Exercises 128

9 Heat Capacities and Equations of State

9.1 Introduction 130
9.2 Heat Capacities 130
9.3 Worked Examples on Heat Capacities 131
9.4 Equations of State 139
9.5 Worked Examples on Equations of State 141
9.6 Exercises 145

10 Phase Changes
10.1 The Enthalpy of a Phase Change (Latent Heat) 147
10.2 Worked Examples on the Enthalpy of a Phase Change 148
10.3 The Clapeyron-Clausius Equation 153
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 10.4 Worked Examples on the Clapeyron-Clausius Equation 154
10.5 The Equation of Clausius 157
10.6 Worked Example on the Equation of Clausius 158
10.7 Exercises 159

11 The Third Law of Thermodynamics

11.1 The Third Law of Thermodynamics 161
11.2 Worked Examples on the Third Law 161
11.3 Planck's and Simon's Versions of the Third Law 164
11.4 Worked Example on Absolute Entropy 165
11.5 Allotropic Transformations 165
11.6 Worked Example on Allotropic Transformations 166
11.7 Exercises 167

12 Irreversible Processes
12.1 Irreversible Processes and Thermodynamics 168
12.2 The Joule Process 168
12.3 Worked Examples on the Joule Process 169
12.4 The Joule-Thomson Process 173
12.5 Worked Examples on the Joule-Thomson Process 174
12.6 Exercises 182

13 A Simple Kinetic Theory of Gases

13.1 A Simple Kinetic Theory of Gases 183
13.2 Worked Examples on a Kinetic Theory of Gases 185
13.3 Exercises 190

14 Heat Transfer
14.1 Introduction 191
14.2 Heat Conduction 191
14.3 A General Approach to Solving Heat Conduction Problems 192
14.4 Worked Examples on Heat Conduction 193
14.5 Heat Convection 197
14.6 Worked Examples on Heat Convection 198
14.7 Thermal Radiation 202
14.8 Worked Examples on Thermal Radiation 204
14.9 Exercises 208

Recommended Reading 210

Index 211

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 Preface

Thermodynamics is one of the major subjects of classical phenomenological physics, a

subject of great power and beauty. Nevertheless, it is, for many students, a difficult
subject and one that they do not understand on a first (and often, only) reading. To them
the subject seems to be a collection of subtle concepts, linked by countless equations with
no underlying framework.
Despite its forbidding nature, thermodynamics is a subject with a wide range of
applications and is a vital component in the education of physical scientists. However,
the lack of understanding so often encountered leaves the student with a gap between
wanting to able to use the theory and being able to do so. One way of promoting
understanding and bridging this gap is through problem-based learning. The aim of this
approach is to make students 'doers of the word, not hearers only' by providing detailed
solutions to a carefully selected range of problems, showing how principles and concepts
may be applied to particular situations, and then offering the student situations that differ
slightly but which can be tackled by an extension of the approaches that have been used
in the solved problems.
Learning how to use the theory of thermodynamics through problem-solving is the
approach followed in this book, which is aimed at undergraduates in the physical sciences
and in engineering taking a first course in thermodynamics or thermal physics. The book
starts with a summary of the important basic concepts in thermodynamics and establishes
the basic vocabulary and outlook. The core topics in classical thermodynamics are then
examined in a series of chapters that include a brief introduction to each topic, where
important results are stated and, sometimes, derived, followed by a number of examples
worked out in detail.
One of the powerful features of classical thermodynamics is that it provides rela-
tionships between the properties of a system. Consequently, only a small number of
properties need to be 'explained' at the atomic level. In the simplest treatments this is
done under the heading of kinetic theory and this book contains a chapter on a simple
kinetic theory of gases. Also important is the rate of energy transfer between a system
and its surroundings, so the final chapter deals with the very practical topic of heat
transfer.
The book assumes a knowledge of elementary calculus, including partial differentia-
tion, and SI units are used throughout.

Michael Sprackling
January 1993

viii