Advanced Thermodynamics
for Engineers
Desmond E Winterbone
FEng, BSc, PhD, DSc, FIMechE, MSAE
Thermodynamics and Fluid Mechanics Division
Department of Mechanical Engineering
UMIST
A member of the Hodder Headline Group
LONDON SYDNEY AUCKLAND
Copublished in North, Central and South America by
John Wiley & Sons,he., New York Toronto
,First published in Great Britain 1997 by Arnold,
a member of the Hodder Headline Group,
338 Euston Road, London NW1 3BH
Copublished in North, Central and South America by
John Wiley & Sons, Inc., 605 Third Avenue,
New York, NY 10158-0012
0 1997 D E Winterbone
All rights reserved. No part of this publication may be reproduced or
transmitted in any form or by any means, electronically or mechanically,
including photocopying, recording or any information storage or retrieval
system, without either prior permission in writing from the publisher or a
licence permitting restricted copying. In the United Kingdom such licences
are issued by the Copyright Licensing Agency: 90 Tottenham Court Road,
London WIP 9HE.
Whilst the advice and information in this book is believed to be true and
accurate at the date of going to press, neither the author nor the publisher
can accept any legal responsibility or liability for any errors or omissions
that may be made.
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
Library of Congress Cataloging-in-PublicationData
A catalog record for this book is available from the Library of Congress
ISBN 0 340 67699 X (pb) 0 470 23718 X (Wiley)
Typeset in 10/12 pt Times by Mathematical Composition Setters Ltd, Salisbury, Wilts
Printed and bound in Great Britain by J W Anowsmith Ltd, Bristol
, Contents
Preface ix
...
Xlll
structure
Symbols xv
1 State of Equilibrium 1
1.1 Equilibrium of a thermodynamic system 2
1.2 Helmholtz energy (Helmholtz function) 5
1.3 Gibbs energy (Gibbs function) 6
1.4 The use and significance of the Helmholtz and Gibbs energies 6
1.5 Concluding remarks 9
Problems 10
2 Availability and Exergy 13
2.1 Displacement work 13
2.2 Availability 14
2.3 Examples 15
2.4 Available and non-available energy 21
2.5 Irreversibility 21
2.6 Graphical representation of available energy and irreversibility 25
2.7 Availability balance for a closed system 27
2.8 Availability balance for an open system 34
2.9 Exergy 36
2.10 The variation of flow exergy for a perfect gas 42
2.1 1 Concluding remarks 43
Problems 43
3 Pinch Technology 47
3.1 A heat transfer network without a pinch problem 49
3.2 A heat transfer network with a pinch point 56
3.3 Concluding remarks 60
Problems 61
, vi Contents
4 Rational Efficiency of a Powerplant 64
4.1 The influence of fuel properties on thermal efficiency 64
4.2 Rational efficiency 65
4.3 Rankinecycle 69
4.4 Examples 71
4.5 Concluding remarks 82
Problems 82
5 Efficiency of Heat Engines at Maximum Power 85
5.1 Efficiency of an internally reversible heat engine when producing maximum
power output 85
5.2 Efficiency of combined cycle internally reversible heat engines when
producing maximum power output 92
5.3 Concluding remarks 96
Problems 96
6 General Thermodynamic Relationships (single component
systems, or systems of constant composition 1 100
6.1 The Maxwell relationships 100
6.2 Uses of the thermodynamicrelationships 104
6.3 Tdr relationships 108
6.4 Relationships between specific heat capacities 111
6.5 The Clausius-Clapeyron equation 115
6.6 Concluding remarks 118
Problems 118
7 Equations of State 121
7.1 Ideal gas law 121
7.2 Van der Waals’equation of state 123
7.3 Law of corresponding states 125
7.4 Isotherms or isobars in the two-phase region 129
7.5 Concluding remarks 131
Problems 132
8 Liquefaction of Gases 135
8.1 Liquefaction by cooling - method (i) 135
8.2 Liquefaction by expansion - method (ii) 140
8.3 The Joule-Thomson effect 141
8.4 Linde liquefaction plant 148
8.5 Inversion point on p-v-T surface for water 150
8.6 Concludingremarks 155
Problems 155
9 Thermodynamic Properties of Ideal Gases and Ideal Gas
Mixtures of Constant Composition 158
9.1 Molecular weights 158
for Engineers
Desmond E Winterbone
FEng, BSc, PhD, DSc, FIMechE, MSAE
Thermodynamics and Fluid Mechanics Division
Department of Mechanical Engineering
UMIST
A member of the Hodder Headline Group
LONDON SYDNEY AUCKLAND
Copublished in North, Central and South America by
John Wiley & Sons,he., New York Toronto
,First published in Great Britain 1997 by Arnold,
a member of the Hodder Headline Group,
338 Euston Road, London NW1 3BH
Copublished in North, Central and South America by
John Wiley & Sons, Inc., 605 Third Avenue,
New York, NY 10158-0012
0 1997 D E Winterbone
All rights reserved. No part of this publication may be reproduced or
transmitted in any form or by any means, electronically or mechanically,
including photocopying, recording or any information storage or retrieval
system, without either prior permission in writing from the publisher or a
licence permitting restricted copying. In the United Kingdom such licences
are issued by the Copyright Licensing Agency: 90 Tottenham Court Road,
London WIP 9HE.
Whilst the advice and information in this book is believed to be true and
accurate at the date of going to press, neither the author nor the publisher
can accept any legal responsibility or liability for any errors or omissions
that may be made.
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
Library of Congress Cataloging-in-PublicationData
A catalog record for this book is available from the Library of Congress
ISBN 0 340 67699 X (pb) 0 470 23718 X (Wiley)
Typeset in 10/12 pt Times by Mathematical Composition Setters Ltd, Salisbury, Wilts
Printed and bound in Great Britain by J W Anowsmith Ltd, Bristol
, Contents
Preface ix
...
Xlll
structure
Symbols xv
1 State of Equilibrium 1
1.1 Equilibrium of a thermodynamic system 2
1.2 Helmholtz energy (Helmholtz function) 5
1.3 Gibbs energy (Gibbs function) 6
1.4 The use and significance of the Helmholtz and Gibbs energies 6
1.5 Concluding remarks 9
Problems 10
2 Availability and Exergy 13
2.1 Displacement work 13
2.2 Availability 14
2.3 Examples 15
2.4 Available and non-available energy 21
2.5 Irreversibility 21
2.6 Graphical representation of available energy and irreversibility 25
2.7 Availability balance for a closed system 27
2.8 Availability balance for an open system 34
2.9 Exergy 36
2.10 The variation of flow exergy for a perfect gas 42
2.1 1 Concluding remarks 43
Problems 43
3 Pinch Technology 47
3.1 A heat transfer network without a pinch problem 49
3.2 A heat transfer network with a pinch point 56
3.3 Concluding remarks 60
Problems 61
, vi Contents
4 Rational Efficiency of a Powerplant 64
4.1 The influence of fuel properties on thermal efficiency 64
4.2 Rational efficiency 65
4.3 Rankinecycle 69
4.4 Examples 71
4.5 Concluding remarks 82
Problems 82
5 Efficiency of Heat Engines at Maximum Power 85
5.1 Efficiency of an internally reversible heat engine when producing maximum
power output 85
5.2 Efficiency of combined cycle internally reversible heat engines when
producing maximum power output 92
5.3 Concluding remarks 96
Problems 96
6 General Thermodynamic Relationships (single component
systems, or systems of constant composition 1 100
6.1 The Maxwell relationships 100
6.2 Uses of the thermodynamicrelationships 104
6.3 Tdr relationships 108
6.4 Relationships between specific heat capacities 111
6.5 The Clausius-Clapeyron equation 115
6.6 Concluding remarks 118
Problems 118
7 Equations of State 121
7.1 Ideal gas law 121
7.2 Van der Waals’equation of state 123
7.3 Law of corresponding states 125
7.4 Isotherms or isobars in the two-phase region 129
7.5 Concluding remarks 131
Problems 132
8 Liquefaction of Gases 135
8.1 Liquefaction by cooling - method (i) 135
8.2 Liquefaction by expansion - method (ii) 140
8.3 The Joule-Thomson effect 141
8.4 Linde liquefaction plant 148
8.5 Inversion point on p-v-T surface for water 150
8.6 Concludingremarks 155
Problems 155
9 Thermodynamic Properties of Ideal Gases and Ideal Gas
Mixtures of Constant Composition 158
9.1 Molecular weights 158
