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Thermochemical Processes
Principles and Models
Thermochemical Processes
Principles and Models
C.B. Alcock DSc, FRSC
OXFORD AUCKLAND BOSTON JOHANNESBURG MELBOURNE NEWDELHI
Butterworth-Heinemann
Linacre House, Jordan Hill, Oxford OX2 8DP 225 Wildwood Avenue, Woburn, MA 01801-2041
A division of Reed Educational and Professional Publishing Ltd
First published 2001
C.B. Alcock 2001
All rights reserved. No part of this publication
may be reproduced in any material form (including photocopying or storing in any medium by electronic means and whether or not transiently or incidentally to some other use of this publication) without the written permission of the copyright holder except
in accordance with the provisions of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London, England W1P 9HE. Applications for the copyright holder’s written permission
to reproduce any part of this publication should be addressed to the publishers
British Library Cataloguing in Publication Data Alcock, C. B.
Thermochemical processes:principles and models
1 Thermodynamics 2 Chemical processes 3 Materials at high temperatures
I Title 660.20969
Library of Congress Cataloguing in Publication Data Alcock, C. B.
Thermochemical processes:principles and models/C.B. Alcock. p. cm.
Includes bibliographical references. ISBN 0 7506 5155 5
1 Thermodynamics 2 Chemical processes 3 Materials at high temperatures I Title
TP155.2.T45 T47 2000
6600.2969–dc21 00-049367
ISBN 0 7506 5155 5
Typeset by Laser Words, Chennai, India Printed in Great Britain
Contents
Preface xi
Part 1: Processes with gaseous reaction control 1
1 Vapour deposition processes 3
Vapour deposition for the preparation of thin films 3 Vapour pressure data for the elements 4
The kinetic theory of a gas in a container 4 Molecular effusion 6
Vapour deposition of elements 6
The deposition rate on a cool substrate 8 Vapour deposition of alloys 8
Vapour deposition of compounds 10
Free evaporation coefficients of solids 11
Other techniques for the preparation of thin films 16
Single and epitaxial films in semiconducting systems 16 Thin film production by the sputtering of metals 17
The production of nanoparticles 20 Coating with thin diamond films 22
Plasma evaporation and pyrolysis of carbon to form Fullerenes 23 Materials science and the formation of thin films 24
The formation of nuclei from the vapour phase 24 The formation of a film from nuclei 28
Grain growth in the initial deposit 30 Point defects in solids 31
Edge and screw dislocations 33 Interfacial energies in solid systems 35
Bibliography 38
Appendix: Vapour pressure data for the elements 38
2 Gaseous reaction kinetics and molecular decomposition 42 Theories of reaction kinetics 42
Thermal energies and the structures of molecules 43 The collision theory of gaseous reactions 45 Transition state theory of gaseous reactions 47 Empirical estimates of the activation energy 49
The order of chemical reactions 50
vi Contents
Time dependence of the extent of reaction 52 Chain reactions 52
Combustion chain reactions 53
Chain reactions in the combustion of gaseous fuels 56 Fuel/air mixing in combustion systems 58
The thermal efficiencies of combustion engines 59 Bibliography 62
Molecular dissociation and chain reactions in chemical vapour deposition 62 Thermochemical data for the dissociation of gaseous molecules 63
Bond character in gaseous heteronuclear compounds 64 Hybridization of covalent bonds 66
Bond energies of gaseous polyvalent metal halides 67
Thermal decomposition of hydrides and organometallic compounds 68 Bibliography 71
Radiation and electron decomposition of molecules 72 Photochemical reactions 73
Dissociation cross-sections 75
Substrate heating by transmitted radiation 77 Radiation and convection cooling of the substrate 82 Laser production of thin films 82
Molecular decomposition in plasma systems 84 Bibliography 85
3 Vapour phase transport processes 86 Vapour transport processes 86
Thermodynamics and the optimization of vapour phase transport 86 The direction of vapour transport across a thermal gradient 89
The choice of halogen in transport reactions 91
The vapour phase refining and separation of metals 91
The thermodynamics of the vapour phase transport of compounds 93 Multicomponent thermodynamics in gaseous systems 95 Sintering by vapour phase transport 99
Grain growth by vapour phase transport 100 Vapour transport in flowing systems 102 Transport along a thermal gradient 102 Mass transport across a flowing gas 103 Material deposition from a flowing gas 106
Transport and thermal properties of gases 108 Equations of state for ideal and real gases 112
Molecular interactions and the properties of real gases 114 Bibliography 117
4 Heterogeneous gas–solid surface reactions 118 The zeroth order reaction 118
Adsorption of gases on solids 119
Surface structures of catalytic materials 124 Adsorption and the surface energies of metals 125
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