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Originally published in 1970, this book gives a comprehensive account of the properties of ice, the connections between them and the way in which they derive from the structure of the water molecule and the small mass of the proton. The properties are discussed in terms of quantum mechanics and solid state theory with emphasis on physical principles rather than on theoretical models. The book is intended as an exemplification of the principles of chemical physics for beginning graduate students in physics of physical chemistry and as a text and reference book on the properties of ice for research workers in glaciology, cloud physics, meteorology and associated fields. Although the author assumes a familiarity with fundamental physics, he has taken some trouble to make his account self-contained by reference to the underlying principles in every case or by more detailed discussion where the application is not a standard one.
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CAMBRIDGE MONOGRAPHS ON PHYSICS GENERAL EDITORS A. HERZENBERG, P H . D . Reader in Theoretical Physics in the University of Manchester M- M. WOOLFSON, D.Sc. Professor of Theoretical Physics in the University of York J. M. ZIMAN, D.PHIL., F.R.S. Professor of Theoretical Physics in the University of Bristol THE CHEMICAL PHYSICS OF ICE THE CHEMICAL PHYSICS OF ICE N. H. FLETCHER Professor of Physics in the University of New England Armidaley New South Wales CAMBRIDGE AT THE UNIVERSITY PRESS 1970 CAMBRIDGE UNIVERSITY PRESS Cambridge, New York, Melbourne, Madrid, Cape Town, Singapore, Sao Paulo, Delhi Cambridge University Press The Edinburgh Building, Cambridge CB2 8RU, UK Published in the United States of America by Cambridge University Press, New York www.cambridge.org Information on this title: www.cambridge.org/9780521112307 © Cambridge University Press 1970 This publication is in copyright. Subject to statutory exception and to the provisions of relevant collective licensing agreements, no reproduction of any part may take place without the written permission of Cambridge University Press. First published 1970 This digitally printed version 2009 A catalogue record for this publication is available from the British Library Library of Congress Catalogue Card Number: 74-75825 ISBN 978-0-521-07597-8 hardback ISBN 978-0-521-11230-7 paperback CONTENTS Page Preface Note on Units ix xi CHAPTER I 1.1 1.2 1.3 1.4 The water molecule Electronic structure Molecular vibrations Spectral properties Forces between molecules i 13 15 18 CHAPTER 2 2.1 2.2 2.3 2.4 Structure and energy of ordinary ice Crystal structure of Ice I h Proton positions in ice Residual entropy associated with proton disorder Hydrogen bonding and cohesive energy 23 28 34 38 CHAPTER 3 3- 1 Other forms of ice The phase diagram of ice 3-2 3-3 Ice Ic 3-7 3-8 Ice VI Vitreous ice 3 4 Ice II 3-5 Ice III and Ice IX 3-6 Ice IV and Ice V Ice VII and Ice VIII 5° 57 60 60 64 66 68 70 VI CONTENTS CHAPTER 4 Liquid water and freezing 4.1 Experimental information on water structure page 73 4.2 Structural models 76 4.3 4.4 Homogeneous nucleation of freezing Heterogeneous nucleation 85 97 CHAPTER 5 Crystal growth 5.1 5.2 5.3 Basic theory Freezing of water Growth from the vapour 104 111 119 CHAPTER 6 Thermal properties and lattice dynamics 6.1 Thermal expansion 130 6.2 6.3 Heat capacity and lattice vibration spectrum Thermal conductivity 134 143 CHAPTER 7 Point defects 7.1 7.2 7.3 7.4