PHYSICAL CHEMISTRY OF ORGANIC SOLVENT SYSTEMS

PHYSICAL CHEMISTRY OF ORGANIC SOLVENT SYSTEMS

PHYSICAL CHEMISTRY OF ORGANIC SOLVENT SYSTEMS Edited by A. K. Covington and T. Dickinson Department of Physical Chemistry, University of Newcastle upon Tyne, Newcastle, England PLENUM PRESS LONDON AND NEW YORK 1973

Library of Congress Catalog Card Number: 72-77042 ISBN-13: 978-1-4684-1961-0 e-isbn-13: 978-1-4684-1959-7 DOl: 10.1007/978-1-4684-1959-7 Copyright 1973 by Plenum Publishing Company Ltd Plenum Publishing Company Ltd Davis House 8 Scrubs Lane Harlesden London NWlO 6SE Telephone 01-969 4727 U.S. Edition published by Plenum Publishing Corporation 227 West 17th Street New York, New York 10011 All Rights Reseverved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher

Preface We believe this to be the first monograph devoted to the physicochemical properties of solutions in organic solvent systems. Although there have been a number of books on the subject of non-aqueous solvents 1-4, they have been devoted, almost entirely, to inorganic solvents such as liquid ammonia, liquid sulphur dioxide, etc. A variety of new solvents such as dimethylformamide, dimethylsulphoxide and propylene carbonate have become commercially available over the last twenty years. Solutions in these solvents are of technological interest in connection with novel battery systems and chemical synthesis, while studies of ion solvation and transport properties have fostered academic interest. This monograph is primarily concerned with electrolytic solutions although discussion of non-electrolyte solutions has not been excluded. We have deliberately omitted consideration of the important area of solvent extraction, since this has been adequately covered elsewhere. Our contributors were asked to review and discuss their respective areas with particular reference to differences in technique necessitated by use of non-aqueous solvents while not reiterating facts well-known from experience with aqueous solutions. We have striven to build their contributions into a coherent and consistent whole. We thank our contributors for following our suggestions so ably and for their forebearance in the face of our editorial impositions. In including a substantial quantity of numerical results in the form of appendices, we hope that this monograph will become a handbook for all working in the field of organic systems. It will have served its purpose admirably if it achieves our intention of stimulating further progress, for its initiation arose out of our own difficulties of starting research activities in the area. We are grateful to Professor R. A. Robinson for compiling Table 1.3.1 and the other Appendices of Chapter 1, and for reading the whole of the text at the proof stage. We also wish to thank Miss Jennifer M. Thain for helping with the onerous task of preparing the index. Newcastle upon Tyne A. K. Covington T. Dickinson. 1. A. K. Holliday and A. G. Massey, Inorganic Chemistry in Non-aqueous Solvents, Pergamon, Oxford 1965. 2. J. J. Lagowski (Ed.) The Chemistry of Non-aqueous Solvents. Vols I, II. Academic Press New York. 1966, 1967. 3. T. C. Waddington (Ed.). Non-aqueous Solvent Systems, Academic Press London 1965. 4. T. C. Waddington, Non-aqueous Solvents, Nelson, London 1969. 5. J. Jander and C. Lafrenz, Ionizing Solvents, Verlag Chemie-Wiley, Weinheim, (1970). v

Contributors O. R. Brown Electrochemistry Research Laboratory, Department of Physical Chemistry, University of Newcastle upon Tyne, England. A. K. Covington Department of Physical Chemistry, University of Newcastle upon Tyne, England. C. M. Criss Department of Chemistry, University of Miami, Coral Gables, Florida 33124, U.S.A. T. Dickinson Electrochemisty Research Laboratory, Department of Physical Chemistry, University of Newcastle upon Tyne, England. R. Fermindez-Prini Department of Chemistry, University of Maryland, College Park, Maryland 20742, U.S.A. R. Garnsey Central Electricity Generating Board, Research Laboratories, Kelvin Avenue, Leatherhead, Surrey, England. T. E. Gough Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada. D. E. Irish Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada. E. J. King Department of Chemistry, Barnard College, Columbia University, New York, U.S.A. I. R. Lantzke Department of Physical Chemistry, University of Newcastle upon Tyne, England R. Payne Air Force Cambridge Laboratories, L. G. Hanscom Field, Bedford, Massachusetts, U.S.A. (the late) J. E. Prue Department of Chemistry, The University, Reading, Berkshire, England. M. Salomon National Aeronautics and Space-Administration, Electronics Research Center, Cambridge, Massachusetts, U.S.A. M. Spiro Department of Chemistry, Imperial College of Science and Technology, London S. W. 7, England. D. W. Watts School of Chemistry, University of Western Australia, Nedlands, W.A. 6009, Australia. vii

Contents Preface Contributors v Vll Introduction and Solvent Properties 2 Thermodynamic Measurements Part 1 Solubility, Calorimetry, Volume Measurements and Viscosities Part 2 Electrochemical Measurements Part 3 Precision Cryoscopy Part 4 Interpretation of Thermodynamic Data A. K. Covington and T. Dickinson C. M. Criss M. Salomon R. Garnsey and J. E. Prue C. M. Criss and M. Salomon 23 137 221 253 3 Acid-base Behaviour E.J. King 331 4 Spectroscopic Measurements Part 1 Electronic Absorption Spectroscopy Part 2 Infrared and Raman Spectroscopy Part 3 E.S.R. Spectroscopy Part 4 N.M.R. Spectroscopy I. R. Lantzke D. E. Irish T. E. Gough 1. R. Lantzke 405 433 461 483 5 Conductance and Transference Numbers Part 1 Conductance Part 2 Transference Numbers Part 3 Ionic Conductances ix R. Fernandez-Prini M. Spiro M. Spiro 525 615 635

x Contents 6 Reaction Kinetics and Mechanism D. W. Watts 681 7 Electrode Processes Part 1 The Electrical Double Layer R.Payne 733 Part 2 Electrode Reactions O. R. Brown 747 Subject Index 783