P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=cover.html Page i The Properties of Solvents P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ i.html Page ii Wile y Series in Solution Chemistr y Editor-in-Chief P. G. T. Fo gg , Universit y o f North London, U K Editorial Board W. E. Acree, University of North Texas, USA A. Bylicki, Polish Academy of Sciences, Warsaw, Poland A. F. Danil de Namor, University of Surrey, UK H. J. M. Grünbauer, Dow Benelux NV, Ternauzen, The Netherlands S. Krause, Rensselaer Polytechnic Institute, Troy, USA A. E. Mather, University of Alberta, Canada H. Ohtaki, Ritsumeikan University, Kusatsu, Japan A. D. Pelton, Ecole Polytechnique de Montréal, Canada M. Salomon, US Army (ARL), Physical Sciences Directorate, Fort Monmouth, USA A. Skrzecz, Polish Academy of Sciences, Warsaw, Poland R. P. T. Tomkins, New Jersey Institute of Technology, USA W. E. Waghorne, University College, Dublin, Ireland B. A. Wolf, Johannes-Gutenberg-Universität, Mainz, Germany C. L. Youn g , Universit y o f Melbourne Australia Volume 1 pH and Buffer Theory—A New Approach H Rilbe Chalmers Universit y o f Technolo gy , Gothenbur g , Sweden Volume 2 Octanol-Water Partition Coefficients: Fundamentals and Physical Chemistry J Sangster San g ster Research Laboratories, Montreal, Canada Volume 3 Crystallization Processes Edited by H Ohtaki R itsumeikan Universit y , Kusatsu, Japan Volume 4 The Properties of Solvents Y Marcus The Hebrew Universit y o f Jerusalem, Israe l P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ ii.html Page iii The Properties of Solvents Wiley Series in Solution Chemistry: Volume 4 Y. Marcus The Hebrew Universit y of Jerusalem, Israel P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ iii.html Page iv Copyright © 1998 John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex PO19 1UD, En g lan d N ational 01243 779777 International (+44) 1243 779777 e-mail (for orders and customer service enquiries): cs-books@wiley.co.uk Visit our Home Page on http://www.wiley.co.uk or htt p ://www.wile y .com Re p rinted October 1999 All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act, 1988 or under the terms o f a licence issued by the Copyright Licensing Agency, 90 Tottenham Court Road, London, UK W1P 9HE, without the p ermission in writin g of the Publisher. Other Wile y Editorial O ff ices John Wiley & Sons, Inc., 605 Third Avenue, N ew York, NY 10158-0012, USA WILEY-VCH Verlag GmbH, Pappelallee 3, D-69469 Weinheim, German y Jacaranda Wiley Ltd, 33 Park Road, Milton, Queensland 4064, Australi a John Wiley & Son (Asia) Pte Ltd, 2 Clementi Loop #02–01, Jin Xin g Distri p ark, Sin g a p ore 129809 John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W 1L1, Canada L ibrar y o f Con g ress Catalo g in g -in- P ublication Data Marcus, Y. The properties of solvents / Yitzhak Marcus. p . cm. - (Wiley series in solution chemistry ; v. 4) Includes bibliographical references and index. ISBN 0-471-98369-1 (alk. paper) 1. Solvents. 2. Solution (Chemistry) I. Title. II. Series. Q544.M37 1999 541.3 ′ 482-dc21 98-18212 CIP B ritish Librar y Catalo g uin g in Publication Data A catalo g ue record for this book is available from the British Librar y P á g ina 1 de 2Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ iv.html ISBN 0 471 98369 1 T yp eset in 10/12 p t Times b y Ke y tec T yp esettin g Ltd, Brid p ort, Dorset Printed and bound in Great Britain b y Biddles, Guildford, Surre y This book is printed on acid-free paper responsibly manufactured from sustainable forestry, in which at least two trees are p lanted for each one used for p a p er p roduction. P á g ina 2 de 2Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ iv.html Page v Contents Series Preface vii Preface ix List of S y mbols xi Chapter 1 Introduction 1 1 A Surve y of Useful Solvents 1 2 Solvent Purit y and Purification Methods 13 3 Tests of Solvent Purit y 15 4 Toxicit y and Other Hazards of Solvents 25 References 32 Chapter 2 Solvent Effects 34 1 Solvation 34 2 Solution Com p osition 36 3 Solvent Effects on Solubilit y and Partition 44 4 Solvent Effects on Chemical E q uilibria 50 5 Solvent Effects on Reaction Rates 55 6 Solvent Effects in S p ectrosco py 58 7 Solvent Effects in Electrochemistr y 62 References 65 P á g ina 1 de 2Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ v.html Chapter 3 Ph y sical Pro p erties of Solvents 67 1 The Li q uid Ran g e of Solvents 68 2 The P -V- T Pro p erties of Solvents 79 3 Va p orization Pro p erties of Solvents 81 4 The Heat Ca p acit y of Solvents 85 5 The Molecular Sizes of Solvents 85 6 Electrical and O p tical Pro p erties 94 7 Ma g netic Pro p erties of Solvents 109 8 Surface and Trans p ort Pro p erties 110 9 Water and Heav y Wate r 125 References 127 P á g ina 2 de 2Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ v.html Page vi Chapter 4 Chemical Pro p erties of Solvents 131 1 The Structuredness of Solvents 131 2 Solvent Polarit y 142 3 Electron-Pair Donicit y 154 4 H y dro g en Bondin g Abilit y 160 5 Solvent Softness 163 6 Solvent Acidit y and Basicit y 165 7 A q ueous Solubilit y and Partition 174 8 Windows for S p ectrosco py and Electrochemistr y 187 References 199 Chapter 5 A pp lications 203 1 A Surve y of T yp ical A pp lications 203 2 A pp lications in Solvent Extraction 210 3 A pp lications in Electrochemistr y 215 4 A pp lications in Or g anic Chemistr y 218 5 A pp lications in Pol y mer Science and Technolo gy 225 6 S p ecial Features of Water As Solvent 230 References 232 Index 235 P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ vi.html Page vii Series Preface There are many aspects of solution chemistry. This is apparent from the wide range of topics which have been discussed during recent International Conferences on Solution Chemistry and International Symposia on Solubility Phenomena. The Wiley Series in Solution Chemistry was launched to fill the need to present authoritative, comprehensive and upto-date accounts of these many aspects. Internationally recognized experts from research or teaching institutions in various countries have been invited to contribute to the Series. Volumes in print or in preparation cover experimental investigation, theoretical interpretation and p rediction of physical chemical properties and behaviour of solutions. They also contain accounts of industrial a pp lications and environmental conse q uences of p ro p erties of solutions. Subject areas for the Series include: solutions of electrolytes, liquid mixtures, chemical equilibria in solution, acid-base equilibria, vapour-liquid equilibria, liquid-liquid equilibria, solid-liquid equilibria, equilibria in analytical chemistry, dissolution of gases in liquids, dissolution and precipitation, solubility in cryogenic solvents, molten salt systems, solubility measurement techniques, solid solutions, reactions within the solid phase, ion transport reactions away from the interface (i.e. in homogeneous, bulk systems), liquid crystalline systems, solutions of macrocyclic compounds (including macrocyclic electrolytes), polymer systems, molecular dynamic simulations, structural chemistry of liquids and solutions, predictive techniques for properties of solutions, complex and multi- component solutions applications, of solution chemistry to materials and metallurgy (oxide solutions, alloys, mattes etc.), medical aspects of solubility, and environmental issues involving solution p henomena and homo g eneous com p onent p henomena. Current and future volumes in the Series include both single-authored and multi-authored research monographs and reference level works as well as edited collections of themed reviews and articles. The y all contain com p rehensive biblio g ra p hies. Volumes in the Series are important reading for chemists, physicists, chemical engineers and technolo g ists as well as environmental scientists in academic and industrial institutions. PETER FOGG MAY 1996 P á g ina 1 de 1Document 11/10/2003htt p ://emedia.netlibrar y .com/nlreader/nlreader.dll?bookid=17984&filename=Pa g e _ vii.html [...]... exhaustive, and to provide these with appropriate annotations I hope that the long lists of references [following] the extensive tables do not detract too much from the readability of the book I preferred to have the tables right at the place where the data are discussed or where they can be employed by the reader as an illustration to the points discussed, rather than have them relegated to appendixes.'... some permutations of the elements of the name or the Chemical Abstracts name are used as synonyms In a few cases, Tables and text in other sections of the book refer to these synonyms rather than to the names in the second column, but the serial number shown should prevent any errors of identification In order to specify the solvent more clearly, its linear structural formula is given in the fourth column,... other kinds of atoms in organic molecules The entries in this column help in locating the solvent in formula indexes and listings made according to the compositional formula A further aid in the location of the solvents and their exact specification is the Chemical Abstracts name, shown in the sixth column of Table 1.1, and the Chemical Abstracts (CAS) Registry Number, shown in the seventh The Chemical... more important function belongs Water is considered to be the smallest alkanol, but ammonia, rather than as the shortest amine, is included with the inorganic solvents Table 1.1 shows the solvents on the List, that are dealt with in the following sections of the book An ordinal number in the first column identifies the solvents and can be used for their consistent sequencing Several alternative names can... book to be useful and handy, rather than trying in vain to be comprehensive and encyclopedic The solvents that are included in the extensive compilations of physical and chemical properties shown in this book (the List, referred to as such in this book) have been selected so as to cover the major classes of solvents, and bring several examples of each class The properties of solvents that have not been... accorded the appropriate space A classification scheme for solvents needs, therefore, to reflect to some extent the uses for which the solvents are put Many classification schemes have been proposed, and a single major property, that may form the basis for the usefulness of solvents for certain applications, can often be employed in order to classify solvents On the other hand, a few selected properties. .. space the common abbreviations Me ≡ methyl and Ph ≡ phenyl are used and c- - denotes a cyclic compound (Bicyclic solvents, such as quinoline, could not be illustrated by this device.) The compositional formula in the fifth column follows the convention of alphabetical listing of the atoms in the molecule of the solvent, but with 'C' for carbon being followed first by 'H' for hydrogen, before other... solvent in the List Water, being the most abundant, extensively employed, and a very useful solvent, has always been accorded very wide attention by chemists of all subdisciplines who have been studying solutions As an antithesis, the keyword 'non-aqueous' has figured in the titles of many treatments of other solvents Inorganic solvents have long been considered to be the typical 'non-aqueous solvents' ,... data have been reported However, for most of the more extensive tables, many blank spaces have been left, and in some cases entire rows of data have been left blank This was done with the hope of calling attention to the lack of reliable data, and the expectation that some of these blanks may be filled within the useful lifetime of this book (and its author) Y MARCUS JERUSALEM, JUNE 1998 http://emedia.netlibrary.com/nlreader/nlreader.dll?bookid=17984&filename=Page_x.html... selection of the solvents for which the data are included in this book (the List) is discussed in the Introduction I am solely responsible for such choices, regarding solvents and data, as have been made I will be grateful for indications of errors, oversights, and further useful data that may be brought to my attention Some of the tables are confined to those solvents from the List for which the relevant . Pro p erties of Solvents 67 1 The Li q uid Ran g e of Solvents 68 2 The P -V- T Pro p erties of Solvents 79 3 Va p orization Pro p erties of Solvents 81 4 The Heat Ca p acit y of Solvents 85 5 The. antithesis, the keyword 'non-aqueous' has figured in the titles of many treatments of other solvents. Inorganic solvents have long been considered to be the typical 'non-aqueous solvents& apos;,. supplement the former or to supersede them if deemed necessary. Access to the p rimary sources has been through the abstracts up to 1996. The selection of the solvents for which the data are