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Dictionary of Chemistry [6Th Ed.]

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Dictionary of Chemistry [6Th Ed.] A Dictionary of Chemistry SIXTH EDITION Edited by JOHN DAINTITH 3 1 Great Clarendon Street, Oxford OX2 6DP Great Clarendon Street, Oxford ox2 6dp Oxford University Press is a department of the University of Oxford. It furthers the University’s objective of excellence in research, scholarship, and education by publishing worldwide in Oxford New York Auckland Cape Town Dar es Salaam Hong Kong Karachi Kuala Lumpur Madrid Melbourne Mexico City Nairobi New Delhi Shanghai Taipei Toronto With offices in Argentina Austria Brazil Chile Czech Republic France Greece Guatemala Hungary Italy Japan Poland Portugal Singapore South Korea Switzerland Thailand Turkey Ukraine Vietnam Oxford is a registered trade mark of Oxford University Press in the UK and in certain other countries Published in the United States by Oxford University Press Inc., New York © Market House Books Ltd. 1985, 1990, 1996, 2000, 2004, 2008 The moral rights of the author have been asserted Database right Oxford University Press (maker) First published 1985 as A Concise Dictionary of Chemistry Second edition 1990 Third edition 1996 Fourth edition 2000 Fifth edition 2004 Sixth edition 2008 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, without the prior permission in writing of Oxford University Press, or as expressly permitted by law, or under terms agreed with the appropriate reprographics rights organization. Enquiries concerning reproduction outside the scope of the above should be sent to the Rights Department, Oxford University Press, at the address above You must not circulate this book in any other binding or cover and you must impose this same condition on any acquirer British Library Cataloguing in Publication Data Data available Library of Congress Cataloging in Publication Data Data available Typeset by Market House Books Ltd. Printed in Great Britain by Clays Ltd, St Ives plc ISBN 978–0–19–920463–2 10987654321 Contents Preface vii Credits viii Dictionary 1 Atomic Theory Chronology 49 Biochemistry Chronology 70 Crystal Defects (Feature) 152 Explosives Chronology 217 Plastics Chronology 422 Polymers (Feature) 430 Appendices The Greek alphabet 569 Fundamental constants 569 SI units 570 The electromagnetic spectrum 572 The periodic table 573 The chemical elements 574 Nobel prizes in chemistry 576 Useful websites 583 Preface This dictionary was originally derived from the Concise Science Dictionary, first published by Oxford University Press in 1984 (fifth edition, retitled Dictionary of Science, 2005). It consisted of all the entries relating to chemistry in this dictionary, including physical chemistry, as well as many of the terms used in biochemistry. Subsequent editions included special feature articles on important topics as well as several chronologies tracing the history of some topics and short biographical entries on the chemists and other scientists who have been responsible for the development of the subject. For this sixth edition the text has been fully revised and some entries have been substantially expanded. In addition over 350 new entries have been added covering all branches of the subject. The coverage of certain fields, in particular biochemistry, forensic chemistry, and chemoinformatics, has been expanded. A further improvement has been the inclusion of about 90 additional chemical structures. An asterisk placed before a word used in an entry indicates that this word can be looked up in the dictionary and will provide further explanation or clarification. However, not every word that appears in the dictionary has an asterisk placed before it. Some entries simply refer the reader to another entry, indicating either that they are synonyms or abbreviations or that they are most conveniently explained in one of the dictionary’s longer articles or features. Synonyms and abbreviations are usually placed within brackets immediately after the headword. Terms that are explained within an entry are highlighted by being printed in boldface type. The more physical aspects of physical chemistry and the physics itself will be found in A Dictionary of Physics, which is a companion volume to this dictionary. A Dictionary of Biology contains a more thorough coverage of the biophysical and biochemical entries from the Dictionary of Science together with the entries relating to biology. SI units are used throughout this book and its companion volumes. J.D. 2007 A AAR See amino acid racemization. heit-size degrees has been used: this is the Rankine scale. AAS See atomic absorption spec- troscopy. absolute alcohol See ethanol. abherent See release agent. absolute conÜguration A way of denoting the absolute structure of an ab-initio calculation A method of optical isomer (see optical activity). calculating atomic and molecular Two conventions are in use: The d–l structure directly from the Ürst prin- convention relates the structure of ciples of quantum mechanics, with- the molecule to some reference mol- out using quantities derived from ecule. In the case of sugars and simi- experiment (such as ionization ener- lar compounds, the dextrorotatory gies found by spectroscopy) as para- form of glyceraldehyde meters. Ab-initio calculations require (HOCH CH(OH)CHO), 2,3-dihydroxy- a large amount of numerical compu- 2 propanal) was used. The rule is as tation; the amount of computing follows. Write the structure of this time required increases rapidly as molecule down with the asymmetric the size of the atom or molecule in- carbon in the centre, the –CHO creases. The development of comput- group at the top, the –OH on the ing power has enabled the properties right, the –CH OH at the bottom, and of both small and large molecules to 2 the –H on the left. Now imagine that be calculated accurately, so that this the central carbon atom is at the cen- form of calculation can now replace tre of a tetrahedron with the four *semi-empirical calculations. Ab- groups at the corners and that the –H initio calculations can, for example, and –OH come out of the paper and be used to determine the bond the –CHO and –CH OH groups go lengths and bond angles of molecules 2 into the paper. The resulting three- by calculating the total energy of the dimensional structure was taken to molecule for a variety of molecular be that of d-glyceraldehyde and geometries and Ünding which confor- called d-glyceraldehyde. Any com- mation has the lowest energy. pound that contains an asymmetric absolute 1. Not dependent on or carbon atom having this conÜgura- relative to anything else, e.g. *ab- tion belongs to the d-series. One hav- solute zero. 2. Denoting a tempera- ing the opposite conÜguration ture measured on an absolute scale, belongs to the l-series. It is important a scale of temperature based on ab- to note that the preÜxes d- and l- do solute zero. The usual absolute scale not stand for dextrorotatory and now is that of thermodynamic *tem- laevorotatory (i.e. they are not the perature; its unit, the kelvin, was for- same as d- and l-). In fact the arbitrary merly called the degree absolute (°A) conÜguration assigned to d-glycer- and is the same size as the degree aldehyde is now known to be the cor- Celsius. In British engineering prac- rect one for the dextrorotatory form, tice an absolute scale with Fahren- although this was not known at the absolute configuration 2 CHO CHO CHO a H C OH C HCOH HOH CH OH CH OH CH OH 2 2 2 planar formula structure in 3 Fischer projection dimensions D-(+)-glyceraldehyde (2,3-dihydroxypropanal) H COOH C H CH COOH CH NH 3 3 2 NH 2 D-alanine (R is CH2 in the CORN rule). The molecule is viewed with H on top 1 1 C C 3 2 2 3 Rconfiguration Sconfiguration RS system. The lowest priority group is behind the chiral carbon atom Absolute configuration time. However, all d-compounds are being viewed along the H–C bond be- not dextrorotatory. For instance, the tween the hydrogen and the asym- acid obtained by oxidizing the –CHO metric carbon atom. If the clockwise group of glyceraldehyde is glyceric order of the other three groups is acid (1,2-dihydroxypropanoic acid). –COOH, –R, –NH2, the amino acid be- By convention, this belongs to the d- longs to the d-series; otherwise it be- series, but it is in fact laevorotatory; longs to the l-series. This is known as i.e. its name can be written as d- the CORN rule. glyceric acid or l-glyceric acid. To The r–s convention is a convention avoid confusion it is better to use + based on priority of groups attached (for dextrorotatory) and – (for laevo- to the chiral carbon atom. The order d rotatory), as in -(+)-glyceraldehyde of priority is I, Br, Cl, SO3H, OCOCH3, d and -(–)-glyceric acid. OCH3, OH, NO2, NH2, COOCH3, d l The – convention can also be CONH2, COCH3, CHO, CH2OH, C6H5, used with alpha amino acids (com- C2H5, CH3, H, with hydrogen lowest. pounds with the –NH2 group on the The molecule is viewed with the same carbon as the –COOH group). In group of lowest priority behind the this case the molecule is imagined as chiral atom. If the clockwise arrange- 3 abundance ment of the other three groups is in spread over a range of values of the descending priority, the compound frequency ν it is useful to deÜne a a belongs to the r-series; if the de- quantity called the integrated ab- scending order is anticlockwise it is sorption coefÜcient, A, which is the in the s-series. d-(+)-glyceraldehyde is integral of all the absorption coefÜ- r-(+)-glyceraldehyde. See illustration. cients in the band, i.e. A = ∫ε(ν)dν. This quantity characterizes the inten- absolute temperature See ab- sity of a transition.
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