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Comprehensive Inorganic Chemistry EDITORIAL BOARD J. C. BAILAR JR., Urbana H. J. EMELEUS, F.R.S., Cambridge f S I R RONALD NYHOLM, F.R.S., London A. F. TROTMAN-DICKENSON, Cardiff {Executive Editor) The Chemistry of LITHIUM William A. Hart and O. F. Beumel Jr. SODIUM, POTASSIUM, RUBIDIUM, CESIUM AND FRANCIUM Thomas P. Whaley Chapters 7 and 8 of Comprehensive Inorganic Chemistry PERGAMON PRESS OXFORD SYDNEY . . NEW YORK PARIS . TORONTO BRAUNSCHWEIG Pergamon Press Offices: U.K. U.S.A. CANADA AUSTRALIA FRANCE WEST G E R M A N Y Pergamon Press Ltd., Headington Hill Hall, Oxford, OX3 OBW, England Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A. Pergamon of Canada Ltd., 207 Queen's Quay West, Toronto 1, Canada Pergamon Press (Aust.) Pty. Ltd., 19a Boundary Street, Rushcutters Bay, N.S.W. 2011, Australia Pergamon Press SARL, 24 rue des Ecoles, 75240 Paris, Cedex 05, France Pergamon Press GmbH, D-3300 Braunschweig, Postfach 2923, Burgplatz 1, West Germany Copyright © Pergamon Press 1973 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, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publishers First edition 1973 Reprinted, with corrections, from Comprehensive Inorganic Chemistry. 1975 Library of Congress Catalog Card No. 77-189736 Printed in Great Britain by A. Wheaton & Co, Exeter ISBN 0 08-018852 4 (hard cover) ISBN 0 08 018799 4 (Flexicover) PREFACE The excellent reception that has been accorded t o Comprehensive Inorganic Chemistry since the simultaneous publication of the five volumes of the complete work has been accompanied by the plea that sections should be m a d e available in a form that would enable specialists t o purchase copies for their o w n use. T o meet this demand the publishers have decided t o issue selected chapters and groups o f chapters as separate editions. These chapters will, apart from the corrections o f misprints and the addition of prefatory material and individual indices, appear just as they did in the m a i n work. Extensive revision w o u l d delay publication and greatly raise the cost, so limiting the circulation o f these definitive reviews. A . F . TROTMAN-DICKENSON Executive vii Editor 7. LITHIUM A N D ITS COMPOUNDS WILLIAM A. HART and O . F. BEUMEL, JR. Foote Mineral Company, Pennsylvania THE ELEMENT Lithium, the lightest of the alkali metals, has an atomic number of 3 and an atomic weight of 6.94 i. Lithium exhibits oxidation states of zero and plus one and is clearly an alkali metal. However, lithium and its compounds are not always typical of the other alkali metals. The high ionic charge density and the strong tendency for lithium to form a monopositive ion strongly influence the stability of lithium compounds and the type of bond which lithium forms with other atoms, ions and radicals. The unusually high charge density of the lithium ion is a crucial factor in setting lithium and its compounds apart from the other alkali metals and their compounds. Both the normal and unusual characteristics of lithium will be described in this chapter. DISCOVERY The lithium-containing minerals, petalite and spodumene, were discovered by Jose de Andrada between 1790 and 1800 on Uto Island in Sweden . In 1817, J. A. Arfvedson discovered the new alkali metal, lithium, in petalite. He noted that lithium carbonate is sparingly soluble, that the hydroxide is much less soluble than the hydroxides of the other alkali metals, and that lithium compounds are similar to those of the alkaline earth metals. Arfvedson later fou