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Comprehensive Inorganic Chemistry EDITORIAL BOARD J. C. BAILAR JR., Urbana H. J. EMELÉUS, F.R.S., Cambridge tSIR RONALD NYHOLM, F.R.S., London A. F. TROTMAN-DICKENSON, Cardiff (Executive Editor) The Chemistry of FLUORINE T. A. O'Donnell Chapter 25 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 GERMANY 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 018784 6 (Hard cover) ISBN 0 08 018783 8 (Flexicover) PREFACE The excellent reception that has been accorded to Comprehensive Inorganic Chemistry since the simultaneous publication of thefivevolumes of the complete work has been accompanied by the plea that sections should be made available in a form that would enable specialists to purchase copies for their own use. To meet this demand the publishers have decided to issue selected chapters and groups of chapters as separate editions. These chapters will, apart from the corrections of misprints and the addition of prefatory material and individual indices, appear just as they did in the main work. Extensive revision would delay publication and greatly raise the cost, so limiting the circulation of these definitive reviews. A. F. TROTMAN-DICKENSON Executive Editor vii 25. FLUORINE T. A. O'DONNELL University of Melbourne For the purposes of organization of data in this treatise as a whole, compounds of fluorine with other elements are regarded formally as fluorides of those other elements. Therefore the detailed physical and chemical properties offluorinecompounds are presented in the appropriate chapters wherefluoridesof individual or grouped elements are discussed. Except for section 1, which gives information on the physical and chemical properties of elementalfluorineitself, this chapter is presented as a series of reviews. Hydrogen fluoride and the halogen fluorides are discussed separately as solvent systems, with particular emphasis on acid-base reactions. For main group fluorides those properties are given which result from the peculiar reactivity of fluorine, e.g. its great strength as an oxidant or the ability of fluoro-ligands to stabilize unusual complexes. Any systematic studies of the chemical reactivity of d- and/-transition metal fluorides, particularly in higher oxida tion states, are relatively recent and have not been reviewed comprehensively. This is done in the last section. Because of its extreme reactivity, elementalfluorinewas not isolated until 1886, by which time most of the other naturally occurring elements were known. From that time until about 1940, most study was associated with the ionicfluoridesor those either of non-metals or transition elements in lower oxidation states. These were the fluorides which were easy to ha