The Chemistry Of Arsenic, Antimony And Bismuth. Pergamon Texts In Inorganic Chemistry

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 ARSENIC, ANTIMONY AND BISMUTH J. D. Smith Chapter 21 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 018778 1 (Hard cover) ISBN 0 08 018777 3 (Flexicover) PREFACE The excellent reception that has been accorded to 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 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 21. ARSENIC, ANTIMONY AND BISMUTH J. D. SMITH University of Sussex The elements of Group V are sometimes known as pnictides. The chemistry of nitrogen and phosphorus has been worked out in great detail: the remaining elements—arsenic, antimony and bismuth—have been less thoroughly studied. As they form a closely related group, they are considered together. Interest centres on the trend from non-metallic to metallic properties with increasing atomic weight. Thus there are many parallels between phosphorus and arsenic, but considerably fewer between phosphorus and bismuth, which is a typical B metal like tin or lead. Arsenic and antimony are important largely because of their intermediate or metalloid character. In the following sections the Group V element is given the symbol E. Halogen atoms are denoted by X and other electro-negative atoms or groups by Y or Z. Electro-positive (metallic) atoms are denoted by the symbol M. 1. THE ELEMENTS 1.1. ARSENIC The yellow pigment orpiment (AS2S3) and red realgar (As4S4) were known to Greek alchemists, who probably also succeeded in isolating the metal. The German Dominican scholar Albertus Magnus (1193-1280) described the preparation of arsenic by heating orpiment with soap, but the alchemists probably thought of the metal as a kind of mercury. The relation between As111 oxide and metallic arsenic, and the similarity between arsenic and tin,