Comprehensive Inorganic Chemistry EDITORIAL BOARD J. C. BAILAR JR., Urbana Η. J. EMELEUS, F.R.S., Cambridge tSIR RONALD NYHOLM, F.R.S., London A. F. TROTMAN-DICKENSON, Cardiff {Executive Editor) The Chemistry of SULPHUR M. SCHMIDT AND W. SIEBERT SELENIUM, TELLURIUM AND POLONIUM K. W. BAGNAU Chapters 23 and 24 of Comprehensive Inorganic Chemistry P E R G A M ON P R E SS OXFORD . NEW YORK . TORONTO SYDNEY . PARIS . BRAUNSCHWEIG Pergamon Press Offices: U.K. Pergamon Press Ltd., Headington Hill Hall, Oxford, OX3 OBW, England U.S.A. Pergamon Press Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A. CANADA Pergamon of Canada Ltd., 207 Queen's Quay West, Toronto 1, Canada AUSTRALIA Pergamon Press (Aust.) Pty. Ltd., 19a Boundary Street, Rushcutters Bay, N.S.W. 2011, Australia FRANCE Pergamon Press SARL, 24 rue des Ecoles, 75240 Paris, Cedex 05, France WEST GERMANY 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 018856 7 (hard cover) ISBN 0 08 018855 9 (Flexicover) PREFACE The excellent reception that has been accorded to Compre­ hensive 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 vn INDEX Actinide sulphides 932 Oxyacids Aluminium sulphides 925 hydrogen peroxide derivatives 882 sulphane derivatives 884 Carbon selenides 983 Peroxodisulphuric acid 883 sulphides 920 Peroxomonosulphuric acid 883 tellurides 983 Phosphorus Carbonyl sulphides 918 polonide 954 Polonium 935 selenide 954 allotropy 941,943 telluride 954 alloys 951 Chalcogens 935 analysis 949 Chamber process for preparation of sulphuric carbonate 984 acid 871 Chromate 989 Chlorosulphonic acid 857 complexes 1005 Claus process 798 halo- 1005 Contact process for preparation of sulphuric nitrogen donor 1007 acid 871 oxoacid 1006 oxygen donor 1007 Dirhodan 916 sulphur donor 1008 Disulphur dihalides 956 monoxide 859 σrgano- 997 Disulphurous acid 880 i8-diketone derivatives 1002 Ditellurium dioxide 968 decafluoride 964 halides 955 Dithionic acid 877 mixed 962 Dithionous acid 881 triaryl 998 health hazard 946 hexafluoride 962 Fluorosulphonic acid 849 history 935 Frasch process 798 hydride 953 Fremy's salt 916 hydroxide 972 iodate 989 Gallium sulphide 925 monoxide 968 Germanium sulphides 921 nitrates 986 Gunpowder 795 occurrence 936 organic 992 Hydrogen sulphide, see also under Sulphanes σrgano- compounds 989 analytical use of 932 phosphate 987 occurrence 796 production 936 properties Iminosulphur fluorides 852 chemical 945, 959 physical properties 853 nuclear 943 Indium sulphide 925 physical 944 purification 938 Lanthanide sulphides 931 salts of organic acids 985 IX INDEX Polonium (cont.) Selenium (cont.) selenate 987 properties selenoxide 988 chemical 945, 949 sulphates 987 nuclear 943 sulphide 981 physical 944 sulphoxide 988 purification 938 tetrabromide 960 salts of organic acids 984 tetrachloride 958 selenates 987 tetraflnoride 958 selenoxide 988 tetraiodide 961 sulphates 987 trioxide 971 sulphides 981 uses 938 sulphoxide 988 Polysulphides 837,926 tetrabromide 960 Polysulphuric acids 876 tetrachloride 958 Pyrites 796 tetrafluoride 957 tetrafluoromethyl nitroxide 968 Raschig hydroxylamine synthesis 916 trihalides σrgano- 995 Selenic acid 972 trioxide 970 Selenides uses 937 Seorganic 992, 1001 Selenocarbonyl compounds Selenenic acids 998 organic 999 Seleninic acids 998 Selenocyanates Selenium 935 organic 1000 allotrophy 940 Selenols 991 alloys 951 Selenones analysis 947 organic 995 carbonates 984 Selenonic acids 999 chloride alkoxides 985 Selenonium salts 997 complexes 1005 Selenopentathionates 981 halo- 1005 Selenosulphates 978 nitrogen donor 1007 Selenotetrathionates 979 oxoacid 1006 Selenotrithionates 979 oxygen donor 1007 Selenous acid 971 sulphur donor 1008 Selenoxides dicyanide 967 organic 994 dihalides 956 Silicon sulphide 921 σrgano- 996 Sulfur, see under Sulphur i3-diketone derivatives 1002 Sulphanes 824,826 dioxide 968 analysis 833 diselenocyanate 968 disulphonic acids 887 dithiocyanates 967 reactions 892 halides 955 structure 891 health hazard 946 sulphite degradation of 897 heterocycles 1003 synthesis 891 hexafluoride 962 hydrogen sulphide 835 history 935 physical properties 836 hydride 953 monosulphonic acids 884, 886 mixed halides 962 polymeric organic derivatives 840 monobromide 955 properties 830 monochloride 955 biological 824 monohalides chemical 833 organic 995 physical 831 nitride 982 saUs 837 occurrence 936 Sulphates σrgano compounds 989 occurrence 797 oxoacids 971 Sulphides, see also under specific elements amido derivatives 975 occurrence 796 oxodihalides 964 transition metal 927, 930 oxohaloacids 976 Sulphonic acid perhalates 989 hydrazine- 914 peroxoacids 978 Sulphur 795 production 936 allotrope modifications 802 INDEX XI Sulphur (cont.) Sulphuric acid (cont,) compounds containing as a solvent system 873 nitrogen and carbon 916 bases in 874 nitrogen and halogen 907 hydroxylamides of 915 nitrogen, oxygen and hydrogen 909 imino derivatives 911 crystalline forms 802 nitrido derivatives 911 cyclodeca- 807 preparation 871 cyclododeca- 807 properties cyclohepta- 806 biological 824 cyclohexa- 805 chemical 872 monoclinic 803 physical 870 mother of pearl-like 805 Sulphurous acid 878 orthorhombic 803 amido derivatives 910 polycatena- 808 imido derivatives 910 diimide 911 Sulphuryl azide 910 dioxide 796, 860 chloride 857 biological properties 825 fluorides 849 infrared spectrum 862 physical properties 861 Telluric acids 972 halides 843 Tellurides bromides 858 organic 992, 1001 chlorides 856 Tellurinic acids 998 fluorides 843 Tellurium 935 iodides 858 alkoxides 985 history 795 allotrophy 941,942 imides 903 alloys 951 physical properties 906 analysis 947 interchalcogen compounds 822 azide trichloride 983 isotopes 813 complexes 1005 molten 808 halo- 1005 viscosity-temperature curve 809 nitrogen donor 1007 monoxide 859 oxoacid 1006 nitrides 898 oxygen donor 1007 occurrence 795 sulphur donor 1008 oxides 859 dihalides 956 nitrogen 909 σrgano- 996 oxyacids 868 jS-diketone derivatives 1002 production 798 dioxide 968 properties halides 955 biological 824 health hazard 946 chemical 814 heterocycles 1003 nuclear 813 hexafluoride 962 physical 813 history 935 purification 800 hydride 953 reactions mixed halides 962 electrophilic degradation 822 monoiodide 956 nucleophilic degradation 817 nitrate 986 of atomic 815 nitride 983 reactivity towards hydrocarbons 817 occurrence 936 -sulphur bonds 893 σrgano compounds 989 trioxide 864 oxoacids 971 infrared spectrum 868 oxofluoroacids 977 reactions 868 oxohalides 964 solubility 867 perhalates 989 peroxoacids 978 uses 799 phosphate 986 vapour 811 production 936 chilled 812 properties partial pressures 812 chemical 945, 949 thermodynamic properties 812 nuclear 943 Sulphuric acid 825, 869 physical 944 acids in 875 purification 938 amino derivatives 911 salts of organic acids 984 XU INDEX Tellurium {cont.) Tellurones selenate 987 organic 995 selenoxide 989 Telluronium salts 997 sulphate 987 Telluropentathionates 981 sulphides 981 Tellurous acid 971 sulphoxide 988 Telluroxides tellurate 987 organic 994 tetrabromide 960 Thallium tetrachloride 958 sulphide 925 tetrafluoride 957 Thionylamides 910 tetraiodide 961 Thionyl thiodibromide 966 chloride 857 trifluoromethyl nitroxide 968 fluorides 848 trihalides Thionylimide 910 σrgano- 995 Thioselenates 978 trioxide 971 Thiosulphuric acid 884 uses 938 Thiotrithiaxyl cation 902 Tellurocarbonyl compounds Transition element sulphides 927, 930 organic 999 Tellurols 991 Wackenroder's liquid 888 Contents of Comprehensive Inorganic Chemistry VOLUME 1 Gold Β F G JOHNSON University of Cambridge The elemeut Hydrogen, ortho- and para-Hydrogen, atomic & R DAVIS Kingston Polytechnic Hydrogen Group IIB Κ Μ MACKAY University of Waikato Β J AYLETT Westfield College, London Hydrides Scandium, Yttrium and Lanthanum Κ Μ MACKAY University of Waikato R C VICKERY Hudson, Florida Deuterium and Tritium Titanium Κ Μ MACKAY University of Waikato & Μ F A DDVE R J Η CLARK University College, Lc-^don University of Nottingham Zirconium and Hafnium _ Proton, protonic acids and hydrogen bond D C BRADLEY & Ρ THORNTON Queen Mary College, J Ε PRUE University of Reading London The monatomic gases: physical properties and production Vanadium A Η COCKETT & Κ C SMITH British Oxygen Co Ltd, R J Η CLARK, University College, London London The chemistry of Niobium and Tantalum The chemistry of Krypton, Xenon and Radon D BROWN Atomic Energy Research Establishment, Harwell Ν BARTLETT University of California, Berkeley & Chromium, Molybdenum and Tungsten F O SLADKY University of Innsbruck Lithium and its compounds C L ROLLINSON University of Maryland W A HART & O F BEUMEL Jr Foote Mineral Co, Manganese Pennsylvania R D W KEMMITT University of Leicester Sodium, Potassium, Rubidium, Cesium and Francium Technetium R D PEACOCK University of Leicester Τ Ρ WHALEY international Minerals and Chemical Corp, Rhenium Illinois R D PEACOCK University of Leicester Beryllium Iron D A EVEREST National Physical Laboratory, Teddington D NICHOLLS University of Liverpool Magnesium, Calcium, Strontium, Barium and Radium Cobalt R D GOODENOUGH & V A STENGER The Dow D NICHOLLS University of Liverpool Chemical Co, Michigan Nickel BΝo rΝo nG REENWOOD University of Leeds D NICHOLLS University of Liverpool Aluminium, Gallium, Indium and Thallium The 2nd and 3rd row elements of group Κ WADE & A J BANISTER University of Durham VIIIA, Β and C Carbon S Ε LIVINGSTONE University of New South Wales A Κ HOLLIDA Y, G HUGHES & S Μ WALKER Index University of Liverpool An introduction to the organic chemistry of the metallic elements Μ L Η GREEN University of Oxford & Ρ POWELL Royal Holloway College VOLUME 4 Silicon The Lanthanides Ε G ROCHOW Harvard University Τ MOELLER Arizona State University Index Carbonyls, Cyanides, Isocyanides and Nitrosyls W Ρ GRIFFITH Imperial College of Science & Technology London VOLUME 2 Compounds of the transition elements involving metal-metal bonds Germanium D L KEPERT University of Western Australia Ε G ROCHOW, Harvard University Tin & Κ VRIEZE University of Amsterdam Ε W ABEL University of Exeter Transition metal hydrogen compounds Lead J C GREEN & Μ L Η GREEN University of Oxford Ε W ABEL University of Exeter Non-stoichiometric compounds: an introductory essay Nitrogen D J Μ BEVAN The Flinders University of South Australia Κ JONES University of Manchester Inst, of Science ά Tungsten bronzes. Vanadium bronzes and related compounds Technology Ρ HAGENMULLER University of Bordeaux f^hosphorus Isopolyanions and heteropolyanions A D F TOY Stauffer Chemical Co, New York D L KEPERT University of Western Australia Arsenic, Antimony and Bismuth Transition metal chemistry J D SMITH University of Sussex Β F G JOHNSON University of Cambridge homogeneous catalysis Ε A V EBSWORTH University of Edinburgh, ΒO rLga SnHo-AtrWan s&iti oΝn Im TeUtaCl KcoEmRp oUunnidvse rasnityd roefl atLeede dass pects of i A CONNOR University of Manchester, & Index J J TURNER Newcastle on Tyne University Sulphur Μ SCHMIDT & W SIEBERT University of Wurzburg Selenium, Tellurium and Polonium VOLUME 5 Κ W BAGNALL University of Manchester FΤl uAo r0in*eD ONNELL University of Melbourne The Actinides J A LEE & J A MARPLES Chlorine, Bromine, Iodine and Astatine G W C MILNER & G PHILLIPS A J DOWNS & C J ADAMS University of Oxford Ρ G MARDON Index Atomic Energy Research Establishment, Harwell C KELLER Kernforschungszentrum, Karlsruhe S Η EBERLE Universitδt Karlsruhe VOLUME 3 Ό BROWN, R Μ DELL & Ρ Ε POTTER AERE, Harwell Κ W BAGNALL University of Manchester J RYDBERG & J O LILJENZIN Chalmers University A°G*MASSEY University of Technology, Loughborough of Technology S AHRLAND University of Lund Ν R THOMPSON ICI, Runcorn Heath Laboratory, Cheshire Master Index INDEPENDENT OPINION "These books are attractively bound and have clear print. Since the length and cost are not prohibitive, this set of books should be well within the budget of most libraries. Not only will the professional chemist find these books useful, but students and other readers will find them a valuable reference source. (Comprehensive Inorganic Chemistry) should be found in every undergraduate and graduate library, as well as industrial libraries. Many professional chemists may even consider them for personal libraries. Highly recommended." Choice—publication of the Association of College and Research Libraries. INDEPENDENT OPINION Volume 1 1467 pp + index dealt with it in a very succinct manner for the majority of the text, which extends to approxi­ "This covers the chemistry of hydrogen, the mately 1500 pages. The two major chapters in the noble gases, and of the elements of Groups lA, book are associated with the chemistry of nitrogen, IIA, HIB, carbon and silicon. The first three approximately 240 pages, and the chemistry of the chapters deal with hydrogen, hydrides, deuterium halogens (excepting fluorine), approximately 500 and tritium and the fourth is an interesting pages. The book thus encompasses in one volume discussion of the proton, protonic acids and the what would normally be a series of books. Both of hydrogen bond. Two chapters follow on the inert the above mentioned chapters are admirable and gases, including interesting and extensive recent the authors, K. Jones on nitrogen with A. J. knowledge about their compounds set out by Downs and C. J. Adams on the halogens, are to be N. Bartlett and F. O. Sladky. Four chapters on commended on both the presentation and coverage. the alkalis and alkaline earths contain a wealth The chapter on the halogens illustrates the real of detail, although perhaps along traditional lines. strength of the series, in that detailed chemical N. N. Greenwood has written an excellent account information is not only presented but discussed in on boron chemistry of book length in itself, and physico-chemical theoretical terms. A scientific another chapter deals at length with much new compendium of this size often suff^ers from the informationabout aluminium, gallium, indium and "catalogue" approach, but the present text presents thallium. Chapters 13 and 15 deal with carbon and the chemistry in critical mode with a realistic silicon. Here it might have been expected that more assessment of the various physical methods used would have been included on the high pressure in property determination. Thus the properties of chemistry of carbon and silicates, and mineral the halogens are discussed in terms of bond chemistry. Chapter 14 by M. L. H. Green and P. energies, bond lengths, vibrational properties, Powell is a useful introduction to the organic e.s.r., n.m.r., n.q.r. and Mossbauer spectroscopy, chemistry of the metallic elements, along modern electronic and magnetic properties and dipole lines of ligand field theory and ideas about metal moments allowing a detailed appraisal of the use complexes. of various modern methods in studying the Throughout this volume, with its different chemical properties reviewed. authors, it is perhaps inevitable that there is some Considering the magnitude of the task under­ lack of uniformity in the extent of detail given. taken, it is extremely pleasing to note the number There are also a few lapses in symbolism, notation, of chapters referring to papers in the 1971 period— and uniformity of units. Yet the whole must be a truly great commendation on the overall editor­ regarded as a highly commendable collection of ship of these volumes. Perhaps a general note in material which will be valuable to chemists of all each volume stating the period covered by the kinds." references would have been of help. In general this Professor Sir Harold Thompson FRS work provides a welcome and unique addition to Oxford the inorganic literature." Professor J. Lewis FRS Cambridge Volume 2 1594 pp + index "Volume 2 is concerned with the chemistry of Volume 3 1370 pp + index the elements of Groups IV, V, VI, VII. The general impression on reading the various chapters of this "This volume covers the chemistry of the ele­ volume is the great eff'ectiveness in reporting a ments of the d-block of the Periodic Table (the considerable amount of chemistry in a very transition elements), with the exception of the digestible form. The systematic presentation Lanthanide elements (Vol. 4), the Actinide applied to each chapter allows a rapid assessment elements (Vol. 5) and some special aspects which of the appropriate chemical information, and are common to many of the transition elements the text is well documented with reference to the (Vol. 4). The volume is therefore concerned original literature plus good review articles for a specifically with the three elements which charac­ more detailed coverage. Perhaps a minor criticism terize each of the ten transition groups, and the of this work lies in the indexing; the subject index chapters are mostly grouped in this way. However, is relatively sparse for a text of such magnitude the six platinum metals are treated in one chapter and it would have been of considerable utility to which is the best way to fit these similar elements have a formulae index to the text. into the overall scheme which is standard for all The area of chemistry covered by this work is five volumes. There are altogether 17 chapters, obviously very great, but it does appear to have written by 14 authors who are internationally