Concise Inorganic Chemistry (4th Edition) - IIT Mandi

1 ' . , :rJOKRODIHARJO DIP : 0 .. ' .DRS. SOEOIJO .. : ' :: .'. ' : !KIP 15-KETlt .. SURABAYA .. Concise Inorganic Chemistry .. ' FOURTH EDITION __ Lee __ ~ Senior Lecturer in Inorganic Chemistr _ _M~'j I Loughborough UniversityofTechn~~~ .J t " . CHAPMAN & HALL Universi1y and Professional Division London New York Tokyo Melbourne Madras UK USA JAPAN AUSTRALIA INDIA Chapman & Hall, 2-6 Boundary Row, London SEI 8HN Chapman & Hall, 29 West 35th Street, New York NYIOOOI Chapman & Hall Japan. Thomson Publishing Japan, Hirakaw~cho Nemoto Building, 7F, 1-7-11 Hirnkawa-cho, Chiyoda-ku, Tokyo 102 Chapman & Hall Australia, Thomas Nelson Australia.

2 102 Dodds Street, South Melbourne, Victoria 3205 Chapman & Hi11l India. R. Seshadri. :12 Sernnd Main Road, CIT East, M<1dras (100 035 First published Fourth edition 1991 1964. 1965. 1977, 1991 J . D. Lee Typeset in i0/12 Times by Typesetter Ltd. _ Priiited in Singapore by Fong & Sons Printers Pte. Ltd. ISBN o 412 40290 4 Aparl from ant fair dealing' for the purposes of resean:h 1.>r private study, or criticism or review. as permitted under the UK Copyright Designs and Patents Act. 1988, this publication may not be reproduced.)

3 Stored. or transmitted. in any form or by any means. without the prior permission in writing of the publishers. or in the case of reprographic reprod11ction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK. or in accordance with the terms of licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to the publishers at the UK address printed .on this page. The publisher makes no representation.

4 Express or implied, with regard to the accuracy of the informifrion contained in this book and cannot . accept any legal responsibility or liability for any errors or omissions that maybe made. British Library Cataloguing in Publication Data Lee. J .D. (John David) 1931- Concise Inorganic Chemistry . - 4th ed. I. Inorganic Chemistry I. Title 546 ISBN 0-412-40290-4 Library of Congress C<ttaloging-in-Publication Data Lce, (John David). l9Jl-Concisc Inorganic Chemistry I J .D. Lee. -4th ed. p. cm. Rev ed: of: A new Concise Inorganic Chemistry .

5 Jrd ed. 1977. Includes hihliogrnphical references and index, ISBN 0-412-40290-4 (phk.) . I. Chemistry . Physical and theoretical. 2. Chemical bonds. I . Lee. (John David). 1931-New inorgi1nic Chemistry ,, II. Title. 1991 5-46-dc20 91-9816 CIP I I Contents Preface to the fourth edition SI units Nomenclature in the period table . PART ONE THEORETICAL CONCEPTS AND HYDROGEN chapter 1 toinic structure and t e eriodic table The atom as a nuc eus with orbital electrons Atomic spectra of hydrogen and the Bohr theory Refinements to the Bohr theory The dual nature of electrons-particles or waves The principle 1.

6 The Schrodinger wave equation ) Radial and angular functions Pauli exclusion principle : Build-up of the elements. i-Iund's rule Sequence of energy fovels ~rrnggemeor pf the eJemepts jh groups in the perjodiG table l Further reading Problems chapter 2 Introduction to bonding Attainment of a stable configuration Types of bonds Trans itions between the main types of bonding -. Ionic bonds Covalent bonds Oxidation numbers Coordinate bOnds Double and triple bonds Metallic bonds and metallic structures Melting points Conductivity Solubility Speed of reactions xxx xx xiv xx xv 1 3 3 4 8 10 ll 12 15 21 21 24 25 """' 27 27 30 30 30 32 32 33 34 34 35 36 39 40 40 40 ).

7 - --- - - - ----L'iJ [ _____ CONTENTS ---- - - -- - -- --- _ _ - I 'l : chapter 3 The ionic bond i -Structures of ionic solids ( .i Radius ratio rules Calculation of some limiting radius ratio values Coordination number 3 (planar triangle) Coordination number 4 (tetrahedral) Coordination number 6 (octahedral) Close packing Classification of ionic structures Ionic compounds of the type AX (ZnS, NaCl, CsCI) Structures of zinc sulphide Sodium chloride structure Caesium. chloride structure Ionic compounds of the type AX2 (CaF2 Ti02, Si02) Calcium fluoride (fluorite) Rutile structure ~-cristobalite (sHica) structure Layer structures (Cd}i, CdCl2, [NiAs]))]

8 Cadmium iodide structure Cadmium chloride structure Nickel arsenide structure Structures containing polyatomic ions A more critical look at radius ratios 43 43 43 44 44 44 45 46 47 47 47 47 48 48 48 48 49 49 49 51 51 51 52 A cautionary word on radius ratios 52 Lattice energy v 54 Features of solids 58 Stoichiometric defects 59 Schottky defects 59 Frenkel defects 59 Nonstoichiometric defects 61 Metal excess 61 F-centres 61 Interstitial ions and electrons 62 Metal deficiency 62 Positive ions absent 63 Extra interstitial negative ions 63 Semiconductors and transistors 63 Rectifiers 65 Photovoltaic cell 66 Transistors 66 Micro-minaturized semiconductor devices -integrated circuits 68 Further reading 68 Problems 69 Chap~er 4 Th(!)

9 Covalent bond \ ---lntroductio-n ' The Lewis theory The octet rule Exceptions to the octet rule ,, Sidgwick-Powell theory 3 Valence shell electron pair repulsion (VSEPR) theory Effect of lone pairs -- Effect of electronegativity lsoelectronic principle . Som~-~x:amples using the VSEPR theory -BF., and the (BF4r ion -Ammonia NH_, Water H20 Phosphorus p_entachloride PCl5 Chlorine trifluoride CIF3 Sulphur tetrafluoride SF4 The triiodide ion lj" Sulphur hexafluoride SF6 Iodine heptafluoride IF7 r Valence bond theory v B Hybridization -The extent of d orbital participation in molecular bonding ~P' Sigma and pi bonds : Molecular orbital method I ---'-J.)

10 _LCAQ method -s-s combinations of orbitals s-p combinations ofotbitals p-p combinations of orbitals p-d combinations of orbitals d-d combinations of orbitals Non- bonding combinations of orbitals Rules for linear combination of atomic orbitals . Examples of molecular orbital treatment for homonuclear diatomic molecules H{ molecule ion H2 molecule Hei molecule ion He2 molecule Li2 molecule Be2 molecule B2 molecule C2 molecule N2 molecule 02 molecule 02ion 72 72 72 72 73 74 74 v 75 76 77 77 77 77 77 78 78 79 79 80 80~ _80, 81 85 87 89 _9cn \.}