Concise Inorganic Chemistry

342 Pages·1991·7.902 MB·English

by  J. D. Lee

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CONCISE
INORGANIC
CHEMISTRY ...
. '
FOURTH EDITION
_ _ J .D.
Lee _ _
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Senior Lecturer in Inorganic Chemistr_ I
UniversityofTechn~~~
Loughborough
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CHAPMAN & HALL
Universi1y and Professional Division
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First published lt.164.
Fourth edition 1991
© 1964. 1965. 1977, 1991 J.D. Lee
· Typeset in i0/12 Times by Best-s.et Typesetter Ltd. _
Priiited in Singapore by Fong & Sons Printers Pte. Ltd.
ISBN o 412 40290 4
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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,J.D. (John David). l9Jl-
Concisc inorganic chemistry I J.D. Lee. -4th ed.
p. cm.
Rev ed: of: A new concise inorganic chemistry. Jrd ed. 1977.
Includes hihliogrnphical references and index,
· ISBN 0-412-40290-4 (phk.) .
I. Chemistry. Physical and theoretical. 2. Chemical bonds.
I. Lee. J.D. (John David). 1931- New concis.e inorgi1nic chemistry,,
II. Title.
OD453.2.L45 1991
5-46-dc20 91-9816
CIP
I
I
Contents
Preface to the fourth edition xxx
SI units xx xiv
Nomenclature in the period table . xx xv
PART ONE THEORETICAL CONCEPTS AND HYDROGEN 1
Chapter 1 toinic structure and t e eriodic table i.. 3
The atom as a nuc eus with orbital electrons · 3
Atomic spectra of hydrogen and the Bohr theory 4
Refinements to the Bohr theory 8
The dual nature of electrons-particles or waves 10
The Heisenberg.uncertainty principle ll
1.
The Schrodinger wave equation · ) 12
Radial and angular functions 15
Pauli exclusion principle :· 21
Build-up of the elements. i-Iund's rule 21
Sequence of energy fovels 24
l·
~rrnggemeor pf the eJemepts jh groups in the perjodiG table 25 """'
Further reading 27
Problems 27
Chapter 2 Introduction to bonding 30
Attainment of a stable configuration 30
Types of bonds 30
Trans·itions between the main types of bonding -. 32
Ionic bonds 32
Covalent bonds 33
Oxidation numbers 34
Coordinate bOnds 34
Double and triple bonds 35
Metallic bonds and metallic structures 36
Melting points 39
Conductivity 40
Solubility 40
Speed of reactions 40 )...
L'iJ [_ ________·_·-----· ------
CONTENTS
----- - --- -----__- I
'l :chapter 3 The ionic bond i 43
· - Structures of ionic solids 43
(.i Radius ratio rules 43
Calculation of some limiting radius ratio values 44
Coordination number 3 (planar triangle) 44
Coordination number 4 (tetrahedral) 44
Coordination number 6 (octahedral) 45
Close packing 46
Classification of ionic structures 47
Ionic compounds of the type AX (ZnS, NaCl, CsCI) 47
Structures of zinc sulphide 47
Sodium chloride structure 47
Caesium.c hloride structure 48
Ionic compounds of the type AX2 (CaF2• Ti02, Si02) 48
Calcium fluoride (fluorite) stru.cture 48
Rutile structure 48
~-cristobalite (sHica) structure 49
Layer structures (Cd}i, CdCl2, [NiAs]) 49
Cadmium iodide structure 49
Cadmium chloride structure 51
Nickel arsenide structure 51
Structures containing polyatomic ions 51
A more critical look at radius ratios 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(! covalent bond \ 72
---lntroductio-n · 72
' The Lewis theory 72
The octet rule 72
Exceptions to the octet rule 73
,, Sidgwick-Powell theory 74
3 Valence shell electron pair repulsion (VSEPR) theory 74 v
Effect of lone pairs ·--· 75
Effect of electronegativity 76
lsoelectronic principle 77
. Som~-~x:amples using the VSEPR theory 77
-BF., and the (BF4r ion - 77
Ammonia NH_, 77
Water H 0 77
2
Phosphorus p_entachloride PCl 78
5
Chlorine trifluoride CIF 78
3
Sulphur tetrafluoride SF4 79
The triiodide ion lj" 79
Sulphur hexafluoride SF6 80
Iodine heptafluoride IF7 80~
·r Valence bond theory v B _80,
· Hybridization 81
· -The extent of d orbital participation in molecular bonding 85
87
~P' Sigma and pi bonds
: · Molecular orbital method 89
_9cn \.,,.,
I ---'-
J._LCAQ method
- s-s combinations of orbitals 90
s-p combinations ofotbitals 93
p-p combinations of orbitals 94
p-d combinations of orbitals 96
d-d combinations of orbitals 96
Non-bonding combinations of orbitals 96
Rules for linear combination of atomic orbitals 97
. Examples of molecular orbital treatment for homonuclear
diatomic molecules 98
H{ molecule ion 99
H molecule 99
2
Hei molecule ion 99
He molecule 99
2
Li molecule 100
2
100
Be molecule
2
B molecule 101
2
C molecule 102
2
N molecule 104
2
0 molecule 105
2
105
02ion
[~iii.) [~-~-- ----··-_----------=--------==~---C_O_N_T_EN_T_S --~ -~=~===~~--~-:-~--~~~~--~~~-=!
o~- ion 107
F molecule J07
2
Examples of molecular orbital treatment for heteronuclear
diatomic molecules 107
· NO molecule 109
CO moh·culc 110
HCI molecule 112
Examples of molecular orbital treatment involving delocalized
n: bonding 112
coj-
Carbonate ion 112
Nitrate ion NO) 114
. Sulphur trioxide SOJ 114
Ozone OJ 115
Nitrite ion NOi 116
Carbon dioxide C0 116
2
Azide ion Nj 117
Summaryof multi-centre n: bonded structures 117
United atom method 118
Further reading 119
Problems 120
Chapter 5 The metallic bond 121
General properties of metals . 121
Conductivity 121
Lustre 122
Malleability and cohesive force 122
Crystal structures of metals 126
Bond lengths 127
Theories of bonding in metals 127
Free electron theory 128
Valence bond theory 128
· Molecular orbital or band theory 128
Conductors. insulators and semiconductors 131
Alloys 132
Ionic compounds 132
Interstitial alloys and related compounds 132
Substitutional alloys 135
Superconductivity 140
Further reading 144
Problems 145
Chapter 6 General properties of the elements 146
Size of atoms and ions 146
Size of atoms 146
Size of ions 146
Problems with ionic radii 148
Trends in ionic radii 148
[ -----_____________c_ O_N_T_E_N_T_s_ ____________~ I CGJ
Ionization energies 149
Electron affinity 153
Born-Haber cycle 154
Polarizing power and polarizability-Fajans' rules 156
Electronegativity 157
Pauling 158
Mulliken 161
Allred and Rochow 162
Metallic character 163
Variable valency and oxidation states 164
Standard electrode potentials and electrochemical series 165
Oxidation-reduction reactions 170
The use of reduction potentials 172
The occurrence and isolation of the elements 178
Mechanical separation Of elements that exist in the native form 178
Thermal decomposition methods 179
Displacement of one element by another 180
High temperature chemical reduction methods 181
Reduction by carbon · 181
Reduction by another metal 18_2
Self-reduction 182
Reduction of oxides with hydrogen 182
Electrolytic reduction 182
In aqueous solution 183
In other solvents 183
In fused melts 183
Factors influencing the choice of extraction process 183
Thermodynamics of reduction processes 183
Horizontal, vertical and diagonal relationships in the periodic
table 189
Further reading. 190
Problems 191
Chapter 7 Coordination compounds 194
Double salts and coordination compounds 194
Werner's work 195
More recent methods of studying complexes 198
Effective atomic numbers 200
Shapes of d orbitals 201 .
Bonding of transition metal complexes 202
Valence bond theory 202
Crystal field theory 202
Molecular orbital theory 202
Valenc_e bond theory 203 v"
Crystal field theory 204 v
Octahedral complexes 205
Effects of crystal field splitting 210
CONTENTS
Tetragonal distortion of octahedral complexes (Jahn-Teller
distortion) 214
Square planar arrangements 217
Tetrahedral complexes 219
v
Chelates 222
Magnetism 225
Extension of the crystal field theory to allow for some covalency 226
Molecular orbital theory ""227
1t acceptors 229
n donors 229
Nomenclature of coordination compounds \/230
Isomerism 232
Polymerization isomerism 232
Ionization isomerism 232
Hydrate isomerism 233
Linkage isomerism 233
Coordination isomerism 233
Coordination position isomerism 234
Geometric isomerism or stereoisomerism 234
Optical isomerism 234
Further reading 236
Problems 236
Ch!tpter 8 Hydrogen and the hydrides 240
Electronic structure 240
Position in the periodic table 240
Abundance of hyc,trogen 241
Preparation of hydrogen 24 I
Properties of molecular hydrogen 243
Isotopes of hydrogen 245
Ortho and para hydrogen 248
m
H~~~
Ionic or salt-like hydrides 249
Covalent hydrides 250
Metallic (or interstitial) hydrides 252
Intermediate hydrides 254
The hydrogen ion 254
Hydrogen bonding -255
./Acids and bases 256
Arrhenius theory 258
Acids and bases in proton solvents 260
Bronsted-Lowry theory 262
Lewis theory 265
The solvent system 265
The Lux-Flood definition 267
The Usanovich definition 267
Hard and soft acids and bases 267
Further reading 268
Problems 271
PART TWO THE s-BLOCK ELEMENTS 273
Chapter 9 dro~p_!:::!h.~-~lk_al!_ ~.e~~J 275
Introduction 275
Occmrence and abundance 275
Extra.ction of the metals 277
Uses of Group I metals and th.eir compounds 278
Electronic structure 280
Size of atoms and ions 280
Density 280
Ionization energy 281
Electronegativity and bond type 281
Born-Haber cycle: energy changes in the formation of ionic
compounds 282
Structures of the metals, hardness, and cohesive energy 285
Melting and boiling points 286
Flame colours and spectra 286
Colour of compounds · 287
Chemical properties 288
Reaction with water 288
Reaction with air 289
Reaction with nitrogen 289
Oxides, hydroxides, peroxides and superoxides 290
Reaction with air 290
Normal oxides - monoxides 290
Hydroxides 290
Peroxides and superoxides 291
Sulphides 293
Sodium hydroxide 294
Sodium hydrogencarbonate (sodium bicarbonate) 294
Sodium sulphate 294
Oxosalts-carbonates, bicarbonates, nitrates and nitrites 295
Halides and polyhalides 296
Hydrides 297
Solubility artd hydration 298
Solutions of metals in liquid ammonia 302
CompO\!ilds with carbon 303
Organie and organometallic compounds 303
Complexes, crowns and crypts 305
Biological importance 308
Differences between lithium and the other Group 1 elements 309
Further reading 311
Problems 312
CONTENTS
Chapter 10 The chlor-alkali industry 315
Leblanc process 315
Weldon and Deacon processes 317
Electrolytic processes 317
Diaphragm cell 318
Mercury cathode cell 319
Quantities 321
Sodium carbonate 321
The Solvay (or ammonia-soda) process 323
Further reading 324
Problems 324
Chapter 11 Group JI - the alkaline earth elements 325
Introduction 325
Electronic structure 325
Occurrence and abundance 325
Extraction of the metals 327
Dow sea water process 329
Dow natural brine process 329
Size of atoms and ions 329
Ionization energy 330
Electronegativity 331
Hydration energies 331
Anomalous behaviour of beryllium 332
Solubility and lattice energy 334
Solutions of the metals in liquid ammonia 335
Chemical properties 335
Reaction with water 335 ·
Hydroxides 336
Hardness of water 337
Reaction with acids and bases 338
Oxides and peroxides 338
Sulphates 341
Nitrates 342
Hydrides 342
Halides 344
Nitrides 345
Carbides 346
Insoluble salts 347
Organometallic compounds 347
Complexes 349
Biological role of Mg2+ and Ca2+ 353
Differences between beryllium and the other Group II elements 353
Further reading 354
Problems 354