INORGANIC

CATHERINE E. HOUSECROFT AND ALAN G. SHARPE

SECOND
EDITION

CHEMISTRY
This book has established itself as a leading textbook in the
subject by offering a fresh and exciting approach to the
teaching of modern inorganic chemistry. It gives a clear
introduction to key principles with strong coverage of
descriptive chemistry of the elements. Special selected
topics chapters are included, covering inorganic kinetics
and mechanism, catalysis, solid state chemistry and
bioinorganic chemistry.
A new full-colour text design and three-dimensional
illustrations bring inorganic chemistry to life. Topic boxes
have been used extensively throughout the book to relate
the chemistry described in the text to everyday life, the
chemical industry, environmental issues and legislation, and
natural resources.

Catherine E. Housecroft is Professor of Chemistry at the

University of Basel, Switzerland. She is the author of a
number of textbooks and has extensive teaching
experience in the UK, Switzerland, South Africa and the
USA. Alan G. Sharpe is a Fellow of Jesus College, University
of Cambridge, UK and has had many years of experience
teaching inorganic chemistry to undergraduates

Many more self-study exercises have been

introduced throughout the book with the
aim of making stronger connections
between descriptive chemistry and
underlying principles.
Additional overview problems have
been added to the end-of-chapter
problem sets.
The descriptive chemistry has been
updated, with many new results from the
literature being included.
Chapter 4 Bonding in polyatomic
molecules, has been rewritten with
greater emphasis on the use of group
theory for the derivation of ligand group
orbitals and orbital symmetry labels.
There is more coverage of supercritical
fluids and green chemistry.
The new full-colour text design enhances
the presentation of the many molecular
structures and 3-D images.

SECOND
EDITION

Supporting this edition

Companion website featuring multiplechoice questions and rotatable 3-D
molecular structures, available at
www.pearsoned.co.uk/housecroft. For full
information including details of lecturer
material see the Contents list inside the
book.
A Solutions Manual, written by Catherine
E. Housecroft, with detailed solutions to
all end-of-chapter problems within the
text is available for purchase separately
ISBN 0131 39926 8.

Cover illustration by Gary Thompson

For additional learning resources visit:

www.pearsoned.co.uk/housecroft

www.pearson-books.com

CATHERINE E. HOUSECROFT
AND ALAN G. SHARPE

Teaching aids throughout the text have been carefully

designed to help students learn effectively. The many
worked examples take students through each calculation or
exercise step by step, and are followed by related self-study
exercises tackling similar problems with answers to help
develop their confidence. In addition, end-of-chapter
problems reinforce learning and develop subject
knowledge and skills. Definitions boxes and end-of-chapter
checklists provide excellent revision aids, while further
reading suggestions, from topical articles to recent
literature papers, will encourage students to explore topics
in more depth.

New to this edition

INORGANIC
CHEMISTRY

CATHERINE E. HOUSECROFT AND ALAN G. SHARPE

INORGANIC

CHEMISTRY
SECOND
SECOND
EDITION
EDITION

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Visit the Inorganic Chemistry, second edition Companion Website at

www.pearsoned.co.uk/housecroft to nd valuable student learning material
including:
.
.
.
.

Multiple choice questions to help test your learning

Web-based problems for Chapter 3
Rotatable 3D structures taken from the book
Interactive Periodic Table

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Pearson Education Limited

Edinburgh Gate
Harlow
Essex CM20 2JE
England
and Associated Companies throughout the world
Visit us on the World Wide Web at:
www.pearsoned.co.uk
First edition 2001
Second edition 2005
# Pearson Education Limited 2001, 2005
The rights of Catherine E. Housecroft and Alan G. Sharpe to be
identied as the authors of this Work have been asserted by them in
accordance with the Copyright, Designs and Patents Act 1988.
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,
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either the prior written permission of the publisher or a licence permitting
restricted copying in the United Kingdom issued by the Copyright
Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP.
All trademarks used herein are the property of their respective owners.
The use of any trademark in this text does not vest in the author or
publisher any trademark ownership rights in such trademarks, nor does
the use of such trademarks imply any aliation with or endorsement of
this book by such owners.
ISBN 0130-39913-2
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress
10 9 8 7 6 5 4 3 2
09 08 07 06 05
Typeset in 912 /12 pt Times by 60
Printed by Ashford Colour Press Ltd., Gosport

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Contents

Preface to the second edition

Preface to the rst edition

1 Some basic concepts

xxxi
xxiii

1.1

Introduction
Inorganic chemistry: it is not an isolated branch of chemistry
The aims of Chapter 1

1
1
1

1.2

Fundamental particles of an atom

1.3

Atomic number, mass number and isotopes

Nuclides, atomic number and mass number
Relative atomic mass
Isotopes

2
2
2
2

1.4

Successes in early quantum theory

Some important successes of classical quantum theory
Bohrs theory of the atomic spectrum of hydrogen

3
4
5

1.5

An introduction to wave mechanics

The wave-nature of electrons
The uncertainty principle
The Schrodinger wave equation

6
6
6
6

1.6

Atomic orbitals
The quantum numbers n, l and ml
The radial part of the wavefunction, Rr
The radial distribution function, 4
r2 Rr2
The angular part of the wavefunction, A; 
Orbital energies in a hydrogen-like species
Size of orbitals
The spin quantum number and the magnetic spin quantum number
The ground state of the hydrogen atom

9
9
10
11
12
13
13
15
16

1.7

Many-electron atoms
The helium atom: two electrons
Ground state electronic congurations: experimental data
Penetration and shielding

16
16
16
17

1.8

The periodic table

17

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vi

Contents

The aufbau principle

Ground state electronic congurations
Valence and core electrons
Diagrammatic representations of electronic congurations

21
21
22
22

1.10

Ionization energies and electron affinities

Ionization energies
Electron anities

23
23
25

1.11

Bonding models: an introduction

A historical overview
Lewis structures

26
26
26

1.12

Homonuclear diatomic molecules: valence bond (VB) theory

Uses of the term homonuclear
Covalent bond distance, covalent radius and van der Waals radius
The valence bond (VB) model of bonding in H2
The valence bond (VB) model applied to F2 , O2 and N2

27
27
27
27
28

1.13

Homonuclear diatomic molecules: molecular orbital (MO) theory

An overview of the MO model
Molecular orbital theory applied to the bonding in H2
The bonding in He2 , Li2 and Be2
The bonding in F2 and O2
What happens if the sp separation is small?

29
29
29
31
32
33

1.14

The octet rule

36

1.15

Electronegativity values
Pauling electronegativity values, P
Mulliken electronegativity values, M
AllredRochow electronegativity values, AR
Electronegativity: nal remarks

36
37
37
38
38

Dipole moments

39
39
40

1.9

1.16

Polar diatomic molecules

Molecular dipole moments

1.17

1.18
1.19

Which orbital interactions should be considered?

Hydrogen uoride
Carbon monoxide

MO theory: heteronuclear diatomic molecules

41
41
42
42

Isoelectronic molecules

43

Molecular shape and the VSEPR model

43
43
47
48

Valence-shell electron-pair repulsion theory

Structures derived from a trigonal bipyramid
Limitations of VSEPR theory

1.20

Molecular shape: geometrical isomerism

Square planar species
Octahedral species
Trigonal bipyramidal species
High coordination numbers
Double bonds

48
48
48
49
49
49

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Contents

2 Nuclear properties

vii

53

2.1

Introduction

53

2.2

Nuclear binding energy

Mass defect and binding energy
The average binding energy per nucleon

53
53
54

2.3

Radioactivity
Nuclear emissions
Nuclear transformations
The kinetics of radioactive decay
Units of radioactivity

55
55
55
56
57

2.4

Artificial isotopes
Bombardment of nuclei by high-energy a-particles and neutrons
Bombardment of nuclei by slow neutrons

57
57
57

2.5

Nuclear fission
The ssion of uranium-235
The production of energy by nuclear ssion
Nuclear reprocessing

58
58
60
61

2.6

Syntheses of transuranium elements

61

2.7

The separation of radioactive isotopes

Chemical separation
The SzilardChalmers eect

62
62
62

2.8

Nuclear fusion

62

2.9

Applications of isotopes
Infrared (IR) spectroscopy
Kinetic isotope eects
Radiocarbon dating
Analytical applications

63
63
64
64
65

2.10

Sources of 2 H and 13 C
Deuterium: electrolytic separation of isotopes
Carbon-13: chemical enrichment

65
65
65

2.11

Multinuclear NMR spectroscopy in inorganic chemistry

Which nuclei are suitable for NMR spectroscopic studies?
Chemical shift ranges
Spinspin coupling
Stereochemically non-rigid species
Exchange processes in solution

67
68
68
69
72
73

2.12

Mossbauer spectroscopy in inorganic chemistry

The technique of Mossbauer spectroscopy
What can isomer shift data tell us?

73
73
75

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viii

Contents

An introduction to molecular symmetry

79

3.1

Introduction

79

3.2

Symmetry operations and symmetry elements

Rotation about an n-fold axis of symmetry
Reection through a plane of symmetry (mirror plane)
Reection through a centre of symmetry (inversion centre)
Rotation about an axis, followed by reection through a plane perpendicular
to this axis
Identity operator

79
80
80
82

3.3

Successive operations

84

3.4

Point groups
C1 point group
C1v point group
D1h point group
Td , Oh or Ih point groups
Determining the point group of a molecule or molecular ion

85
85
85
85
86
86

3.5

Character tables: an introduction

89

3.6

Why do we need to recognize symmetry elements?

90

Infrared spectroscopy
How many vibrational modes are there for a given molecular species?
Selection rule for an infrared active mode of vibration
Linear (D1h or C1v ) and bent (C2v ) triatomic molecules
XY3 molecules with D3h or C3v symmetry
XY4 molecules with Td or D4h symmetry
Observing IR spectroscopic absorptions: practical problems

90
90
91
92
92
93
94

Chiral molecules

95

3.7

3.8

82
82

Bonding in polyatomic molecules

100

4.1

Introduction

100

4.2

Valence bond theory: hybridization of atomic orbitals

What is orbital hybridization?
sp Hybridization: a scheme for linear species
sp2 Hybridization: a scheme for trigonal planar species
sp3 Hybridization: a scheme for tetrahedral and related species
Other hybridization schemes

100
100
101
102
103
104

4.3

Valence bond theory: multiple bonding in polyatomic molecules

C2 H4
HCN
BF3

105
105
105
106

4.4

Molecular orbital theory: the ligand group orbital approach and

application to triatomic molecules
Molecular orbital diagrams: moving from a diatomic to polyatomic species

107
107

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Contents

MO approach to the bonding in linear XH2 : symmetry matching by inspection

MO approach to bonding in linear XH2 : working from molecular symmetry
A bent triatomic: H2 O

ix

107
109
109

Molecular orbital theory applied to the polyatomic molecules BH3 ,

NH3 and CH4
BH3
NH3
CH4
A comparison of the MO and VB bonding models

112
112
113
115
116

4.6

Molecular orbital theory: bonding analyses soon become complicated

117

4.7

Molecular orbital theory: learning to use the theory objectively

-Bonding in CO2
[NO3 ]

SF6
Three-centre two-electron interactions
A more advanced problem: B2 H6

119
119
120
120
123
124

5 Structures and energetics of metallic and ionic solids

131

4.5

5.1

Introduction

131

5.2

Packing of spheres
Cubic and hexagonal close-packing
The unit cell: hexagonal and cubic close-packing
Interstitial holes: hexagonal and cubic close-packing
Non-close-packing: simple cubic and body-centred cubic arrays

131
131
132
133
134

5.3

The packing-of-spheres model applied to the structures of elements

Group 18 elements in the solid state
H2 and F2 in the solid state
Metallic elements in the solid state

134
134
134
134

5.4

Polymorphism in metals
Polymorphism: phase changes in the solid state
Phase diagrams

136
136
136

5.5

Metallic radii

136

5.6

Melting points and standard enthalpies of atomization of metals

137

5.7

Alloys and intermetallic compounds

Substitutional alloys
Interstitial alloys
Intermetallic compounds

139
139
139
140

5.8

Bonding in metals and semiconductors

Electrical conductivity and resistivity
Band theory of metals and insulators
The Fermi level
Band theory of semiconductors

141
141
141
142
143