Inorganic Chemistry Housecroft PDF

Preview

Summary

CATHERINE E. HOUSECROFT AND ALAN G. SHARPE INORGANIC SECOND EDITION CHEMISTRY CATHERINE E. HOUSECROFT AND ALAN G. SHARPE INORGANIC CHEMISTRY INORGANIC 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 c...

Description

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

Black plate (1,1)

Black plate (2,1)

Visit the Inorganic Chemistry, second edition Companion Website at www.pearsoned.co.uk/housecroft to find 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

Black plate (3,1)

Black plate (4,1)

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 identified 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, electronic, mechanical, photocopying, recording, or otherwise, without 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 affiliation 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

Black plate (5,1)

Contents

Preface to the second edition Preface to the first edition

1 Some basic concepts

xxxi xxiii

1

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

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 Bohr’s 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 Schro¨dinger wave equation

6 6 6 6

1.6

Atomic orbitals The quantum numbers n, l and ml The radial part of the wavefunction, RðrÞ The radial distribution function, 4
r2 RðrÞ2 The angular part of the wavefunction, Að; Þ 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 configurations: experimental data Penetration and shielding

16 16 16 17

1.8

The periodic table

17

Black plate (6,1)

vi

Contents

The aufbau principle Ground state electronic configurations Valence and core electrons Diagrammatic representations of electronic configurations

21 21 22 22

1.10

Ionization energies and electron affinities Ionization energies Electron affinities

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 s–p 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 Allred–Rochow electronegativity values, AR Electronegativity: final 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 fluoride 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

Black plate (7,1)

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

58 58 60 61

2.6

Syntheses of transuranium elements

61

2.7

The separation of radioactive isotopes Chemical separation The Szilard–Chalmers effect

62 62 62

2.8

Nuclear fusion

62

2.9

Applications of isotopes Infrared (IR) spectroscopy Kinetic isotope effects 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 Spin–spin coupling Stereochemically non-rigid species Exchange processes in solution

67 68 68 69 72 73

2.12

Mo¨ssbauer spectroscopy in inorganic chemistry The technique of Mo¨ssbauer spectroscopy What can isomer shift data tell us?

73 73 75

Black plate (8,1)

viii

Contents

3

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 Reflection through a plane of symmetry (mirror plane) Reflection through a centre of symmetry (inversion centre) Rotation about an axis, followed by reflection 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

4

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

Black plate (9,1)

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

Black plate (10,1)

x

Contents

Semiconductors Intrinsic semiconductors Extrinsic (n- and p-type) semiconductors

143 143 143

5.10

Sizes of ions Ionic radii Periodic trends in ionic radii

144 144 145

5.11

Ionic lattices The rock salt (NaCl) lattice The caesium chloride (CsCl) lattice The fluorite (CaF2 ) lattice The antifluorite lattice The zinc blende (ZnS) lattice: a diamond-type network The b-cristobalite (SiO2 ) lattice The wurtzite (ZnS) structure The rutile (TiO2 ) structure The CdI2 and CdCl2 lattices: layer structures The perovskite (CaTiO3 ) lattice: a double oxide

146 148 149 149 149 149 150 151 151 151 152

5.12

Crystal structures of semiconductors

152

5.13

Lattice energy: estimates from an electrostatic model Coulombic attraction within an isolated ion-pair Coulombic interactions in an ionic lattice Born forces The Born–Lande´ equation Madelung constants Refinements to the Born–Lande´ equation Overview

152 152 153 153 154 154 155 155

5.14

Lattice energy: the Born–Haber cycle

155

5.15

Lattice energy: ‘calculated’ versus ‘experimental’ values

156

Applications of lattice energies Estimation of electron affinities Fluoride affinities Estimation of standard enthalpies of formation and disproportionation The Kapustinskii equation

157 157 157 157 158

Defects in solid state lattices: an introduction Schottky defect Frenkel defect Experimental observation of Schottky and Frenkel defects

158 158 158 159

Acids, bases and ions in aqueous solution

162

6.1

Introduction

162

6.2

Properties of water Structure and hydrogen bonding The self-ionization of water Water as a Brønsted acid or base

162 162 163 163

5.9

5.16

5.17

6

Black plate (11,1)

Contents

xi

6.3

Definitions and units in aqueous solution Molarity and molality Standard state Activity

165 165 165 165

6.4

Some Brønsted acids and bases Carboxylic acids: examples of mono-, di- and polybasic acids Inorganic acids Inorganic bases: hydroxides Inorganic bases: nitrogen bases

166 166 167 167 168

6.5

The energetics of acid dissociation in aqueous solution Hydrogen halides H2 S, H2 Se and H2 Te

169 169 170

6.6

Trends within a series of oxoacids EOn (OH)m

170

Aquated cations: formation and acidic properties Water as a Lewis base Aquated cations as Brønsted acids

171 171 172

6.8

Amphoteric oxides and hydroxides Amphoteric behaviour Periodic trends in amphoteric properties

173 173 173

6.9

Solubilities of ionic salts Solubility and saturated solutions Sparingly soluble salts and solubility products The energetics of the dissolution of an ionic salt:
sol Go The energetics of the dissolution of an ionic salt: hydration of ions Solubilities: some concluding remarks

174 174 174 175 176 177

6.10

Common-ion effect

178

6.11

Coordination complexes: an introduction Definitions and terminology Investigating coordination complex formation

178 178 179

6.12

Stability constants of coordination complexes Determination of stability constants Trends in stepwise stability constants Thermodynamic considerations of complex formation: an introduction

180 182 182 182

6.13

Factors affecting the stabilities of complexes containing only monodentate ligands Ionic size and charge Hard and soft metal centres and ligands

186 186 187

6.7

7 Reduction and oxidation 7.1

Introduction Oxidation and reduction Oxidation states Stock nomenclature

192 192 192 192 193

Black plate (12,1)

xii

Contents

Standard reduction potentials, E o , and relationships between E o ,
Go and K Half-cells and galvanic cells Defining and using standard reduction potentials, E o Dependence of reduction potentials on cell condition...