3 - [Catherine-Housecroft, -Alan-G.-Sharpe]-Inorganic-C (BookZZ.org)

3 - [Catherine-Housecroft, -Alan-G.-Sharpe]-Inorganic-C (BookZZ.org)

(Parte 1 de 6)

Housecroft & Sharpe’s Inorganic Chemistryis established as the leading textbook in the field and has been fully updated in this third edition. Designed as a student text, Inorganic Chemistryfocuses on teaching the underlying principles of inorganic chemistry in a modern and relevant way.

Within a single text, Inorganic Chemistryprovides a balanced introduction to core physical–inorganic principles and to the descriptive chemistry of the elements. Using worked examples and self-study exercises, Inorganic Chemistryreinforces the links between these two key themes. Special selected topics chapters are also included, covering inorganic kinetics and mechanism, catalysis, solid state chemistry and bioinorganic chemistry. New to this edition is a section on carbon nanotubes included in the chapter dealing with solid state chemistry.

Inorganic Chemistry has been carefully designed with teaching aids throughout to enhance learning. A stunning full-colour text design and three-dimensional illustrations bring inorganic chemistry to life. Topic boxes have been used extensively to relate the chemistry to issues in everyday life, the chemical industry, the environment and legislation, and natural resources. New to this edition are also experimental techniquesboxes introducing physical methods such as diffraction methods, computational chemistry, ESR spectroscopy and HPLC.

Numerous worked examples take students through each calculation or exercise step by step. They are followed by related self-study exercises, complete with answers, to help build further confidence. New self-study exercises have been added throughout the book. End-of-chapter problems (including ‘overview’ 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, encourage students to explore topics in more depth.

Catherine E. Housecroftis 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. Sharpeis a Fellow of Jesus College, University of Cambridge, UK and has had many years of experience teaching inorganic chemistry to undergraduates.

New to this edition

•The coverage of ‘basic concepts’ has been split into two chapters (Chapters 1 and 2).

•Updated coverage of recent advances in basic inorganic chemistry.

•Improved coverage of the use group theory in infrared spectroscopy (Chapter 4), of charge transfer bands and UV-VIS spectroscopy (Chapter 21), of term symbols and microstates (Chapter 21), and of magnetism (Chapter 21).

•New sections on superacids (Chapter 9) and carbon nanotubes (Chapter 28).


•Many new self-study exercises have been added to the descriptive chemistry •New experimental techniquesboxes.

•Updated applicationsand resources, environmentaland biological boxes. In selected boxes, photographs have been included for the first time.

Supporting this edition

•Companion Website available at w.pearsoned.co.uk/housecroft Featuring multiple choice questions (including additional questions for this edition) and rotatable 3-D molecular structures.

•PowerPoint figures and tables for lecturers.

•A short Guide for Lecturerswritten by

Catherine E. Housecroft.

•A Solutions Manual, written by Catherine

E. Housecroft, with detailed solutions to all end-of-chapter problems within the text is available for separate purchase, ISBN 978-0-13-204849-1.


Cover illustration by Gary Thompson

For additional learning resources visit: w.pearsoned.co.uk/housecroft

9780131755536.qxd 10/1/07 2:26 PM Page 1

Visit the Inorganic Chemistry, third edition Companion Website at w.pearsoned.co.uk/housecroft to find valuable student learning material including:

. Multiple choice questions to help test your learning . Rotatable three-dimensional structures taken from the book . Interactive periodic table

Pearson Education Limited Edinburgh Gate Harlow Essex CM20 2JE England and Associated Companies throughout the world

Visit us on the World Wide Web at: w.pearsoned.co.uk

First published 2001 Second edition 2005 Third edition published 2008

# Pearson Education Limited 2001, 2008

The rights of Catherine E. Housecroft and Alan G. Sharpe to be identified as 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, Saffron House, 6–10 Kirby Street, London EC1N 8TS.

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: 978-0-13-175553-6

British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library

Typeset in 912 /12pt Times by 73

Printed and bound by Rotolito Lombarda, Italy

The publisher’s policy is to use paper manufactured from sustainable forests.

Summary of contents

Preface xxxvi Acknowledgements xxxviii

1 Basic concepts: atoms 1 2 Basic concepts: molecules 30 3 Nuclear properties 58 4 An introduction to molecular symmetry 8 5 Bonding in polyatomic molecules 115 6 Structures and energetics of metallic and ionic solids 148 7 Acids, bases and ions in aqueous solution 181 8 Reduction and oxidation 212 9 Non-aqueous media 236 10 Hydrogen 261 1 Group 1: the alkali metals 284 12 The group 2 metals 305 13 The group 13 elements 325 14 The group 14 elements 376 15 The group 15 elements 433 16 The group 16 elements 490 17 The group 17 elements 532 18 The group 18 elements 561 19 Organometallic compounds of s- and p-block elements 574

20 d-Block metal chemistry: general considerations 611 21 d-Block metal chemistry: coordination complexes 637 2 d-Block metal chemistry: the first row metals 686 23 d-Block metal chemistry: the second and third row metals 744 24 Organometallic compounds of d-block elements 806 25 The f-block metals: lanthanoids and actinoids 854 26 d-Block metal complexes: reaction mechanisms 880 27 Catalysis and some industrial processes 905 28 Some aspects of solid state chemistry 938 29 The trace metals of life 962

Appendices 9 Answers to non-descriptive problems 1024 Index 1042 vi Summary of contents


Preface xxxvi Acknowledgements xxxviii

1 Basic concepts: atoms 1

1.1 Introduction 1

Inorganic chemistry: it is not an isolated branch of chemistry 1 The aims of Chapters 1 and 2 1

1.2 Fundamental particles of an atom 1

1.3 Atomic number, mass number and isotopes 2

Nuclides, atomic number and mass number 2 Relative atomic mass 2 Isotopes 2

1.4 Successes in early quantum theory 3

Some important successes of classical quantum theory 4 Bohr’s theory of the atomic spectrum of hydrogen 5

1.5 An introduction to wave mechanics 6

The wave-nature of electrons 6 The uncertainty principle 6 The Schro dinger wave equation 6

1.6 Atomic orbitals 9

The quantum numbers n, l and ml 9 The radial part of the wavefunction, RðrÞ 1

The radial distribution function, 4 r2RðrÞ2 12 The angular part of the wavefunction, Að ; Þ 13 Orbital energies in a hydrogen-like species 15 Size of orbitals 15 The spin quantum number and the magnetic spin quantum number 15 The ground state of the hydrogen atom 17

1.7 Many-electron atoms 17

The helium atom: two electrons 17 Ground state electronic configurations: experimental data 18 Penetration and shielding 18

1.8 The periodic table 20

1.9 The aufbau principle 2

Ground state electronic configurations 2 Valence and core electrons 23 Diagrammatic representations of electronic configurations 23

1.10 Ionization energies and electron affinities 24

Ionization energies 24 Electron affinities 26

2.1 Bonding models: an introduction 30

A historical overview 30 Lewis structures 30

2.2 Homonuclear diatomic molecules: valence bond (VB) theory 31

Uses of the term homonuclear 31 Covalent bond distance, covalent radius and van der Waals radius 31

The valence bond (VB) model of bonding in H2 32 The valence bond (VB) model applied to F2 ,O 2 and N2 3

2.3 Homonuclear diatomic molecules: molecular orbital (MO) theory 3

An overview of the MO model 3

Molecular orbital theory applied to the bonding in H2 3 The bonding in He2,L i2 and Be2 36

The bonding in F2 and O2 36 What happens if the s p separation is small? 38

2.4 The octet rule and isoelectronic species 40

The octet rule: first row p-block elements 40 Isoelectronic species 41 The octet rule: heavier p-block elements 41

2.5 Electronegativity values 42

Pauling electronegativity values, P 42 Mulliken electronegativity values, M 4 Allred–Rochow electronegativity values, AR 4 Electronegativity: final remarks 4

2.6 Dipole moments 4

Polar diatomic molecules 4 Molecular dipole moments 45

2.7 MO theory: heteronuclear diatomic molecules 46

Which orbital interactions should be considered? 46 Hydrogen fluoride 47 Carbon monoxide 48

2.8 Molecular shape and the VSEPR model 48

Valence-shell electron-pair repulsion model 48 Structures derived from a trigonal bipyramid 53 Limitations of the VSEPR model 53

2.9 Molecular shape: stereoisomerism 54

Square planar species 54 Octahedral species 54 viii Contents

Trigonal bipyramidal species 5 High coordination numbers 5 Double bonds 5

3 Nuclear properties 58

3.1 Introduction 58

3.2 Nuclear binding energy 58

Mass defect and binding energy 58 The average binding energy per nucleon 59

3.3 Radioactivity 60

Nuclear emissions 60 Nuclear transformations 60 The kinetics of radioactive decay 61 Units of radioactivity 62

3.4 Artificial isotopes 62

Bombardment of nuclei by high-energy a-particles and neutrons 62 Bombardment of nuclei by ‘slow’ neutrons 63

3.5 Nuclear fission 63

The fission of uranium-235 63 The production of energy by nuclear fission 64 Nuclear reprocessing 64

3.6 Syntheses of transuranium elements 64

3.7 The separation of radioactive isotopes 67

Chemical separation 67 The Szilard–Chalmers effect 67

3.8 Nuclear fusion 67

3.9 Applications of isotopes 69

Infrared (IR) spectroscopy 69 Kinetic isotope effects 70 Radiocarbon dating 70 Analytical applications 71

3.10 Sources of 2H and 13C7 2

Deuterium: electrolytic separation of isotopes 72 Carbon-13: chemical enrichment 72

3.1 Multinuclear NMR spectroscopy in inorganic chemistry 72

Which nuclei are suitable for NMR spectroscopic studies? 72 Chemical shift ranges 73 Spin–spin coupling 73 Stereochemically non-rigid species 78 Exchange processes in solution 79

3.12 Mossbauer spectroscopy in inorganic chemistry 82

The technique of Mo ssbauer spectroscopy 82 What can isomer shift data tell us? 82

Contents ix

4 An introduction to molecular symmetry 8

4.1 Introduction 8

4.2 Symmetry operations and symmetry elements 8

Rotation about an n-fold axis of symmetry 89 Reflection through a plane of symmetry (mirror plane) 89 Reflection through a centre of symmetry (inversion centre) 91 Rotation about an axis, followed by reflection through a plane perpendicular to this axis 91 Identity operator 91

4.3 Successive operations 93

4.4 Point groups 94

Td, Oh or Ih point groups 95 Determining the point group of a molecule or molecular ion 95

4.5 Character tables: an introduction 98

4.6 Why do we need to recognize symmetry elements? 9

4.7 Vibrational spectroscopy 100

How many vibrational modes are there for a given molecular species? 100 Selection rules for an infrared or Raman active mode of vibration 101

Linear (D1h or C1v) and bent (C2v) triatomic molecules 101 Bent molecules XY2: using the C2v character table 103 XY3 molecules with D3h symmetry 104 XY3 molecules with C3v symmetry 106 XY4 molecules with Td or D4h symmetry 107 XY6 molecules with Oh symmetry 108 Metal carbonyl complexes, M(CO)n 108

Metal carbonyl complexes M(CO)6 nXn 109 Observing IR spectroscopic absorptions: practical problems 110

4.8 Chiral molecules 110

5 Bonding in polyatomic molecules 115

5.1 Introduction 115

5.2 Valence bond theory: hybridization of atomic orbitals 115

What is orbital hybridization? 115 sp Hybridization: a scheme for linear species 116 sp2 Hybridization: a scheme for trigonal planar species 117 sp3 Hybridization: a scheme for tetrahedral and related species 118 Other hybridization schemes 119

5.3 Valence bond theory: multiple bonding in polyatomic molecules 120 x Contents

5.4 Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules 122

Molecular orbital diagrams: moving from a diatomic to polyatomic species 122

MO approach to bonding in linear XH2: symmetry matching by inspection 122 MO approach to bonding in linear XH2: working from molecular symmetry 124 A bent triatomic: H2O 124

5.5 Molecular orbital theory applied to the polyatomic molecules BH3, NH3 and CH4 127

CH4 130 A comparison of the MO and VB bonding models 131

5.6 Molecular orbital theory: bonding analyses soon become complicated 133

5.7 Molecular orbital theory: learning to use the theory objectively 135

SF6 138 Three-centre two-electron interactions 141

6 Structures and energetics of metallic and ionic solids 148

6.1 Introduction 148

6.2 Packing of spheres 148

Cubic and hexagonal close-packing 148 The unit cell: hexagonal and cubic close-packing 149 Interstitial holes: hexagonal and cubic close-packing 150 Non-close-packing: simple cubic and body-centred cubic arrays 151

6.3 The packing-of-spheres model applied to the structures of elements 151

Group 18 elements in the solid state 152

H2 and F2 in the solid state 152 Metallic elements in the solid state 152

6.4 Polymorphism in metals 153

Polymorphism: phase changes in the solid state 153 Phase diagrams 154

6.5 Metallic radii 154

6.6 Melting points and standard enthalpies of atomization of metals 155

6.7 Alloys and intermetallic compounds 155

Substitutional alloys 155 Interstitial alloys 155 Intermetallic compounds 158

6.8 Bonding in metals and semiconductors 158

Electrical conductivity and resistivity 158 Band theory of metals and insulators 158

Contents xi

The Fermi level 160 Band theory of semiconductors 161

6.9 Semiconductors 161

Intrinsic semiconductors 161 Extrinsic (n- and p-type) semiconductors 161

6.10 Sizes of ions 162

Ionic radii 163 Periodic trends in ionic radii 163

6.1 Ionic lattices 164

The rock salt (NaCl) structure type 165 The caesium chloride (CsCl) structure type 167

The fluorite (CaF2) structure type 168 The antifluorite structure type 168

The zinc blende (ZnS) structure type: a diamond-type network 169

The b-cristobalite (SiO2) structure type 169 The wurtzite (ZnS) structure type 169

The rutile (TiO2) structure type 169 CdI2 and CdCl2: layer structures 170 The perovskite (CaTiO3) structure type: a double oxide 170

6.12 Crystal structures of semiconductors 171

(Parte 1 de 6)