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Provides robust coverage of the different branches of chemistry – with unique depth in
organic chemistry in an introductory text – helping students to develop a solid understanding
of chemical principles, how they interconnect, and how they can be applied to our lives.

KEY FEATURES
• Chapters are grouped into inorganic, physical and organic components, with integrating
themes highlighted throughout. This provides flexibility and highlights the connections
between different areas.
• Topic boxes throughout the book highlight the applications of chemistry in industry,
biology, the environment and the laboratory. These help students to understand the
relevance of chemistry to everyday life.
• The text is four-colour throughout with three-dimensional computer-generated artwork,
and is supported by CHIME graphics on the companion website, helping students to
visualise chemical structures.
• Definition boxes and end-of-chapter checklists provide excellent revision aids.
• End-of-chapter problems reinforce learning and develop subject knowledge; in this
edition, answers to non-descriptive problems have been added at the end of the book.
• A companion website at www.pearsoned.co.uk/housecroft features multiple-choice
questions, rotatable three-dimensional molecular structures, and a Mathematics Tutor. For
full information and details of the OneKey resource available with this book, see prelim
page xx.

Catherine E. Housecroft and Edwin C. Constable are both Professors of Chemistry at the
University of Basel, Switzerland. They have extensive international teaching experience and
their research interests include supramolecular chemistry, nanotechnology, organometallic
and cluster chemistry. In 1997 Professor Constable was awarded the prestigious Howard
lectureship for pre-eminence in organic chemistry or related disciplines by the University of
Sydney, Australia.

CHEMISTRY

CHEMISTRY

Catherine E. Housecroft and Edwin C. Constable

Catherine E. Housecroft and Edwin C. Constable

CHEMISTRY
3rd Edition

3rd Edition

Cover illustration by Gary Thompson

www.pearson-books.com

Catherine E. Housecroft
Edwin C. Constable

Visit the Chemistry, Third Edition Companion Website at
www.pearsoned.co.uk/housecroft to find valuable student
learning material including:
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Multiple choice questions to help test your learning
Rotatable 3D structures taken from the book
Mathematics Tutor
Annotated links to relevant sites on the web


CHEMISTRY
An Introduction to Organic, Inorganic and
Physical Chemistry
3rd edition

Catherine E. Housecroft
Edwin C. Constable


Pearson Education Limited
Edinburgh Gate
Harlow
Essex CM20 2JE
England
and Associated Companies throughout the world
Visit us on the World Wide Web at:

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First published under the Longman imprint 1997
Second edition 2002
Third edition 2006
# Pearson Education Limited 1997, 2006
The rights of Catherine E. Housecroft and Edwin C. Constable 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
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All trademarks used herein are the property of their respective owners. The use of any
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or endorsement of this book by such owners.
ISBN 0 131 27567 4
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
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The publisher’s policy is to use paper manufactured from sustainable forests.


Summary of contents

Preface
About the authors
Acknowledgements

xxi
xxiii
xxviii

1

Some basic concepts

1

2

Thermochemistry

56

3

Atoms and atomic structure

79

4

Homonuclear covalent bonds

118

5

Heteronuclear diatomic molecules

167

6

Polyatomic molecules: shapes

200

7

Polyatomic molecules: bonding

236

8

Ions

263

9

Elements

301

10

Mass spectrometry

330

11

Introduction to spectroscopy

344

12

Vibrational and rotational spectroscopies

356

13

Electronic spectroscopy

387

14

NMR spectroscopy

401

15

Reaction kinetics

428

16

Equilibria

487

17

Thermodynamics

530

18

Electrochemistry

575

19

The conductivity of ions in solution

597

20

Periodicity

609

21

Hydrogen and the s-block elements

623

22

p-Block and high oxidation state d-block elements

668

23

Coordination complexes of the d-block metals

737

24

Carbon compounds: an introduction

792

25

Acyclic and cyclic alkanes

831


vi

Summary of contents

26

Alkenes and alkynes

839

27

Polar organic molecules: an introduction

904

28

Halogenoalkanes

911

29

Ethers

943

30

Alcohols

961

31

Amines

987

32

Aromatic compounds

1007

33

Carbonyl compounds

1060

34

Aromatic heterocyclic compounds

1111

35

Molecules in nature

1150

Appendices

1184

Answers to non-descriptive problems

1221

Index

1235


Contents

Preface

About the authors
Acknowledgements
1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19

2
2.1
2.2
2.3
2.4
2.5
2.6

2.7
2.8
2.9
2.10

Some basic concepts

xxi
xxiii
xxviii
1

What is chemistry and why is it important?
What is the IUPAC?
SI units
The proton, electron and neutron
The elements
States of matter
Atoms and isotopes
The mole and the Avogadro constant
Gas laws and ideal gases
The periodic table
Radicals and ions
Molecules and compounds: bond formation
Molecules and compounds: relative molecular mass and moles
Concentrations of solutions
Reaction stoichiometry
Oxidation and reduction, and oxidation states
Empirical, molecular and structural formulae
Basic nomenclature

Final comments
Problems

1
3
3
6
7
8
11
14
14
24
26
28
29
30
32
39
45
48
52
53

Thermochemistry

56

Factors that control reactions
Change in enthalpy of a reaction

Measuring changes in enthalpy: calorimetry
Standard enthalpy of formation
Calculating standard enthalpies of reaction
Enthalpies of combustion
Hess’s Law of Constant Heat Summation
Thermodynamic and kinetic stability
Phase changes: enthalpies of fusion and vaporization
An introduction to intermolecular interactions
Summary
Problems

56
57
58
63
64
66
68
71
71
74
76
76


viii

Contents

3

3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
3.17
3.18
3.19
3.20
3.21

4
4.1
4.2
4.3
4.4
4.5
4.6
4.7

4.8
4.9
4.10
4.11
4.12
4.13
4.14
4.15
4.16
4.17
4.18

Atoms and atomic structure

79

The importance of electrons
The classical approach to atomic structure
The Bohr atom – still a classical picture
Quanta
Wave–particle duality
The uncertainty principle
The Schroădinger wave equation
Probability density
The radial distribution function, 4r2 RðrÞ2
Quantum numbers
Atomic orbitals
Relating orbital types to the principal quantum number
More about radial distribution functions
Applying the Schroădinger equation to the hydrogen atom

Penetration and shielding
The atomic spectrum of hydrogen and selection rules
Many-electron atoms
The aufbau principle
Electronic configurations
The octet rule
Monatomic gases
Summary
Problems

79
80
81
82
82
83
84
86
87
88
90
94
94
96
98
100
106
106
108
111

112
116
117

Homonuclear covalent bonds

118

Introduction
Measuring internuclear distances
The covalent radius of an atom
An introduction to bond energy: the formation of the diatomic
molecule H2
Bond energies and enthalpies
The standard enthalpy of atomization of an element
Determining bond enthalpies from standard heats of formation
The nature of the covalent bond in H2
Lewis structure of H2
The problem of describing electrons in molecules
Valence bond (VB) theory
Molecular orbital (MO) theory
What do the VB and MO theories tell us about the molecular
properties of H2 ?
Homonuclear diatomic molecules of the first row elements – the
s-block
Orbital overlap of p atomic orbitals
Bond order
Relationships between bond order, bond length and bond enthalpy
Homonuclear diatomic molecules of the first row p-block elements:
F2 and O2

118
119
123
125
127
129
133
134
135
136
137
139
144
144
146
148
149
149


Contents

4.19
4.20
4.21
4.22
4.23

5

5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
5.10
5.11
5.12
5.13
5.14
5.15
5.16

6
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
6.11
6.12

6.13

ix

Orbital mixing and – crossover
Homonuclear diatomic molecules of the first row p-block elements:
B2 , C2 and N2
Periodic trends in the homonuclear diatomic molecules of the first
row elements
The diatomic species O2 , [O2 ]ỵ , [O2 ] and [O2 ]2
Group trends among homonuclear diatomic molecules
Summary
Problems

152

158
159
160
164
165

Heteronuclear diatomic molecules

167

Introduction
Lewis structures for HF, LiF and LiH
The valence bond approach to the bonding in HF, LiF and LiH
The molecular orbital approach to the bonding in a heteronuclear

diatomic molecule
The molecular orbital approach to the bonding in LiH, LiF and HF
Bond enthalpies of heteronuclear bonds
Electronegativity – Pauling values ( P )
The dependence of electronegativity on oxidation state and bond order
An overview of the bonding in HF
Other electronegativity scales
Polar diatomic molecules
Isoelectronic species
The bonding in CO by the Lewis and valence bond approaches
The bonding in carbon monoxide by MO theory
[CN] and [NO]ỵ : two ions isoelectronic with CO
[NO]ỵ , NO and [NO]ÿ
Summary
Problems

167
168
168
170
172
177
179
181
182
182
183
186
187
189

193
196
197
197

Polyatomic molecules: shapes

200

Introduction
The geometries of triatomic molecules
Molecules larger than triatomics described as having linear or bent
geometries
Geometries of molecules within the p-block: the first row
Heavier p-block elements
Mid-chapter problems
The valence-shell electron-pair repulsion (VSEPR) model
The VSEPR model: some ambiguities
The Kepert model
Application of the Kepert model
An exception to the Kepert model: the square planar geometry
Stereoisomerism
Two structures that are close in energy: the trigonal bipyramid and
square-based pyramid
Shape and molecular dipole moments

200
203

154

205
206
208
211
212
218
220
220
222
222
226
228


x

Contents

6.14

7
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8

7.9

8
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14
8.15
8.16
8.17
8.18
8.19

9
9.1
9.2

Carbon: an element with only three common geometries
Summary
Problems

232
233
234

Polyatomic molecules: bonding

236

Introduction
Molecular shape and the octet rule: the first row elements
Molecular shape and the octet rule: the heavier p-block elements
Valence bond theory and hybridization
Hybridization and molecular shape in the p-block
Hybridization: the -bonding framework
Hybridization: the role of unhybridized atomic orbitals
Molecular orbital theory and polyatomic molecules
How do the VB and MO pictures of the bonding in methane compare?
Summary
Problems

236
236
243
247
253
254
255
257
259

261
261

Ions

263

Introduction
Electron density maps
Ionization energy
Trends in ionization energies
Electron affinity
Electrostatic interactions between ions
Ionic lattices
The sodium chloride (rock salt) structure type
Determining the stoichiometry of a compound from the solid state
structure: NaCl
The caesium chloride structure type
The fluorite (calcium fluoride) structure type
The rutile (titanium(IV) oxide) structure type
The structures of the polymorphs of zinc(II) sulfide
Sizes of ions
Lattice energy – a purely ionic model
Lattice energy – experimental data
A comparison of lattice energies determined by the Born–Lande´
equation and the Born–Haber cycle
Polarization of ions
Determining the Avogadro constant from an ionic lattice
Summary
Problems

263
265
266
267
273
275
277
279

296
297
297
298
299

Elements

301

Introduction
Close-packing of spheres

301
301

280
282
282
283

285
286
290
294


Contents

9.3
9.4
9.5
9.6
9.7
9.8
9.9
9.10
9.11
9.12
9.13

10
10.1
10.2
10.3
10.4
10.5

11
11.1
11.2

11.3
11.4
11.5

12
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8

xi

Simple cubic and body-centred cubic packing of spheres
A summary of the similarities and differences between close-packed
and non-close-packed arrangements
Crystalline and amorphous solids
Solid state structures of the group 18 elements
Elemental solids containing diatomic molecules
Elemental molecular solids in groups 15 and 16
A molecular allotrope of carbon: C60
Solids with infinite covalent structures
The structures of metallic elements at 298 K
Metallic radius
Metallic bonding
Summary
Problems

305
307
308
308
309
311
314
316
321
324
324
328
328

Mass spectrometry

330

Introduction
Recording a mass spectrum
Isotope distributions
Fragmentation patterns
Case studies
Summary
Problems

330
330
332

336
337
341
342

Introduction to spectroscopy

344

What is spectroscopy?
The relationship between the electromagnetic spectrum and
spectroscopic techniques
Timescales
The Beer–Lambert Law
Colorimetry
Summary
Problems

344
346
347
348
349
353
353

Vibrational and rotational spectroscopies

356

Introduction
The vibration of a diatomic molecule
Infrared spectra of diatomic molecules
Infrared spectroscopy of triatomic molecules
Vibrational degrees of freedom
The use of IR spectroscopy as an analytical tool
Deuteration: the effects on IR spectroscopic absorptions
Rotating molecules and moments of inertia

356
356
362
363
366
367
376
378


xii

Contents

12.9

13
13.1
13.2
13.3
13.4

13.5
13.6

14
14.1
14.2
14.3
14.4
14.5
14.6
14.7
14.8
14.9

15
15.1
15.2
15.3
15.4
15.5
15.6
15.7
15.8
15.9
15.10
15.11
15.12
15.13

Rotational spectroscopy of linear rigid rotor molecules

Summary
Problems

380
383
383

Electronic spectroscopy

387

Introduction
Absorption of ultraviolet and visible light
Electronic transitions in the vacuum-UV
Choosing a solvent for UV–VIS spectroscopy
-Conjugation
The visible region of the spectrum
Summary
Problems

387
387
389
389
390
397
399
400

NMR spectroscopy

401

Introduction
Nuclear spin states
Recording an NMR spectrum
Nuclei: resonance frequencies, isotope abundances and chemical shift
values
Choosing a solvent for NMR spectroscopy
Molecules with one environment
Molecules with more than one environment
1
H NMR spectra: chemical environments
Nuclear spin–spin coupling between nuclei with I ¼ 12
Summary
Problems

401
401
402
404
407
407
408
411
414
425
426

Reaction kinetics

428

Introduction
Rate equations: the dependence of rate on concentration
Does a reaction show a zero, first or second order dependence on A?
Rate equations for reactions with more than one reactant
Integrated rate equations
Radioactive decay
The dependence of rate on temperature: the Arrhenius equation
Catalysis and autocatalysis
Reversible reactions
Elementary reactions and molecularity
Microscopic reaction mechanisms: unimolecular and bimolecular
elementary steps
Combining elementary steps into a reaction mechanism
Proposing a mechanism consistent with experimental rate data

428
432
435
441
443
450
453
458
461
463
465
466

469


Contents

15.14
15.15

16
16.1
16.2
16.3
16.4
16.5
16.6
16.7
16.8
16.9

17
17.1
17.2
17.3
17.4
17.5
17.6
17.7
17.8
17.9
17.10

17.11
17.12

18
18.1
18.2
18.3
18.4
18.5
18.6
18.7
18.8

xiii

Radical chain reactions
Michaelis–Menten kinetics
Summary
Problems

472
475
480
482

Equilibria

487

Introduction

Le Chatelier’s principle
Equilibrium constants
Acid–base equilibria
Acids and bases in aqueous solution: pH
Acids and bases in aqueous solution: speciation
Buffer solutions
Acid–base titrations
Acid–base indicators
Summary
Problems

487
488
489
495
502
507
510
516
524
526
528

Thermodynamics

530

Introduction
Internal energy, U
The bomb calorimeter

Heat capacities
The variation of ÁH with temperature: Kirchhoff’s equation
Equilibrium constants and changes in Gibbs energy
The temperature dependence of ÁG o and Kp : some experimental data
The relationship between ÁGo and K: the reaction isotherm
Gibbs energy, enthalpy and entropy
Entropy: the Second and Third Laws of Thermodynamics
Enthalpy changes and solubility
Solubility product constant, Ksp
Summary
Problems

530
533
538
540
542
544
547
551
555
557
565
567
571
572

Electrochemistry

575

Introduction
The Daniell cell and some definitions
The standard hydrogen electrode and standard reduction potentials
The effect of solution concentration on E o : the Nernst equation
Reference electrodes
Electrolytic cells
Faraday’s Laws of Electrolysis
Selected applications of electrochemical cells
Summary
Problems

575
577
579
585
587
588
591
592
594
595


xiv

Contents

19
19.1

19.2
19.3

20
20.1
20.2
20.3
20.4
20.5
20.6

21
21.1
21.2
21.3
21.4
21.5
21.6
21.7
21.8
21.9
21.10
21.11
21.12
21.13

22
22.1
22.2
22.3

22.4
22.5
22.6
22.7

The conductivity of ions in solution

597

Some definitions and units
Molar conductivities of strong and weak electrolytes
Conductivity changes during reactions
Summary
Problems

597
598
603
607
607

Periodicity

609

Introduction
Ground state electronic configurations
Melting and boiling points, and enthalpies of atomization
First ionization energies and electron affinities
Metallic, covalent and ionic radii

Periodicity in groups 1 and 18
Summary
Problems

609
610
612
614
617
619
620
621

Hydrogen and the s-block elements

623

Introduction
The element hydrogen
What does hydride imply?
Binary hydrides of the s- and d-block metals
Binary hydrides of group 13 elements
Binary hydrides of group 14 elements
Binary hydrides of group 15 elements
Hydrogen bonding
Hydrides of group 16 elements
Binary compounds containing hydrogen and group 17 elements:
hydrogen halides
Group 1: the alkali metals
The group 2 metals

Diagonal relationships in the periodic table: lithium and magnesium
Summary
Problems

623
624
630
631
633
638
638
641
646
651
654
658
664
665
666

p-Block and high oxidation state d-block elements

668

Introduction
Oxidation states
Group 13: boron
Group 13: aluminium
Group 13: gallium, indium and thallium
Group 14: carbon and silicon

Group 14: germanium, tin and lead

668
669
670
675
679
681
689


Contents

22.8
22.9
22.10
22.11
22.12
22.13
22.14

23
23.1
23.2
23.3
23.4
23.5
23.6
23.7
23.8

23.9
23.10
23.11
23.12
23.13
23.14

24
24.1
24.2
24.3
24.4
24.5
24.6
24.7
24.8
24.9
24.10

25
25.1
25.2

xv

Group 15: nitrogen and phosphorus
Group 15: arsenic, antimony and bismuth
Group 16: oxygen and sulfur
Group 16: selenium and tellurium
Group 17: the halogens

Group 18: the noble gases
Some compounds of high oxidation state d-block elements
Summary
Problems

693
709
713
721
723
730
732
735
735

Coordination complexes of the d-block metals

737

Introduction: some terminology
Electronic configurations of the d-block metals and their ions
Ligands
The electroneutrality principle
Isomerism
The formation of first row d-block metal coordination complexes
Ligand exchange and complex stability constants
Hard and soft metals and donor atoms
The thermodynamic stability of hexaaqua metal ions
Colours
Crystal field theory

Electronic spectra
Magnetism: the spin-only formula
Metal carbonyl compounds
Summary
Problems

737
741
743
751
753
756
765
768
770
773
774
779
780
784
788
789

Carbon compounds: an introduction

792

Introduction
Drawing structural formulae
Types of carbon compounds

Hydrocarbon frameworks and nomenclature
Primary, secondary, tertiary and quaternary carbon atoms
Isomerism
Constitutional isomerism
Stereoisomerism and diastereoisomers
Conformation
Some general features of a reaction mechanism
Summary
Problems

792
792
794
799
805
806
807
809
820
823
826
827

Acyclic and cyclic alkanes

831

Cycloalkanes: structures and nomenclature
Cycloalkanes: ring conformation and ring strain

831
833


xvi

Contents

25.3
25.4
25.5
25.6
25.7
25.8
25.9

26
26.1
26.2
26.3
26.4
26.5
26.6
26.7
26.8
26.9
26.10
26.11
26.12
26.13

27
27.1
27.2
27.3
27.4

28
28.1
28.2
28.3
28.4
28.5
28.6

Physical properties of alkanes
Industrial interconversions of hydrocarbons
Synthesis of cycloalkanes
Reactions of straight chain alkanes
The chlorination of CH4 : a radical chain reaction
Competitive processes: the chlorination of propane and
2-methylpropane
Reactions of cycloalkanes
Summary
Problems

838
841
842
846

848

Alkenes and alkynes

859

Structure, bonding and spectroscopy
Cycloalkenes: structures and nomenclature
Syntheses of acyclic and cyclic alkenes
Reactions of alkenes 1: an introduction
The mechanism of electrophilic addition
Reactions of alkenes 2: additions and C¼C oxidation and cleavage
Radical substitution and addition in alkenes
Polymerization of alkenes
Double bond migration and isomerization in alkenes
Hydroboration of alkenes
Synthesis of alkynes
Reactions of alkynes
Protection of a terminal alkyne: the Me3 Si protecting group
Summary
Problems

859
862
863
867
869
876
881
883

889
890
891
892
898
900
901

Polar organic molecules: an introduction

904

Chapter aims
Electronegativities and polar bonds
Molecular dipole moments
Inductive and field effects
Summary
Problems

904
904
905
907
909
910

Halogenoalkanes

911

Structure and nomenclature
Synthesis of halogenoalkanes
Physical properties
Reactions of halogenoalkanes: formation of Grignard and
organolithium reagents
Reactions of halogenoalkanes: nucleophilic substitution versus
elimination
Nucleophilic substitution

911
912
914

851
855
856
857

915
918
918


Contents

28.7
28.8
28.9

29

29.1
29.2
29.3
29.4
29.5
29.6

30
30.1
30.2
30.3
30.4
30.5
30.6

31
31.1
31.2
31.3
31.4
31.5
31.6

32
32.1
32.2
32.3

xvii

Elimination reactions
Nucleophilic substitution in competition with elimination reactions
Selected reactions of halogenoalkanes
Summary
Problems

931
936
937
939
940

Ethers

943

Introduction
Structure and nomenclature
Synthesis
Physical properties
Identification of ethers by IR spectroscopy
Reactivity of ethers
Summary
Problems

943
943
946
949
953

954
959
959

Alcohols

961

Structure and nomenclature
Industrial manufacture and synthesis
Physical properties
Spectroscopic characteristics of alcohols
Reactivity of alcohols
Protection of OH groups
Summary
Problems

961
962
970
972
975
981
984
985

Amines

987

Structure and nomenclature
Inversion at nitrogen in amines
Synthesis
Physical properties of amines
Spectroscopic characterization of amines
Reactivity
Summary
Problems

987
990
991
994
998
1000
1004
1005

Aromatic compounds

1007

An introduction to aromatic hydrocarbons
The structure of benzene and its delocalized bonding
Aromaticity and the Huăckel (4n ỵ 2) rule

1007
1008
1011

xviii

Contents

32.4
32.5
32.6
32.7
32.8
32.9
32.10
32.11
32.12
32.13
32.14

33
33.1
33.2
33.3
33.4
33.5
33.6
33.7
33.8
33.9
33.10
33.11
33.12

33.13
33.14
33.15
33.16

34
34.1
34.2
34.3
34.4
34.5
34.6
34.7
34.8
34.9
34.10

Spectroscopy
Nomenclature
Industrial production of benzene
Physical properties of benzene
Reactivity of benzene
The mechanism of electrophilic substitution
Orientation effects, and ring activation and deactivation
Mid-chapter problems
Toluene
Phenol
Nitrobenzene and aniline
Nucleophilic substitution in aromatic rings
Summary

Problems

1014
1017
1019
1019
1020
1023
1028
1033
1033
1036
1045
1054
1056
1057

Carbonyl compounds

1060

The family of carbonyl compounds
Naming carbonyl compounds
The polar C¼O bond
Structure and bonding
IR and NMR spectroscopy
Keto–enol tautomerism
Aldehydes and ketones: synthesis
Carboxylic acids: synthesis
Esters: synthesis and hydrolysis

Amides: synthesis
Acyl chlorides: synthesis
Carbonyl compounds as acids
Enolate ions in synthesis: electrophilic substitution reactions
Nucleophilic attack at the C¼O carbon atom
Nucleophilic attack at C¼O: the aldol reaction
Nucleophilic attack at C¼O: Claisen condensation
Summary
Problems

1060
1061
1064
1066
1069
1071
1072
1075
1078
1082
1083
1084
1090
1095
1102
1104
1107
1108

Aromatic heterocyclic compounds

1111

Why study heterocyclic compounds?
Isoelectronic replacements for CH and CH2 units
Nomenclature
Structures of and bonding in aromatic heterocycles
Physical properties and uses
Pyrrole, furan and thiophene: syntheses
Pyrrole, furan and thiophene: reactivity
Pyridine and pyrylium ion: syntheses
Pyridine: reactivity
Pyrylium ion: reactivity

1111
1118
1119
1120
1123
1124
1126
1133
1136
1144


Contents

34.11

35
35.1
35.2
35.3
35.4
35.5
35.6
35.7

Appendix
Appendix
Appendix
Appendix
Appendix
Appendix

1
2
3
4
5
6

Appendix 7
Appendix 8
Appendix 9
Appendix 10
Appendix 11
Appendix 12
Appendix 13

Appendix 14

§

xix

Nitrogen-containing heterocycles with more than one heteroatom
Summary
Problems

1144
1147
1148

Molecules in nature

1150

The molecules of life
Monosaccharides
Disaccharides and polysaccharides
Amino acids
Peptides
Proteins
Nucleobases, nucleotides and nucleic acids
Summary
Problems

1150
1150

1157
1160
1163
1169
1173
1181
1182

Appendices

1184

Mathematical symbols
Greek letters with pronunciations
Abbreviations and symbols for quantities and units
The electromagnetic spectrum
Naturally occurring isotopes and their abundances
Van der Waals, metallic, covalent and ionic radii for the s-, p- and
first row d-block elements
Pauling electronegativity values (P ) for selected elements of the
periodic table
Ground state electronic configurations of the elements and ionization
energies for the first five ionizations
Electron affinities
Standard enthalpies of atomization (Áa H o ) of the elements at 298 K
Thermodynamic properties of selected compounds
Selected standard reduction potentials (298 K)
Trivial names in common use for selected inorganic and organic
compounds, inorganic ions and organic substituents
Some regular polyhedra

1184
1185
1186
1190
1192

Answers to non-descriptive problems

1221

Index

1235

Appendices 13 and 14 can be found on the companion website at www.pearsoned.co.uk/housecroft

1195
1198
1199
1202
1203
1204
1219
§
§


xx

Contents

Supporting resources
Visit www.pearsoned.co.uk/housecroft to find valuable online
resources
Companion Website for students
.
.
.
.

Multiple choice questions to help test your learning
Rotatable 3D structures taken from the book
Mathematics Tutor
Annotated links to relevant sites on the web

For instructors
.
.
.

Complete, downloadable Instructor’s Manual
PowerPoint slides that can be downloaded and used as OHTs
Rotatable 3D structures taken from the book

Also: The Companion Website provides the following features:
.
.

.

Search tool to help locate specific items of content
E-mail results and profile tools to send results of quizzes to
instructors
Online help and support to assist with website usage and
troubleshooting

For more information please contact your local Pearson Education
sales representative or visit
www.pearsoned.co.uk/housecroft

OneKey: All you and your students
need to succeed
OneKey is an exclusive new resource for
instructors and students, giving you access to
the best online teaching and learning tools
24 hours a day, 7 days a week.
OneKey means all your resources are in one
place for maximum convenience, simplicity and success.
A OneKey product is available for Chemistry, Third Edition for use
with BlackboardTM, WebCT and CourseCompass. It contains:
.
.
.

A test bank of over 5000 questions
Video clips of experiments
Simulations and interactions

For more information about the OneKey product please contact

your local Pearson Education sales representative or visit
www.pearsoned.co.uk/onekey


Preface

In the third edition of Chemistry, our aims continue to be to provide a single
book that addresses the requirements of a first year university chemistry
course and brings together those areas of chemistry that traditionally have
been taught apart from one another. In this new edition, we have tried to
take into account some of the feedback from colleagues around the world.
Although the core content is based upon attainment expectations in the
United Kingdom educational system, we hope that the entry level is now
appropriate for a wider cross-section of science students. The structure of the
book closely follows that of the second edition. On going to this new
edition, we have strengthened the first chapter by including more worked
examples that cover basic topics such as masses and moles, concentrations
of solutions, reaction stoichiometry and balancing equations. We have
expanded the coverage of thermochemistry, and this now appears as a new
Chapter 2. Throughout the book, we continue to highlight the relevance of
chemistry and related disciplines to everyday life, often through the use of
topic boxes. We have tried to introduce examples with which students
either will be familiar or will have read about in the popular press. This is
an essential way of motivating students who are studying what is often
perceived to be a difficult subject. Because of the number of biological science
students who are now using Chemistry, we have paid increased attention to
topics of biological relevance and have introduced more Environment and
biology topic boxes. With this in mind, a new chapter introduces aromatic
heterocyclic compounds to provide a sound chemical basis for subsequent
discussion of the structure and function of biological molecules.

Feedback from readers of the second edition has been invaluable as we
have considered revisions for the book. Once again, we have agonized about
the level of mathematics, especially in chapters dealing with quantum
mechanics and thermodynamics. We continue to take the view that, although
qualitative discussions are helpful as a way of introducing a student to a
topic, a full understanding cannot be achieved without the use of rigorous
mathematics. Where necessary, mathematical support material is presented
in Theoretical and chemical background topic boxes, and students are also
guided to the Mathematics Tutor that is part of the accompanying website
(www.pearsoned.co.uk/housecroft). One of the topics in this tutor deals
with significant figures and decimal places. Readers should note that in the
worked examples in this book in which several steps are worked in full, we
round off the answer at the end of each step.
We make every effort to keep up to date with recommendations put
forward by the IUPAC, and a significant change in Chapter 14 arises from
the 2001 recommendations of the IUPAC concerning the reporting of
chemical shifts in NMR spectroscopy. The recommendation to write, for
example,  4.5 ppm, reverses the previous recommendation (1972) to report
the value as  4.5.


xxii

Preface

As in the previous edition of Chemistry, the three-dimensional molecular
structures in the book have been drawn using atomic coordinates accessed
from the Cambridge Crystallographic Data Base and implemented through
the ETH in Zuărich, or from the Protein Data Bank ( />We are grateful to colleagues whom we acknowledged in the preface to the
second edition, and to the review panel set up by the publisher. Additional

thanks go to Professors Robin Harris, Ken McKendrick, Helma Wennemers
and John Nielsen for specific comments about the second edition of the
book, to Professor Ron Gillespie for his thoughts on bonding in inorganic
molecules, to Dr Egbert Figgemeier for invaluable discussions relating to
thermodynamics, and to Professor Neil Connelly for keeping us informed
about recent changes to the IUPAC guidelines for inorganic nomenclature.
As always, we are indebted to our colleagues at Pearson Education who have
guided the schedule for the project and have developed the accompanying
website. We extend warm thanks to Bridget Allen, Kevin Ancient, Melanie
Beard, Patrick Bonham, Pauline Gillett, Simon Lake, Mary Lince, Paul Nash
and Ros Woodward.
Finally, this book is dedicated to Philby and Isis. Our loyal companions are
never far from the computer and have contributed to the project in a unique way
that only Siamese cats know how. A little older, certainly; a little wiser, possibly.
Catherine E. Housecroft
Edwin C. Constable
Basel, March 2005


About the authors

Photo: Pam Marshall

Chemistry draws on the experience of this husband
and wife author team over 25 years of teaching
chemistry in the United Kingdom, North America,
Switzerland and South Africa to school, college
and university students. After her PhD in
Durham, Catherine E. Housecroft began her
career as a teacher at Oxford Girls’ High School

and went on to teach general chemistry to nursing
majors at St Mary’s College, Notre Dame, USA,
and then to undergraduates at the University of
New Hampshire. She returned to the UK in 1986
as a teaching Fellow of Newnham College and
Lector at Trinity College, Cambridge, later
becoming a Royal Society Research Fellow and
then university lecturer in Inorganic Chemistry in
Cambridge, where she chaired the Teaching
Committee in the chemistry department. After
his DPhil in Oxford, Edwin C. Constable moved
to the University of Cambridge where he became
a university lecturer in Inorganic Chemistry. He
was a teaching Fellow of Robinson College in Cambridge, and has lectured
in and tutored both inorganic and organic chemistry.
After Cambridge, the authors held faculty positions in the Department of
Chemistry at the University of Basel, Switzerland. From 2000 to 2002, they
held positions as Professors of Chemistry at the University of Birmingham,
UK. In 2002, they returned to the University of Basel and are currently
Professors in the Department of Chemistry there.
Professor Housecroft has a theoretical and experimental organometallic
and supramolecular chemistry research background and has published over
250 research papers and review articles. Professor Constable’s research
areas span both organic and inorganic chemistry, with particular interest
in supramolecular chemistry and nanotechnology; he has published over
350 research papers. Both are established authors and have published both
general and inorganic chemistry texts as well as books on specialist topics.
Professor Housecroft is an Executive Editor of the international journal
Polyhedron, and Professor Constable serves on the editorial boards of several
international journals.

xxiv

Guided tour of the book

Chapter introductions outline the core content
of the chapter.

Cross-references in the margins allow students to
make links between different areas of chemistry
and see it as a more integrated whole.

Key definitions are highlighted in the text.

Topic boxes
relate
chemistry in
each chapter
to real
life examples
from biology,
the
environment
and
commercial
and laboratory
applictions, or
provide
relevant

theoretical
background.