Shriver and atkins inorganic chemistry, 5th edition ( PDFDrive )

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The elements

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Name

Symbol

Atomic

number

Molar mass
(g molϪ1)

Name

Symbol

Atomic
number

Molar mass
(g molϪ1)

Actinium
Aluminium (aluminum)
Americium
Antimony
Argon
Arsenic
Astatine
Barium
Berkelium
Beryllium
Bismuth
Bohrium
Boron
Bromine
Cadmium

Caesium (cesium)
Calcium
Californium
Carbon
Cerium
Chlorine
Chromium
Cobalt
Copernicum
Copper
Curium
Darmstadtium
Dubnium
Dysprosium
Einsteinium
Erbium
Europium
Fermium
Fluorine
Francium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Hassium
Helium
Holmium
Hydrogen
Indium

Iodine
Iridium
Iron
Krypton
Lanthanum
Lawrencium
Lead
Lithium
Lutetium
Magnesium
Manganese

Ac
Al
Am
Sb
Ar
As
At
Ba
Bk
Be
Bi
Bh
B
Br
Cd
Cs
Ca
Cf

C
Ce
Cl
Cr
Co
?
Cu
Cm
Ds
Db
Dy
Es
Er
Eu
Fm
F
Fr
Gd
Ga
Ge
Au
Hf
Hs
He
Ho
H
In
I
Ir
Fe

Kr
La
Lr
Pb
Li
Lu
Mg
Mn

89
13
95
51
18
33
85
56
97
4
83
107
5
35
48
55
20
98
6
58
17

24
27
112
29
96
110
105
66
99
68
63
100
9
87
64
31
32
79
72
108
2
67
1
49
53
77
26
36
57
103

82
3
71
12
25

227
26.98
243
121.76
39.95
74.92
210
137.33
247
9.01
208.98
264
10.81
79.90
112.41
132.91
40.08
251
12.01
140.12
35.45
52.00
58.93
?

63.55
247
271
262
162.50
252
167.27
151.96
257
19.00
223
157.25
69.72
72.64
196.97
178.49
269
4.00
164.93
1.008
114.82
126.90
192.22
55.84
83.80
138.91
262
207.2
6.94
174.97

24.31
54.94

Meitnerium
Mendelevium
Mercury
Molybdenun
Neodymium
Neon
Neptunium
Nickel
Niobium
Nitrogen
Nobelium
Osmium
Oxygen
Palladium
Phosphorus
Platinum
Plutonium
Polonium
Potassium
Praseodymium
Promethium
Protactinium
Radium
Radon
Rhenium
Rhodium
Roentgenium

Rubidium
Ruthenium
Rutherfordium
Samarium
Scandium
Seaborgium
Selenium
Silicon
Silver
Sodium
Strontium
Sulfur
Tantalum
Technetium
Tellurium
Terbium
Thallium
Thorium
Thulium
Tin
Titanium
Tungsten
Uranium
Vanadium
Xenon
Ytterbium
Yttrium
Zinc
Zirconium

Mt
Md
Hg
Mo
Nd
Ne
Np
Ni
Nb
N
No
Os
O
Pd
P
Pt
Pu
Po
K
Pr
Pm
Pa
Ra
Rn
Re
Rh
Rg
Rb
Ru
Rf

Sm
Sc
Sg
Se
Si
Ag
Na
Sr
S
Ta
Tc
Te
Tb
TI
Th
Tm
Sn
Ti
W
U
V
Xe
Yb
Y
Zn
Zr

109
101
80

42
60
10
93
28
41
7
102
76
8
46
15
78
94
84
19
59
61
91
88
86
75
45
111
37
44
104
62
21
106

34
14
47
11
38
16
73
43
52
65
81
90
69
50
22
74
92
23
54
70
39
30
40

268
258
200.59
95.94
144.24
20.18

237
58.69
92.91
14.01
259
190.23
16.00
106.42
30.97
195.08
244
209
39.10
140.91
145
231.04
226
222
186.21
102.91
272
85.47
101.07
261
150.36
44.96
266
78.96
28.09
107.87

22.99
87.62
32.06
180.95
98
127.60
158.93
204.38
232.04
168.93
118.71
47.87
183.84
238.03
50.94
131.29
173.04
88.91
65.41
91.22

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Shriver & Atkins’

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Shriver & Atkins’

W. H. Freeman and Company
New York

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© 2010 P.W. Atkins, T.L. Overton, J.P. Rourke, M.T. Weller,
and F.A. Armstrong
All rights reserved.
ISBN 978–1–42–921820–7
Published in Great Britain by Oxford University Press
This edition has been authorized by Oxford University Press for sale in the
United States and Canada only and not for export therefrom.
First printing
W. H. Freeman and Company,
41 Madison Avenue, New York, NY 10010
www.whfreeman.com

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Shriver and Atkins' Inorganic Chemistry, Fifth Edition

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Preface
Our aim in the fifth edition of Shriver and Atkins’ Inorganic Chemistry is to provide a

comprehensive and contemporary introduction to the diverse and fascinating discipline of
inorganic chemistry. Inorganic chemistry deals with the properties of all of the elements
in the periodic table. These elements range from highly reactive metals, such as sodium,
to noble metals, such as gold. The nonmetals include solids, liquids, and gases, and range
from the aggressive oxidizing agent fluorine to unreactive gases such as helium. Although
this variety and diversity are features of any study of inorganic chemistry, there are underlying patterns and trends which enrich and enhance our understanding of the discipline.
These trends in reactivity, structure, and properties of the elements and their compounds
provide an insight into the landscape of the periodic table and provide a foundation on
which to build understanding.
Inorganic compounds vary from ionic solids, which can be described by simple applications of classical electrostatics, to covalent compounds and metals, which are best
described by models that have their origin in quantum mechanics. We can rationalize and
interpret the properties of most inorganic compounds by using qualitative models that
are based on quantum mechanics, such as atomic orbitals and their use to form molecular
orbitals. The text builds on similar qualitative bonding models that should already be familiar from introductory chemistry courses. Although qualitative models of bonding and
reactivity clarify and systematize the subject, inorganic chemistry is essentially an experimental subject. New areas of inorganic chemistry are constantly being explored and new
and often unusual inorganic compounds are constantly being synthesized and identified.
These new inorganic syntheses continue to enrich the field with compounds that give us
new perspectives on structure, bonding, and reactivity.
Inorganic chemistry has considerable impact on our everyday lives and on other scientific disciplines. The chemical industry is strongly dependent on it. Inorganic chemistry
is essential to the formulation and improvement of modern materials such as catalysts,
semiconductors, optical devices, superconductors, and advanced ceramic materials. The
environmental and biological impact of inorganic chemistry is also huge. Current topics
in industrial, biological, and environmental chemistry are mentioned throughout the book
and are developed more thoroughly in later chapters.
In this new edition we have refined the presentation, organization, and visual representation. All of the book has been revised, much has been rewritten and there is some completely new material. We have written with the student in mind, and we have added new
pedagogical features and have enhanced others.
The topics in Part 1, Foundations, have been revised to make them more accessible
to the reader with more qualitative explanation accompanying the more mathematical
treatments.
Part 2, The elements and their compounds, has been reorganized. The section starts with

a new chapter which draws together periodic trends and cross references forward to the
descriptive chapters. The remaining chapters start with hydrogen and proceed across the
periodic table from the s-block metals, across the p block, and finishing with the d- and
f-block elements. Most of these chapters have been reorganized into two sections: Essentials describes the essential chemistry of the elements and the Detail provides a more thorough account. The chemical properties of each group of elements and their compounds are
enriched with descriptions of current applications. The patterns and trends that emerge are
rationalized by drawing on the principles introduced in Part 1.
Part 3, Frontiers, takes the reader to the edge of knowledge in several areas of current
research. These chapters explore specialized subjects that are of importance to industry,
materials, and biology, and include catalysis, nanomaterials, and bioinorganic chemistry.
All the illustrations and the marginal structures—nearly 1500 in all—have been redrawn and are presented in full colour. We have used colour systematically rather than just
for decoration, and have ensured that it serves a pedagogical purpose.

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We are confident that this text will serve the undergraduate chemist well. It provides ther a c k e r - s o f t w a r e
theoretical building blocks with which to build knowledge and understanding of inorganic
chemistry. It should help to rationalize the sometimes bewildering diversity of descriptive
chemistry. It also takes the student to the forefront of the discipline and should therefore
complement many courses taken in the later stages of a programme.
Peter Atkins
Tina Overton
Jonathan Rourke
Mark Weller
Fraser Armstrong
Mike Hagerman
.

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Acknowledgements
We have taken care to ensure that the text is free of errors. This is difficult in a rapidly
changing field, where today’s knowledge is soon replaced by tomorrow’s. We would
particularly like to thank Jennifer Armstrong, University of Southampton; Sandra Dann,
University of Loughborough; Rob Deeth, University of Warwick; Martin Jones, Jennifer
Creen, and Russ Egdell, University of Oxford, for their guidance and advice.
Many of the figures in Chapter 27 were produced using PyMOL software; for more
information see DeLano, W.L. The PyMOL Molecular Graphics System (2002), De Lano
Scientific, San Carlos, CA, USA.
We acknowledge and thank all those colleagues who so willingly gave their time and
expertise to a careful reading of a variety of draft chapters.
Rolf Berger, University of Uppsala, Sweden

Richard Henderson, University of Newcastle

Harry Bitter, University of Utrecht, The Netherlands

Eva Hervia, University of Strathclyde

Richard Blair, University of Central Florida

Brendan Howlin, University of Surrey

Andrew Bond, University of Southern Denmark, Denmark

Songping Huang, Kent State University

Darren Bradshaw, University of Liverpool

Carl Hultman, Gannon University

Paul Brandt, North Central College

Stephanie Hurst, Northern Arizona University

Karen Brewer, Hamilton College

Jon Iggo, University of Liverpool

George Britovsek, Imperial College, London

S. Jackson, University of Glasgow

Scott Bunge, Kent State University

Michael Jensen, Ohio University

David Cardin, University of Reading

Pavel Karen, University of Oslo, Norway

Claire Carmalt, University College London

Terry Kee, University of Leeds

Carl Carrano, San Diego State University

Paul King, Birbeck, University of London

Neil Champness, University of Nottingham

Rachael Kipp, Suffolk University

Ferman Chavez, Oakland University

Caroline Kirk, University of Loughborough

Ann Chippindale, University of Reading

Lars Kloo, KTH Royal Institute of Technology, Sweden

Karl Coleman, University of Durham

Randolph Kohn, University of Bath

Simon Collison, University of Nottingham

Simon Lancaster, University of East Anglia

Bill Connick, University of Cincinnati

Paul Lickiss, Imperial College, London

Stephen Daff, University of Edinburgh

Sven Lindin, University of Stockholm, Sweden

Sandra Dann, University of Loughborough

Paul Loeffler, Sam Houston State University

Nancy Dervisi, University of Cardiff

Paul Low, University of Durham

Richard Douthwaite, University of York

Astrid Lund Ramstrad, University of Bergen, Norway

Simon Duckett, University of York

Jason Lynam, University of York

A.W. Ehlers, Free University of Amsterdam, The Netherlands

Joel Mague, Tulane University

Anders Eriksson, University of Uppsala, Sweden

Francis Mair, University of Manchester

Andrew Fogg, University of Liverpool

Mikhail Maliarik, University of Uppsala, Sweden

Margaret Geselbracht, Reed College

David E. Marx, University of Scranton

Gregory Grant, University of Tennessee

Katrina Miranda, University of Arizona

Yurii Gun’ko, Trinity College Dublin

Grace Morgan, University College Dublin

Simon Hall, University of Bristol

Ebbe Nordlander, University of Lund, Sweden

Justin Hargreaves, University of Glasgow

Lars Ưhrstrưm, Chalmers (Goteborg), Sweden

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T. B. Rauchfuss, University of Illinois

Jake Soper, Georgia Institute of Technology

Jan Reedijk, University of Leiden, The Netherlands

Jonathan Steed, University of Durham

David Richens, St Andrews University

Gunnar Svensson, University of Stockholm, Sweden

Denise Rooney, National University of Ireland, Maynooth

Andrei Verdernikov, University of Maryland

Graham Saunders, Queens University Belfast

Ramon Vilar, Imperial College, London

Ian Shannon, University of Birmingham

Keith Walters, Northern Kentucky University

P. Shiv Halasyamani, University of Houston

Robert Wang, Salem State College

Stephen Skinner, Imperial College, London

David Weatherburn, University of Victoria, Wellington

Bob Slade, University of Surrey

Paul Wilson, University of Bath

Peter Slater, University of Surrey

Jingdong Zhang, Denmark Technical University

LeGrande Slaughter, Oklahoma State University

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Sheila Smith, University of Michigan

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Dan Price, University of Glasgow

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Ivan Parkin,
University College London

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Acknowledgements

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About the book

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Inorganic chemistry is an extensive subject that at first sight can seem daunting. We have
made every effort to help by organizing the information in this textbook systematically,
and by including numerous features that are designed to make learning inorganic chemistry more effective and more enjoyable. Whether you work through the book chronologically or dip in at an appropriate point in your studies, this text will engage you and help you
to develop a deeper understanding of the subject. We have also provided further electronic
resources in the accompanying Book Companion Site. The following paragraphs explain
the features of the text and website in more detail.

Organizing the information
Key points
The key points act as a summary of the main take-home
message(s) of the section that follows. They will alert you to

the principal ideas being introduced.

2.1 The octet rule
Key point: Atoms share electron pairs until they have acquired an octet of valence electrons.

Lewis found that he could account for the existence of a wide range of molecules by proposing the octet rule:

Context boxes
The numerous context boxes illustrate the diversity of inorganic chemistry and its applications to advanced materials,
industrial processes, environmental chemistry, and everyday
life, and are set out distinctly from the text itself.

B OX 11.1 Lithium batteries
The very negative standard potential and low molar mass of lithium make
it an ideal anode material for batteries. These batteries have high specific
energy (energy production divided by the mass of the battery) because
lithium metal and compounds containing lithium are relatively light in
comparison with some other materials used in batteries, such as lead and
zinc. Lithium batteries are common, but there are many types based on
different lithium compounds and reactions.
The lithium rechargeable battery, used in portable computers and phones,
mainly uses Li1ϪxCoO2 (x Ͻ 1) as the cathode with a lithium/graphite anode,

the redox reaction in a similar way to the cobalt. The latest generation of
electric cars uses lithium battery technology rather than lead-acid cells.
Another popular lithium battery uses thionyl chloride, SOCl2. This system
produces a light, high-voltage cell with a stable energy output. The overall
reaction in the battery is
2 Li(s) ϩ 3 SOCl2(l) q LiCl(s) ϩ S(s) ϩ SO2(l)
The battery requires no additional solvent as both SOCl2 and SO2 are

liquids at the internal battery pressure. This battery is not rechargeable as

Further reading
Each chapter lists sources where more information can be
found. We have tried to ensure that these sources are easily
available and have indicated the type of information each one
provided.

FURTHER READING
P. Atkins and J. de Paula, Physical chemistry. Oxford University Press
and W.H. Freeman & Co (2010). An account of the generation and
use of character tables without too much mathematical background.
For more rigorous introductions, see: J.S. Ogden, Introduction to
molecular symmetry. Oxford University Press (2001).

Resource section
At the back of the book is a collection of resources, including
an extensive data section and information relating to group
theory and spectroscopy.

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Examples and Self-tests
E X A M PL E 6 .1 Identifying symmetry elements

Identify the symmetry elements in the eclipsed and staggered conformations of an ethane molecule.
Answer We need to identify the rotations, reflections, and inversions that leave the molecule apparently
unchanged. Don’t forget that the identity is a symmetry operation. By inspection of the molecular models,
we see that the eclipsed conformation of a CH3CH3 molecule (1) has the elements E, C3, C2, ␴h, ␴v, and S3.
The staggered conformation (2) has the elements E, C3, ␴d, i, and S6.
Self-test 6.1 Sketch the S4 axis of an NHϩ4 ion. How many of these axes does the ion possess?

We have provided numerous Worked examples throughout the
text. Each one illustrates an important aspect of the topic under
discussion or provides practice with calculations and problems.
Each Example is followed by a Self-test, where the answer
is provided as a check that the method has been mastered.
Think of Self-tests as in-chapter exercises designed to help
you monitor your progress.

Exercises
EXERCISES
6.1 Draw sketches to identify the following symmetry elements: (a)
a C3 axis and a ␴v plane in the NH3 molecule, (b) a C4 axis and a ␴h
plane in the square-planar [PtCl4]2– ion.

220, 213, and 83 cm–1. Detailed analysis of the 369 and 295 cm–1
bands show them to arise from totally symmetric modes. Show that
the Raman spectrum is consistent with a trigonal-bipyamidal geometry.

6.2 Which of the following molecules and ions has (a) a centre of
inversion, (b) an S4 axis: (i) CO2, (ii) C2H2, (iii) BF3, (iv) SO42–?

6.9 How many vibrational modes does an SO3 molecule have (a) in
the plane of the nuclei, (b) perpendicular to the molecular plane?

6.3 Determine the symmetry elements and assign the point group of
(a) NH2Cl, (b) CO32–, (c) SiF4, (d) HCN, (e) SiFClBrI, (f) BF4–.

6.10 What are the symmetry species of the vibrations of (a) SF6, (b)
BF3 that are both IR and Raman active?

6.4 How many planes of symmetry does a benzene molecule possess?
What chloro-substituted benzene of formula C6HnCl6–n has exactly
four planes of symmetry?

6.11 What are the symmetry species of the vibrational modes of a C6v
molecule that are neither IR nor Raman active?

6.5 Determine the symmetry elements of objects with the same shape
as the boundary surface of (a) an s orbital, (b) a p orbital, (c) a dxy
orbital, (d) a dz^2 orbital.
6.6 (a) Determine the symmetry group of an SO32– ion. (b) What is
the maximum degeneracy of a molecular orbital in this ion? (c) If
the sulfur orbitals are 3s and 3p, which of them can contribute to
molecular orbitals of this maximum degeneracy?
6.7 (a) Determine the point group of the PF5 molecule. (Use VSEPR, if
necessary, to assign geometry.) (b) What is the maximum degeneracy
of its molecular orbitals? (c) Which P3p orbitals contribute to a
molecular orbital of this degeneracy?

6.12 The [AuCl4]– ion has D4h symmetry. Determine the
representations ⌫ of all 3N displacements and reduce it to obtain the
symmetry species of the irreducible representations.

There are many brief Exercises at the end of each chapter.
Answers are found in the Answers section and fully worked
answers are available in the separate Solutions manual. The
Exercises can be used to check your understanding and gain
experience and practice in tasks such as balancing equations,
predicting and drawing structures, and manipulating data.

6.13 How could IR and Raman spectroscopy be used to distinguish
between: (a) planar and pyramidal forms of PF3, (b) planar and
90º-twisted forms of B2F4 (D2h and D2d, respectively).
6.14 (a) Take the four hydrogen 1s orbitals of CH4 and determine how
they transform under Td. (b) Confirm that it is possible to reduce this
representation to A1 + T2. (c) With which atomic orbitals on C would
it be possible to form MOs with H1s SALCs of symmetry A1 + T2?
6.15 Consider CH4. Use the projection operator method to construct
the SALCs of A1 + T2 symmetry that derive from the four H1s orbitals.

Problems
PROBLEMS
6.1 Consider a molecule IF3O2 (with I as the central atom). How many
isomers are possible? Assign point group designations to each isomer.
6.2 (a) Determine the point group of the most symmetric planar
conformation of B(OH)3 and the most symmetric nonplanar

conformation of B(OH)3. Assume that the BϪOϪH bond angles are
109.5º in all conformations. (b) Sketch a conformation of B(OH)3
that is chiral, once again keeping all three BϪOϪH bond angles
equal to 109.5º.

The Problems are more demanding in content and style than the

Exercises and are often based on a research paper or other additional source of information. Problems generally require a discursive response and there may not be a single correct answer. They
may be used as essay type questions or for classroom discussion.

New Molecular Modelling Problems
Over the past two decades computational chemistry has
evolved from a highly specialized tool, available to relatively
few researchers, into a powerful and practical alternative to
experimentation, accessible to all chemists. The driving force
behind this evolution is the remarkable progress in computer
technology. Calculations that previously required hours or days
on giant mainframe computers may now be completed in a fraction of time on a personal computer. It is natural and necessary
that computational chemistry finds its way into the undergraduate chemistry curriculum. This requires a hands-on approach,
just as teaching experimental chemistry requires a laboratory.
With this edition we have the addition of new molecular
modelling problems for almost every chapter, which can be
found on the text’s companion web site. The problems were
written to be performed using the popular Spartan StudentTM
software. With purchase of this text, students can purchase
Wavefunction’s Spartan StudentTM at a significant discount
from www.wavefun.com/cart/spartaned.html using the code
WHFICHEM. While the problems are written to be performed using Spartan StudentTM they can be completed using
any electronic structure program that allows Hartree-Fock,
density functional, and MP2 calculations.

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About the Book Companion Site
The Book Companion Site which accompanies this book provides teaching and learning
resources to augment the printed book. It is free of charge, and provides additional material for download, much of which can be incorporated into a virtual learning environment.
You can access the Book Companion Site by visiting
www.whfreeman.com/ichem5e
Please note that instructor resources are available only to registered adopters of the textbook. To register, simply visit www.whfreeman.com/ichem5e and follow the appropriate
links. You will be given the opportunity to select your own username and password, which
will be activated once your adoption has been verified.
Student resources are openly available to all, without registration.

Instructor resources
Artwork
An instructor may wish to use the figures from this text in a lecture. Almost all the figures
are available in PowerPoint® format and can be used for lectures without charge (but not
for commercial purposes without specific permission).

Tables of data
All the tables of data that appear in the chapter text are available and may be used under
the same conditions as the figures.

New Molecular Modelling Problems
With this edition we have the addition of new molecular modelling problems for almost
every chapter, which can be found on the text’s companion web site. The problems were
written to be performed using the popular Spartan StudentTM software. With purchase of this

text, students can purchase Wavefunction’s Spartan StudentTM at a significant discount from
www.wavefun.com/cart/spartaned.html using the code WHFICHEM. While the problems
are written to be performed using Spartan StudentTM they can be completed using any electronic structure program that allows Hartree-Fock, density functional, and MP2 calculations.

Student resources
3D rotatable molecular structures
Nearly all the numbered molecular structures featured in the book are available in a
three-dimensional, viewable, rotatable form along with many of the crystal structures
and bioinorganic molecules. These have been produced in collaboration with Dr Karl
Harrison, University of Oxford.

Group theory tables
Comprehensive group theory tables are available for downloading.

Videos of chemical reactions
Video clips showing demonstrations of inorganic chemistry reactions are available for
viewing.

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As with the previous edition, Michael Hagerman, Christopher Schnabel, and Kandalam

Ramanujachary have produced the solutions manual to accompany this book. A Solution Manual (978-142-925255-3) provides completed solutions to most end of chapter
Exercises and Self-tests.

Spartan Student discount
With purchase of this text, students can purchase Wavefunction’s Spartan StudentTM at a
significant discount at www.wavefun.com/cart/spartaned.html using the code WHFICHEM.

Answers to Self-tests and Exercises
Please visit the Book Companion Site at www.whfreeman.com/ichem5e/ to download a
PDF document containing answers to the end-of-chapter exercises in this book.

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Summary of contents
Part 1 Foundations

1

1

Atomic structure

2

Molecular structure and bonding

34

3

The structures of simple solids

65

4

Acids and bases

111

5

Oxidation and reduction

147

6

Molecular symmetry

179

7

An introduction to coordination compounds

199

8

Physical techniques in inorganic chemistry

223

3

Part 2 The elements and their compounds
9

255

Periodic trends

257

10

Hydrogen

274

11

The Group 1 elements

293

12

The Group 2 elements

309

13

The Group 13 elements

325

14

The Group 14 elements

350

15

The Group 15 elements

375

16

The Group 16 elements

398

17

The Group 17 elements

419

18

The Group 18 elements

440

19

The d-block elements

449

20

d-Metal complexes: electronic structure and properties

473

21

Coordination chemistry: reactions of complexes

507

22

d-Metal organometallic chemistry

534

23

The f-block metals

579

Part 3 Frontiers

599

24

Solid-state and materials chemistry

601

25

Nanomaterials, nanoscience, and nanotechnology

653

26

Catalysis

690

27

Biological inorganic chemistry

722

Resource section 1:
Resource section 2:
Resource section 3:
Resource section 4:
Resource section 5:
Resource section 6:

Selected ionic radii
Electronic properties of the elements
Standard potentials
Character tables
Symmetry-adapted orbitals
Tanabe–Sugano diagrams

783
785
787

800
805
809

813

Index

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Contents
Part 1 Foundations

1

3

The structures of simple solids

The description of the structures of solids

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65
66

Atomic structure

3

3.1 Unit cells and the description of crystal structures

66

The origin of the elements

4

3.2 The close packing of spheres

68

3.3 Holes in close-packed structures

70

1

1.1 The nucleosynthesis of light elements
1.2 The nucleosynthesis of heavy elements

5
6

The structures of metals and alloys

71

The structures of hydrogenic atoms

8

3.4 Polytypism

72

1.3 Spectroscopic information

8

3.5 Non-close-packed structures

72

1.4 Some principles of quantum mechanics

9

3.6 Polymorphism of metals

73

10

3.7 Atomic radii of metals

74

15

3.8 Alloys

75

1.5 Atomic orbitals
Many-electron atoms
1.6 Penetration and shielding

16

1.7 The building-up principle

18

1.8 The classification of the elements

20

1.9 Atomic parameters

22

83
86

32

3.12 The calculation of lattice enthalpies

88

33

3.13 Comparison of experimental and theoretical values

90

3.14 The Kapustinskii equation

91

3.15 Consequences of lattice enthalpies

91

EXERCISES
PROBLEMS

Lewis structures

The energetics of ionic bonding

77

87

32

Molecular structure and bonding

3.9 Characteristic structures of ionic solids
3.10 The rationalization of structures

77

3.11 Lattice enthalpy and the Born–Haber cycle

FURTHER READING

2

Ionic solids

34
34

Defects and nonstoichiometry

95

2.1 The octet rule

34

3.16 The origins and types of defects

96

2.2 Resonance

35

3.17 Nonstoichiometric compounds and solid solutions

99

2.3 The VSEPR model

36

The electronic structures of solids

101

39

3.18 The conductivities of inorganic solids

101

2.4 The hydrogen molecule

39

3.19 Bands formed from overlapping atomic orbitals

101

2.5 Homonuclear diatomic molecules

40

3.20 Semiconduction

104

2.6 Polyatomic molecules

40

FURTHER INFORMATION 3.1 The Born–Mayer equation

42

FURTHER READING

107

2.7 An introduction to the theory

43

EXERCISES

108

2.8 Homonuclear diatomic molecules

45

PROBLEMS

108

2.9 Heteronuclear diatomic molecules

48

Valence bond theory

Molecular orbital theory

2.10 Bond properties

50

2.11 Polyatomic molecules

52

2.12 Molecular shape in terms of molecular orbitals

56

Structure and bond properties

58

2.14 Bond strength

59

2.15 Electronegativity and bond enthalpy

59

62

EXERCISES

62

PROBLEMS

63

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111

4.1 Proton transfer equilibria in water

112

4.2 Solvent levelling

119

4.3 The solvent system definition of acids and bases

121

Characteristics of Brønsted acids

61

FURTHER READING

Acids and bases

Brønsted acidity

58

2.13 Bond length

2.16 Oxidation states

4

106

122

4.4 Periodic trends in aqua acid strength

122

4.5 Simple oxoacids

123

4.6 Anhydrous oxides

126

4.7 Polyoxo compound formation

127

4.8 Nonaqueous solvents

129

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6.3 Polar molecules

186

4.10 Group characteristics of Lewis acids

133

6.4 Chiral molecules

187

136

6.5 Molecular vibrations

188

4.11 The fundamental types of reaction

137

4.12 Hard and soft acids and bases

138

6.6 Symmetry-adapted linear combinations

191

4.13 Thermodynamic acidity parameters

140

6.7 The construction of molecular orbitals

192

4.14 Solvents as acids and bases

141

6.8 The vibrational analogy

194

Applications of acid–base chemistry

142

4.15 Superacids and superbases

142

4.16 Heterogeneous acid–base reactions

143

The symmetries of molecular orbitals

Representations
6.9 The reduction of a representation
6.10 Projection operators

191

194
194
196

FURTHER READING

144

FURTHER READING

197

EXERCISES

144

EXERCISES

197

PROBLEMS

145

PROBLEMS

197

Oxidation and reduction

Reduction potentials

147

7

An introduction to coordination compounds

148

The language of coordination chemistry

199

148

7.1 Representative ligands

200

5.2 Standard potentials and spontaneity

149

7.2 Nomenclature

202

5.3 Trends in standard potentials

151

Constitution and geometry

203

5.4 The electrochemical series

153

7.3 Low coordination numbers

204

5.5 The Nernst equation

154

7.4 Intermediate coordination numbers

204

156

7.5 Higher coordination numbers

206

156

7.6 Polymetallic complexes

208

5.6 The influence of pH
5.7 Reactions with water

157

5.8 Oxidation by atmospheric oxygen

159

7.7 Square-planar complexes

209

5.9 Disproportionation and comproportionation

160

7.8 Tetrahedral complexes

210

161

7.9 Trigonal-bipyramidal and square-pyramidal
complexes

210

5.10 The influence of complexation
5.11 The relation between solubility and standard
potentials
The diagrammatic presentation of potential data

Isomerism and chirality

208

162

7.10 Octahedral complexes

211

162

7.11 Ligand chirality

214

5.12 Latimer diagrams

162

5.13 Frost diagrams

164

7.12 Formation constants

215

5.14 Pourbaix diagrams

168

7.13 Trends in successive formation constants

216

5.15 Natural waters

169

7.14 The chelate and macrocyclic effects

218

169

7.15 Steric effects and electron delocalization

219

Chemical extraction of the elements

The thermodynamics of complex formation

215

5.16 Chemical reduction

170

FURTHER READING

220

5.17 Chemical oxidation

174

EXERCISES

221

174

PROBLEMS

221

5.18 Electrochemical extraction
FURTHER READING

175

EXERCISES

176

8

PROBLEMS

177

Diffraction methods

Physical techniques in inorganic chemistry
8.1 X-ray diffraction

6

199

5.1 Redox half-reactions

Redox stability

Molecular symmetry

An introduction to symmetry analysis

179
179

8.2 Neutron diffraction
Absorption spectroscopy

223
223
223
226
227

6.1 Symmetry operations, elements and point groups

179

8.3 Ultraviolet–visible spectroscopy

228

6.2 Character tables

183

8.4 Infrared and Raman spectroscopy

230

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4.9 Examples of Lewis acids and bases
Reactions and properties of lewis acids and bases

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10.5 Reactions of dihydrogen

8.5 Nuclear magnetic resonance

233

10.6 Compounds of hydrogen

283

8.6 Electron paramagnetic resonance

238

10.7 General methods for synthesis

291

8.7 Mössbauer spectroscopy

240

FURTHER READING

291
292
292

241

EXERCISES

8.8 Photoelectron spectroscopy

241

PROBLEMS

8.9 X-ray absorption spectroscopy

242

Ionization-based techniques

8.10 Mass spectrometry
Chemical analysis

243

11 The Group 1 elements

245

Part A: The essentials

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8.11 Atomic absorption spectroscopy

245

11.1 The elements

8.12 CHN analysis

246

11.2 Simple compounds

295

8.13 X-ray fluorescence elemental analysis

247

11.3 The atypical properties of lithium

296

8.14 Thermal analysis

247

Part B: The detail

293

296

Magnetometry

249

11.4 Occurrence and extraction

Electrochemical techniques

249

11.5 Uses of the elements and their compounds

297

Computational techniques

250

11.6 Hydrides

298

FURTHER READING

251

11.7 Halides

299
300
301

EXERCISES

252

11.8 Oxides and related compounds

PROBLEMS

253

11.9 Sulfides, selenides, and tellurides
11.10 Hydroxides

Part 2 The elements and their compounds
9

Periodic trends

Periodic properties of the elements

255

296

301

11.11 Compounds of oxoacids

302

11.12 Nitrides and carbides

304

257

11.13 Solubility and hydration

304

257

11.14 Solutions in liquid ammonia

305

257

11.15 Zintl phases containing alkali metals

305

9.2 Atomic parameters

257

11.16 Coordination compounds

305

9.3 Occurrence

261

11.17 Organometallic compounds

307

9.4 Metallic character

263

9.1 Valence electron configurations

9.5 Oxidation states

264

Periodic characteristics of compounds

265

9.6 Coordination numbers

265

9.7 Bond enthalpy trends

265

9.8 Anomalies

266

9.9 Binary compounds

268

9.10 Wider aspects of periodicity

270

FURTHER READING

272

EXERCISES

272

PROBLEMS

273

FURTHER READING

308

EXERCISES

308

PROBLEMS

308

12 The Group 2 elements
Part A: The essentials

309
309

12.1 The elements

309

12.2 Simple compounds

310

12.3 The anomalous properties of beryllium

311

Part B: The detail

312

12.4 Occurrence and extraction

312

12.5 Uses of the elements and their compounds

313
314

10 Hydrogen

274

12.6 Hydrides

Part A: The essentials

274

12.7 Halides

315

10.1 The element

274

12.8 Oxides, sulfides, and hydroxides

316

10.2 Simple compounds

276

12.9 Nitrides and carbides

317

Part B: The detail
10.3 Nuclear properties
10.4 Production of dihydrogen

12.10 Salts of oxoacids

318

279

12.11 Solubility, hydration, and beryllates

320

280

12.12 Coordination compounds

321

279

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323

14.11 Oxides of germanium, tin, and lead

365

EXERCISES

323

14.12 Compounds with nitrogen

365

PROBLEMS

324

14.13 Carbides

366

14.14 Silicides

368

14.15 Extended silicon–oxygen compounds

368

325

14.16 Organosilicon compounds

371

13.1 The elements

325

14.17 Organometallic compounds

371

13.2 Compounds

327

FURTHER READING

373

13.3 Boron clusters

329

EXERCISES

373

330

PROBLEMS

373

13 The Group 13 elements
Part A: The essentials

Part B: The detail

325

13.4 Occurrence and recovery

330

13.5 Uses of the elements and their compounds

330

15 The Group 15 elements

375

13.6 Simple hydrides of boron

330

Part A: The essentials

375

13.7 Boron trihalides

333

15.1 The elements

13.8 Boron–oxygen compounds

334

15.2 Simple compounds

376

13.9 Compounds of boron with nitrogen

335

15.3 Oxides and oxanions of nitrogen

377

Part B: The detail

375

378

13.10 Metal borides

337

13.11 Higher boranes and borohydrides

338

15.4 Occurrence and recovery

378

13.12 Metallaboranes and carboranes

342

15.5 Uses

379

13.13 The hydrides of aluminium and gallium

344

15.6 Nitrogen activation

381

13.14 Trihalides of aluminium, gallium, indium,

and thallium

15.7 Nitrides and azides

382

344

15.8 Phosphides

382

13.15 Low-oxidation-state halides of aluminium,
gallium, indium, and thallium

345

15.9 Arsenides, antimonides, and bismuthides

383

15.10 Hydrides

383

13.16 Oxo compounds of aluminium, gallium, indium,
and thallium

346

15.11 Halides

385

13.17 Sulfides of gallium, indium, and thallium

346

15.12 Oxohalides

386

13.18 Compounds with Group 15 elements

346

15.13 Oxides and oxoanions of nitrogen

387

13.19 Zintl phases

347

15.14 Oxides of phosphorus, arsenic, antimony, and bismuth

390

13.20 Organometallic compounds

347

15.15 Oxoanions of phosphorus, arsenic, antimony, and bismuth

391

FURTHER READING

348

15.16 Condensed phosphates

391

EXERCISES

348

15.17 Phosphazenes

393

PROBLEMS

348

15.18 Organometallic compounds of arsenic,
antimony, and bismuth

394

14 The Group 14 elements
Part A: The essentials

350
350

14.1 The elements

350

14.2 Simple compounds

352

14.3 Extended silicon–oxygen compounds

353

Part B: The detail

354

14.4 Occurrence and recovery

354

14.5 Diamond and graphite

354

14.6 Other forms of carbon

356

14.7 Hydrides

358

14.8 Compounds with halogens

359

14.9 Compounds of carbon with oxygen and sulfur

361

FURTHER READING

396

EXERCISES

396

PROBLEMS

397

16 The Group 16 elements

Part A: The essentials

398
398

16.1 The elements

398

16.2 Simple compounds

400

16.3 Ring and cluster compounds

402

Part B: The detail

403

16.4 Oxygen

403

16.5 Reactivity of oxygen

404

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404

18.6 Reactions of xenon fluorides

16.7 Selenium, tellurium, and polonium

405

18.7 Xenon–oxygen compounds

444

16.8 Hydrides

406

18.8 Xenon insertion compounds

445

16.9 Halides

407

18.9 Organoxenon compounds

445

16.10 Metal oxides

409

18.10 Coordination compounds

446

16.11 Metal sulfides, selenides, tellurides, and polonides

409

18.11 Other compounds of noble gases

446

16.12 Oxides

410

FURTHER READING

447

16.13 Oxoacids of sulfur

412

EXERCISES

447

16.14 Polyanions of sulfur, selenium, and tellurium

415

PROBLEMS

447

16.15 Polycations of sulfur, selenium, and tellurium

416

16.16 Sulfur–nitrogen compounds

416

FURTHER READING

417

EXERCISES

417

PROBLEMS

418

19 The d-Block elements
The elements
19.1 Occurrence and recovery
19.2 Physical properties
Trends in chemical properties

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449
449
449
450
453

17 The Group 17 elements

419

19.3 Oxidation states across a series

453

Part A: The essentials

419

19.4 Oxidation states down a group

456

419

19.5 Structural trends

458

17.2 Simple compounds

421

19.6 Noble character

459

17.3 The interhalogens

422

Representative compounds

460

424

19.7 Metal halides

460

424

19.8 Metal oxides and oxido complexes

460

17.5 Molecular structure and properties

425

19.9 Metal sulfides and sulfide complexes

464

17.6 Reactivity trends

427

19.10 Nitrido and alkylidyne complexes

466

17.7 Pseudohalogens

427

19.11 Metal–metal bonded compounds and clusters

466

17.8 Special properties of fluorine compounds

428

FURTHER READING

471

17.9 Structural features

429

EXERCISES

472

17.10 The interhalogens

429

PROBLEMS

472

17.11 Halogen oxides

432

17.12 Oxoacids and oxoanions

433

17.13 Thermodynamic aspects of oxoanion redox reactions

434

17.14 Trends in rates of oxoanion redox reactions

435

17.15 Redox properties of individual oxidation states

435

17.16 Fluorocarbons

437

17.1 The elements

Part B: The detail
17.4 Occurrence, recovery, and uses

20 d-Metal complexes: electronic
structure and properties

473

Electronic structure

473

20.1 Crystal-field theory

473

20.2 Ligand-field theory

483

Electronic spectra

487

FURTHER READING

438

20.3 Electronic spectra of atoms

487

EXERCISES

438

20.4 Electronic spectra of complexes

493

PROBLEMS

439

20.5 Charge-transfer bands

497

20.6 Selection rules and intensities

499

20.7 Luminescence

501

18 The Group 18 elements
Part A: The essentials

440
440

18.1 The elements

440

18.2 Simple compounds

441

Part B: The detail

Magnetism

502

20.8 Cooperative magnetism

502

20.9 Spin crossover complexes

504

442

18.3 Occurrence and recovery

442

18.4 Uses

442

18.5 Synthesis and structure of xenon fluorides

442

FURTHER READING

504

EXERCISES

505

PROBLEMS

505

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22.18 d-Block carbonyls

553

507

22.19 Metallocenes

560

21.1 Rates of ligand substitution

507

22.20 Metal–metal bonding and metal clusters

564

21.2 The classification of mechanisms

509

Ligand substitution reactions

Ligand substitution in square-planar complexes

Reactions

568

512

22.21 Ligand substitution

568

21.3 The nucleophilicity of the entering group

513

22.22 Oxidative addition and reductive elimination

571

21.4 The shape of the transition state

514

22.23 σ-Bond metathesis

572

Ligand substitution in octahedral complexes

517

22.24 1,1-Migratory insertion reactions

573

21.5 Rate laws and their interpretation

517

22.25 1,2-Insertions and β-hydride elimination

574

21.6 The activation of octahedral complexes

519

21.7 Base hydrolysis

522

22.26 α-, β-, and δ-Hydride eliminations and
cyclometallations

575

21.8 Stereochemistry

522

FURTHER READING

21.9 Isomerization reactions

523

EXERCISES

576

524

PROBLEMS

577

Redox reactions

576

21.10 The classification of redox reactions

524

21.11 The inner-sphere mechanism

524

23 The f-Block elements

579

21.12 The outer-sphere mechanism

527

The elements

579

Photochemical reactions

530

23.1 Occurrence and recovery

579

23.2 Physical properties and applications

580

21.13 Prompt and delayed reactions

530

21.14 d–d and charge-transfer reactions

530

21.15 Transitions in metal–metal bonded systems

531

FURTHER READING

532

Lanthanoid chemistry
23.3 General trends

581
581

23.4 Electronic, optical, and magnetic properties

583
586

EXERCISES

532

23.5 Binary ionic compounds

PROBLEMS

533

23.6 Ternary and complex oxides

588

23.7 Coordination compounds

589

22 d-Metal organometallic chemistry
Bonding

534
535

22.1 Stable electron configurations

535

22.2 Electron count preference

536

22.3 Electron counting and oxidation states
22.4 Nomenclature
Ligands

23.8 Organometallic compounds
Actinoid chemistry
23.9 General trends

590
592
593

23.10 Electronic spectra

594

537

23.11 Thorium and uranium

595

539

23.12 Neptunium, plutonium, and americium

596

540

FURTHER READING

597

22.5 Carbon monoxide

540

EXERCISES

597

22.6 Phosphines

542

PROBLEMS

598

22.7 Hydrides and dihydrogen complexes

543

22.8 η1-Alkyl, -alkenyl, -alkynyl, and -aryl ligands

544

22.9 η -Alkene and -alkyne ligands

545

2

PART 3 FRONTIERS

599

22.10 Nonconjugated diene and polyene ligands

545

24 Solid-state and materials chemistry

601

22.11 Butadiene, cyclobutadiene, and cyclooctatetraene

546

Synthesis of materials

602

22.12 Benzene and other arenes

548

24.1 The formation of bulk material

602

22.13 The allyl ligand

549

24.2 Chemical deposition

604

22.14 Cyclopentadiene and cycloheptatriene

550

Defects and ion transport

605

22.15 Carbenes

551

24.3 Extended defects

605

22.16 Alkanes, agostic hydrogens, and noble gases

552

24.4 Atom and ion diffusion

606

22.17 Dinitrogen and nitrogen monoxide

552

24.5 Solid electrolytes

607

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Compounds

507

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21 Coordination
chemistry: reactions of
complexes

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24.6 Monoxides of the 3d metals

611

FURTHER READING

24.7 Higher oxides and complex oxides

613

EXERCISES

687

24.8 Oxide glasses

623

PROBLEMS

688

24.9 Nitrides and fluorides

625

Chalcogenides, intercalation compounds, and
metal-rich phases

627

24.10 Layered MS2 compounds and intercalation

627

24.11 Chevrel phases and chalcogenide thermoelectrics

630

Framework structures
24.12 Structures based on tetrahedral oxoanions
24.13 Structures based on octahedra and tetrahedra

631

687

26 Catalysis

690

General principles

690

26.1 The language of catalysis
26.2 Homogeneous and heterogeneous catalysts
Homogeneous catalysis

691
694
694

631

26.3 Alkene metathesis

695

636

26.4 Hydrogenation of alkenes

696

639

26.5 Hydroformylation

698

24.14 Metal hydrides

639

26.6 Wacker oxidation of alkenes

700

24.15 Other inorganic hydrogen storage materials

641

26.7 Asymmetric oxidations

701

642

26.8 Palladium-catalysed C–C bond-forming reactions

701

Hydrides and hydrogen-storage materials

Inorganic pigments
24.16 Coloured solids

642

24.17 White and black pigments

643

Semiconductor chemistry

26.9 Methanol carbonylation: ethanoic acid synthesis
Heterogeneous catalysis

703
704

644

26.10 The nature of heterogeneous catalysts

704

24.18 Group 14 semiconductors

645

26.11 Hydrogenation catalysts

709

24.19 Semiconductor systems isoelectronic with silicon

645

26.12 Ammonia synthesis

709

647

26.13 Sulfur dioxide oxidation

710

24.20 Fullerides

647

24.21 Molecular materials chemistry

648

26.14 Catalytic cracking and the interconversion of
aromatics by zeolites

710

26.15 Fischer–Tropsch synthesis

713

Molecular materials and fullerides

FURTHER READING

650

EXERCISES

651

26.16 Alkene polymerization

713

PROBLEMS

651

26.17 Electrocatalysis

717

26.18 New directions in heterogeneous catalysis

25 Nanomaterials, nanoscience, and
nanotechnology
Fundamentals

Hybrid catalysis

653
653

718
718

26.19 Tethered catalysts

719

26.20 Biphasic systems

719

25.1 Terminology and history

653

FURTHER READING

720

25.2 Novel optical properties of nanomaterials

654

EXERCISES

720

657

PROBLEMS

721

Characterization and fabrication
25.3 Characterization methods

657

25.4 Top-down and bottom-up fabrication

658

25.5 Templated synthesis using frameworks, supports,
and substrates
Self-assembled nanostructures
25.6 Control of nanoarchitecture
25.7 One-dimensonal control: carbon nanotubes and
inorganic nanowires

662
666
666
669

27 Biological inorganic chemistry

722

The organization of cells

722

27.1 The physical structure of cells

722

27.2 The inorganic composition of cells

723

Transport, transfer, and transcription

731

27.3 Sodium and potassium transport

731

27.4 Calcium signalling proteins

733
734

25.8 Two-dimensional control: quantum wells and
solid-state superlattices

672

27.5 Zinc in transcription

25.9 Three-dimensional control

675

27.6 Selective transport and storage of iron

735

681

27.7 Oxygen transport and storage

738

25.10 DNA and nanomaterials

681

27.8 Electron transfer

741

25.11 Natural and artificial nanomaterials: biomimetics

682

Bioinorganic nanomaterials

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25.12 Bionanocomposites

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Metal
oxides, nitrides, and fluorides

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27.21 The contributions of individual elements

777

27.10 Enzymes dealing with H2O2 and O2

751

27.22 Future directions

778

27.11 The reactions of cobalt-containing enzymes

759

27.12 Oxygen atom transfer by molybdenum and

tungsten enzymes
Biological cycles

763

27.13 The nitrogen cycle

765
768

Sensors
27.15 Iron proteins as sensors
27.16 Proteins that sense Cu and Zn levels

FURTHER READING

779

EXERCISES

780

PROBLEMS

781

Resource section

783

765

27.14 The hydrogen cycle

768
768
771

Biomineralization

771

The chemistry of elements in medicine

772

27.17 Chelation therapy

773

27.18 Cancer treatment

773

27.19 Anti-arthritis drugs

775

27.20 Imaging agents

775

Resource section 1:
Resource section 2:
Resource section 3:
Resource section 4:
Resource section 5:
Resource section 6:
Index

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Catalytic

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Selected ionic radii
Electronic properties of the elements
Standard potentials
Character tables
Symmetry-adapted orbitals
Tanabe–Sugano diagrams

783
785
787
800
805
809

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