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The elements
Name Symbol Atomic Molar mass Name Symbol Atomic Molar mass
number (g mol−1) number (g mol−1)
Actinium Ac 89 227 Mercury Hg 80 200.59
Aluminium (aluminum) Al 13 26.98 Molybdenun Mo 42 95.95
Americium Am 95 243 Moscovium Mc 115 289
Antimony Sb 51 121.76 Neodymium Nd 60 144.24
Argon Ar 18 39.95 Neon Ne 10 20.18
Arsenic As 33 74.92 Neptunium Np 93 237
Astatine At 85 210 Nickel Ni 28 58.69
Barium Ba 56 137.33 Nihonium Nh 113 286
Berkelium Bk 97 247 Niobium Nb 41 92.91
Beryllium Be 4 9.01 Nitrogen N 7 14.01
Bismuth Bi 83 208.98 Nobelium No 102 259
Bohrium Bh 107 270 Oganesson Og 118 294
Boron B 5 10.81 Osmium Os 76 190.23
Bromine Br 35 79.90
Oxygen O 8 16.00
Cadmium Cd 48 112.41
Palladium Pd 46 106.42
Caesium (cesium) Cs 55 132.91
Phosphorus P 15 30.97
Calcium Ca 20 40.08
Platinum Pt 78 195.08
Californium Cf 98 251
Plutonium Pu 94 244
Carbon C 6 12.01
Polonium Po 84 209
Cerium Ce 58 140.12
Chlorine Cl 17 35.45 Potassium K 19 39.10
Chromium Cr 24 52.00 Praseodymium Pr 59 140.91
Cobalt Co 27 58.93 Promethium Pm 61 145
Copernicum Cn 112 285 Protactinium Pa 91 231.04
Copper Cu 29 63.55 Radium Ra 88 226
Curium Cm 96 247 Radon Rn 86 222
Darmstadtium Ds 110 281 Rhenium Re 75 186.21
Dubnium Db 105 270 Rhodium Rh 45 102.91
Dysprosium Dy 66 162.50 Roentgenium Rg 111 281
Einsteinium Es 99 252 Rubidium Rb 37 85.47
Erbium Er 68 167.27 Ruthenium Ru 44 101.07
Europium Eu 63 151.96 Rutherfordium Rf 104 267
Fermium Fm 100 257 Samarium Sm 62 150.36
Flerovium Fl 114 289 Scandium Sc 21 44.96
Fluorine F 9 19.00 Seaborgium Sg 106 269
Francium Fr 87 223 Selenium Se 34 78.97
Gadolinium Gd 64 157.25 Silicon Si 14 28.09
Gallium Ga 31 69.72 Silver Ag 47 107.87
Germanium Ge 32 72.63 Sodium Na 11 22.99
Gold Au 79 196.97 Strontium Sr 38 87.62
Hafnium Hf 72 178.49 Sulfur S 16 32.06
Hassium Hs 108 270 Tantalum Ta 73 180.95
Helium He 2 4.00 Technetium Tc 43 98
Holmium Ho 67 164.93 Tellurium Te 52 127.60
Hydrogen H 1 1.008 Tennessine Ts 117 293
Indium In 49 114.82 Terbium Tb 65 158.93
Iodine I 53 126.90 Thallium TI 81 204.38
Iridium Ir 77 192.22 Thorium Th 90 232.04
Iron Fe 26 55.85
Thulium Tm 69 168.93
Krypton Kr 36 83.80
Tin Sn 50 118.71
Lanthanum La 57 138.91
Titanium Ti 22 47.87
Lawrencium Lr 103 262
Tungsten W 74 183.84
Lead Pb 82 207.2
Uranium U 92 238.03
Lithium Li 3 6.94
Vanadium V 23 50.94
Livermorium Lv 116 293
Lutetium Lu 71 174.97 Xenon Xe 54 131.29
Magnesium Mg 12 24.31 Ytterbium Yb 70 173.05
Manganese Mn 25 54.94 Yttrium Y 39 88.91
Meitnerium Mt 109 278 Zinc Zn 30 65.41
Mendelevium Md 101 258 Zirconium Zr 40 91.22
 INORGANIC
CHEMISTRY

7th edition

MARK WELLER JONATHAN ROURKE

University of Bath University of Warwick

TINA OVERTON FRASER ARMSTRONG

Monash University University of Oxford

1
 3
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© T. L. Overton, J. P. Rourke, M. T. Weller, and F. A. Armstrong 2018
The moral rights of the authors have been asserted
Fourth edition 2006
Fifth edition 2010
Sixth edition 2014
Impression: 1
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Preface
Introducing Inorganic Chemistry
Our aim in the seventh edition of Inorganic Chemistry is to
provide a comprehensive, fully updated, and contemporary
introduction to the diverse and fascinating discipline of inor-
ganic chemistry. Inorganic chemistry deals with the properties
of all of the elements in the periodic table. Those classified as
metallic range from the highly reactive sodium and barium to
the noble metals, such as gold and platinum. The nonmetals
include solids, liquids, and gases, and their properties encom-
pass those of the aggressive, highly-oxidizing fluorine and the
unreactive gases such as helium. Although this variety and di-
versity are features of any study of inorganic chemistry, there
are underlying patterns and trends which enrich and enhance
our understanding of the subject. 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 the foundation on which to build a deeper understand-
ing of the chemistry of the elements and their compounds.
Inorganic compounds vary from ionic solids, which can be
described by simple extensions of classical electrostatics, to
covalent compounds and metals, which are best described by
models that have their origins in quantum mechanics. We can
rationalize and interpret the properties of many inorganic com-
pounds by using qualitative models that are based on quantum
mechanics, including the interaction of atomic orbitals to form
molecular orbitals and the band structures of solids. The text
builds on similar qualitative bonding models that should al-
ready be familiar from introductory chemistry courses.
Making inorganic chemistry relevant
Although qualitative models of bonding and reactivity clarify
and systematize the subject, inorganic chemistry is essentially
an experimental subject. Inorganic chemistry lies at the heart
of many of the most important recent advances in chemistry.
New, often unusual, inorganic compounds and materials are
constantly being synthesized and identified. Modern inorganic
syntheses continue to enrich the field with compounds that
give us fresh perspectives on structure, bonding, and reactivity.
Inorganic chemistry has considerable impact on our every-
day lives and on other scientific disciplines. The chemical indus-
try depends strongly on inorganic chemistry as it is essential to
the formulation and improvement of the modern materials and
compounds used as catalysts, energy storage materials, semi-
conductors, optoelectronics, superconductors, and advanced
ceramics. The environmental, biological and medical impacts
of inorganic chemistry on our lives are enormous. Current
topics in industrial, materials, biological, and environmental
chemistry are highlighted throughout the early sections of the
book to illustrate their importance and encourage the reader to
explore further. These aspects of inorganic chemistry are then
developed more thoroughly later in the text including, in this
edition, a brand-new chapter devoted to green chemistry.
What is new to this edition?
In this new edition we have refined the presentation, or-
ganization, and visual representation. The book has been
extensively revised, much has been rewritten and there is
some completely new material, including additional content
on characterization techniques in chapter 8. The text now
includes twelve new boxes that showcase recent develop-
ments and exciting discoveries; these include boxes 11.3 on
sodium ion batteries, 13.7 on touchscreens, 23.2 on d-orbit-
al participation in lanthanoid chemistry, 25.1 on renewable
energy, and 26.1 on cellulose degradation.
We have written our book with the student in mind, and
have added new pedagogical features and enhanced others.
Additional context boxes on recent innovations link theory
to practice, and encourage understanding of the real-world
significance of inorganic chemistry. Extended examples,
self-test questions, and new exercises and tutorial problems
stimulate thinking, and encourage the development of data
analysis skills, and a closer engagement with research. We
have also improved the clarity of the text with a new two-
column format throughout. Many of the 2000 illustrations
and the marginal structures have been redrawn, many have
been enlarged for improved clarity, and all are presented in
full colour. We have used colour systematically rather than
just for decoration, and have ensured that it serves a peda-
gogical purpose, encouraging students to recognize patterns
and trends in bonding and reactivity.
How is this textbook organized?
The topics in Part 1, Foundations, have been revised to make
them more accessible to the reader, with additional qualitative
explanation accompanying the more mathematical treatments.
The material has been reorganized to allow a more coherent
progression through the topics of symmetry and bonding and
to present the important topic of catalysis early on in the text.
Part 2, The elements and their compounds, has been thor-
oughly updated, building on the improvements made in earlier
editions, and includes additional contemporary contexts such
as solar cells, new battery materials, and touchscreen tech-
nology. The opening chapter draws together periodic trends
and cross references ahead of their more detailed treatment in
the subsequent descriptive chapters. These chapters start with
hydrogen and proceed across the periodic table, taking in the
s-block metals and the diverse elements of the p block, before
ending with extensive coverage of the d- and f-block elements.
vi Preface

Each of these chapters is organized into two sections: Es-
sentials describes the fundamental chemistry of the elements
and the Detail provides a more extensive account. The chem-
ical properties of each group of elements and their com-
pounds are further enriched with descriptions of current ap-
plications and recent advances made in inorganic chemistry.
The patterns and trends that emerge are rationalized by
drawing on the principles introduced in Part 1. Chapter 22
has been expanded considerably to include homogeneous
catalytic processes that rely on the organometallic chemistry
described there, with much of this new material setting the
scene for the new chapter on green chemistry in Part 3.
Part 3, Expanding our horizons, takes the reader to the fore-
front of knowledge in several areas of current research. These
chapters explore specialized, vibrant topics that are of impor-
tance to industry and biology, and include the new Chapter
25 on green chemistry. A comprehensive chapter on mate-
rials chemistry, Chapter 24, covers the latest discoveries in
energy materials, heterogeneous catalysis, and nanomaterials.
Chapter 26 discusses the natural roles of different elements in
biological systems and the various and extraordinarily subtle
ways in which each one is exploited; for instance, at the ac-
tive sites of enzymes where they are responsible for catalytic
activities that are essential for living organisms. Chapter 27
describes how medical science is exploiting the ‘stranger’ ele-
ments, such as platinum, gold, lithium, arsenic and synthetic
technetium, to treat and diagnose illness.
We are confident that this text will serve the undergradu-
ate chemist well. It provides the theoretical building blocks
with which to build knowledge and understanding of the
distinctions between chemical elements and should help to
rationalize the sometimes bewildering diversity of descriptive
inorganic 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 of study.
Mark Weller
Tina Overton
Jonathan Rourke
Fraser Armstrong

About the authors

Mark Weller is Professor of Chemistry at the University of Bath and President of the Materials Chemistry Division of the
Royal Society of Chemistry. His research interests cover a wide range of synthetic and structural inorganic chemistry including
photovoltaic compounds, zeolites, battery materials, and specialist pigments; he is the author of over 300 primary literature
publications in these fields. Mark has taught both inorganic chemistry and physical chemistry methods at undergraduate and
postgraduate levels for over 35 years, with his lectures covering topics across materials chemistry, the inorganic chemistry of the
s- and f- block elements, and analytical methods applied to inorganic compounds. He is a co-author of OUP’s Characterisation
Methods in Inorganic Chemistry and an OUP Primer (23) on Inorganic Materials Chemistry.

Tina Overton is Professor of Chemistry Education at Monash University in Australia and Honorary Professor at the
­University of Nottingham, UK. Tina has published on the topics of critical thinking, context and problem-based learning,
the development of problem solving skills, work-based learning and employability, and has co-authored several textbooks
in inorganic chemistry and skills development. She has been awarded the Royal Society of C
­ hemistry’s HE Teaching Award,
Tertiary Education Award and Nyholm Prize, the Royal Australian Chemical Institute’s Fensham Medal, and is a National
Teaching Fellow and Senior ­Fellow of the Higher Education Academy.

Jonathan Rourke is Associate Professor of Chemistry at the University of Warwick. He received his PhD at the University of
Sheffield on organometallic polymers and liquid crystals, followed by postdoctoral work in Canada with Professor Richard
Puddephatt and back in Britain with Duncan Bruce. His initial independent research career began at Bristol University and
then at Warwick, where he’s been ever since. Over the years Dr Rourke has taught most aspects of inorganic chemistry, all the
way from basic bonding, through symmetry analysis to advanced transition metal chemistry.

Fraser Armstrong is a Professor of Chemistry at the University of Oxford and a Fellow of St John’s College, Oxford. In 2008,
he was elected as a Fellow of the Royal Society of London. His interests span the fields of electrochemistry, renewable energy,
hydrogen, enzymology, and biological inorganic chemistry, and he heads a research group investigating electrocatalysis by
enzymes. He was an Associate Professor at the University of California, Irvine, before joining the Department of Chemistry
at Oxford in 1993.
Acknowledgements
We would particularly like to acknowledge the inspirational role and major contributions of Peter Atkins, whose early
­editions of Inorganic Chemistry formed the foundations of this text.
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 thank all those colleagues who so willingly gave their time and expertise to a careful reading
of a variety of draft chapters.
Many of the figures in Chapter 26 were produced using PyMOL software; for more information see W.L. DeLano, The PyMOL
­Molecular Graphics System (2002), De Lano Scientific, San Carlos, CA, USA.
Dawood Afzal, Truman State University
Helen Aspinall, University of Liverpool
Kent Barefield, Georgia Tech
Rolf Berger, University of Uppsala
Harry Bitter, Wageningen University
Richard Blair, University of Central Florida
Andrew Bond, University of Cambridge
Darren Bradshaw, University of Southampton
Paul Brandt, North Central College
Karen Brewer, Hamilton College
George Britovsek, Imperial College, London
Scott Bunge, Kent State University
David Cardin, University of Reading
Claire Carmalt, University College London
Carl Carrano, San Diego State University
Gareth W. V. Cave, Nottingham Trent University
Neil Champness, University of Nottingham
Ferman Chavez, Oakland University
Ann Chippindale, University of Reading
Karl Coleman, University of Durham
Simon Collinson, Open University
William Connick, University of Cincinnati
Peter J Cragg, University of Brighton
Stephen Daff, University of Edinburgh
Sandra Dann, University of Loughborough
Marcetta Y. Darensbourg, Texas A&M University
Nancy Dervisi, University of Cardiff
Richard Douthwaite, University of York
Simon Duckett, University of York
Jeremiah Duncan, Plymouth State University
A.W. Ehlers, Free University of Amsterdam
Mari-Ann Einarsrud, Norwegian University of
Science and Technology
Anders Eriksson, University of Uppsala
Andrew Fogg, University of Chester
Andrew Frazer, University of Central Florida
René de Gelder, Radboud University
Margaret Geselbracht, Reed College
Dean M. Giolando, University of Toledo
Christian R. Goldsmith, Auburn University
Gregory Grant, University of Tennessee
Yurii Gun’ko, Trinity College Dublin
Simon Hall, University of Bristol
Justin Hargreaves, University of Glasgow
Tony Hascall, Northern Arizona University
Zachariah Heiden, Washington State University
Richard Henderson, University of Newcastle
Eva Hervia, University of Strathclyde
Michael S. Hill, University of Bath
Jan Philipp Hofmann, Eindhoven University of
Technology
Martin Hollamby, Keele University
Brendan Howlin, University of Surrey
Songping Huang, Kent State University
Carl Hultman, Gannon University
Stephanie Hurst, Northern Arizona University
Jon Iggo, University of Liverpool
Karl Jackson, Virginia Union University
S. Jackson, University of Glasgow
Michael Jensen, Ohio University
Pavel Karen, University of Oslo
Terry Kee, University of Leeds
Paul King, Birbeck, University of London
Rachael Kipp, Suffolk University
Caroline Kirk, University of Edinburgh
Lars Kloo, KTH Royal Institute of Technology
Randolph Kohn, University of Bath
Simon Lancaster, University of East Anglia
Paul Lickiss, Imperial College, London
Sven Lindin, Lund University
Paul Loeffler, Sam Houston State University
Jose A. Lopez-Sanchez, University of Liverpool
Paul Low, University of Western Australia
Michael Lufaso, University of North Florida
Astrid Lund Ramstad, Norwegian Labour
­Inspection Authority
Jason Lynam, University of York
Joel Mague, Tulane University
Mary F. Mahon, University of Bath
Frank Mair, University of Manchester
Sarantos Marinakis, Queen Mary, University of
London
Andrew Marr, Queen’s University Belfast
David E. Marx, University of Scranton
John McGrady, University of Oxford
Roland Meier, Friedrich-Alexander University
Ryan Mewis, Manchester Metropolitan University
John R Miecznikowski, Fairfield University
Suzanna C. Milheiro, Western New England University
Katrina Miranda, University of Arizona
Liviu M. Mirica, Washington University in St. Louis
Grace Morgan, University College Dublin
Ebbe Nordlander, University of Lund
Michael North, University of York
Charles O’Hara, University of Strathclyde
Lars Öhrström, Chalmers (Goteborg)
Edwin Otten, University of Groningen
Ivan Parkin, University College London
Stephen Potts, University College London
Dan Price, University of Glasgow
Robert Raja, University of Southampton
T. B. Rauchfuss, University of Illinois
Jan Reedijk, University of Leiden
Denise Rooney, National University of Ireland,
Maynooth
Peter J. Sadler FRS, Warwick University
Graham Saunders, Waikato University
Ian Shannon, University of Birmingham
P. Shiv Halasyamani, University of Houston
Stephen Skinner, Imperial College, London
Bob Slade, University of Surrey
Peter Slater, University of Birmingham
LeGrande Slaughter, University of
Northern Texas
Martin B. Smith, University of Loughborough
Sheila Smith, University of Michigan
Jake Soper, Georgia Institute of Technology
David M. Stanbury, Auburn University
Jonathan Steed, University of Durham
Gunnar Svensson, University of Stockholm
Zachary J. Tonzetich, University of Texas at San
Antonio
Ryan J. Trovitch, Arizona State University
Hernando A.Trujillo, Wilkes University
Fernando J. Uribe-Romo, University of Central
Florida
Aldrik Velders, Wageningen University
Andrei Verdernikov, University of Maryland
Ramon Vilar, Imperial College, London
Keith Walters, Northern Kentucky University
Robert Wang, Salem State College
David Weatherburn, University of Victoria, Wellington
Eric J. Werner, The University of Tampa
Michael K. Whittlesey, University of Bath
Craig Williams, University of Wolverhampton
Scott Williams, Rochester Institute of Technology
Paul Wilson, University of Southampton
John T. York, Stetson University
Nigel A. Young, University of Hull
Jingdong Zhang, Denmark Technical University
About the book
Inorganic Chemistry provides numerous learning features
to help you master this wide-ranging subject. In addition,
the text has been designed so that you can either work
through the chapters chronologically, or dip in at an ap-
propriate point in your studies. The book’s online resources
provide support to you in your learning.
The material in this book has been logically and systemat-
ically laid out in three distinct sections. Part 1, Foundations,
outlines the underlying principles of inorganic chemistry,
Organizing the information
Key points
The key points outline the main take-home message(s) of
the section that follows. These will help you to focus on the
principal ideas being introduced in the text.
p you avoid making common mistakes.
KEY POINTS The blocks of the periodic table reflect the identity of
the orbitals that are occupied last in the building-up process. The
period number is the principal quantum number of the valence shell.
The group number is related to the number of valence electrons.
The layout of the periodic table reflects the electronic
structure of the atoms of the elements (Fig. 1.22). We can
Context boxes
Context boxes demonstrate the diversity of inorganic chem-
istry and its wide-ranging applications to, for example, ad-
vanced materials, industrial processes, environmental chem-
istry, and everyday life.
BOX 26.1 How does a copper enzyme degrade cellulose?
Most of the organic material that is produced by photosynthesis
is unavailable for use by industry or as fuels. Biomass largely
consists of polymeric carbohydrates—polysaccharides such
as cellulose and lignin, that are very difficult to break down
to simpler sugars as they are resistant to hydrolysis. However,
a breakthrough has occurred with the discovery that certain
which are built on in the subsequent two sections. Part 2,
The elements and their compounds, divides the descriptive
chemistry into ‘essentials’ and ‘details’, enabling you to eas-
ily draw out the key principles behind the reactions, before
exploring them in greater depth. Part 3, Expanding our ho-
rizons, introduces you to exciting interdisciplinary research
at the forefront of inorganic chemistry.
The paragraphs below describe the learning features of
the text and online resources in further detail.
Notes on good practice
In some areas of inorganic chemistry, the nomenclature
commonly in use can be confusing or archaic. To address
this we have included brief ‘notes on good practice’ to help
A NOTE ON GOOD PRACTICE
In expressions for equilibrium constants and rate equations,
we omit the brackets that are part of the chemical formula
of the complex; the surviving square brackets denote molar
concentration of a species (with the units mol dm−3 removed).
h d f bl l d h
Further reading
Each chapter lists sources where further information can be
found. We have tried to ensure that these sources are easily
available and have indicated the type of information each
one provides.
FURTHER READING
P.T. Anastas and J.C. Warner, Green chemistry: theory and practice.
Oxford University Press (1998). The definitive guide to green
chemistry.
M. Lancaster, Green chemistry: an introductory text. Royal Society
of Chemistry (2002). A readable text with industrial examples.

Resource section
At the back of the book is a comprehensive collection of
resources, including an extensive data section and informa-
tion relating to group theory and spectroscopy.
Resource section 1
Selected ionic radii
Ionic radii are given (in picometres, pm) for the most com-
mon oxidation states and coordination geometries. The
coordination number is given in parentheses, (4) refers to
tetrahedral and (4SP) refers to square planar. All d-block
species are low-spin unless labelled with †, in which case
About the book ix
values for high-spin are quoted. Most data are taken
R.D. Shannon, Acta Crystallogr., 1976, A32, 751,
values for other coordination geometries can be
Where Shannon values are not available, Pauling ioni
are quoted and are indicated by *.

Problem solving

Brief illustrations Exercises

A Brief illustration shows you how to use equations or
concepts that have just been introduced in the main text,
and will help you to understand how to manipulate data
correctly.
A BRIEF ILLUSTRATION
The cyclic silicate anion [Si3O9]n− is a six-membered ring with
alternating Si and O atoms and six terminal O atoms, two on
each Si atom. Because each terminal O atom contributes −1 to
the charge, the overall charge is −6. From another perspective,
the conventional oxidation numbers of silicon and oxygen, +4
d 2 ti l l i di t h f 6 f th i
Worked examples and Self-tests
Numerous worked Examples provide a more detailed illus-
tration of the application of the material being discussed.
Each one demonstrates an important aspect of the topic
under discussion or provides practice with calculations and
problems. Each Example is followed by a Self-test designed
to help you monitor your progress.
There are many brief Exercises at the end of each chapter.
You can find the answers online and fully worked answers
are available in the separate Solutions manual (see below).
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 manipu-
lating data.
Tutorial Problems
The Tutorial 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. Tutorial
problems generally require a discursive response and there
may not be a single correct answer. They may be used as es­
say type questions or for classroom discussion.
TUTORIAL PROBLEMS
3.1 Consider a molecule IF3O2 (with I as the central atom). How
many isomers are possible? Assign point group designations to
each isomer.

EXAMPLE 17.3 Analysing the recovery of Br2 from
brine
Show that from a thermodynamic standpoint bromide ions can
be oxidized to Br2 by Cl2 and by O2, and suggest a reason why O2
is not used for this purpose.
Answer We need to consider the relevant standard potentials
3.2 How many isomers are there for ‘octahedral’ molecules with
the formula MA3B3, where A and B are monoatomic ligands?
Solutions Manual
A Solutions Manual (ISBN: 9780198814689) by Alen
­Hadzovic is available to accompany the text and provides
complete solutions to the self-tests and end-of-chapter
exercises.
Online resources

The online resources that accompany this book provide a

number of useful teaching and learning resources to aug-
ment the printed book, and are free of charge.
The site can be accessed at: www.oup.com/uk/ichem7e/

Please note that lecturer resources are available only to

r­ egistered adopters of the textbook. To register, simply visit
www.oup.com/uk/ichem7e/ and follow the appropriate
links.
Student resources are openly available to all, without
registration.

For registered adopters of the text:

Figures and tables from the book
Lecturers can find the artwork and tables from the book lectures without charge (but not for commercial purposes
online in ready-to-download format. These can be used for without specific permission).

For students:
3D rotatable molecular structures
Numbered structures can be found online as interactive
3D structures. Type the following URL into your browser,
­adding the relevant structure number:
www.chemtube3d.com/weller7/[chapter numberS[structure
number].
For example, for structure 10 in Chapter 1, type
www.chemtube3d.com/weller7/1S10.

Those figures with in the caption can also be found

online as interactive 3D structures. Type the following URL
into your browser, adding the relevant figure number:
www.chemtube3d.com/weller7/[chapter number]F[figure
number].
For example, for Figure 4 in chapter 7, type ­
www.chemtube3d.com/weller7/7F04.

Visit www.chemtube3d.com/weller7/[chapter number] for

all interactive structures organised by chapter.

Group theory tables Answers to Self-tests and Exercises

Comprehensive group theory tables are available to A PDF document containing final answers to the end-of-
download. chapter exercises in this book can be downloaded online.
Summary of contents
PART 1 Foundations 1
1 Atomic structure 3
2 Molecular structure and bonding 33
3 Molecular symmetry 62
4 The structures of simple solids 90
5 Acids and bases 149
6 Oxidation and reduction 185
7 An introduction to coordination compounds 216
8 Physical techniques in inorganic chemistry 244

PART 2 The elements and their compounds 287

9 Periodic trends 289
10 Hydrogen 311
11 The Group 1 elements 336
12 The Group 2 elements 358
13 The Group 13 elements 380
14 The Group 14 elements 412
15 The Group 15 elements 445
16 The Group 16 elements 474
17 The Group 17 elements 500
18 The Group 18 elements 526
19 The d-block elements 538
20 d-Metal complexes: electronic structure and properties 568
21 Coordination chemistry: reactions of complexes 604
22 d-Metal organometallic chemistry 633
23 The f-block elements 689

PART 3 Expanding our horizons: advances and applications 719

24 Materials chemistry and nanomaterials 721
25 Green chemistry 809
26 Biological inorganic chemistry 824
27 Inorganic chemistry in medicine 885

Resource section 1: Selected ionic radii 901

Resource section 2: Electronic properties of the elements 903
Resource section 3: Standard potentials 905
Resource section 4: Character tables 918
Resource section 5: Symmetry-adapted orbitals 922
Resource section 6: Tanabe–Sugano diagrams 926

Index929
Detailed contents
Glossary of chemical abbreviations xxi 3.1 Symmetry operations, elements,
and point groups 63

PAR T 1 Foundations 1 3.2 Character tables 69

Applications of symmetry 71
3.3 Polar molecules 71
1 Atomic structure 3
3.4 Chiral molecules 72
The structures of hydrogenic atoms 7
3.5 Molecular vibrations 73
1.1 Spectroscopic information 7
The symmetries of molecular orbitals 77
1.2 Some principles of quantum mechanics 8
3.6 Symmetry-adapted linear combinations 77
1.3 Atomic orbitals 9
3.7 The construction of molecular orbitals 77
Many-electron atoms 15
3.8 The vibrational analogy 80
1.4 Penetration and shielding 15
Representations 81
1.5 The building-up principle 18
3.9 The reduction of a representation 81
1.6 The classification of the elements 20
3.10 Projection operators 82
1.7 Atomic properties 23
3.11 Polyatomic molecules 83
FURTHER READING 31
EXERCISES 31 FURTHER READING 88
TUTORIAL PROBLEMS 32 EXERCISES 88
TUTORIAL PROBLEMS 89

2 Molecular structure and bonding 33

4 The structures of simple solids 90
Lewis structures 33
The description of the structures of solids 91
2.1 The octet rule 34
4.1 Unit cells and the description of crystal
2.2 Resonance 35
structures 91
2.3 The VSEPR model 35
4.2 The close packing of spheres 94
Valence bond theory 38
4.3 Holes in close-packed structures 97
2.4 The hydrogen molecule 38
The structures of metals and alloys 100
2.5 Homonuclear diatomic molecules 39
4.4 Polytypism 101
2.6 Polyatomic molecules 40
4.5 Nonclose-packed structures 101
Molecular orbital theory 42
4.6 Polymorphism of metals 102
2.7 An introduction to the theory 42
4.7 Atomic radii of metals 103
2.8 Homonuclear diatomic molecules 45
4.8 Alloys and interstitials 104
2.9 Heteronuclear diatomic molecules 48
Ionic solids 108
2.10 Bond properties 51
4.9 Characteristic structures of ionic solids 109
Bond properties, reaction enthalpies, and kinetics 53
4.10 The rationalization of structures 117
2.11 Bond length 53
The energetics of ionic bonding 121
2.12 Bond strength and reaction enthalpies 54
4.11 Lattice enthalpy and the Born–Haber
2.13 Electronegativity and bond enthalpy 55 cycle 122
2.14 An introduction to catalysis 57 4.12 The calculation of lattice enthalpies 123
FURTHER READING 59 4.13 Comparison of experimental and
EXERCISES 59 theoretical values 125
TUTORIAL PROBLEMS 61 4.14 The Kapustinskii equation 127
4.15 Consequences of lattice enthalpies 128
3 Molecular symmetry 62 Defects and nonstoichiometry 131
An introduction to symmetry analysis 62 4.16 The origins and types of defects 131
xiv Detailed contents

4.17 Nonstoichiometric compounds and solid solutions 135 Redox stability 193
The electronic structures of solids 137 6.6 The influence of pH 193
4.18 The conductivities of inorganic solids 137 6.7 Reactions with water 194
4.19 Bands formed from overlapping atomic orbitals 138 6.8 Oxidation by atmospheric oxygen 196
4.20 Semiconduction 142 6.9 Disproportionation and comproportionation 196
Further information: the Born–Mayer equation 144 6.10 The influence of complexation 197
FURTHER READING 145 6.11 The relation between solubility and
EXERCISES 145 standard potentials 198
TUTORIAL PROBLEMS 148 Diagrammatic presentation of potential data 199
6.12 Latimer diagrams 199
5 Acids and bases 149 6.13 Frost diagrams 200
Brønsted acidity 150 6.14 Proton-coupled electron transfer:
5.1 Proton transfer equilibria in water 151 Pourbaix diagrams 204

Characteristics of Brønsted acids 157 6.15 Applications in environmental chemistry:

natural waters 205
5.2 Periodic trends in aqua acid strength 157
Chemical extraction of the elements 206
5.3 Simple oxoacids 158
6.16 Chemical reduction 206
5.4 Anhydrous oxides 161
6.17 Chemical oxidation 210
5.5 Polyoxo compound formation 162
6.18 Electrochemical extraction 210
Lewis acidity 164
FURTHER READING 211
5.6 Examples of Lewis acids and bases 164
EXERCISES 212
5.7 Group characteristics of Lewis acids 165 TUTORIAL PROBLEMS 214
5.8 Hydrogen bonding 168
Reactions and properties of Lewis acids and bases 170 7 An introduction to coordination compounds 216
5.9 The fundamental types of reaction 170 The language of coordination chemistry 217
5.10 Factors governing interactions between 7.1 Representative ligands 218
Lewis acids and bases 171
7.2 Nomenclature 221
5.11 Thermodynamic Lewis acidity parameters 173
Constitution and geometry 222
Nonaqueous solvents 174
7.3 Low coordination numbers 222
5.12 Solvent levelling 174
7.4 Intermediate coordination numbers 223
5.13 The Hammett acidity function and its
application to strong, concentrated acids 175 7.5 Higher coordination numbers 225

5.14 The solvent system definition of acids 7.6 Polymetallic complexes 227
and bases 176 Isomerism and chirality 227
5.15 Solvents as acids and bases 176 7.7 Square-planar complexes 228
Applications of acid–base chemistry 180 7.8 Tetrahedral complexes 230
5.16 Superacids and superbases 180 7.9 Trigonal-bipyramidal and square-pyramidal
5.17 Heterogeneous acid–base reactions 180 complexes 230

FURTHER READING 181 7.10 Octahedral complexes 231

EXERCISES 181 7.11 Ligand chirality 235
TUTORIAL PROBLEMS 184 The thermodynamics of complex formation 237
7.12 Formation constants 237
6 Oxidation and reduction 185
7.13 Trends in successive formation constants 238
Reduction potentials 186
7.14 The chelate and macrocyclic effects 239
6.1 Redox half-reactions 186
7.15 Steric effects and electron
6.2 Standard potentials and spontaneity 187 delocalization 240
6.3 Trends in standard potentials 190 FURTHER READING 242
6.4 The electrochemical series 191 EXERCISES 242
6.5 The Nernst equation 192 TUTORIAL PROBLEMS 243
 Detailed contents xv
8 Physical techniques in inorganic chemistry 244 9.11 Anomalous nature of the first member
of each group 308
Diffraction methods 245
FURTHER READING 309
8.1 X-ray diffraction 245
EXERCISES 310
8.2 Neutron diffraction 249
TUTORIAL PROBLEMS 310
Absorption and emission spectroscopies 251
8.3 Ultraviolet–visible spectroscopy 252 10 Hydrogen 311
8.4 Fluorescence or emission spectroscopy 255 Part A: The essentials 311
8.5 Infrared and Raman spectroscopy 256 10.1 The element 312
Resonance techniques 260 10.2 Simple compounds 313
8.6 Nuclear magnetic resonance 260 Part B: The detail 317
8.7 Electron paramagnetic resonance 266 10.3 Nuclear properties 317
8.8 Mössbauer spectroscopy 268 10.4 Production of dihydrogen 318
Ionization-based techniques 269 10.5 Reactions of dihydrogen 321
8.9 Photoelectron spectroscopy 269 10.6 Compounds of hydrogen 322
8.10 X-ray absorption spectroscopy 270 10.7 General methods for synthesis of binary
8.11 Mass spectrometry 271 hydrogen compounds 332

Chemical analysis 274 FURTHER READING 333

EXERCISES 334
8.12 Atomic absorption spectroscopy 274
TUTORIAL PROBLEMS 335
8.13 CHN analysis 274
8.14 X-ray fluorescence elemental analysis 275
11 The Group 1 elements 336
8.15 Thermal analysis 276
Part A: The essentials 336
Magnetometry and magnetic susceptibility 278
11.1 The elements 337
Electrochemical techniques 279
11.2 Simple compounds 338
Microscopy 281
11.3 The atypical properties of lithium 340
8.16 Scanning probe microscopy 281
Part B: The detail 340
8.17 Electron microscopy 282
11.4 Occurrence and extraction 340
FURTHER READING 283 11.5 Uses of the elements and their compounds 341
EXERCISES 283
11.6 Hydrides 344
TUTORIAL PROBLEMS 285
11.7 Halides 345
11.8 Oxides and related compounds 346
PAR T 2 The elements and their
compounds  287 11.9 Sulfides, selenides, and tellurides 348
11.10 Hydroxides 348
11.11 Compounds of oxoacids 349
9 Periodic trends 289
11.12 Nitrides and carbides 351
Periodic properties of the elements 289
11.13 Solubility and hydration 352
9.1 Valence electron configurations 289
11.14 Solutions in liquid ammonia 352
9.2 Atomic parameters 290
11.15 Zintl phases containing alkali metals 353
9.3 Occurrence 295
11.16 Coordination compounds 353
9.4 Metallic character 296
11.17 Organometallic compounds 355
9.5 Oxidation states 297
FURTHER READING 356
Periodic characteristics of compounds 300
EXERCISES 356
9.6 Presence of unpaired electrons 300 TUTORIAL PROBLEMS 357
9.7 Coordination numbers 301
9.8 Bond enthalpy trends 301 12 The Group 2 elements 358
9.9 Binary compounds 302 Part A: The essentials 359
9.10 Wider aspects of periodicity 305 12.1 The elements 359
xvi Detailed contents

12.2 Simple compounds 360 14 The Group 14 elements 412

12.3 The anomalous properties of beryllium 361 Part A: The essentials 413
Part B: The detail 362 14.1 The elements 413
12.4 Occurrence and extraction 362 14.2 Simple compounds 415
12.5 Uses of the elements and their compounds 363 14.3 Extended silicon–oxygen compounds 416
12.6 Hydrides 365 Part B: The detail 417
12.7 Halides 365 14.4 Occurrence and recovery 417
12.8 Oxides, sulfides, and hydroxides 367 14.5 Diamond and graphite 418
12.9 Nitrides and carbides 369 14.6 Other forms of carbon 419
12.10 Salts of oxoacids 370 14.7 Hydrides 423
12.11 Solubility, hydration, and beryllates 374 14.8 Compounds with halogens 425
12.12 Coordination compounds 374 14.9 Compounds of carbon with oxygen and sulfur 428
12.13 Organometallic compounds 375 14.10 Simple compounds of silicon with oxygen 431
12.14 Lower oxidation state Group 2 compounds 377 14.11 Oxides of germanium, tin, and lead 433
FURTHER READING 378 14.12 Compounds with nitrogen 433
EXERCISES 378 14.13 Carbides 434
TUTORIAL PROBLEMS 378 14.14 Silicides 436
14.15 Extended silicon–oxygen compounds 437
13 The Group 13 elements 380 14.16 Organosilicon and organogermanium
Part A: The essentials 381 compounds 440
13.1 The elements 381 14.17 Organometallic compounds 441
13.2 Compounds 382 FURTHER READING 442
13.3 Boron clusters and borides 385 EXERCISES 443
TUTORIAL PROBLEMS 444
Part B: The detail 386
13.4 Occurrence and recovery 387
15 The Group 15 elements 445
13.5 Uses of the elements and their compounds 387
Part A: The essentials 446
13.6 Simple hydrides of boron 388
15.1 The elements 446
13.7 Boron trihalides 391
15.2 Simple compounds 447
13.8 Boron–oxygen compounds 393
15.3 Oxides and oxoanions of nitrogen 449
13.9 Compounds of boron with nitrogen 394
Part B: The detail 450
13.10 Metal borides 396
15.4 Occurrence and recovery 450
13.11 Higher boranes and borohydrides 397
15.5 Uses 450
13.12 Metallaboranes and carboranes 402
15.6 Nitrogen activation 453
13.13 The hydrides of aluminium, gallium, indium,
and thallium 404 15.7 Nitrides and azides 454
13.14 Trihalides of aluminium, gallium, indium, 15.8 Phosphides 455
and thallium 405
15.9 Arsenides, antimonides, and bismuthides 456
13.15 Low oxidation state halides of aluminium,
15.10 Hydrides 456
gallium, indium, and thallium 405
15.11 Halides 459
13.16 Oxo compounds of aluminium, gallium,
indium, and thallium 406 15.12 Oxohalides 460
13.17 Sulfides of gallium, indium, and thallium 407 15.13 Oxides and oxoanions of nitrogen 460
13.18 Compounds with Group 15 elements 407 15.14 Oxides of phosphorus, arsenic, antimony,
and bismuth 465
13.19 Zintl phases 408
15.15 Oxoanions of phosphorus, arsenic,
13.20 Organometallic compounds 408
antimony, and bismuth 466
FURTHER READING 410 15.16 Condensed phosphates 467
EXERCISES 410
15.17 Phosphazenes 468
TUTORIAL PROBLEMS 411
 Detailed contents xvii
15.18 Organometallic compounds of arsenic, 17.15 Redox properties of individual oxidation
antimony, and bismuth 469 states 520
FURTHER READING 471 17.16 Fluorocarbons 522
EXERCISES 471 FURTHER READING 523
TUTORIAL PROBLEMS 473 EXERCISES 523
TUTORIAL PROBLEMS 524
16 The Group 16 elements 474
Part A: The essentials 475 18 The Group 18 elements 526
16.1 The elements 475 Part A: The essentials 527
16.2 Simple compounds 476 18.1 The elements 527
16.3 Ring and cluster compounds 478 18.2 Simple compounds 527
Part B: The detail 478 Part B: The detail 528
16.4 Oxygen 478 18.3 Occurrence and recovery 528
16.5 Reactivity of oxygen 481 18.4 Uses 529
16.6 Sulfur 481 18.5 Synthesis and structure of xenon fluorides 530
16.7 Selenium, tellurium, and polonium 483 18.6 Reactions of xenon fluorides 531
16.8 Hydrides 484 18.7 Xenon–oxygen compounds 532
16.9 Halides 487 18.8 Xenon insertion compounds 533
16.10 Metal oxides 487 18.9 Organoxenon compounds 534
16.11 Metal sulfides, selenides, tellurides, and polonides 488 18.10 Coordination compounds 534
16.12 Oxides 489 18.11 Other compounds of noble gases 535
16.13 Oxoacids of sulfur 491 FURTHER READING 535
16.14 Polyanions of sulfur, selenium, and tellurium 495 EXERCISES 536
TUTORIAL PROBLEMS 536
16.15 Polycations of sulfur, selenium, and tellurium 496
16.16 Sulfur–nitrogen compounds 496
19 The d-block elements 538
FURTHER READING 497
EXERCISES 498 Part A: The essentials 539
TUTORIAL PROBLEMS 498 19.1 Occurrence and recovery 539
19.2 Chemical and physical properties 539
17 The Group 17 elements 500 Part B: The detail 542
Part A: The essentials 501 19.3 Group 3: scandium, yttrium, and lanthanum 542
17.1 The elements 501 19.4 Group 4: titanium, zirconium, and hafnium 543
17.2 Simple compounds 502 19.5 Group 5: vanadium, niobium, and tantalum 545
17.3 The interhalogens 503 19.6 Group 6: chromium, molybdenum, and tungsten 549
Part B: The detail 505 19.7 Group 7: manganese, technetium, and rhenium 554
17.4 Occurrence, recovery, and uses 505 19.8 Group 8: iron, ruthenium, and osmium 556
17.5 Molecular structure and properties 508 19.9 Group 9: cobalt, rhodium, and iridium 558
17.6 Reactivity trends 510 19.10 Group 10: nickel, palladium, and platinum 559
17.7 Pseudohalogens 510 19.11 Group 11: copper, silver, and gold 561
17.8 Special properties of fluorine compounds 511 19.12 Group 12: zinc, cadmium, and mercury 563
17.9 Structural features 512 FURTHER READING 566
17.10 The interhalogens 513 EXERCISES 567
TUTORIAL PROBLEMS 567
17.11 Halogen oxides 516
17.12 Oxoacids and oxoanions 517
17.13 Thermodynamic aspects of oxoanion 20 d-Metal complexes: electronic structure
redox reactions 518
and properties 568
17.14 Trends in rates of oxoanion redox reactions 519
Electronic structure 568
xviii Detailed contents

20.1 Crystal-field theory 569 Ligands 640

20.2 Ligand-field theory 579 22.5 Carbon monoxide 640
Electronic spectra 583 22.6 Phosphines 642
20.3 Electronic spectra of atoms 584 22.7 Hydrides and dihydrogen complexes 643
20.4 Electronic spectra of complexes 588 22.8 η -Alkyl, -alkenyl, -alkynyl, and -aryl ligands
1
644
20.5 Charge-transfer bands 593 22.9 η -Alkene and -alkyne ligands
2
645
20.6 Selection rules and intensities 595 22.10 Nonconjugated diene and polyene ligands 646
20.7 Luminescence 597 22.11 Butadiene, cyclobutadiene, and cyclooctatetraene 646
Magnetism 598 22.12 Benzene and other arenes 648
20.8 Cooperative magnetism 598 22.13 The allyl ligand 649
20.9 Spin-crossover complexes 600 22.14 Cyclopentadiene and cycloheptatriene 650
FURTHER READING 601 22.15 Carbenes 652
EXERCISES 601 22.16 Alkanes, agostic hydrogens, and noble gases 653
TUTORIAL PROBLEMS 602 22.17 Dinitrogen and nitrogen monoxide 653
Compounds 654
21 Coordination chemistry: reactions 22.18 d-Block carbonyls 654
of complexes 604
22.19 Metallocenes 660
Ligand substitution reactions 605
22.20 Metal–metal bonding and metal clusters 664
21.1 Rates of ligand substitution 605
Reactions 667
21.2 The classification of mechanisms 606
22.21 Ligand substitution 667
Ligand substitution in square-planar complexes 610
22.22 Oxidative addition and reductive elimination 670
21.3 The nucleophilicity of the entering group 610
22.23 σ-Bond metathesis 671
21.4 The shape of the transition state 611
22.24 1,1-Migratory insertion reactions 671
Ligand substitution in octahedral complexes 614
22.25 1,2-Insertions and β-hydride elimination 672
21.5 Rate laws and their interpretation 614
α-, γ-, and δ-Hydride eliminations and
22.26 
21.6 The activation of octahedral complexes 615 cyclometallations 673
21.7 Base hydrolysis 619 Catalysis 673
21.8 Stereochemistry 619 22.27 Alkene metathesis 674
21.9 Isomerization reactions 620 22.28 Hydrogenation of alkenes 675
Redox reactions 621 22.29 Hydroformylation 677
21.10 The classification of redox reactions 621 22.30 Wacker oxidation of alkenes 679
21.11 The inner-sphere mechanism 622 22.31 Palladium-catalysed C–C bond-forming
21.12 The outer-sphere mechanism 624 reactions 679
Photochemical reactions 627 22.32 Oligomerization and polymerization 681
21.13 Prompt and delayed reactions 628 FURTHER READING 685
21.14 d–d and charge-transfer reactions 628 EXERCISES 685
TUTORIAL PROBLEMS 687
21.15 Transitions in metal–metal bonded systems 629
FURTHER READING 630
EXERCISES 630 23 The f-block elements 689
TUTORIAL PROBLEMS 631 The elements 690
23.1 The valence orbitals 690
22 d-Metal organometallic chemistry 633 23.2 Occurrence and recovery 691
Bonding 635 23.3 Physical properties and applications 692
22.1 Stable electron configurations 635 Lanthanoid chemistry 693
22.2 Electron-count preference 636 23.4 General trends 693
22.3 Electron counting and oxidation states 637 23.5 Optical and magnetic properties 696
22.4 Nomenclature 639 23.6 Binary ionic compounds 700
 Detailed contents xix
23.7 Ternary and complex oxides 702 Molecular materials and fullerides 776
23.8 Coordination compounds 703 24.21 Fullerides 776
23.9 Organometallic compounds 706 24.22 Molecular materials chemistry 777
Actinoid chemistry 709 Nanomaterials 781
23.10 General trends 709 24.23 Nanomaterial terminology and history 781
23.11 Electronic spectra of the actinoids 712 24.24 Solution-based synthesis of nanoparticles 782
23.12 Thorium and uranium 713 24.25 Vapour-phase synthesis of nanoparticles
via solutions or solids 783
23.13 Neptunium, plutonium, and americium 715
24.26 Templated synthesis of nanomaterials using
FURTHER READING 716
frameworks, supports, and substrates 784
EXERCISES 716
24.27 Characterization and formation of
TUTORIAL PROBLEMS 717
nanomaterials using microscopy 786
Nanostructures and properties 787
PAR T 3 Expanding our horizons: 24.28 One-dimensional control: carbon nanotubes
advances and applications 719 and inorganic nanowires 787
24.29 Two-dimensional control: graphene,
quantum wells, and solid-state superlattices 789
24 Materials chemistry and nanomaterials 721
24.30 Three-dimensional control: mesoporous
Synthesis of materials 722 materials and composites 792
24.1 The formation of bulk materials 722
24.31 Special optical properties of nanomaterials 796
Defects and ion transport 725
Heterogeneous nanoparticle catalysts 798
24.2 Extended defects 725
24.32 The nature of heterogeneous catalysts 799
24.3 Atom and ion diffusion 726
24.33 Reactions involving heterogeneous
24.4 Solid electrolytes 727 nanoparticle catalysts 803
Metal oxides, nitrides, and fluorides 731 FURTHER READING 804
24.5 Monoxides of the 3d metals 732 EXERCISES 805
24.6 Higher oxides and complex oxides 734 TUTORIAL PROBLEMS 806
24.7 Oxide glasses 745
24.8 Nitrides, fluorides, and mixed-anion phases 747 25 Green chemistry 809
Sulfides, intercalation compounds, and Twelve principles 810
metal-rich phases 749 25.1 Prevention 810
24.9 Layered MS2 compounds and intercalation 750
25.2 Atom economy 811
24.10 Chevrel phases and chalcogenide thermoelectrics 753
25.3 Less hazardous chemical species 812
Framework structures and heterogeneous
25.4 Designing safer chemicals 813
catalysis in porous materials 754
24.11 Structures based on tetrahedral oxoanions 755
25.5 Safer solvents and auxiliaries 813

24.12 Structures based on linked octahedral and 25.6 Design for energy efficiency 815
tetrahedral metal centres 758 25.7 Use of renewable feedstocks 816
24.13 Zeolites and microporous structures in 25.8 Reduce derivatives 817
heterogeneous catalysis 763
25.9 Catalysis 818
Hydrides and hydrogen-storage materials 765
25.10 Design for degradation 820
24.14 Metal hydrides 766
25.11 Real-time analysis for pollution prevention 821
24.15 Other inorganic hydrogen-storage materials 768
25.12 Inherently safer chemistry for accident prevention 821
Optical properties of inorganic materials 769
FURTHER READING 822
24.16 Coloured solids 770
EXERCISES 822
24.17 White and black pigments 771
TUTORIAL PROBLEMS 823
24.18 Photocatalysts 772
Semiconductor chemistry 773 26 Biological inorganic chemistry 824
24.19 Group 14 semiconductors 774 The organization of cells 825
24.20 Semiconductor systems isoelectronic with silicon 775 26.1 The physical structure of cells 825
xx Detailed contents

26.2 The inorganic composition of living FURTHER READING 882

organisms 825 EXERCISES 883
26.3 Biological metal-coordination sites 828 TUTORIAL PROBLEMS 884
Metal ions in transport and communication 833
27 Inorganic chemistry in medicine 885
26.4 Sodium and potassium transport 833
The chemistry of elements in medicine 885
26.5 Calcium signalling proteins 835
27.1 Inorganic complexes in cancer treatment 887
26.6 Selective transport and storage of iron 836
27.2 Anti-arthritis drugs 890
26.7 Oxygen transport and storage 839
27.3 Bismuth in the treatment of gastric ulcers 891
26.8 Electron transfer 842
27.4 Lithium in the treatment of bipolar disorders 892
Catalytic processes 848
27.5 Organometallic drugs in the treatment of malaria 892
26.9 Acid–base catalysis 848
27.6 Metal complexes as antiviral agents 893
26.10 Enzymes dealing with H2O2 and O2 855
27.7 Metal drugs that slowly release CO:
26.11 Enzymes dealing with radicals and an agent against post-operative stress 895
alkyl groups 864
27.8 Chelation therapy 895
26.12 Oxygen atom transfer by molybdenum
and tungsten enzymes 868 27.9 Imaging agents 896
26.13 Hydrogenases, enzymes that 27.10 Nanoparticles in directed drug delivery 898
activate H2 869
27.11 Outlook 899
26.14 The nitrogen cycle 871
FURTHER READING 899
Metals in gene regulation 874 EXERCISES 900
27.15 Transcription factors and the role of Zn 874 TUTORIAL PROBLEMS 900
26.16 Iron proteins as sensors 875
Resource section 1 Selected ionic radii 901
26.17 Proteins that sense Cu and Zn levels 878
Resource section 2 Electronic properties of the elements 903
26.18 Biomineralization 878 Resource section 3 Standard potentials 905
Perspectives 880 Resource section 4 Character tables 918
26.19 The contributions of individual Resource section 5 Symmetry-adapted orbitals  922
elements 880 Resource section 6 Tanabe–Sugano diagrams 926
26.20 Future directions 881
Index  929
Glossary of chemical abbreviations
Ac acetyl, CH3CO
acac acetylacetonato
aq aqueous solution species
bpy 2,2′-bipyridine
cod 1,5-cyclooctadiene
cot cyclooctatetraene
Cp cyclopentadienyl
Cp* pentamethylcyclopentadienyl
Cy cyclohexyl
cyclam tetraazacyclotetradecane
dien diethylenetriamine
DMF dimethylformamide
DMSO dimethyl sulfoxide
η hapticity
edta ethylenediaminetetraacetato
en ethylenediamine (1,2-diaminoethane)
Et ethyl
gly glycinato
Hal halide
Pr
i
isopropyl
L a ligand
µ signifies a bridging ligand
M a metal
Me methyl
mes mesityl, 2,4,6-trimethylphenyl
Ox an oxidized species
ox oxalato
Ph phenyl
phen phenanthroline
py pyridine
Red a reduced species
Sol solvent, or a solvent molecule
soln nonaqueous solution species
t
Bu tertiary butyl
THF tetrahydrofuran
TMEDA N,N,N′,N′-tetramethylethylenediamine
trien 2,2′,2′′-triaminotriethylene
X generally halogen, also a leaving group or an anion
Y an entering group
 PART

1
Foundations
The eight chapters in this part of the book lay the foundations of inorganic chemistry.

The first four chapters develop an understanding of the structures of atoms, the bonding in molecules
and solids, and the role symmetry plays in chemistry. Chapter 1 introduces the structure of atoms in
terms of quantum theory and describes important periodic trends in their properties. Chapter 2 devel-
ops molecular structure in terms of increasingly sophisticated models of covalent bonding and explores
how the energetics of reactions form the basis of understanding catalysis.

Chapter 3 shows how a systematic consideration of the symmetry of molecules can be used to discuss
the bonding and structure of molecules and help interpret data from some of the techniques described
in Chapter 8. Chapter 4 describes ionic bonding, the structures and properties of a range of typical sol-
ids, the role of defects in materials, and the electronic properties of solids.

The next two chapters focus on two major types of reactions. Chapter 5 explains how acid–base
properties are defined, measured, and applied across a wide area of chemistry. Chapter 6 describes oxi-
dation and reduction, and demonstrates how electrochemical data can be used to predict and explain
the outcomes of reactions in which electrons are transferred between molecules. Chapter 7 describes
the coordination compounds of the elements where we discuss bonding, structure, and reactions of
complexes, and see how symmetry considerations can provide insight into this important class of com-
pounds. Chapter 8 provides a toolbox for inorganic chemistry: it describes a wide range of the instru-
mental techniques that are used to identify and determine the structures and compositions of inorganic
compounds.
Atomic structure
The structures of hydrogenic atoms
1.1 Spectroscopic information
1.2 Some principles of quantum mechanics
1.3 Atomic orbitals
Many-electron atoms
1.4 Penetration and shielding
1.5 The building-up principle
1.6 The classification of the elements
1.7 Atomic properties
Further reading
Exercises
Tutorial problems
The observation that the universe is expanding has led to the
current view that about 14 billion years ago the currently
visible universe was concentrated into a point-like region
that exploded in an event called the Big Bang. With initial
temperatures immediately after the Big Bang of about 109 K,
the fundamental particles produced in the explosion had too
much kinetic energy to bind together in the forms we know
today. However, the universe cooled as it expanded, the par-
ticles moved more slowly, and they soon began to adhere
together under the influence of a variety of forces. In par-
ticular, the strong force, a short-range but powerful attrac-
tive force between nucleons (protons and neutrons), bound
these particles together into nuclei. As the temperature fell
still further, the electromagnetic force, a relatively weak but
long-range force between electric charges, bound electrons
to nuclei to form atoms, and the universe acquired the poten-
tial for complex chemistry and the existence of life (Box 1.1).
About two hours after the start of the universe, the
temperature had fallen so much that most of the matter was
Those figures with an in the caption can be found online as interactive 3D
structures. Type the following URL into your browser, adding the relevant figure
number: www.chemtube3d.com/weller7/[chapter number]F[figure number]. For
example, for Figure 3 in Chapter 7, type www.chemtube3d.com/weller7/7F03.
1
This chapter lays the foundations for the explanation of the trends
in the physical and chemical properties of all inorganic com-
pounds. To understand the behaviour of molecules and solids
we need to understand atoms: our study of inorganic chemistry
must therefore begin with a review of their structures and proper-
ties. We start with a discussion of the origin of matter in the solar
system and then consider the development of our understand-
ing of atomic structure and the behaviour of electrons in atoms.
We introduce quantum theory qualitatively and use the results
to rationalize properties such as atomic radii, ionization energy,
electron affinity, and electronegativity. A knowledge of these
properties allows us to begin to understand the diverse chemical
properties of nearly 120 elements known today.
in the form of H atoms (89%) and He atoms (11%). In one
sense, not much has happened since then for, as Fig. 1.1
shows, hydrogen and helium remain overwhelmingly the
most abundant elements in the universe. However, nuclear
reactions have formed dozens of other elements and have
immeasurably enriched the variety of matter in the universe,
and thus given rise to the whole area of chemistry (Boxes
1.2 and 1.3).
Table 1.1 summarizes the properties of the subatomic
particles that we need to consider in chemistry. All the
known elements—by 2018 all up to 118 had been con-
firmed—that are formed from these subatomic particles are
distinguished by their atomic number, Z, the number of
protons in the nucleus of an atom of the element. Many
elements have a number of isotopes, which are atoms with
the same atomic number but different atomic masses. These
isotopes are distinguished by the mass number, A, which is
the total number of protons and neutrons in the nucleus.
The mass number is also sometimes termed the nucleon
Many of the numbered structures can also be found online as interactive 3D
structures: visit www.chemtube3d.com/weller7/[chapter number] for all 3D resources
organized by chapter.
4 1 Atomic structure
BOX 1.1 How are elements created?
The earliest stars resulted from the gravitational condensation
of clouds of H and He atoms. This gave rise to high temperatures
and densities within the clouds, and fusion reactions began as
nuclei merged together.
Energy is released when light nuclei fuse together to give
elements of higher atomic number. Nuclear reactions are very
much more energetic than normal chemical reactions because
the strong force which binds protons and neutrons together
is much stronger than the electromagnetic force that binds
electrons to nuclei. Whereas a typical chemical reaction might
release about 103 kJ mol−1, a nuclear reaction typically releases a
million times more energy, about 109 kJ mol−1.
Elements up to Z = 26 (iron) were formed inside stars. These
elements are the products of the nuclear fusion reactions
referred to as ‘nuclear burning’. The burning reactions, which
should not be confused with chemical combustion, involved
H and He nuclei and a complicated fusion cycle catalysed
by C nuclei. The stars that formed in the earliest stages of the
evolution of the cosmos lacked C nuclei and used noncatalysed
H-burning. Nucleosynthesis reactions are rapid at temperatures
of 5–10 × 106 K. Here we have another contrast between
chemical and nuclear reactions, because chemical reactions
take place at temperatures a hundred thousand times lower.
Moderately energetic collisions between atoms or molecules
can result in chemical change, but only highly vigorous
collisions can provide the energy required to bring about most
nuclear transformations.
The elements beyond iron ( Z > 26) are produced in significant
quantities when hydrogen burning is complete and the collapse
of the star’s core raises its density to 108 kg m−3 (about 105 times
the density of water) and the temperature to 108 K. Under these
extreme conditions, a star will become a red giant and helium
burning can occur.
The high abundance of iron and nickel in the universe is
consistent with these elements having the most stable of
all nuclei. This stability is expressed in terms of the binding
energy, which is the difference in energy between the nucleus
itself and the same numbers of individual protons and neutrons.
This binding energy is often presented in terms of the difference
in mass between the nucleus and its individual protons and
neutrons because, according to Einstein’s theory of relativity,
number. Hydrogen, for instance, has three isotopes. In
each case Z = 1, indicating that the nucleus contains one
proton. The most abundant isotope has A = 1, denoted 1H,
its nucleus consisting of a single proton. Far less abundant
(only 1 atom in 6000) is deuterium, with A = 2. This mass
number indicates that, in addition to a proton, the nucleus
contains one neutron. The formal designation of deuterium
is 2H, but it is commonly denoted D. The third, short-lived,
mass and energy are related by E = mc 2 , where c is the speed
of light. Therefore, if the mass of a nucleus differs from the
total mass of its components by ∆m = mnucleons − mnucleus , then its
binding energy is Ebind = ( ∆m)c 2 . The binding energy of 56Fe, for
example, is the difference in energy between the 56Fe nucleus
and 26 protons and 30 neutrons. A positive binding energy
corresponds to a nucleus that has a lower, more favourable,
energy (and lower mass) than its constituent nucleons.
Figure B1.1 shows the binding energy per nucleon, Ebind/A
(obtained by dividing the total binding energy by the number
of nucleons), for all the isotopes. Iron and nickel occur at the
maximum of the curve, showing that their nucleons are bound
together more strongly than in any other nuclide. Harder to see
from the graph is an alternation of binding energies as the atomic
number varies from even to odd, with even-Z nuclides slightly
more stable than their odd-Z neighbours. There is a corresponding
alternation in cosmic abundances, with nuclides of even atomic
number being marginally more abundant than those of odd
atomic number. This stability of even-Z nuclides is attributed to
the lowering of energy by pairing nucleons in the nucleus.
16
O
12
C
8
Fe
4
He
Binding energy per nucleon / MeV 56
58
60
6 55
57
59
Li
7
4
2
2
D
0
10 30 50 70 90
Atomic number, Z
FIGURE B1.1 Nuclear binding energies. The greater the
binding energy, the more stable is the nucleus. Note the
alternation in stability shown in the inset.
radioactive isotope of hydrogen is tritium, 3H or T. Its
nucleus consists of one proton and two neutrons. In cer-
tain cases it is helpful to display the atomic number of the
element as a left suffix; so the three isotopes of hydrogen
would then be denoted 11 H, 12H, and 13H. Hydrogen is the
only element for which there are such significant chemical
distinctions between the isotopes that the isotopes warrant
individual names.
 Atomic structure 5
10
O Si
Ca Fe

H Earth's crust
6 Sr Ba
Pb
log (mass fraction, ppb)

Ar
He Ne
–2 Kr
Xe

Rn
–6
10 30 50 70 90
Atomic number, Z

11
Sun
O
H)

Fe
12

7
log (atoms per 10

F
3
Sc

Li
As FIGURE 1.1 The abundances of the elements in the
–1
10 30 50 70 90 Earth’s crust and the Sun. Elements with odd Z are less
Atomic number, Z stable than their neighbours with even Z.

BOX 1.2 What are nuclear fusion and nuclear fission?

If two nuclei with mass numbers lower than 56 merge to produce undergo fission into (among many other modes) xenon-140
a new nucleus with a larger nuclear binding energy, the excess and strontium-93 nuclei:
energy is released. This process is called fusion. For example,
two neon-20 nuclei may fuse to give a calcium-40 nucleus:
236
92
U → 140
54
Xe + 38
93
Sr + 3 01n
The values of Ebind/A for 236U, 140Xe, and 93Sr nuclei are 7.6, 8.4,
2 20 Ne → 40 Ca
10 20 and 8.7 MeV, respectively. Therefore, the energy released in this
The value of the binding energy per nucleon, Ebind/A, for 20Ne reaction is (140 × 8.4) + (93 × 8.7) − (236 × 7.6) MeV = 191.5 MeV
is approximately 8.0 MeV. Therefore, the total binding energy for the fission of each 236U nucleus.
of the species on the left-hand side of the equation is 2 × 20 × Fission can also be induced by bombarding heavy elements
8.0 MeV = 320 MeV. The value of Ebind/A for 40Ca is close to 8.6 MeV with neutrons:
and so the total energy of the species on the right-hand side is
40 × 8.6 MeV = 344 MeV. The difference in the binding energies
235
92
U + 01n → fission products + neutrons
of the products and reactants is therefore 24 MeV. The kinetic energy of fission products from 235U is about 165 MeV,
For nuclei with A > 56 , binding energy can be released when that of the neutrons is about 5 MeV, and the γ-rays produced have
they split into lighter products with higher values of Ebind/A. an energy of about 7 MeV. The fission products are themselves
This process is called fission. For example, uranium-236 can radioactive and decay by β-, γ-, and X-radiation, releasing about
6 1 Atomic structure
23 MeV. In a nuclear fission reactor the neutrons that are not
consumed by fission are captured with the release of about 10 MeV.
The energy produced is reduced by about 10 MeV, which escapes
from the reactor as radiation, and about 1 MeV which remains
as undecayed fission products in the spent fuel. Therefore, the
total energy produced for one fission event is about 200 MeV, or
32 pJ. It follows that about 1 W of reactor heat (where 1 W = 1 J s −1)
corresponds to about 3.1× 1010 fission events per second. A nuclear
reactor producing 3 GW has an electrical output of approximately
1 GW and corresponds to the fission of 3 kg of 235U per day.
The use of nuclear power is controversial in large part on
account of the risks associated with the highly radioactive,
BOX 1.3 Technetium—what is a synthetic element?
A synthetic element is one that does not occur naturally on
Earth but that can be artificially generated by nuclear reactions.
The first synthetic element was technetium ( Tc, Z = 43), named
from the Greek word for ‘artificial’. Its discovery—or more
precisely, its preparation—filled a gap in the periodic table
and its properties matched those predicted by Mendeleev. The
longest-lived isotope of technetium (98Tc) has a half-life of 4.2
million years so any produced when the Earth was formed has
long since decayed. Technetium is produced in red-giant stars.
The most widely used isotope of technetium is 99mTc, where
the ‘m’ indicates a metastable isotope. Technetium-99m emits
high-energy γ-rays but has a relatively short half-life of 6.01
hours. These properties make the isotope particularly attractive
for use in vivo as the γ-ray energy is sufficient for it to be
detected outside the body and its half-life means that most of it
will have decayed within 24 hours. Consequently, 99mTc is widely
TABLE 1.1 Subatomic particles of relevance to chemistry
Particle Symbol Mass/mu*
Electron e − 5.486 × 10−4
Proton p 1.0073
Neutron n 1.0087
Photon γ 0
Neutrino ν c. 0
Positron e + 5.486 × 10 −4
α particle α [ He
4 2+
nucleus]
2
β particle β [e− ejected from nucleus]
γ photon γ [electromagnetic radiation from nucleus]
* Masses are expressed relative to the atomic mass constant, mu = 1.6605 × 10−27 kg.
†
The elementary charge is e = 1.602 × 10 –19 C.
long-lived spent fuel. The declining stocks of fossil fuels,
however, make nuclear power very attractive as it is estimated
that stocks of uranium could last for hundreds of years. The cost
of uranium ores is currently very low and 100 g of uranium oxide
generates as much energy as sixty barrels of oil or 20 tonnes of
coal. The increased use of nuclear power would also drastically
reduce the rate of emission of greenhouse gases into the
atmosphere. The environmental drawback with nuclear power
is the storage and disposal of radioactive waste and the public
are nervous about possible nuclear accidents, such as that in
Fukushima in 2011, and the misuse of nuclear capabilities in
pursuit of political ambitions.
used in nuclear medicine, for example in radiopharmaceuticals
for imaging and in functional studies of the brain, bones, blood,
lungs, liver, heart, thyroid gland, and kidneys (Section 27.9).
Technetium-99m is generated through nuclear fission in nuclear
power plants but a more useful laboratory source of the isotope
is a technetium generator, which uses the decay of 99Mo to 99mTc.
The half-life of 99Mo is 66 hours, which makes it more
convenient for transport and storage than 99mTc itself. Most
commercial generators are based on 99Mo in the form of the
molybdate ion, MoO 24−, adsorbed on Al2O3. The 99 MoO 24− ion
decays by beta emission to the pertechnetate ion, 99mTcO42−,
which is less tightly bound to the alumina (Section 27.8).
99
Mo → 99m Tc + −01 β
Sterile saline solution is washed through a column of the
immobilized 99Mo and the 99mTc solution is collected.
Mass number Charge/e† Spin
0 −1 ½
1 +1 ½
1 0 ½
0 0 1
0 0 ½
0 +1 ½
4 +2 0
0 −1 ½
0 0 1

The structures of hydrogenic atoms
So far we have discussed the nuclear properties of the ele-
ments. As chemists we are much more interested in the
electronic structure of atoms and the organization of the
periodic table is a direct consequence of periodic variations
in the electronic structure of atoms. Initially, we consider
hydrogen-like or hydrogenic atoms, which have only one
electron and so are free of the complicating effects of elec-
tron–electron repulsions. Hydrogenic atoms include ions
such as He+ and C5+ (found in the interiors of stars) as well
as the hydrogen atom itself. Then we use the concepts that
these atoms introduce to build up an approximate descrip-
tion of the structures of many-electron atoms (or polyelec-
tron atoms).
1.1 Spectroscopic information
KEY POINTS Spectroscopic observations on hydrogen atoms sug-
gest that an electron can occupy only certain energy levels and that the
emission of discrete frequencies of electromagnetic radiation occurs
when an electron makes a transition between these levels.
Electromagnetic radiation is emitted when an electric dis-
charge is applied to hydrogen gas. When passed through a
prism or diffraction grating, this radiation is found to con-
sist of a series of components: one in the ultraviolet region,
one in the visible region, and several in the infrared region
of the electromagnetic spectrum (Fig. 1.2; Box 1.4). The
nineteenth-century spectroscopist Johann Rydberg found
that all the wavelengths (λ, lambda) can be described by
the expression
1  1 1
= R  2 − 2  (1.1)
λ n
 1 n2
Visible
2000
1000
800
600
500
400
300
200
Total
Balmer
Paschen
Brackett
The structures of hydrogenic atoms 7
where R is the Rydberg constant, an empirical constant with
the value 1.097 × 107 m−1. The n are integers, with n1 = 1, 2,
. . . and n2 = n1 + 1, n1 + 2, . . .. The series with n1 = 1 is called
the Lyman series and lies in the ultraviolet region. The series
with n1 = 2 lies in the visible region and is called the Balmer
series. The infrared series include the Paschen series (n1 = 3)
and the Brackett series (n1 = 4).
The energy of a photon is given by the equation E = hν ,
where h is Planck’s constant, 6.626 × 10−34 J s, and ν is fre-
quency, the number of times per second that a wave travels
through a complete cycle, expressed in units of hertz, where
1 Hz = 1 s −1. We can use this expression and the equation
ν = c / λ , where c is the speed of light (2.998 × 108 m s −1) and
λ is wavelength in metres, to derive the expression E = hc/λ.
The quantity 1/λ is referred to as the wavenumber ν , and
gives the number of wavelengths in a given distance: it is
directly proportional to the energy of the photon.
The structure of the spectrum is explained if it is sup-
posed that the emission of radiation takes place when an
electron makes a transition from a state of energy − hcR/n22
to a state of energy − hcR/n12 and that the energy difference,
which is equal to hcR(1/n12 − 1/n22 ), is carried away as a pho-
ton of energy, E = hc/λ. By equating E = hcR(1/n12 − 1/n22 ) and
E = hc/λ, and cancelling hc, we obtain eqn 1.1.
A NOTE ON GOOD PRACTICE
Although wavelength is usually expressed in nano- or
picometres, wavenumbers are usually expressed in cm−1, or
reciprocal centimetres. A wavenumber of 1 cm−1 denotes one
complete wavelength in a distance of 1 cm. 1 cm−1 is equivalent
to 11.96 J mol−1.
λ /nm
150
120
100
Lyman
FIGURE 1.2 The spectrum of atomic
hydrogen and its analysis into series.
8 1 Atomic structure
BOX 1.4 How do sodium atoms light our streets?
The emission of light when atoms are excited is put to good use
in lighting streets in many parts of the world. The widely used
yellow street lamps are based on the emission of light from
excited sodium atoms.
Low pressure sodium (LPS) lamps consist of a glass tube
coated with indium tin oxide (ITO). The indium tin oxide reflects
infrared light and transmits visible light. Two inner glass tubes
hold solid sodium and a small amount of neon and argon, the
same mixture as found in neon lights. When the lamp is turned
The question these observations raise is why the energy
of the electron in the atom is limited to the values −hcR/n2
and why R has the value observed. An initial attempt to
explain these features was made by Niels Bohr in 1913
using an early form of quantum theory in which he sup-
posed that the electron could exist in only certain circu-
lar orbits. Although he obtained the correct value of R,
his model was later shown to be untenable as it conflicted
with the version of quantum theory developed by Erwin
Schrödinger and Werner Heisenberg in 1926.
EXAMPLE 1.1 Predicting the wavelength of lines in
the atomic spectrum of hydrogen
Predict the wavelengths of the first three lines in the Balmer
series.
Answer For the Balmer series, n1 = 2 and n2 = 3, 4, 5, 6. So if
1  1 1
we substitute into eqn 1.1 we obtain = R  2 − 2  for the first
λ 2 3 
line which gives 1 513 888 m−1 or 661 nm. Using values of n2 = 4
and 5 for the next two lines give values of λ of 486 and 434 nm,
respectively.
Self-test 1.1 (a) Predict the wavenumber and wavelength of
the second line in the Paschen series. (b) Calculate the values
of n1 and n2 for the line in the Lyman series with a wavelength
of 103 nm.
1.2 Some principles of quantum mechanics
KEY POINTS Electrons can behave as particles or as waves; solution
of the Schrödinger equation gives wavefunctions, which describe the
location and properties of electrons in atoms. The probability of find-
ing an electron at a given location is proportional to the square of the
wavefunction. Wavefunctions generally have regions of positive and
negative amplitude, and may undergo constructive or destructive in-
terference with one another.
In 1924, Louis de Broglie suggested that because electromag-
netic radiation could be considered to consist of particles
on the neon and argon emit a red glow which heats the sodium
metal. Within a few minutes, the sodium starts to vaporize, the
electrical discharge excites electrons in the atoms to a high
energy level, and they re-emit the energy as yellow light.
One advantage of these lamps over other types of street
lighting is that they do not lose light output as they age. They
do, however, use more energy towards the end of their life
which may make them less attractive from environmental and
economic perspectives.
called photons yet at the same time exhibit wave-like prop-
erties, such as interference and diffraction, then the same
might be true of electrons. This dual nature is called wave–
particle duality. An immediate consequence of duality is
that it is impossible to know the linear momentum (the
product of mass and velocity) and the location of an elec-
tron (and any particle) simultaneously. This restriction is
called the Heisenberg uncertainty principle that states that
the product of the uncertainty in momentum and the uncer-
tainty in position cannot be less than a quantity of the order
of Planck’s constant (specifically, ½, where  = /2π).1
Schrödinger formulated an equation that took account of
wave–particle duality and accounted for the motion of elec-
trons in atoms. To do so, he introduced the wavefunction,
ψ (psi), a mathematical function of the position coordinates
x, y, and z, which describes the behaviour of an electron.
The Schrödinger equation, of which the wavefunction is a
solution, for an electron free to move in one dimension is
Kinetic energy
contribution
 Potential energy
contribution Total energy
 dψ
2 2     (1.2)
− + V ( x )ψ (x ) = Eψ (x)
2me dx 2
where me is the mass of an electron, V is the potential energy
of the electron, and E is its total energy. The Schrödinger
equation is a second-order differential equation that can be
solved exactly for a number of simple systems (such as a
hydrogen atom) and can be solved numerically for many
more complex systems (such as many-electron atoms and
molecules). However, we shall use only qualitative aspects of
its solutions. The generalization of eqn 1.2 to three dimen-
sions is straightforward, but we do not need its explicit form.
One crucial feature of eqn 1.2 and its analogues in three
dimensions and the imposition of certain requirements
(called ‘boundary conditions’) is that physically acceptable
1
 (pronounced h-bar) is the reduced Planck constant. It is used
when angular frequency in radians per second is more appropriate
than cycles per second.

Probability
density, ψ 2
Wavefunction, ψ
Phase + −
Probability density, ψ 2
FIGURE 1.3 The Born interpretation of the wavefunction is that
its square is a probability density. There is zero probability density
at a node. The shaded bar represents the probability density.
solutions exist only for certain values of E. Therefore, the
quantization of energy, the fact that an electron can possess
only certain discrete energies in an atom, follows naturally
from the Schrödinger equation.
A wavefunction contains all the dynamical information
possible about the electron, including where it is and how
fast it is travelling. As Heisenberg’s uncertainty principle
means it is impossible to know all this information simul-
taneously, this leads naturally to the concept of the prob-
ability of finding an electron at a given location. Specifically,
the probability of finding an electron at a given location
is proportional to the square of the wavefunction at that
point, ψ 2. According to this interpretation, there is a high
probability of finding the electron where ψ 2 is large, and the
electron will not be found where ψ 2 is zero (Fig. 1.3). The
quantity ψ 2 is called the probability density of the electron.
It is a ‘density’ in the sense that the product of ψ 2 and the
infinitesimal volume element dτ = dxdydz (where τ is tau)
is proportional to the probability of finding the electron in
that volume. The probability is equal to ψ 2dτ if the wave-
function is ‘normalized’. A normalized wavefunction is one
that is scaled so that the total probability of finding the elec-
tron somewhere is 1. The wavefunction of an electron in an
atom is called an atomic orbital.
Like other waves, wavefunctions in general have regions
of positive and negative amplitude, or sign. To help keep
track of the relative signs of different regions of a wavefunc-
tion, or atomic orbital, in illustrations we label regions of
opposite sign with dark and light shading corresponding to
+ and − signs, respectively. The sign of the wavefunction is of
crucial importance when two wavefunctions spread into the
same region of space and interact. Then a positive region of
one wavefunction may add to a positive region of the other
wavefunction to give a region of enhanced amplitude. This
enhancement is called constructive interference (Fig. 1.4a).
It means that, where the two wavefunctions spread into the
same region of space, such as occurs when two atoms are
The structures of hydrogenic atoms 9
Resultant
Wave 1
Wave 2
(a)
Wave 1 Resultant
Wave 2
(b)
FIGURE 1.4 Wavefunctions interfere where they spread into the
same region of space. (a) If they have the same sign in a region,
they interfere constructively and the total wavefunction has an
enhanced amplitude in the region. (b) If the wavefunctions have
opposite signs, then they interfere destructively, and the resulting
superposition has a reduced amplitude.
close together, there may be a significantly enhanced prob-
ability of finding the electrons in that region. Conversely, a
positive region of one wavefunction may be cancelled by a
negative region of the second wavefunction (Fig. 1.4b). This
destructive interference between wavefunctions reduces the
probability that an electron will be found in that region. As
we shall see, the interference of wavefunctions is of great
importance in the explanation of chemical bonding.
1.3 Atomic orbitals
Chemists use hydrogenic atomic orbitals to develop models
that are central to the interpretation of inorganic chemistry,
and we shall spend some time describing their shapes and
significance.
(a) Hydrogenic energy levels
KEY POINTS The energy of the bound electron is determined by n,
the principal quantum number; in addition, l specifies the magnitude
of the orbital angular momentum and ml specifies the orientation of
that angular momentum.
Each of the wavefunctions obtained by solving the
Schrödinger equation for a hydrogenic atom is uniquely
labelled by a set of three integers called quantum numbers.
These quantum numbers are designated n, l, and ml: n is
called the principal quantum number, l is the orbital angu-
lar momentum quantum number (formerly the ‘azimuthal
quantum number’), and ml is called the magnetic quantum
number. Each quantum number specifies a physical property
of the electron: n specifies the energy, l labels the magnitude
of the orbital angular momentum, and ml labels the orienta-
tion of that angular momentum. The value of n also indicates
the size of the orbital, with larger n, high-energy orbitals,
10 1 Atomic structure

more diffuse than low n, compact, tightly bound, low-energy n

orbitals. The value of l also indicates the angular shape of the Z =1 Z =2 ∞
orbital, with the number of lobes increasing as l increases. –R/9
4
The value of ml also indicates the orientation of these lobes. 2
–R/4
The allowed energies are specified by the principal quan- 3
tum number, n. For a hydrogenic atom of atomic number Z,
they are given by
–R 1
hcRZ 2
En = − (1.3)
n2
2
with n = 1, 2, 3, . . . and

Energy
mee4
R= (1.4)
8h3cε02

(The fundamental constants in this expression are given

inside the back cover.) The calculated numerical value of R
is 1.097 × 107 m −1, in excellent agreement with the empiri-
cal value determined spectroscopically by Rydberg. For
future reference, the value of hcR corresponds to 13.6 eV or
1312.196 kJ mol−1.

A NOTE ON GOOD PRACTICE

An electronvolt is the amount of kinetic energy gained by an
electron as it accelerates through a potential of one volt. It is a 1
useful, but non-SI, unit. In chemistry, kinetic energy gained by
a mole of electrons passing through a potential of one volt is FIGURE 1.5 The quantized energy levels of an H atom ( Z = 1)
96.485 kJ mol−1. The approximation 1 eV ≈ 100 kJ mol−1 is worth and an He+ ion ( Z = 2 ). The energy levels of a hydrogenic atom are
remembering. The Faraday constant, F, the electric charge of a proportional to Z 2.
mole of electrons is 96 485 C mol−1.

The energies given by eqn 1.3 are all negative, signifying
that the energy of the electron in a bound state is lower than
a widely separated stationary electron and nucleus. The zero
of energy (at n = ∞) corresponds to the electron and nucleus
being widely separated and stationary. Positive values of
the energy correspond to unbound states of the electron in
which it may travel with any velocity and hence possess any
energy. Finally, because the energy is proportional to 1/n2,
the energy levels in the bound state converge as the energy
increases (becomes less negative, Fig. 1.5).
The value of l specifies the magnitude of the orbital angu-
lar momentum through {l (l + 1)}1/2 , with l = 0, 1, 2, . . .. We
can think of l as indicating the momentum with which the
electron circulates around the nucleus via the lobes of the
orbital. As we shall see shortly, the third quantum number
ml specifies the orientation of this momentum, for instance
whether the circulation is clockwise or anticlockwise.
(b) Shells, subshells, and orbitals
KEY POINTS All orbitals with a given value of n belong to the same
shell, all orbitals of a given shell with the same value of l belong to the
same subshell, and individual orbitals are distinguished by the value of ml.
In a hydrogenic atom, all orbitals with the same value of
n have the same energy and are said to be degenerate. The
principal quantum number therefore defines a series of
shells of the atom, or sets of orbitals with the same value
of n and hence with the same energy and approximately
the same radial extent. Shells with n = 1, 2, 3, . . . are some-
times referred to as K, L, M, . . . shells, for example when
electronic transitions between these shells are referred to in
X-ray spectroscopy.
The orbitals belonging to each shell are classified into
subshells distinguished by a quantum number l. For a
given value of n, the quantum number l can have the val-
ues l = 0, 1, . . ., n − 1, giving n different values in all. For
example, the shell with n = 1 consists of just one subshell
with l = 0 , the shell with n = 2 consists of two subshells,
one with l = 0 and the other with l = 1, the shell with n = 3
consists of three subshells, with values of l of 0, 1, and
2. It is common practice to refer to each subshell by a
letter:
Value of l 0 1 2 3 4 ...
Subshell designation s p d f g ...

For most purposes in chemistry we need consider only s, p,
d, and f subshells.2
A subshell with quantum number l consists of 2l + 1 indi-
vidual orbitals. These orbitals are distinguished by the mag-
netic quantum number, ml, which can have the 2l + 1 integer
values from +l down to −l. This quantum number speci-
fies the component of orbital angular momentum around
an arbitrary axis (commonly designated z) passing through
the nucleus. So, for example, a d subshell of an atom (l = 2)
consists of five individual atomic orbitals that are distin-
guished by the values ml = +2, + 1, 0, − 1, − 2. An f subshell
(l = 3) consists of seven individual atomic orbitals with the
values ml = +3, + 2, + 1, 0, − 1, − 2, − 3.
A NOTE ON GOOD PRACTICE
Write the sign of ml even when it is positive. Thus, we write
ml = +2 , not ml = 2 .
The practical conclusion for chemistry from these rules
is that there is only one orbital in an s subshell (l = 0), the
one with ml = 0: this orbital is called an s orbital. There are
three orbitals in a p subshell (l = 1), with quantum numbers
ml = +1, 0, − 1; they are called p orbitals. The five orbitals of
a d subshell (l = 2) are called d orbitals, with quantum num-
bers ml = + 2, + 1, 0, − 1, − 2 and so on (Fig. 1.6).
EXAMPLE 1.2 Identifying orbitals from quantum
numbers
Which set of orbitals is defined by n = 4 and l = 1? How many
orbitals are there in this set?
Answer We need to remember that the principal quantum
number n identifies the shell and that the orbital quantum
number l identifies the subshell. The subshell with l = 1 consists
of p orbitals. The allowed values of ml = +l, . . ., −l give the number
of orbitals of that type. In this case, ml = +1, 0, and −1. There are
therefore three 4p orbitals.
Self-test 1.2 (a) Which set of orbitals is defined by the quantum
numbers n = 3 and l = 2? How many orbitals are there in this
set? (b) What are the quantum numbers n and l that define a 5f
orbital? How many orbitals are there in this set?
(c) Electron spin
KEY POINTS The intrinsic spin angular momentum of an electron is
defined by the two quantum numbers s and ms. Four quantum numbers
are needed to define the state of an electron in a hydrogenic atom.
2
The orbital labels s, p, d, and f come from terms used to describe
groups of lines in the atomic spectra. They stand for sharp, principal,
diffuse, and fundamental, respectively.
The structures of hydrogenic atoms 11
Subshells
s p d f
4
3
Shell
2
1
FIGURE 1.6 The classification of orbitals into subshells (same
value of l) and shells (same value of n).
In addition to the three quantum numbers required to spec-
ify the spatial distribution of an electron in a hydrogenic
atom, two more quantum numbers are needed to define the
state of an electron. These additional quantum numbers
relate to the intrinsic angular momentum of an electron, its
spin. This evocative name suggests that an electron can be
regarded as having an angular momentum arising from a
spinning motion, rather like the daily rotation of the earth
as it travels in its annual orbit around the sun. However,
spin is a quantum mechanical property and this analogy
must be viewed with great caution.
Spin is described by two quantum numbers, s and ms.
The former is the analogue of l for orbital motion but it
is restricted to the single, unchangeable value s = ½. The
magnitude of the spin angular momentum is given by the
expression {s(s + 1)}1/2, so when we substitute for s = ½ we
find that this magnitude is fixed at 12 3 for any electron.
The second quantum number, the spin magnetic quantum
number, ms, may take only two values, +½ (anticlockwise
spin, imagined from above) and −½ (clockwise spin). The
two states are often represented by the two arrows ↑ (‘spin-
up’, ms = + 12 ) and ↓ (‘spin-down’, ms = − 12 ) or by the Greek
letters α and β, respectively.
Because the spin state of an electron must be specified if
the state of the atom is to be specified fully, it is common
to say that the state of an electron in a hydrogenic atom is
characterized by four quantum numbers, namely n, l, ml,
and ms.
(d) Nodes
KEY POINT Regions where wavefunctions pass through zero are
called nodes. Inorganic chemists generally find it adequate to use visu-
al representations of atomic orbitals rather than mathematical expres-
sions. However, we need to be aware of the mathematical expressions
that underlie these representations.
Because the potential energy of an electron in the field of a
nucleus is spherically symmetric (it is proportional to Z/r
and independent of orientation relative to the nucleus), the
orbitals are best expressed in terms of the spherical polar
coordinates defined in Fig. 1.7, rather than the Cartesian
12 1 Atomic structure

z
1.8
θ
ϕ

2
3/
Radial wavefunction, R/(Z/a0)
r
y 1.2

x 0.6
1s

FIGURE 1.7 Spherical polar coordinates: r is the radius, θ (theta) 3s

the colatitude, and ϕ (phi) the azimuth. 0
2s

coordinates, x, y, and z. In these coordinates, the orbitals all 10 20 30

Radius, Zr/a0
have the form
Variation with angle FIGURE 1.8 The radial wavefunctions of the 1s, 2s, and 3s

Variation with radius  
ψ nlm = Rnl (r) × Ylm (θ ,φ)  (1.5) hydrogenic orbitals. Note that the number of radial nodes is 0, 1,
l l

and 2, respectively. Each orbital has a nonzero amplitude at the

This expression reflects the simple idea that a hydrogenic
orbital can be written as the product of a function R(r) of
the radius (the distance the electron is from the nucleus)
and a function Y(θ,ϕ) of the angular coordinates. The posi-
tions where either component of the wavefunction passes
through zero are called nodes. Consequently, there are two
types of nodes. Radial nodes occur where the radial compo-
nent of the wavefunction passes through zero and angular
nodes occur where the angular component of the wavefunc-
tion passes through zero. The numbers of both types of
node increase with increasing energy and are related to the
quantum numbers n and l. The total number of radial and
angular nodes for any orbital is equal to n − 1.
nucleus (at r = 0).
has no radial node because its radial wavefunction does not
pass through zero anywhere. For any series of the same type
of orbital, the first occurrence has no radial node, the sec-
ond has one radial node, and so on.
Although an electron in an s orbital may be found at the
nucleus, an electron in any other type of orbital will not be
found there. We shall soon see that this apparently minor
detail, which is a consequence of the absence of orbital
angular momentum when l = 0, is one of the key concepts
for understanding the layout of the periodic table and the
chemistry of the elements.

(e) The radial variation of atomic orbitals

KEY POINT An s orbital has nonzero amplitude at the nucleus; all
1
other orbitals (those with l > 0) vanish at the nucleus.

Figures 1.8 and 1.9 show the radial variations of some 0.8

atomic orbitals. A 1s orbital, the wavefunction with n = 1,

Radial wavefunction, R/(Z/a0)3/2

l = 0, and ml = 0, decays exponentially with distance from the 0.6

nucleus and never passes through zero (it has no nodes). All
orbitals decay exponentially at sufficiently great distances 0.4
from the nucleus and this distance increases as n increases.
2p
Some orbitals oscillate through zero close to the nucleus and 0.2
thus have one or more radial nodes before beginning their
final exponential decay. As the principal quantum number 0
of an electron increases, it is likely to be found further away
3p
from the nucleus and its energy increases. –0.2
An orbital with quantum numbers n and l has n − l − 1 0 10 20 30
Radius, Zr/a0
radial nodes. This oscillation is evident in the 2s orbital, the
orbital with n = 2, l = 0, and ml = 0, which passes through FIGURE 1.9 The radial wavefunctions of the 2p and 3p
zero once and hence has one radial node. A 3s orbital passes hydrogenic orbitals. Note that the number of radial nodes is 0 and
through zero twice and so has two radial nodes (Fig. 1.8). 1, respectively. Each orbital has zero amplitude at the nucleus (at
A 2p orbital (one of the three orbitals with n = 2 and l = 1) r = 0).

Radial distribution function, r2R2
3s
2s
1s
Radius, Zr/a0
FIGURE 1.10 The 1s, 2s, and 3s orbitals showing the radial nodes.
EXAMPLE 1.3 Predicting numbers of radial nodes
How many radial nodes do 3p, 3d, and 4f orbitals each have?
Answer We need to make use of the fact that the number of
radial nodes is given by the expression n − l − 1 and use it to
find the number of radial nodes using values of n and l. The 3p
orbitals have n = 3 and l = 1 and so the number of radial nodes
is n − l − 1 = 1. The 3d orbitals have n = 3 and l = 2. Therefore, the
number of radial nodes is n − l − 1 = 0. The 4f orbitals have n =
4 and l = 3 and the number of radial nodes is n − l − 1 = 0. The
3d and 4f orbitals are the first occurrence of the d and f orbitals
so this also indicates that they will have no radial node. The 3p
orbitals are the second occurrence of the p orbitals and so we
would expect them to have one radial node.
Self-test 1.3 (a) How many radial nodes does a 5s orbital have?
(b) Which p orbital has two radial nodes?
(f) The radial distribution function
KEY POINT A radial distribution function gives the probability that an
electron will be found at a given distance from the nucleus, regardless
of the direction.
The Coulombic (electrostatic) force that binds the electron
is centred on the nucleus, so it is often of interest to know
the probability of finding an electron at a given distance
from the nucleus, regardless of its direction. This informa-
tion enables us to judge how tightly the electron is bound.
The total probability of finding the electron in a spherical
shell of radius r and thickness dr is the integral of ψ 2dτ over
all angles. This result is written P(r)dr, where P(r) is called
the radial distribution function. In general,
P(r) = r2R(r)2(1.6)
The structures of hydrogenic atoms 13
R2
r2R2
r2
0 1 2 3 4 5
Radius, Zr/a0
FIGURE 1.11 The radial distribution function, r2R2, of a hydrogenic
1s orbital. r2R2 is the product of r2 (which increases as r increases)
and the square of the radial component of the wavefunction Ψ
(labelled R2 in the figure and which decreases exponentially). The
radial distribution function passes through a maximum at r = a0/Z.
(For s orbitals, this expression is the same as P = 4πr2ψ 2.)
If we know the value of P at some radius r, then we can
state the probability of finding the electron somewhere in
a shell of thickness dr at that radius simply by multiplying
P by dr.
Because the wavefunction of a 1s orbital decreases expo-
nentially with distance from the nucleus and the factor r2
in eqn 1.6 increases, the radial distribution function of a
1s orbital goes through a maximum (Fig. 1.11). Therefore,
there is a distance at which the electron is most likely to
be found. In general, this most probable distance decreases
as the nuclear charge increases (because the electron is
attracted more strongly to the nucleus), and specifically
a0
rmax =  (1.7)
Z
where a0 is the Bohr radius, a0 = ε02/πmee2, a quantity that
appeared in Bohr’s formulation of his model of the atom;
its numerical value is 52.9 pm. The most probable distance
increases as n increases because the higher the energy, the
more likely it is that the electron will be found far from the
nucleus.
EXAMPLE 1.4 Interpreting radial distribution
functions
Figure 1.12 shows the radial distribution functions for 2s and 2p
hydrogenic orbitals. Which orbital gives the electron a greater
probability of close approach to the nucleus?
Answer By examining Fig. 1.12 we can see that the radial
distribution function of a 2p orbital approaches zero near
14 1 Atomic structure
the nucleus faster than a 2s electron does. This difference is a
consequence of the fact that a 2p orbital has zero amplitude
at the nucleus on account of its orbital angular momentum.
The 2s electron has a greater probability of close approach to
the nucleus indicated by the inner maximum. Note that the 2s
orbital extends further into space.
Self-test 1.4 Which orbital, 3p or 3d, gives an electron a greater
probability of being found close to the nucleus?
Radial distribution function, r2R2
2p
2s
0 15
Radius, Zr/a0
FIGURE 1.12 The radial distribution functions of hydrogenic
orbitals. Although the 2p orbital is on average closer to the
nucleus (note where its maximum lies), an electron in a 2s
orbital has a high probability of being close to the nucleus on
account of the inner maximum.
(g) The angular variation of atomic orbitals
KEY POINTS The boundary surface of an orbital indicates the region
of space within which the electron is most likely to be found; orbitals
with the quantum number l have l nodal planes.
The angular wavefunction expresses the variation of angle
around the nucleus and this describes the orbital’s angu-
lar shape. An s orbital has the same amplitude at a given
distance from the nucleus whatever the angular coordi-
nates of the point of interest: that is, an s orbital is spheri-
cally symmetrical. The orbital is normally represented
by a spherical surface with the nucleus at its centre. The
surface is called the boundary surface of the orbital, and
defines the region of space within which there is a high
(typically 90%) probability of finding the electron. This
boundary surface is what chemists draw to represent the
shape of an orbital. The planes on which the angular wave-
function passes through zero are called angular nodes or
nodal planes. An electron will not be found anywhere on
a nodal plane. A nodal plane cuts through the nucleus and
separates the regions of positive and negative sign of the
wavefunction.
z
y
x
FIGURE 1.13 The spherical boundary surface of an s orbital.
In general, an orbital with the quantum number l has l
nodal planes. An s orbital, with l = 0, has no nodal plane and
the boundary surface of the orbital is spherical (Fig. 1.13).
All orbitals with l > 0 have amplitudes that vary with angle
and, for p orbitals, ml values of +1, 0, and −1. In the most
common graphical representation, the boundary surfaces of
the three p orbitals of a given shell are identical apart from
the fact that their axes lie parallel to each of the three different
Cartesian axes centred on the nucleus, and each one possesses
a nodal plane passing through the nucleus (Fig. 1.14). In the
diagrammatic representation of the orbitals the two lobes are
shaded differently (dark and light respectively) or labelled ‘+’
and ‘−’ to indicate that one has a positive and one has a nega-
tive amplitude. This representation is the origin of the labels px,
py, and pz. Each p orbital, with l = 1, has a single nodal plane.
The boundary surfaces and labels we use for the d and f
orbitals are shown in Figs 1.15 and 1.16, respectively. The d z 2
orbital looks different from the remaining d orbitals. There
are in fact six possible combinations of double dumb-bell
shaped orbitals around three axes: three with lobes between
the axes, as in dxy, dyz, and dzx, and three with lobes along the
axis. However, only five d orbitals are allowed. One of these
orbitals is assigned d x − y and lies along the x and y axes. The
2 2
remaining orbital is the d2 z − x − y from the algebra which is
2 2 2
simplified to d z and can be thought of as the superposition
2
of the remaining two combinations, the d z − y and the other 2 2
the d z − x . Note that a d orbital (with l = 2) has two nodal
2 2
planes that intersect at the nucleus; a typical f orbital (l = 3)
has three nodal planes.
z z z
+
− − y
+
+ y
y
x x −
x
px py pz
FIGURE 1.14 The representation of the boundary surfaces of the
p orbitals. Each orbital has one nodal plane running through the
nucleus. For example, the nodal plane of the pz orbital is the xy-
plane. The darkly shaded lobe has a positive amplitude, the more
lightly shaded one is negative.

z
y
x
dx2–y2
dz2
dzx dyz dxy
x y fy3–3yx2
f5z3–3zr2 f5xz2–3xr2
fxyz
fzx2–zy2 fx3–3xy2
Many-electron atoms
As we have remarked, a ‘many-electron atom’ is an atom
with more than one electron, so even He, with two elec-
trons, is technically a many-electron atom. The exact
solution of the Schrödinger equation for an atom with
N electrons would be a function of the 3N coordinates
of all the electrons. It would be extremely challenging
to find exact formulas for such complicated functions;
however, it is straightforward to perform numerical
computations by using widely available software to
obtain precise energies and probability densities. This
software can also generate graphical representations of
the resulting orbitals that can assist in the interpreta-
tion of the properties of the atom. For most of inorganic
chemistry we rely on the orbital approximation, in which
each electron occupies an atomic orbital that resembles
those found in hydrogenic atoms. When we say that an
electron ‘occupies’ an atomic orbital, we mean that it is
described by the corresponding wavefunction and set of
quantum numbers.
Many-electron atoms 15
FIGURE 1.15 One representation of the boundary surfaces
of the d orbitals. Four of the orbitals have two perpendicular
nodal planes that intersect in a line passing through the
nucleus. In the dz2 orbital, the nodal surface forms two cones
that meet at the nucleus.
f5yz2–yr2
FIGURE 1.16 One representation of the
boundary surfaces of the f orbitals. Other
representations (with different shapes) are also
sometimes encountered.
1.4 Penetration and shielding
KEY POINTS The ground-state electron configuration is a specifica-
tion of the orbital occupation of an atom in its lowest energy state. The
exclusion principle forbids more than two electrons to occupy a single
orbital. The nuclear charge experienced by an electron is reduced by
shielding by other electrons, including those in the same shell. Trends
in effective nuclear charge can be used to rationalize the trends in
many properties. As a result of the combined effects of penetration and
shielding, the order of energy levels in a shell of a many-electron atom
is s < p < d < f.
It is quite easy to account for the electronic structure of the
helium atom in its ground state, its state of lowest energy.
According to the orbital approximation, we suppose that
both electrons occupy an atomic orbital that has the same
spherical shape as a hydrogenic 1s orbital. However, the
orbital will be more compact because, as the nuclear charge
of helium is greater than that of hydrogen, the electrons are
drawn in towards the nucleus more closely than is the one
16 1 Atomic structure
electron of an H atom. The ground-state configuration of
an atom is a statement of the orbitals its electrons occupy
in the ground state. For helium, with two electrons in the 1s
orbital, the ground-state configuration is denoted 1s2 (read
as ‘one s two’).
As soon as we come to the next atom in the periodic table,
lithium (Z = 3), we encounter several major new features.
The configuration 1s3 is forbidden by a fundamental feature
of nature known as the Pauli exclusion principle:
No more than two electrons may occupy a single orbital
and, if two do occupy a single orbital, then their spins
must be paired.
By ‘paired’ we mean that one electron spin must be ↑
(ms = +½) and the other ↓ (ms = −½); the pair is denoted
↑↓. Another way of expressing the principle is to note that,
because an electron in an atom is described by four variable
quantum numbers, n, l, ml, and ms, no two electrons can
have the same four quantum numbers. The Pauli principle
was introduced originally to account for the absence of cer-
tain transitions in the spectrum of atomic helium.
Because the configuration 1s3 is forbidden by the Pauli
exclusion principle, the third electron must occupy an orbital
of the next higher shell, the shell with n = 2. The question
that now arises is whether the third electron occupies a 2s
orbital or one of the three 2p orbitals. To answer this ques-
tion, we need to examine the energies of the two subshells
and the effect of the other electrons in the atom. Although
2s and 2p orbitals have the same energy in a hydrogenic
atom, spectroscopic data and calculations show that this is
not the case in a many-electron atom.
In the orbital approximation, we treat the repulsion
between electrons in an approximate manner by supposing
that the electronic charge is distributed spherically around
the nucleus. Then each electron moves in the attractive field
of the nucleus and also experiences an average repulsive
charge from the other electrons. According to classical elec-
trostatics, the field that arises from a spherical distribution
of charge is equivalent to the field generated by a single
point charge at the centre of the distribution (Fig. 1.17). This
Charge does
not contribute
r
Charge
contributes
FIGURE 1.17 The electron at the r radius experiences a repulsion
from the total charge within the sphere of radius r; charge outside
that radius has no net effect.
negative charge reduces the actual charge of the nucleus, Z,
to Zeff, where Zeff is called the effective nuclear charge.
This effective nuclear charge depends on the values of n
and l of the electron of interest because electrons in differ-
ent shells and subshells approach the nucleus to different
extents. The reduction of the true nuclear charge to the effec-
tive nuclear charge by the other electrons is called shield-
ing. The effective nuclear charge is sometimes expressed in
terms of the true nuclear charge and an empirical shielding
constant, σ, by writing Zeff = Z − σ. The shielding constant
can be determined by fitting hydrogenic orbitals to those
computed numerically. It can also be approximated by using
the empirical set of rules, Slater’s rules.
Slater’s rules attribute a numerical contribution to elec-
trons in an atom in the following way:
Write out the electron configuration of the atom and
group orbitals together in the form
(1s)(2s2p)(3s3p)(3d)(4s4p)(4d)(4f)(5s5p) etc.
If the outermost electron is in an s or p orbital,
Each of the other electrons in the (ns np) grouping con-
tributes 0.35 to σ;
Each electron in the n − 1 shell contributes 0.85 to σ;
Each electron in lower shells contributes 1.0 to σ.
If the outermost electron is in a d or f orbital,
Each of the other electrons in the (nd) or (nf) grouping
contributes 0.35 to σ;
Each electron in lower shells or earlier groupings contrib-
utes 1.0 to σ.
For example, to calculate the shielding constant for the out-
ermost electron, and hence the effective nuclear charge of
fluorine, F, we first write down the electron configuration
with appropriate groupings:
(1s2)(2s22p5)
Then σ = (6 × 0.35) + (2 × 0.85) = 3.80 and, therefore, Zeff = Z − σ
= 9 − 3.80 = 5.20. The values of Zeff calculated this way are not
the same as those given in Table 1.2 although they do follow the
same pattern. The Slater model is an approximation and does
not, of course, take into account the difference between s and
p orbitals or the effects of spin correlation (Section 1.5a).
EXAMPLE 1.5 Calculating screening constants
Calculate the shielding constants for the outermost electron
in Mg.
Answer We need to write down the electron configuration of
the atom and group the orbitals as described above: Mg (1s2)
(2s22p6)(3s2). We can now calculate the shielding constant by
 Many-electron atoms 17
assigning values to each electron other than the outermost one.
So for Mg we have S = (1 × 0.35) + (8 × 0.85) + (2 × 1.0) = 9.15.

Self-test 1.5 (a) Calculate the shielding constant for the

outermost electron in Si. (b) Calculate the effective nuclear

Radial distribution function, r2R2

charge on the outermost electron in Cl.
2p
The closer to the nucleus that an electron can approach,
the closer the value of Zeff is to Z itself because the electron
is repelled less by the other electrons present in the atom. 2s

With this point in mind, consider a 2s electron in the Li

atom. There is a nonzero probability that the 2s electron can
be found inside the 1s shell and experience the full nuclear
charge (Fig. 1.18). The potential for the presence of an elec-
tron inside shells of other electrons is called penetration. A
2p electron does not penetrate so effectively through the
core, the filled inner shells of electrons, because its wavefunc-
tion goes to zero at the nucleus. As a consequence, it is more
fully shielded from the nucleus by the core electrons. We can
conclude that in a many-electron atom a 2s electron has a
lower energy (is bound more tightly) than a 2p electron, and
therefore that the 2s orbital will be occupied before the 2p
orbitals, giving a ground-state electron configuration for Li
of 1s22s1. This configuration is commonly denoted [He]2s1,
where [He] denotes the atom’s helium-like 1s2 core.
The pattern of orbital energies in lithium, with 2s lower
than 2p, and in general ns lower than np, is a general fea-
ture of many-electron atoms. This pattern can be seen from
Table 1.2, which gives the calculated values of Zeff for all
atomic orbitals in the ground-state electron configuration
of atoms. The typical trend in effective nuclear charge is
an increase across a period, for in most cases the increase
in the positive nuclear charge in successive elements is not
fully cancelled by the additional electron. The values in the
0 15
Radius, Zr/a0
FIGURE 1.18 The penetration of a 2s electron through the
inner core is greater than that of a 2p electron because the latter
vanishes at the nucleus. Therefore, the 2s electrons are less
shielded than the 2p electrons.
table also confirm that an s electron in the outermost shell
of the atom is generally less shielded than a p electron of
that shell. So, for example, Zeff = 5.13 for a 2s electron in an
F atom, whereas for a 2p electron Zeff = 5.10, a lower value.
Similarly, the effective nuclear charge is larger for an elec-
tron in an np orbital than for one in an nd orbital.
As a result of penetration and shielding, the order of
energies in many-electron atoms is typically ns, np, nd, nf
because, in a given shell, s orbitals are the most penetrating
and f orbitals are the least penetrating. The overall effect
of penetration and shielding is depicted in the energy-level
diagram for a neutral atom shown in Fig. 1.19.

TABLE 1.2 Effective nuclear charge, Zeff

H He
4f
4d
Z 1 2 4p
4s Z < 21
1s 1.00 1.69 3p Z ≥ 21
3s 3d
Li Be B C N O F Ne 2p
Energy

Z 3 4 5 6 7 8 9 10
2s
1s 2.69 3.68 4.68 5.67 6.66 7.66 8.65 9.64
2s 1.28 1.91 2.58 3.22 3.85 4.49 5.13 5.76
2p 2.42 3.14 3.83 4.45 5.10 5.76
Na Mg Al Si P S Cl Ar
Z 11 12 13 14 15 16 17 18
1s
1s 10.63 11.61 12.59 13.57 14.56 15.54 16.52 17.51
2s 6.57 7.39 8.21 9.02 9.82 10.63 11.43 12.23 FIGURE 1.19 A schematic diagram of the energy levels of a
2p 6.80 7.83 8.96 9.94 10.96 11.98 12.99 14.01 many-electron atom with Z < 21 (as far as calcium). There is a
change in order for Z ≥ 21 (from scandium onwards). This is the
3s 2.51 3.31 4.12 4.90 5.64 6.37 7.07 7.76
diagram that justifies the building-up principle, with up to two
3p 4.07 4.29 4.89 5.48 6.12 6.76 electrons being allowed to occupy each orbital.
18 1 Atomic structure
Energy
FIGURE 1.20 A more detailed portrayal of the
energy levels of many-electron atoms in the
periodic table. The inset shows a magnified view
of the order near Z = 20, where the 3d series of
elements begins.
Figure 1.20 summarizes the energies of the orbitals
through the periodic table. The effects are quite subtle,
and the order of the orbitals depends strongly on the
numbers of electrons present in the atom and may change
on ionization. For example, the effects of penetration are
very pronounced for 4s electrons in K and Ca, and in
these atoms the 4s orbitals lie lower in energy than the
3d orbitals. However, from Sc through Zn, the 3d orbit-
als in the neutral atoms lie close to but lower than the
4s orbitals. In atoms from Ga (Z ≥ 31) onwards, the 3d
orbitals lie well below the 4s orbital in energy, and the
outermost electrons are unambiguously those of the 4s
and 4p subshells.
EXAMPLE 1.6 Accounting for trends in effective
nuclear charge
From Table 1.2 the increase in Zeff (2p) between C and N is
0.69 whereas the increase between N and O (2p) is only 0.62.
Suggest a reason why the increase in Zeff for a 2p electron
is smaller between N and O than between C and N given the
configurations of the atoms listed above.
Answer We need to identify the general trend and then think
about an additional effect that might modify it. In this case, we
expect to see an increase in effective nuclear charge across a
period and indeed we do. However, on going from C to N, the
additional electron occupies an empty 2p orbital whereas on
going from N to O, the additional electron must occupy a 2p
orbital that is already occupied by one electron. It therefore
experiences stronger electron–electron repulsion. Electron–
electron repulsion contributes to the overall shielding effect
and so the increase in Zeff is not as great.
K
3d Ca 4p
n
5
Sc
4s
Ti
4
V
2
1 25 50 75 100
Atomic number, Z
Self-test 1.6 (a) Account for the larger increase in effective
nuclear charge for a 2p electron on going from B to C compared
with a 2s electron on going from Li to Be. (b) Account for the
increase in effective nuclear charge on going from B to Al.
1.5 The building-up principle
The ground-state electron configurations of many-electron
atoms are determined experimentally by spectroscopy and
are summarized in Resource section 2. To account for them,
we need to consider both the effects of penetration and
shielding on the energies of the orbitals and the role of the
Pauli exclusion principle. The building-up principle (which
is also known as the Aufbau principle and is described
below) is a procedure that leads to plausible ground-state
configurations. It is not infallible, but it is an excellent start-
ing point for the discussion. Moreover, as we shall see, it
provides a theoretical framework for understanding the
structure and implications of the periodic table.
(a) Ground-state electron configurations
KEY POINTS The order of occupation of atomic orbitals follows the
order 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, . . .. Degenerate orbitals are occupied
singly before being doubly occupied; certain modifications of the order
of occupation occur for d and f orbitals.
According to the building-up principle, orbitals of neutral
atoms are treated as being occupied in the order determined
in part by the principal quantum number and in part by
penetration and shielding:
Order of occupation: 1s 2s 2p 3s 3p 4s 3d 4p . . .

Each orbital can accommodate up to two electrons. Thus,
the three orbitals in a p subshell can accommodate a total of
six electrons and the five orbitals in a d subshell can accom-
modate up to ten electrons. The ground-state configurations
of the first five elements are therefore expected to be
H He Li Be B
1s 1
1s2
1s 2s2 1
1s 2s
2 2
1s22s22p1
This order agrees with experiment. When more than one
orbital of the same energy is available for occupation, such
as when the 2p orbitals begin to be filled in boron and car-
bon, we adopt Hund’s rule:
When more than one orbital has the same energy, elec-
trons occupy separate orbitals and do so with parallel
spins (↑↑).
The occupation of separate orbitals of the same value
of l (such as a px orbital and a py orbital) can be under-
stood in terms of the weaker repulsive interactions that
exist between electrons occupying different regions of
space (electrons in different orbitals) than between those
occupying the same region of space (electrons in the same
orbital). The requirement of parallel spins for electrons
that do occupy different orbitals is a consequence of a
quantum mechanical effect called spin correlation, the ten-
dency for two electrons with parallel spins to stay apart
from one another and hence to repel each other less. The
energy associated with this effect is called the correlation
energy. An additional factor that stabilizes arrangements
of electrons with parallel spins is an exchange energy. The
exchange energy is the extra stability that a parallel spin
configuration (↑↑) gains because the electrons are indistin-
guishable and interchangeable. When two electrons with
parallel spins exchange positions in degenerate orbitals,
energy is released. If one of the electrons of a pair with
parallel spins is removed then this exchange energy is lost.
Consequently, arrangements of electrons in degenerate
orbitals with large numbers of parallel spins are stabilized
relative to those without. The highest exchange energy
occurs with a half-filled shell when the largest number of
electrons with parallel spins exists. The consequence of
this is that half-filled shells, such as p3, d5, and f7, are par-
ticularly stable arrangements as removing an electron from
these configurations requires the input of energy to over-
come the greatest amount of exchange energy. Removing
one electron from the d5 configuration (↑↑↑↑↑) to give
(↑↑↑↑) reduces the number of pairs of electrons with
parallel spins, and hence the possible number of electron
exchanges, from 10 to 6 if each possible pair of electrons
is considered. One result of this preference for arrange-
ments with half-filled shells is that the ground state of the
chromium atom is 4s13d5 rather than 4s23d4 as the former
maximizes the exchange energy.
Many-electron atoms 19
It is arbitrary which of the p orbitals of a subshell is occu-
pied first because they are degenerate, but it is common to
adopt the alphabetical order px, py, pz. It then follows from
the building-up principle that the ground-state configura-
tion of C is 1s22s22px12p1y or, more simply, 1s22s22p2. If we
recognize the helium-like core (1s2), an even briefer notation
is [He]2s22p2, and we can think of the electronic valence
structure of the atom as consisting of two paired 2s elec-
trons and two parallel 2p electrons surrounding a closed
helium-like core. The electron configurations of the remain-
ing elements in the period are similarly
C N O F Ne
[He]2s 2p [He]2s 2p [He]2s 2p [He]2s 2p
2 2 2 3 2 4 2 5
[He]2s22p6
The 2s22p6 configuration of neon is another example of a
closed shell, a shell with its full complement of electrons.
The configuration 1s22s22p6 is denoted [Ne] when it occurs
as a core.
The ground-state configuration of Na is obtained by adding
one more electron to a neon-like core, and is [Ne]3s1, showing
that it consists of a single electron outside a completely filled
1s22s22p6 core. Now a similar sequence of filling subshells
begins again, with the 3s and 3p orbitals complete at argon,
with configuration [Ne]3s23p6, which can be denoted [Ar].
Because the 3d orbitals are so much higher in energy, this
configuration is effectively closed. Moreover, the 4s orbital is
next in line for occupation, so the configuration of K is analo-
gous to that of Na, with a single electron outside a noble-gas
core: specifically, it is [Ar]4s1. The next electron, for Ca, also
enters the 4s orbital, giving [Ar]4s2, which is the analogue
of Mg. However, in the next element, Sc, the added electron
occupies a 3d orbital, and filling of the d orbitals begins.
(b) Exceptions
The energy levels in Figs 1.19 and 1.20 are for individual
atomic orbitals and do not fully take into account repulsion
between electrons. For elements with an incompletely filled
d subshell, the determination of actual ground states by
spectroscopy and calculation shows that it is advantageous
to occupy orbitals predicted to be higher in energy (the 4s
orbitals). The explanation for this order is that the occupa-
tion of the 4s orbitals can result in a reduction in the repul-
sions between electrons that would occur if the 3d orbitals
were occupied. It is essential when assessing the total energy
of the electrons to consider all contributions to the energy
of a configuration, not merely the one-electron orbital ener-
gies. Spectroscopic data show that the ground-state configu-
rations of these atoms, the first row transition metals, are
mostly of the form 3dn4s2, with the 4s orbitals fully occupied
despite individual 3d orbitals being lower in energy.
An additional feature, another consequence of spin cor-
relation and exchange energies, is that in some cases a lower
20 1 Atomic structure
total energy may be obtained by forming a half-filled or
filled d subshell, even though that may mean moving an
s electron into the d subshell. Therefore, as a half-filled d
shell is approached the ground-state configuration is likely
to be d5s1 and not d4s2 (as for Cr). As a full d subshell is
approached the configuration is likely to be d10s1 rather
than d9s2 (as for Cu) or d10s0 rather than d8s2 (as for Pd).
A similar effect occurs where f orbitals are being occupied,
and a d electron may be moved into the f subshell so as to
achieve an f7 or an f14 configuration, with a net lowering
of energy.
For cations and complexes of the d-block elements the
removal of electrons reduces the effect of electron–elec-
tron repulsions and the 3d orbital energies fall well below
that of the 4s orbitals. Consequently, all d-block cations
and complexes have dn configurations and no electron in
the outermost s orbital. For example, the configuration of
Fe is [Ar]3d64s2 whereas in [Fe(CO)5] the configuration
is [Ar]3d8 and Fe2+ has the configuration [Ar]3d6. For the
purposes of chemistry, the electron configurations of the
d-block ions are more important than those of the neu-
tral atoms. In later chapters (starting in Chapter 19), we
shall see the great significance of the configurations of the
d-metal ions, for the subtle modulations of their energies
provide the basis for the explanations of important proper-
ties of their compounds.
EXAMPLE 1.7 Deriving an electron configuration
Predict the ground-state electron configurations of (a) P, (b) Ti,
and (c) Ti3+.
Answer We need to use the building-up principle and Hund’s
rule to populate atomic orbitals with electrons. (a) For the P
atom, for which Z = 15, we must add 15 electrons in the order
specified above, with no more than two electrons in any one
orbital. This procedure results in the configuration [Ne]3s23p3
with the three 3p electrons each in a different p orbital with
parallel spins. (b) For the neutral Ti atom, for which Z = 22,
we must add 22 electrons in the order specified above, with
no more than two electrons in any one orbital. This results
in the configuration [Ar]4s23d2, with the two 3d electrons in
different orbitals with parallel spins. However, because the
3d orbitals lie below the 4s orbitals for elements beyond Ca,
it is usual to reverse the order in which they are written. The
configuration is therefore reported as [Ar]3d24s2. (c) The Ti
cation has 19 electrons. We should fill the orbitals in the order
specified above remembering, however, that the cation will
have a dn configuration and no electrons in the s orbital. The
configuration of Ti3+ is therefore [Ar]3d1.
Self-test 1.7 (a) Predict the ground-state electron configurations
of Ni and Ni2+. (b) Predict the ground-state electron configurations
of Cu, Cu+, and Cu2+.
1.6 The classification of the elements
KEY POINTS The elements are broadly divided into metals, nonmet-
als, and metalloids according to their physical and chemical properties;
the organization of elements into the form resembling the modern pe-
riodic table is accredited to Mendeleev.
A useful broad division of elements is into metals and non-
metals. Metallic elements (such as iron and copper) are
typically lustrous, malleable, ductile, electrically conduct-
ing solids at about room temperature. Nonmetals are often
gases (oxygen), liquids (bromine), or solids that do not
conduct electricity appreciably (sulfur). The chemical impli-
cations of this classification should already be clear from
introductory chemistry:
1. Metallic elements combine with nonmetallic elements to
give compounds that are typically hard, nonvolatile sol-
ids (for example sodium chloride).
2. When combined with each other, the nonmetals often
form volatile molecular compounds (for example carbon
dioxide).
3. When metals combine (or simply mix together) they
produce alloys that have most of the physical charac-
teristics of metals (for example brass from copper and
zinc).
Some elements have properties that make it difficult to clas-
sify them as metals or nonmetals. These elements are called
metalloids. Examples of metalloids are silicon, germanium,
arsenic, and tellurium.
A NOTE ON GOOD PRACTICE
You will sometimes see metalloids referred to as ‘semimetals’.
This name is best avoided because a semimetal has a well-
defined and quite distinct meaning in solid state physics (see
Section 4.19).
(a) The periodic table
A more detailed classification of the elements is the one
devised by Dmitri Mendeleev in 1869; this scheme is famil-
iar to every chemist, and many non-chemists, as the periodic
table. Mendeleev arranged the known elements in order of
increasing atomic weight (molar mass). This arrangement
resulted in families of elements with similar chemical prop-
erties, which he arranged into the groups of the periodic
table. For example, the fact that C, Si, Ge, and Sn all form
hydrides of the general formula EH4 suggests that they
belong to the same group. That N, P, As, and Sb all form
hydrides with the general formula EH3 suggests that they
belong to a different group. Other compounds of these ele-
ments show family similarities, as in the formulas CF4 and
SiF4 in the first group, and NF3 and PF3 in the second.

Cs
70
60
Rb
)
–1
50 K
Molar atomic volume / (cm mol
Xe
3
40
He Kr
Eu
30
Na Ar
20
10
B
0
10 30 50
Atomic number, Z
Mendeleev concentrated on the chemical properties of the
elements. At about the same time Lothar Meyer in Germany
was investigating their physical properties, and found that
similar values repeated periodically with increasing molar
mass. Figure 1.21 shows a classic example, where the molar
volume of the element (its volume per mole of atoms) at 1
bar and 298 K is plotted against atomic number.
Mendeleev provided a spectacular demonstration of the
usefulness of the periodic table by predicting the general
chemical properties, such as the numbers of bonds they
form, of unknown elements such as gallium, germanium
and scandium corresponding to gaps in his original periodic
table. (He also predicted elements that we now know can-
not exist, and denied the presence of elements that we now
BOX 1.5 How far can the periodic table expand?
In January 2016 the International Union of Pure and Applied
Chemistry (IUPAC) announced the discovery of four new
elements, so completing the seventh row of the periodic table.
These were elements with atomic numbers 113, 115, 117, and
118 and were given the temporary, and rather uninspiring,
names ununtrium, Uut, ununpentium, UUp, ununseptimum,
Uus, and ununoctium, Uuo. They have since been named as
nihonium, Nh, muscovium, Mc, tennessine, Ts, and organesson,
Og. The procedures for naming new elements are clearly laid
out by IUPAC. The claim for the discovery of a new element
is verified by IUPAC and the International Union of Pure and
Applied Physics (IUPAP) and then formally assigned to a group
of scientists or a laboratory. The IUPAC Inorganic Chemistry
Committee then invites the discoverers to propose a name and
a symbol. These must fall within strict guidelines. The name
Many-electron atoms 21
Yb
Po
Cm
U
70 90 FIGURE 1.21 The periodic variation of molar
volume with atomic number.
know do exist, but that is overshadowed by his positive
achievement.) The same process of inference from periodic
trends is still used by inorganic chemists to rationalize trends
in the physical and chemical properties of compounds and
to suggest the synthesis of previously unknown compounds.
For instance, by recognizing that carbon and silicon are in
the same family, the existence of alkenes R2C=CR2 suggests
that R2Si=SiR2 ought to exist too. Compounds with silicon–
silicon double bonds (disilaethenes) do indeed exist, but
it was not until 1981 that chemists succeeded in isolating
one. The periodic trends in the properties of the elements
are explored further in Chapter 9. The periodic table is an
iconic and evolving representation of the known elements
and is still being added to today (Box 1.5).
can be based on a mythological concept, a mineral, a person, a
place or a property and should have an ending that fits in with
other elements in the appropriate part of the periodic table. For
example, elements in groups 1 to 16 must end in ‘ium’, those
in group 17 would end in ‘ine’ and those in group 18 must end
in ‘on’.
Element 113 was synthesized in Japan and its discoverers
suggested the name nihonium to reflect that. Nihon is one
of two ways to say ‘Japan’ and means ‘land of the rising
sun’. Nihonium is the first element to be discovered in Asia.
Similarly, elements 114 and 117 were named in honour of the
geographical regions in which their discoverers carried out their
science, those being Moscow and Tennessee, USA, respectively.
The discoverers of element 118 were based in Moscow and the
USA and, in proposing organesson, chose to honour scientist
22 1 Atomic structure

Yuri Organessian for his contribution to the chemistry and
physics of the superheavy elements.
Although the announcement of these new elements
was made by the IUPAC, the discovery of new so-called
superheavy elements is largely the domain of physicists rather
than chemists. These massive and very unstable elements are
synthesized in extremely small amounts (in some cases, less
than 5 atoms) by nuclear fusion in a heavy ion accelerator.
This fuses together two nuclei containing many protons,
generating an immense repulsive force which immediately
leads to nuclear fission in all but a tiny proportion of cases.
Even these few atoms of the new superheavy element are very
unstable and decay almost immediately by radioactive decay,
producing new isotopes of known lighter elements. The four
new elements were produced by firing 48Ca at californium or
berkelium targets but the 48Ca does not carry enough protons
to produce new superheavies. The race has already started
to identify new targets in order to create elements 119 and
even heavier superheavy elements. The periodic table seems
destined to expand even further as we proceed through the
twenty-first century. Indeed, elements beyond 118 may be
known, and named, by the time this text is due for its next
revision, though the instability of any new element means
practical applications are unlikely.

(b) The format of the periodic table

KEY POINTS The blocks of the periodic table reflect the identity of
the orbitals that are occupied last in the building-up process. The
period number is the principal quantum number of the valence shell.
The group number is related to the number of valence electrons.
The layout of the periodic table reflects the electronic
structure of the atoms of the elements (Fig. 1.22). We can
now see, for instance, that a block of the table indicates
the type of subshell currently being occupied according to
the building-up principle. Each period, or row, of the table
corresponds to the completion of the s, p, d, and f subshells
of a given shell. The period number is the value of the prin-
cipal quantum number n of the shell which according to
the building-up principle is currently being occupied in the
main groups of the table. For example, Period 2 corresponds
to the n = 2 shell and the filling of the 2s and 2p subshells.
The group numbers, G, are closely related to the num-
ber of electrons in the valence shell, the outermost shell of
the atom. In the ‘1–18’ numbering system recommended by
IUPAC:
Block: s p d
Number of electrons in valence shell: G G − 10 G
For the purpose of this expression, the ‘valence shell’ of a
d-block element consists of the ns and (n − 1)d orbitals, so
a Sc atom has three valence electrons (two 4s and one 3d
electron). The number of valence electrons for the p-block

Main groups
VIII
18
I II III IV V VI VII
1 H
1 2 13 14 15 16 17

2 Representative elements

Transition metals
3
3 4 5 6 7 8 9 10 11 12
Alkaline earth metals

4
Noble gases
Chalcogens
Alkali metals

Halogens

s Block d Block p Block

Lanthanoids

FIGURE 1.22 The general structure of the periodic Actinoids

table. Compare this template with the complete
table inside the front cover for the identities of the
elements that belong to each block. f Block
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 Ruhetal

Wann im letzten Abendstrahl

Goldne Wolkenberge steigen
Und wie Alpen sich erzeigen,
Frag ich oft mit Tränen:
»Liegt wohl zwischen jenen
Mein ersehntes Ruhetal?«

Ludwig Uhland
 Der Abendfriede

Von Disteldolden tropft der Tau,

Die Wiese schwimmt in Nebelgrau,
Und zitternd über die Blumenflur
Wellt schrill der Schlag der Klosteruhr …

Schwül weht des Abends feuchter Hauch,

Schwer überm Moore liegts wie Hauch
So fahl und grau, – und her und hin
Glimmt’s wie ein Lämplein goldig drin …

Und über Moor und Wiesenrain

Zieht stumm ein Mann im Heiligenschein:
Ein Klostermännlein, grau und krumm,
Ein Heiliger geht im Felde herum …

Sein Lämplein schwingt er dann und wann,

Summt übers Korn den Friedensbann –
Dünn klingt und schrill die Klosteruhr …
Ein Leuchtwurm zieht die goldne Spur …

Hans Benzmann
 Abend

Wir stehn und schaun und sprechen kein Wort –

Der Abend zerflattert auf dunklen Wiesen.
Strenge Schatten kommen vom Torf,
Steigen als stumme Riesen
Über die Schollen behutsam fort
Ins Dorf. –

Wilhelm von Scholz

 Meeresabend

Sie hat den ganzen Tag getobt

Als wie in Zorn und Pein,
Nun bettet sich, nun glättet sich
Die See und schlummert ein.

Und drüber zittert der Abendwind,

Ein mildes, heiliges Wehn,
Das ist der Atem Gottes,
Der schwebet ob den Seen.

Es küßt der Herr aufs Lockenhaupt

Die schlummernde See gelind
Und spricht mit säuselndem Segen:
»Schlaf ruhig, liebes Kind!«

Moritz von Strachwitz

 Ein Tageslauf

Sitz ich sinnend, Haupt in Hand gestützt;

Schöner Tag, hab ich dich recht genützt?

Einen Kuß auf meines Weibes Mund,

Liebesgruß in früher Morgenstund.

Sorg ums Brot in treuer Tätigkeit,

Offnes Wort in scharfem Männerstreit.

Einen guten Becher froh geleert,

Kräftig einem argen Wunsch gewehrt.

Leuchtend kommt aus ewigem Sternenraum

Noch zuletzt ein seliger Dichtertraum.

Sinnend sitz ich, Haupt in Hand gestützt:

Schöner Tag, ich hab dich ausgenützt.

Gustav Falke
 Am Abend

Sinkt der Tag in Abendgluten,

Schwimmt das Tal in Nebelfluten.

Heimlich aus der Himmelsferne

Blinken schon die goldnen Sterne.

Flieg zu Nest und schwimm zum Hafen!

Gute Nacht! Die Welt will schlafen!

Heinrich Seidel
Abendlandschaft

Der Hirt bläst seine Weise,

Von fern ein Schuß noch fällt,
Die Wälder rauschen leise
Und Ströme tief im Feld.

Nur hinter jenem Hügel

Noch spielt der Abendschein –
O hätt ich, hätt ich Flügel,
Zu fliegen da hinein!

Joseph von Eichendorff

 Abendstille

Abendstille, weich und warm,

Kaum ein Hauch zu spüren,
Stehn die Mädchen Arm in Arm
Plaudernd vor den Türen.

Fliegt das Mäulchen noch so spät

Sonder Rast und Maßen,
Horchen, wie der Wagen geht
Durch die stillen Straßen.

Kläfft der Spitz den Rädern zu,

Die gemach entschwinden,
Süße, sanfte Sommerruh
Sinkt ins Laub der Linden.
Nur ein ferner Burschensang
Tönt noch hin und wieder,
Alles lauscht dem Heimatklang
Der gewohnten Lieder.

Lauscht und sieht im Strahlenkleid

Erste Sterne glänzen,
Und die Seele wandert weit
Ohne Ziel und Grenzen.

Carl Busse
 Abendlieder
I.

Die Sonne, die breite behäbige Frau,

Schon rüstet sie sich zur Nacht.
Die Goldsträhnen läßt durch den Himmel sie wehn,
Hat’s Purpurkleid aufgemacht.

Doch unten im Abend ein grauliches Tier,

Ein Drache rührt sich und ruckt.
Den zackigen Rücken drängt er empor –
Frau Sonne, o weh, ist verschluckt.

Der Lurch, was grummelt und grollt er denn?

Er krümmt sich, er bäumt sich, er klafft:
Frau Sonne durchstach ihn von innen her,
Strahlt wieder in glühender Kraft.

Hans Böhm

II.

Der Wächter tutet in sein Horn,

Und stille sind die Straßen;
Vor unserm Fenster nur der Born
Kann nicht vom Plaudern lassen.
Wir wollen schlafen gehn.

Die Lichter löschen langsam aus,

Schwarz hängt die Nacht hernieder;
Der Schlummer geht von Haus zu Haus
Und schließt die Augenlider.
Wir wollen schlafen gehn.

Die Uhr schlägt zehn, die Welt schlief ein.

Die Winde gehen müde.
Vom Himmel glänzt der Sterne Schein.
Kehr auch in unsre Herzen ein,
Du stiller Sternenfriede!
Wir wollen schlafen gehn.

Albert Sergel
 III.

Augen, meine lieben Fensterlein,

Gebt mir schon so lange holden Schein,
Lasset freundlich Bild um Bild herein:
Einmal werdet ihr verdunkelt sein!

Fallen einst die müden Lider zu,

Löscht ihr aus, dann hat die Seele Ruh;
Tastend streift sie ab die Wanderschuh,
Legt sich auch in ihre finstre Truh.

Noch zwei Fünklein sieht sie glimmend stehn

Wie zwei Sternlein, innerlich zu sehn,
Bis sie schwanken und dann auch vergehn,
Wie von eines Falters Fügelwehn.

Doch noch wandl’ ich auf dem Abendfeld,

Nur dem sinkenden Gestirn gesellt;
Trinkt, o Augen, was die Wimper hält,
Von dem goldnen Überfluß der Welt!

Gottfried Keller
 Abendlied

Die Nacht ist niedergegangen,

Die schwarzen Schleier hangen
Nun über Busch und Haus.
Leis rauscht es in den Buchen.
Die letzten Winde suchen
Die vollsten Wipfel sich zum Neste aus.

Noch einmal leis ein Wehen,

Dann bleibt der Atem stehen
Der müden, müden Welt.
Nur noch ein zages Beben
Fühl durch die Nacht ich schweben,
Auf die der Friede seine Hände hält.

Otto Julius Bierbaum

Ein geistlich Abendlied

Es ist so still geworden,

Verrauscht des Abends Wehn,
Nun hört man allerorten
Der Engel Füße gehn.
Rings in die Tale senket
Sich Finsternis mit Macht –
Wirf ab, Herz, was dich kränket
Und was dir bange macht.

Es ruht die Welt im Schweigen,

Ihr Tosen ist vorbei,
Stumm ihrer Freude Reigen
Und stumm ihr Schmerzensschrei.
Hat Rosen sie geschenket,
Hat Dornen sie gebracht –
Wirf ab, Herz, was dich kränket
Und was dir bange macht!

Und hast du heut gefehlet,

O schaue nicht zurück;
Empfinde dich beseelet
Von freier Gnade Glück.
Auch des Verirrten denket
Der Hirt auf hoher Wacht –
Wirf ab, Herz, was dich kränket
Und was dir bange macht!

Nun stehn im Himmelskreise

Die Stern’ in Majestät;
In gleichem festem Gleise
Der goldne Wagen geht.
Und gleich den Sternen lenket
Er deinen Weg zur Nacht –
Wirf ab, Herz, was dich kränket
Und was dir bange macht!

Gottfried Kinkel
Wanderers Nachtlied

Der du von dem Himmel bist,

Alles Leid und Schmerzen stillest,
Den, der doppelt elend ist,
Doppelt mit Erquickung füllest,
Ach, ich bin des Treibens müde!
Was soll all der Schmerz und Lust?
Süßer Friede,
Komm, ach komm in meine Brust!

Wolfgang von Goethe

 Manche Nacht

Wenn die Felder sich verdunkeln,

Fühl ich, wird mein Auge heller;
Schon versucht ein Stern zu funkeln,
Und die Grillen klingen schneller.

Jeder Laut wird bilderreicher,

Das Gewohnte sonderbarer,
Hinterm Wald der Himmel bleicher,
Jeder Wipfel hebt sich klarer.

Und du merkst es nicht im Schreiten,

Wie das Licht verhundertfältigt
Sich entringt den Dunkelheiten,
Plötzlich stehst du überwältigt.

Richard Dehmel
 Die tröstende Nacht

O Nacht – du treue Trösterin!

Wenn ich auf meinem Lager zage,
So schwebst du vor das Fenster hin
Und hörst geduldig meine Klage.
Und wenn ins Kissen ich mit Stöhnen
Mein tränend Angesicht verhülle,
Hör ich auf einmal eine Fülle
Von Wohllaut mir zu Herzen tönen:

»Getrost, getrost! Ich bin ja hier!

Will dich nach jedem Tage heilen
Und werde kommen einst zu dir,
Um immerdar bei dir zu weilen.
Dann ruhst du, selig vom Vergessen
Durchschauert, fern von Tagesrauschen
Und magst dem sanften Liede lauschen,
Das Winde harfen in Zypressen.«

Bruno Wille
 Nachtgefühl

O stille Nacht, o Nacht der Stille,

Zur Ruh gebracht der ganze Wille –
Zum Schlaf bereit das Herz voll Sorgen;
O schöne Zeit bis an den Morgen!

Martin Greif