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Descriptive
Inorganic Chemistry
FIFTH EDITION

Geoff Rayner-Canham
Sir Wilfred Grenfell College
Memorial University

Tina Overton
University of Hull

W. H. FREEMAN AND COMPANY
NEW YORK


Publisher: Clancy Marshall
Acquisitions Editors: Jessica Fiorillo/Kathryn Treadway
Marketing Director: John Britch
Media Editor: Dave Quinn
Cover and Text Designer: Vicki Tomaselli
Senior Project Editor: Mary Louise Byrd
Illustrations: Network Graphics/Aptara
Senior Illustration Coordinator: Bill Page
Production Coordinator: Susan Wein
Composition: Aptara
Printing and Binding: World Color Versailles

Library of Congress Control Number: 2009932448
ISBN-13: 978-1-4292-2434-5
ISBN-10: 1-4292-1814-2
@2010, 2006, 2003, 2000 by W. H. Freeman and Company
All rights reserved
Printed in the United States of America
First printing
W. H. Freeman and Company
41 Madison Avenue
New York, NY 10010
Houndmills, Basingstoke RG21 6XS, England
www.whfreeman.com


Overview
CHAPTER 1

The Electronic Structure of the Atom: A Review

CHAPTER 2

An Overview of the Periodic Table

19

CHAPTER 3

Covalent Bonding

41


CHAPTER 4

Metallic Bonding

81

CHAPTER 5

Ionic Bonding

93

CHAPTER 6

Inorganic Thermodynamics

113

CHAPTER 7

Solvent Systems and Acid-Base Behavior

137

CHAPTER 8

Oxidation and Reduction

167


CHAPTER 9

Periodic Trends

191

CHAPTER 10

Hydrogen

227

CHAPTER 11

The Group 1 Elements: The Alkali Metals

245

CHAPTER 12

The Group 2 Elements: The Alkaline Earth Metals

271

CHAPTER 13

The Group 13 Elements

291


CHAPTER 14

The Group 14 Elements

315

CHAPTER 15

The Group 15 Elements: The Pnictogens

363

CHAPTER 16

The Group 16 Elements: The Chalcogens

409

CHAPTER 17

The Group 17 Elements: The Halogens

453

CHAPTER 18

The Group 18 Elements: The Noble Gases

487


CHAPTER 19

Transition Metal Complexes

499

CHAPTER 20

Properties of the 3d Transition Metals

533

CHAPTER 21

Properties of the 4d and 5d Transition Metals

579

CHAPTER 22

The Group 12 Elements

599

CHAPTER 23

Organometallic Chemistry

611


On the Web

www.whfreeman.com/descriptive5e

CHAPTER 24

The Rare Earth and Actinoid Elements

Appendices
Index

1

651w
A-1
I-1
iii


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Contents
What Is Descriptive Inorganic Chemistry?
Preface
Acknowledgments
Dedication

xiii

xv
xix
xxi

CHAPTER 1

The Electronic Structure of the Atom:
A Review

1

Atomic Absorption Spectroscopy

2

1.1
1.2
1.3
1.4
1.5
1.6

The Schrödinger Wave Equation and Its
Significance
Shapes of the Atomic Orbitals
The Polyelectronic Atom
Ion Electron Configurations
Magnetic Properties of Atoms
Medicinal Inorganic Chemistry:
An Introduction


3
5
9
14
15
16

3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12

Molecular Orbitals for Period 2
Diatomic Molecules
Molecular Orbitals for Heteronuclear
Diatomic Molecules
A Brief Review of Lewis Structures
Partial Bond Order
Formal Charge
Valence-Shell Electron-Pair Repulsion Rules
The Valence-Bond Concept
Network Covalent Substances
Intermolecular Forces


46
50
51
53
54
54
59
61
63

The Origins of the Electronegativity Concept

65

3.13
3.13

66
72

Molecular Symmetry
Symmetry and Vibrational Spectroscopy

Transient Species—A New Direction for Inorganic
Chemistry
74

3.15

Covalent Bonding and the Periodic Table


78

CHAPTER 4
CHAPTER 2

An Overview of the Periodic Table
2.1
2.2
2.3

19

Organization of the Modern
Periodic Table
21
Existence of the Elements
23
Stability of the Elements and Their Isotopes 24

Metallic Bonding

81

4.1
4.2
4.3
4.4
4.5


81
82
84
86
87

Metallic Bonding
Bonding Models
Structure of Metals
Unit Cells
Alloys

The Origin of the Shell Model of the Nucleus

26

Memory Metal: The Shape of Things to Come

88

2.4
2.5
2.6
2.7

27
29
33
35


4.6
4.7

89
90

Classifications of the Elements
Periodic Properties: Atomic Radius
Periodic Properties: Ionization Energy
Periodic Properties: Electron Affinity

Alkali Metal Anions

37

2.8

37

The Elements of Life

CHAPTER 3

Covalent Bonding

41

3.1
3.2
3.3


42
43

Models of Covalent Bonding
Introduction to Molecular Orbitals
Molecular Orbitals for Period 1
Diatomic Molecules

44

Nanometal Particles
Magnetic Properties of Metals

CHAPTER 5

Ionic Bonding

93

5.1
5.2
5.3
5.4
5.5

93
95
96
99


5.6

The Ionic Model and the Size of Ions
Hydrated Salts
Polarization and Covalency
Ionic Crystal Structures
Crystal Structures Involving
Polyatomic Ions
The Bonding Continuum

Concrete: An Old Material with a New Future

105
106
109
v


vi

Contents

8.8

CHAPTER 6

Inorganic Thermodynamics
6.1
6.2

6.3
6.4

Thermodynamics of the Formation
of Compounds
Formation of Ionic Compounds
The Born-Haber Cycle
Thermodynamics of the Solution
Process for Ionic Compounds
Formation of Covalent Compounds

113
114
120
122

8.9
8.10
8.11
8.12
8.13

Electrode Potentials as Thermodynamic
Functions
Latimer (Reduction Potential) Diagrams
Frost (Oxidation State) Diagrams
Pourbaix Diagrams
Redox Synthesis
Biological Aspects


124
127

CHAPTER 9

The Hydrogen Economy

128

Periodic Trends

6.6

129

9.1
9.2
9.3

6.5

Thermodynamic versus Kinetic Factors

CHAPTER 7

Group Trends
Periodic Trends in Bonding
Isoelectronic Series in Covalent
Compounds
Trends in Acid-Base Properties

The (n) Group and (n ϩ 10) Group
Similarities

177
178
180
182
184
185

191
192
195
199
201

Solvent Systems and Acid-Base
Behavior

137

7.1
7.2

138
142

Chemical Topology

206


Antacids

144

9.6

7.3

147

Solvents
Brønsted-Lowry Acids
Brønsted-Lowry Bases

9.4
9.5

202

Isomorphism in Ionic Compounds

207
209

210

Cyanide and Tropical Fish

148


New Materials: Beyond the Limitations of
Geochemistry

7.4

148

9.7

Superacids and Superbases

150

Lithium and Mental Health

211

7.5
7.6
7.7
7.8
7.9

153
155
156
158
161


9.8
9.9
9.10
9.11
9.12

The “Knight’s Move” Relationship
The Early Actinoid Relationships
The Lanthanoid Relationships
“Combo” Elements
Biological Aspects

212
215
216
217
221

Thallium Poisoning: Two Case Histories

223

Trends in Acid-Base Behavior
Acid-Base Reactions of Oxides
Lewis Theory
Pearson Hard-Soft Acid-Base Concepts
Applications of the HSAB Concept
Biological Aspects

Diagonal Relationships


CHAPTER 8

Oxidation and Reduction

167

CHAPTER 10

8.1
8.2
8.3

167
168

Hydrogen

227

10.1
10.2

228
229

8.4
8.5
8.6


Redox Terminology
Oxidation Number Rules
Determination of Oxidation Numbers
from Electronegativities
The Difference between Oxidation
Number and Formal Charge
Periodic Variations of Oxidation
Numbers
Redox Equations

169
171
172
173

Isotopes of Hydrogen
Nuclear Magnetic Resonance

Isotopes in Chemistry

230

10.3

Properties of Hydrogen

231

Searching the Depths of Space for the
Trihydrogen Ion


233

10.4
10.5

233
237

Hydrides
Water and Hydrogen Bonding

Chemosynthesis: Redox Chemistry on the
Seafloor

175

Water: The New Wonder Solvent

238

8.7

176

10.6

239

Quantitative Aspects of Half-Reactions


Clathrates


Contents

10.7

Biological Aspects of Hydrogen
Bonding

241

Is There Life Elsewhere in Our Solar System?

242

10.8

242

Element Reaction Flowchart

vii

Biomineralization: A New Interdisciplinary
“Frontier”

284


12.10
12.11
12.12
12.15

284
285
286
287

Calcium Sulfate
Calcium Carbide
Biological Aspects
Element Reaction Flowcharts

CHAPTER 11

The Group 1 Elements: The Alkali
Metals
11.1
11.2
11.3

Group Trends
Features of Alkali Metal Compounds
Solubility of Alkali Metal Salts

CHAPTER 13

245

246
247
249

Mono Lake

250

11.4
11.5
11.6
11.7
11.8
11.9

252
255
256
257
259
261

Lithium
Sodium
Potassium
Oxides
Hydroxides
Sodium Chloride

Salt Substitutes


261

11.10
11.11
11.12
11.13
11.14

262
262
264
264

Potassium Chloride
Sodium Carbonate
Sodium Hydrogen Carbonate
Ammonia Reaction
Ammonium Ion as a Pseudo–
Alkali-Metal Ion
11.15 Biological Aspects
11.16 Element Reaction Flowcharts

265
265
266

The Group 13 Elements

291


13.1
13.2
13.3

292
293
294

Inorganic Fibers

295

13.4

295

12.1
12.2
12.3
12.4
12.5
12.6
12.7

Group Trends
Features of Alkaline Earth Metal
Compounds
Beryllium
Magnesium

Calcium and Barium
Oxides
Calcium Carbonate

298

13.5
13.6
13.7
13.8
13.9
13.10
13.11
13.12

300
301
306
307
308
309
309
311

Boron Halides
Aluminum
Aluminum Halides
Aluminum Potassium Sulfate
Spinels
Aluminides

Biological Aspects
Element Reaction Flowcharts

CHAPTER 14

The Group 14 Elements
14.1
14.2
14.3

Group Trends
Contrasts in the Chemistry of Carbon
and Silicon
Carbon

315
316
316
318

The Discovery of Buckminsterfullerene

322

271

14.4
14.5

325

326

272
275
276
278
279
280

Moissanite: The Diamond Substitute

327

14.6
14.7

328
330

271

How Was Dolomite Formed?

281

12.8
12.9

282
283


Cement
Calcium Chloride

Boranes

Boron Neutron Capture Therapy

CHAPTER 12

The Group 2 Elements: The Alkaline
Earth Metals

Group Trends
Boron
Borides

Isotopes of Carbon
Carbides
Carbon Monoxide
Carbon Dioxide

Carbon Dioxide, Supercritical Fluid

332

14.8
14.9
14.10
14.11

14.12

333
335
335
338
339

Carbonates and Hydrogen Carbonates
Carbon Sulfides
Carbon Halides
Methane
Cyanides


viii

14.13
14.14
14.15
14.16
14.17

Contents

Silicon
Silicon Dioxide
Silicates
Aluminosilicates
Silicones


339
341
343
345
349

Inorganic Polymers

350

14.18
14.19
14.20
14.21

351
352
353
354

Tin and Lead
Tin and Lead Oxides
Tin and Lead Halides
Tetraethyllead

TEL: A Case History

355


14.22 Biological Aspects
14.23 Element Reaction Flowcharts

356
359

CHAPTER 15

The Group 15 Elements:
The Pnictogens
15.1
15.2

Group Trends
Contrasts in the Chemistry
of Nitrogen and Phosphorus
Overview of Nitrogen Chemistry

363
364
365
368

CHAPTER 16

The Group 16 Elements:
The Chalcogens
16.1
16.2
16.3


Group Trends
Contrasts in the Chemistry of
Oxygen and Sulfur
Oxygen

Oxygen Isotopes in Geology

16.4

409
410
411
412
412

Bonding in Covalent Oxygen
Compounds
Trends in Oxide Properties
Mixed-Metal Oxides

418
419
421

New Pigments through Perovskites

422

16.7

16.8
16.9
16.10
16.11
16.12

Water
Hydrogen Peroxide
Hydroxides
The Hydroxyl Radical
Overview of Sulfur Chemistry
Sulfur

422
424
424
426
426
427

Cosmochemistry: Io, the Sulfur-Rich Moon

428

431
432

16.5
16.6


The First Dinitrogen Compound

369

16.13 Hydrogen Sulfide
16.14 Sulfides

15.4

369

Disulfide Bonds and Hair

432

Propellants and Explosives

370

15.5

371

16.15
16.16
16.17
16.18
16.19
16.20
16.21

16.22
16.23
16.24

434
437
438
440
441
443
445
445
446
448

15.3

Nitrogen
Nitrogen Hydrides

Haber and Scientific Morality

374

15.6
15.7
15.8
15.9
15.10
15.11

15.12
15.13

377
378
379
384
385
386
389
390

Nitrogen Ions
The Ammonium Ion
Nitrogen Oxides
Nitrogen Halides
Nitrous Acid and Nitrites
Nitric Acid and Nitrates
Overview of Phosphorus Chemistry
Phosphorus

Sulfur Oxides
Sulfites
Sulfuric Acid
Sulfates and Hydrogen Sulfates
Other Oxy-Sulfur Anions
Sulfur Halides
Sulfur-Nitrogen Compounds
Selenium
Biological Aspects

Element Reaction Flowcharts

CHAPTER 17

Nauru, the World’s Richest Island

391

15.14
15.15
15.16
15.17
15.18
15.19

393
393
394
395
399
399

The Group 17 Elements: The Halogens 453

Paul Erhlich and His “Magic Bullet”

401

15.29 Element Reaction Flowcharts


402

17.4
17.5

Phosphine
Phosphorus Oxides
Phosphorus Chlorides
Phosphorus Oxo-Acids and Phosphates
The Pnictides
Biological Aspects

17.1
17.2
17.3

Group Trends
Contrasts in the Chemistry of
Fluorine and Chlorine
Fluorine

The Fluoridation of Water

454
455
458
459

Hydrogen Fluoride and Hydrofluoric Acid 460
Overview of Chlorine Chemistry

462


Contents

17.6
17.7
17.8
17.9
17.10

Chlorine
Hydrochloric Acid
Halides
Chlorine Oxides
Chlorine Oxyacids and Oxyanions

463
464
465
469
471

Swimming Pool Chemistry

473

The Discovery of the Perbromate Ion

474


17.11 Interhalogen Compounds and
Polyhalide Ions
17.12 Cyanide Ion as a Pseudo-halide Ion
17.13 Biological Aspects
17.14 Element Reaction Flowcharts

475
477
478
481

CHAPTER 18

The Group 18 Elements:
The Noble Gases
18.1
18.2
18.3
18.4

Group Trends
Unique Features of Helium
Uses of the Noble Gases
A Brief History of Noble Gas
Compounds

487
488
489

489
491

Is It Possible to Make Compounds of the
Early Noble Gases?

492

18.5
18.6
18.7
18.8
18.9

492
494
495
495
496

Xenon Fluorides
Xenon Oxides
Other Noble Gas Compounds
Biological Aspects
Element Reaction Flowchart

CHAPTER 19

Transition Metal Complexes
19.1

19.2
19.3
19.4

Transition Metals
Introduction to Transition Metal
Complexes
Stereochemistries
Isomerism in Transition Metal
Complexes

499
499

521

19.9
19.10
19.11
19.12
19.13

521
523
525
526

More on Electronic Spectra
Ligand Field Theory
Thermodynamic versus Kinetic Factors

Synthesis of Coordination Compounds
Coordination Complexes and the
HSAB Concept
19.14 Biological Aspects

527
529

CHAPTER 20

Properties of the 3d Transition
Metals
20.1
20.2
20.3
20.4
20.5

Overview of the 3d Transition Metals
Group 4: Titanium
Group 5: Vanadium
Group 6: Chromium
Group 7: Manganese

533
534
536
537
538
544


Mining the Seafloor

545

20.6
20.7
20.8
20.9
20.10
20.11

549
558
562
563
569
572

Group 8: Iron
Group 9: Cobalt
Group 10: Nickel
Group 11: Copper
Biological Aspects
Element Reaction Flowcharts

CHAPTER 21

Properties of the 4d and 5d
Transition Metals

21.1
21.2

Comparison of the Transition Metals
Features of the Heavy
Transition Metals
Group 4: Zirconium and Hafnium
Group 5: Niobium and Tantalum
Group 6: Molybdenum and Tungsten
Group 7: Technetium and Rhenium

579
580
581
584
585
586
587

500
502
503

Technetium: The Most Important
Radiopharmaceutical

588

21.7
21.8

21.9
21.10
21.11
21.12

589
590
591
591
591
594

506

19.5
19.6

507

19.7
19.8

The Earth and Crystal Structures

21.3
21.4
21.5
21.6

Platinum Complexes and Cancer Treatment


Naming Transition Metal Complexes
An Overview of Bonding Theories
of Transition Metal Compounds
Crystal Field Theory
Successes of Crystal Field Theory

ix

510
511
517

The Platinum Group Metals
Group 8: Ruthenium and Osmium
Group 9: Rhodium and Iridium
Group 10: Palladium and Platinum
Group 11: Silver and Gold
Biological Aspects


x

Contents

CHAPTER 22

The Group 12 Elements

599


22.1
22.2
22.3
22.4

600
600
603
605

Group Trends
Zinc and Cadmium
Mercury
Biological Aspects

Mercury Amalgam in Teeth

607

22.5

608

Element Reaction Flowchart

23.1
23.2
23.3
23.4

23.5

Introduction to Organometallic
Compounds
Naming Organometallic Compounds
Counting Electrons
Solvents for Organometallic Chemistry
Main Group Organometallic
Compounds

611
612
612
613
614

618

The Death of Karen Wetterhahn

623

23.6

Vitamin B12—A Naturally Occurring
Organometallic Compound

23.13 Complexes with Allyl and 1,3-Butadiene
Ligands
23.14 Metallocenes

23.15 Complexes with ␩6-Arene Ligands
23.16 Complexes with Cycloheptatriene and
Cyclooctatetraene Ligands

644

ON THE WEB www.whfreeman.com/descriptive5e

The Rare Earth and Actinoid
Elements
The Group 3 Elements
The Lanthanoids

651w
653w
653w

Superconductivity

655w

23.3
24.4

656w
659w

The Actinoids
Uranium


A Natural Fission Reactor

661w

24.5

662w

The Postactinoid Elements

APPENDICES

615

Grignard Reagents

Organometallic Compounds of the
Transition Metals
23.7 Transition Metal Carbonyls
23.8 Synthesis and Properties of Simple
Metal Carbonyls
23.9 Reactions of Transition Metal Carbonyls
23.10 Other Carbonyl Compounds
23.11 Complexes with Phosphine Ligands
23.12 Complexes with Alkyl, Alkene, and
Alkyne Ligands

643

CHAPTER 24


24.1
24.2

CHAPTER 23

Organometallic Chemistry

23.17 Fluxionality
23.18 Organometallic Compounds in
Industrial Catalysis

623
625
630
632
633
634
635
638

639
640
642
643

Appendix 1

Appendix 2
Appendix 3

Appendix 4
Appendix 5
Appendix 6
Appendix 7
Appendix 8

Thermodynamic Properties of
Some Selected Inorganic
Compounds
Charge Densities of Selected
Ions
Selected Bond Energies
Ionization Energies of Selected
Metals
Electron Affinities of Selected
Nonmetals
Selected Lattice Energies
Selected Hydration Enthalpies
Selected Ionic Radii

A-1
A-13
A-16
A-18
A-20
A-21
A-22
A-23

ON THE WEB www.whfreeman.com/descriptive5e


Appendix 9

Standard Half-Cell Electrode
Potentials of Selected
Elements

A-25w

ON THE WEB www.whfreeman.com/descriptive5e

Appendix 10 Electron Configuration
of the Elements
INDEX

A-35w
I-1


What Is Descriptive Inorganic Chemistry?

D

escriptive inorganic chemistry was traditionally concerned with the properties of the elements and their compounds. Now, in the renaissance of
the subject, with the synthesis of new and novel materials, the properties are
being linked with explanations for the formulas and structures of compounds
together with an understanding of the chemical reactions they undergo. In
addition, we are no longer looking at inorganic chemistry as an isolated subject
but as a part of essential scientific knowledge with applications throughout
science and our lives. Because of a need for greater contextualization, we have

added more features and more applications.
In many colleges and universities, descriptive inorganic chemistry is offered
as a sophomore or junior course. In this way, students come to know something
of the fundamental properties of important and interesting elements and their
compounds. Such knowledge is important for careers not only in pure or applied
chemistry but also in pharmacy, medicine, geology, and environmental science.
This course can then be followed by a junior or senior course that focuses on
the theoretical principles and the use of spectroscopy to a greater depth than
is covered in a descriptive text. In fact, the theoretical course builds nicely on
the descriptive background. Without the descriptive grounding, however, the
theory becomes sterile, uninteresting, and irrelevant.
Education has often been a case of the “swinging pendulum,” and this
has been true of inorganic chemistry. Up until the 1960s, it was very much
pure descriptive, requiring exclusively memorization. In the 1970s and 1980s,
upper-level texts focused exclusively on the theoretical principles. Now it is apparent that descriptive is very important—not the traditional memorization of
facts but the linking of facts, where possible, to underlying principles. Students
need to have modern descriptive inorganic chemistry as part of their education. Thus, we must ensure that chemists are aware of the “new descriptive
inorganic chemistry.”

xi


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Preface
Inorganic chemistry goes beyond academic interest: it is an important part of our lives.

I


norganic chemistry is interesting—more than that—it is exciting! So much
of our twenty-first-century science and technology rely on natural and synthetic materials, often inorganic compounds, many of which are new and novel.
Inorganic chemistry is ubiquitous in our daily lives: household products, some
pharmaceuticals, our transportation—both the vehicles themselves and the
synthesis of the fuels—battery technology, and medical treatments. There is
the industrial aspect, the production of all the chemicals required to drive our
economy, everything from steel to sulfuric acid to glass and cement. Environmental chemistry is largely a question of the inorganic chemistry of the atmosphere, water, and soil. Finally, there are the profound issues of the inorganic
chemistry of our planet, the solar system, and the universe.
This textbook is designed to focus on the properties of selected interesting,
important, and unusual elements and compounds. However, to understand
inorganic chemistry, it is crucial to tie this knowledge to the underlying chemical principles and hence provide explanations for the existence and behavior
of compounds. For this reason, almost half the chapters survey the relevant
concepts of atomic theory, bonding, intermolecular forces, thermodynamics,
acid-base behavior, and reduction-oxidation properties as a prelude to, and
preparation for, the descriptive material.
For this fifth edition, the greatest change has been the expansion of coverage
of the 4d and 5d transition metals to a whole chapter.
The heavier transition metals have unique trends and patterns, and the
new chapter highlights these. Having an additional chapter on transition metals also better balances the coverage between the main group elements and the
transition elements.
Also, the fifth edition has a second color. With the addition of a second color,
figures are much easier to understand, and tables and text are easier to read.
On a chapter-by-chapter basis, the significant improvements are as follows:
Chapter 1: The Electronic Structure of the Atom: A Review
The Introduction and Section 1.3, The Polyelectronic Atom, have been revised.
Chapter 3: Covalent Bonding
Section 3.11, Network Covalent Substances, has a new subsection: Amorphous
Silicon.
Chapter 4: Metallic Bonding
Section 4.6, Nanometal Particles, was added.

Section 4.7, Magnetic Properties of Metals, was added.
xiii


xiv

Preface

Chapter 5: Ionic Bonding
Section 5.3, Polarization and Covalency, has a new subsection: The IonicCovalent Boundary.
Section 5.4, Ionic Crystal Structures, has a new subsection: Quantum Dots.
Chapter 9: Periodic Trends
Section 9.3, Isoelectronic Series in Covalent Compounds, has been revised and
improved.
Section 9.8, The “Knight’s Move” Relationship, has been revised and improved.
Chapter 10: Hydrogen
Section 10.4, Hydrides, has a revised and expanded subsection: Ionic Hydrides.
Chapter 11: The Group 1 Elements
Section 11.14, Ammonium Ion as a Pseudo–Alkali-Metal Ion, moved from
Chapter 9.
Chapter 13: The Group 13 Elements
Section 13.10, Aluminides, was added.
Chapter 14: The Group 14 Elements
Section 14.2, Contrasts in the Chemistry of Carbon and Silicon, was added.
Section 14.3, Carbon, has a new subsection: Graphene.
Section 14.7, Carbon Dioxide, has a new subsection: Carbonia.
Chapter 15: The Group 15 Elements
Section 15.2, Contrasts in the Chemistry of Nitrogen and Phosphorus, was
added.
Section 15.18, The Pnictides, was added.

Chapter 16: The Group 16 Elements
Section 16.2, Contrasts in the Chemistry of Oxygen and Sulfur, was added.
Section 16.14, Sulfides, has a new subsection: Disulfides.
Chapter 17: The Group 17 Elements
Section 17.2, Contrasts in the Chemistry of Fluorine and Chlorine, was added.
Section 17.12, Cyanide Ion as a Pseudo-halide Ion, moved from Chapter 9.
Chapter 18: The Group 18 Elements
Section 18.7, Other Noble Gas Compounds, was added.
Chapter 19: Transition Metal Complexes
Section 19.10, Ligand Field Theory, was added.
Chapter 20: Properties of the 3d Transition Metals
Section 20.1, Overview of the 3d Transition Metals, was added.
Chapter 21: Properties of the 4d and 5d Transition Metals
NEW CHAPTER added (for details, see the previous page).
Chapter 24: The Rare Earth and Actinoid Elements
This chapter has been significantly revised with the new subsections Scandium,
Yttrium, and Thorium.


Preface

ALSO
Video Clips
Descriptive inorganic chemistry by definition is visual, so what better way to
appreciate a chemical reaction than to make it visual? We now have a series of
at least 60 Web-based video clips to bring some of the reactions to life. The text
has a margin icon to indicate where a reaction is illustrated.
Text Figures and Tables
All the illustrations and tables in the book are available as .jpg files for inclusion
in PowerPoint presentations on the instructor side of the Web site at

www.whfreeman.com/descriptive5e.
Additional Resources
A list of relevant SCIENTIFIC AMERICAN articles is found on the text Web site
at www.whfreeman.com/descriptive5e. The text has a margin icon to indicate
where a Scientific American article is available.
Supplements
The Student Solutions Manual, ISBN: 1-4292-2434-7 contains the worked
solutions to all the odd-numbered end-of-chapter problems.
The Companion Web Site www.whfreeman.com/descriptive5e
Contains the following student-friendly materials: Chapter 24: The Rare Earth
and Actinoid Elements, Appendices, Lab Experiments, Tables, and over 50 useful
videos of elements and metals in reactions and oxidations.
Instructor’s Resource CD-ROM, ISBN: 1-4292-2428-2
Includes PowerPoint and videos as well as all text art and solutions to all problems in the book.
This textbook was written to pass on to another generation our fascination
with descriptive inorganic chemistry. Thus, the comments of readers, both students and instructors, will be sincerely appreciated. Any suggestions for added
or updated additional readings are also welcome. Our current e-mail addresses
are and

xv


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Acknowledgments

M

any thanks must go to the team at W. H. Freeman and Company who have

contributed their talents to the five editions of this book. We offer our sincere
gratitude to the editors of the fifth edition, Jessica Fiorillo, Kathryn Treadway, and
Mary Louise Byrd; of the fourth edition, Jessica Fiorillo, Jenness Crawford, and
Mary Louise Byrd; of the third edition, Jessica Fiorillo and Guy Copes; of the
second edition, Michelle Julet and Mary Louise Byrd; and a special thanks to
Deborah Allen, who bravely commissioned the first edition of the text. Each one of
our fabulous editors has been a source of encouragement, support, and helpfulness.
We wish to acknowledge the following reviewers of this edition, whose
criticisms and comments were much appreciated: Theodore Betley at Harvard
University; Dean Campbell at Bradley University; Maria Contel at Brooklyn
College (CUNY); Gerry Davidson at St. Francis College; Maria Derosa at
Carleton University; Stan Duraj at Cleveland State University; Dmitri Giarkios
at Nova Southeastern University; Michael Jensen at Ohio University–Main
Campus; David Marx at the University of Scranton; Joshua Moore at Tennessee
State University–Nashville; Stacy O’Reilly at Butler University; William Pennington at Clemson University; Daniel Rabinovich at the University of North
Carolina at Charlotte; Hal Rogers at California State University–Fullerton;
Thomas Schmedake at the University of North Carolina at Charlotte; Bradley
Smucker at Austin College; Sabrina Sobel at Hofstra University; Ronald
Strange at Fairleigh Dickinson University–Madison; Mark Walters at New
York University; Yixuan Wang at Albany State University; and Juchao Yan at
Eastern New Mexico University; together with prereviewers: Londa Borer at
California State University–Sacramento; Joe Fritsch at Pepperdine University; Rebecca Roesner at Illinois Wesleyan University, and Carmen Works at
Sonoma College.
We acknowledge with thanks the contributions of the reviewers of the
fourth edition: Rachel Narehood Austin at Bates College; Leo A. Bares at the
University of North Carolina—Asheville; Karen S. Brewer at Hamilton College;
Robert M. Burns at Alma College; Do Chang at Averett University; Georges
Dénès at Concordia University; Daniel R. Derringer at Hollins University;
Carl P. Fictorie at Dordt College; Margaret Kastner at Bucknell University;
Michael Laing at the University of Natal, Durban; Richard H. Langley at

Stephen F. Austin State University; Mark R. McClure at the University of North
Carolina at Pembroke; Louis Mercier at Laurentian University; G. Merga at
Andrews University; Stacy O’Reilly at Butler University; Larry D. Pedersen
at College Misercordia; Robert D. Pike at the College of William and Mary;
William Quintana at New Mexico State University; David F. Rieck at Salisbury
University; John Selegue at the University of Kentucky; Melissa M. Strait at
Alma College; Daniel J. Williams at Kennesaw State University; Juchao Yan at
Eastern New Mexico University; and Arden P. Zipp at the State University of
New York at Cortland.
xvii


xviii

Acknowledgments

And the contributions of the reviewers of the third edition: François Caron
at Laurentian University; Thomas D. Getman at Northern Michigan University; Janet R. Morrow at the State University of New York at Buffalo; Robert
D. Pike at the College of William and Mary; Michael B. Wells at Cambell University; and particularly Joe Takats of the University of Alberta for his comprehensive critique of the second edition.
And the contributions of the reviewers of the second edition: F. C. Hentz
at North Carolina State University; Michael D. Johnson at New Mexico State
University; Richard B. Kaner at the University of California, Los Angeles;
Richard H. Langley at Stephen F. Austin State University; James M. Mayer
at the University of Washington; Jon Melton at Messiah College; Joseph S.
Merola at Virginia Technical Institute; David Phillips at Wabash College; John
R. Pladziewicz at the University of Wisconsin, Eau Claire; Daniel Rabinovich
at the University of North Carolina at Charlotte; David F. Reich at Salisbury
State University; Todd K. Trout at Mercyhurst College; Steve Watton at the
Virginia Commonwealth University; and John S. Wood at the University of
Massachusetts, Amherst.

Likewise, the reviewers of the first edition: E. Joseph Billo at Boston College; David Finster at Wittenberg University; Stephen J. Hawkes at Oregon
State University; Martin Hocking at the University of Victoria; Vake Marganian
at Bridgewater State College; Edward Mottel at the Rose-Hulman Institute of
Technology; and Alex Whitla at Mount Allison University.
As a personal acknowledgment, Geoff Rayner-Canham wishes to especially thank three teachers and mentors who had a major influence on his career:
Briant Bourne, Harvey Grammar School; Margaret Goodgame, Imperial College, London University; and Derek Sutton, Simon Fraser University. And he
expresses his eternal gratitude to his spouse, Marelene, for her support and
encouragement.
Tina Overton would like to thank her colleague Phil King for his invaluable
suggestions for improvements and his assistance with the illustrations. Thanks
must also go to her family, Dave, John, and Lucy, for their patience during the
months when this project filled all her waking hours.


Dedication

C

hemistry is a human endeavor. New discoveries are the result of the work
of enthusiastic people and groups of people who want to explore the
molecular world. We hope that you, the reader, will come to share our own
fascination with inorganic chemistry. We have chosen to dedicate this book to
two scientists who, for very different reasons, never did receive the ultimate
accolade of a Nobel Prize.

Henry Moseley (1887–1915)
Although Mendeleev is identified as the discoverer of the periodic table, his version was based on an increase in atomic mass.
In some cases, the order of elements had to be reversed to match
properties with location. It was a British scientist, Henry Moseley,
who put the periodic table on a much firmer footing by discovering that, on bombardment with electrons, each element emitted X-rays of characteristic wavelengths. The wavelengths fitted

a formula related by an integer number unique to each element.
We know that number to be the number of protons. With the establishment of the atomic number of an element, chemists at last
knew the fundamental organization of the table. Sadly, Moseley
was killed at the battle of Gallipoli in World War I. Thus, one of
the brightest scientific talents of the twentieth century died at the
age of 27. The famous American scientist Robert Milliken commented: “Had
the European War had no other result than the snuffing out of this young life,
that alone would make it one of the most hideous and most irreparable crimes
in history.” Unfortunately, Nobel Prizes are only awarded to living scientists.
In 1924, the discovery of element 43 was claimed, and it was named moseleyum; however, the claim was disproved by the very method that Moseley
had pioneered.

xix


xx

Dedication

Lise Meitner (1878–1968)
In the 1930s, scientists were bombarding atoms of heavy elements
such as uranium with subatomic particles to try to make new elements and extend the periodic table. Austrian scientist Lise Meitner had shared leadership with Otto Hahn of the German research
team working on the synthesis of new elements; the team thought
they had discovered nine new elements. Shortly after the claimed
discovery, Meitner was forced to flee Germany because of her
Jewish ancestry, and she settled in Sweden. Hahn reported to her
that one of the new elements behaved chemically just like barium.
During a famous “walk in the snow” with her nephew, physicist
Otto Frisch, Meitner realized that an atomic nucleus could break
in two just like a drop of water. No wonder the element formed

behaved like barium: it was barium! Thus was born the concept of
nuclear fission. She informed Hahn of her proposal. When Hahn
wrote the research paper on the work, he barely mentioned the
vital contribution of Meitner and Frisch. As a result, Hahn and his colleague
Fritz Strassmann received the Nobel Prize. Meitner’s flash of genius was ignored.
Only recently has Meitner received the acclaim she deserved by the naming of
an element after her, element 109, meitnerium.

Additional reading
Heibron, J. L. H. G. J. Moseley. University of California Press, Berkeley, 1974.
Rayner-Canham, M. F., and G. W. Rayner-Canham. Women in Chemistry:
Their Changing Roles from Alchemical Times to the Mid-Twentieth Century.
Chemical Heritage Foundation, Philadelphia, 1998.
Sime, R. L. Lise Meitner: A Life in Physics. University of California Press,
Berkeley, 1996.
Weeks, M. E., and H. M. Leicester. Discovery of the Elements, 7th ed. Journal
of Chemical Education, Easton, PA, 1968.


CHAPTER

1

The Electronic Structure
of the Atom: A Review
To understand the behavior of inorganic compounds, we need to study
the nature of chemical bonding. Bonding, in turn, relates to the behavior
of electrons in the constituent atoms. Our study of inorganic chemistry,
therefore, starts with a review of the models of the atom and a survey of


1.1 The Schrödinger Wave
Equation and Its Significance

the probability model’s applications to the electron configurations of atoms

Atomic Absorption Spectroscopy

and ions.

1.2

Shapes of the Atomic Orbitals

1.3

The Polyelectronic Atom

1.4

Ion Electron Configurations

1.5

Magnetic Properties of Atoms

I

saac Newton was the original model for the absentminded professor.
Supposedly, he always timed the boiled egg he ate at breakfast; one
morning, his maid found him standing by the pot of boiling water, holding an egg in his hand and gazing intently at the watch in the bottom

of the pot! Nevertheless, it was Newton who initiated the study of the
electronic structure of the atom in about 1700, when he noticed that
the passage of sunlight through a prism produced a continuous visible
spectrum. Much later, in 1860, Robert Bunsen (of burner fame) investigated the light emissions from flames and gases. Bunsen observed
that the emission spectra, rather than being continuous, were series of
colored lines (line spectra).
The proposal that electrons existed in concentric shells had its origin
in the research of two overlooked pioneers: Johann Jakob Balmer, a
Swiss mathematician, and Johannes Robert Rydberg, a Swedish physicist.
After an undistinguished career in mathematics, in 1885, at the age of
60, Balmer studied the visible emission lines of the hydrogen atom and
found that there was a mathematical relationship between the wavelengths. Following from Balmer’s work, in 1888, Rydberg deduced a
more general relationship:

1.6 Medicinal Inorganic Chemistry:
An Introduction

1
1
1
5 RH a 2 2 2 b
l
nf
ni
where l is the wavelength of the emission line, RH is a constant, later
known as the Rydberg constant, and nf and ni are integers. For the
visible lines seen by Balmer and Rydberg, nf had a value of 2. The
Rydberg formula received further support in 1906, when Theodore
Lyman found a series of lines in the far-ultraviolet spectrum of hydrogen,
1



2

CHAPTER 1 • The Electronic Structure of the Atom: A Review

nϭ3
nϭ2
nϭ1
ϩZe

⌬E ϭ hv

FIGURE 1.1 The RutherfordBohr electron-shell model of the
atom, showing the n 5 1, 2, and 3
energy levels.

corresponding to the Rydberg formula with nf 5 1. Then in 1908, Friedrich
Paschen discovered a series of far-infrared hydrogen lines, fitting the equation
with nf 5 3.
In 1913, Niels Bohr, a Danish physicist, became aware of Balmer’s and
Rydberg’s experimental work and of the Rydberg formula. At that time, he
was trying to combine Ernest Rutherford’s planetary model for electrons in an
atom with Max Planck’s quantum theory of energy exchanges. Bohr contended
that an electron orbiting an atomic nucleus could only do so at certain fixed
distances and that whenever the electron moved from a higher to a lower orbit,
the atom emitted characteristic electromagnetic radiation.
Rydberg had deduced his equation from experimental observations of
atomic hydrogen emission spectra. Bohr was able to derive the same equation
from quantum theory, showing that his theoretical work meshed with reality.

From this result, the Rutherford-Bohr model of the atom of concentric electron “shells” was devised, mirroring the recurring patterns in the periodic table
of the elements (Figure 1.1). Thus the whole concept of electron energy levels
can be traced back to Rydberg. In recognition of Rydberg’s contribution, excited
atoms with very high values of the principal quantum number, n, are called
Rydberg atoms.
However, the Rutherford-Bohr model had a number of flaws. For example,
the spectra of multi-electron atoms had far more lines than the simple Bohr
model predicted. Nor could the model explain the splitting of the spectral
lines in a magnetic field (a phenomenon known as the Zeeman effect). Within
a short time, a radically different model, the quantum mechanical model, was
proposed to account for these observations.

Atomic Absorption Spectroscopy

A

glowing body, such as the Sun, is expected to emit a
continuous spectrum of electromagnetic radiation.
However, in the early nineteenth century, a German scientist, Josef von Fraunhofer, noticed that the visible spectrum from the Sun actually contained a number of dark
bands. Later investigators realized that the bands were
the result of the absorption of particular wavelengths by
cooler atoms in the “atmosphere” above the surface of
the Sun. The electrons of these atoms were in the ground
state, and they were absorbing radiation at wavelengths
corresponding to the energies needed to excite them to
higher energy states. A study of these “negative” spectra
led to the discovery of helium. Such spectral studies are
still of great importance in cosmochemistry—the study
of the chemical composition of stars.
In 1955, two groups of scientists, one in Australia and

the other in Holland, finally realized that the absorption
method could be used to detect the presence of elements

at very low concentrations. Each element has a particular absorption spectrum corresponding to the various
separations of (differences between) the energy levels
in its atoms. When light from an atomic emission source
is passed through a vaporized sample of an element, the
particular wavelengths corresponding to the various energy separations will be absorbed. We find that the higher
the concentration of the atoms, the greater the proportion
of the light that will be absorbed. This linear relationship
between light absorption and concentration is known as
Beer’s law. The sensitivity of this method is extremely
high, and concentrations of parts per million are easy to
determine; some elements can be detected at the parts
per billion level. Atomic absorption spectroscopy has
now become a routine analytical tool in chemistry, metallurgy, geology, medicine, forensic science, and many other
fields of science—and it simply requires the movement of
electrons from one energy level to another.


1.1 The Schrödinger Wave Equation and Its Significance

1.1 The Schrödinger Wave Equation and Its Significance
The more sophisticated quantum mechanical model of atomic structure was
derived from the work of Louis de Broglie. De Broglie showed that, just as electromagnetic waves could be treated as streams of particles (photons), moving
particles could exhibit wavelike properties. Thus, it was equally valid to picture
electrons either as particles or as waves. Using this wave-particle duality, Erwin
Schrödinger developed a partial differential equation to represent the behavior
of an electron around an atomic nucleus. One form of this equation, given here
for a one-electron atom, shows the relationship between the wave function of

the electron, C, and E and V, the total and potential energies of the system, respectively. The second differential terms relate to the wave function along each
of the Cartesian coordinates x, y, and z, while m is the mass of an electron, and
h is Planck’s constant.
02°
02°
02°
8p2m
1
1
1
1E 2 V2 ° 5 0
0x2
0y2
0z2
h2
The derivation of this equation and the method of solving it are in the realm
of physics and physical chemistry, but the solution itself is of great importance
to inorganic chemists. We should always keep in mind, however, that the wave
equation is simply a mathematical formula. We attach meanings to the solution
simply because most people need concrete images to think about subatomic
phenomena. The conceptual models that we create in our macroscopic world
cannot hope to reproduce the subatomic reality.
It was contended that the real meaning of the equation could be found
from the square of the wave function, C2, which represents the probability
of finding the electron at any point in the region surrounding the nucleus.
There are a number of solutions to a wave equation. Each solution describes a
different orbital and, hence, a different probability distribution for an electron in that orbital. Each of these orbitals is uniquely defined by a set of three
integers: n, l, and ml. Like the integers in the Bohr model, these integers are
also called quantum numbers.
In addition to the three quantum numbers derived from the original theory,

a fourth quantum number had to be defined to explain the results of an experiment in 1922. In this experiment, Otto Stern and Walther Gerlach found that
passing a beam of silver atoms through a magnetic field caused about half the
atoms to be deflected in one direction and the other half in the opposite direction. Other investigators proposed that the observation was the result of two
different electronic spin orientations. The atoms possessing an electron with
one spin were deflected one way, and the atoms whose electron had the opposite spin were deflected in the opposite direction. This spin quantum number
was assigned the symbol ms.
The possible values of the quantum numbers are defined as follows:
n, the principal quantum number, can have all positive integer values from
1 to q.

3