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 33 34 35 36
As Se Br Kr

Descriptive
51 52 53 54
Sb Te I Xe
83 84 85 86
Bi Po At Rn
115
Uup Inorganic Chemistry
116
Lv
117
Uus
118
Uuo
Sixth Edition
69 70 71 2
Tm Yb Lu 5 6 He 7
101 102 103 B C N
Md Geoff Rayner-Canham
No Lr 5 6 7 8 9 10
B C N O13 F14 Ne15
Tina Overton Al Si P
13 14 15 16 17 18
22 23 24 25 26 27 28
Al 29
Si 30
P S31 Cl32 Ar33
Ti 25 V 26 Cr27 Mn28 Fe29 Co
30 Ni
31 Cu
32 Zn
33 Ga
34 35Ge 36As
40 Mn 41 Fe 42Co 43Ni 44
Cu Zn
45 Ga
46 Ge
47 As
48 Se
49 Br50 Kr51
Zr 43 Nb 44 Mo45 Tc46 Ru
47 Rh
48 Pd
49 Ag
50 Cd
51 52In 53Sn 54Sb
72 Tc 73 Ru 74Rh 75Pd 76
Ag Cd
77 In
78 Sn
79 Sb
80 Te
81 I
82 Xe
83
Hf 75 Ta 76 W77 Re78 Os79 80
Ir 81
Pt 82
Au 83
Hg 84
Tl 85Pb 86Bi
Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
04 105 106 107 108 109 110 111 112 113 114 115
Rf 107Db108 Sg109 Bh110 Hs111 Mt
112 113
Ds 114
Rg 115
Cn 116
Uut 117Fl 118
Uu
Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo

58 59 60 61 62 63 64 65 66 67 68 69
61 62 63 64 65 66 67 68 69 70 71
Ce Pm Pr Sm NdEu PmGd Sm
Tb
Eu
Dy
Gd
Ho
Tb
Er
Dy
Tm
Ho
Yb Lu
Er Tm
0 93 91 94 9295 9396 94
97 95
98 96
99 97
100 98
101 99 103
102 100 101
Th Np Pa Pu UAm NpCm PuBk Am
Cf Cm
Es Bk
Fm Cf
Md NoEs LrFm Md

< 1% 1 - 10% < 1%>10 - 25% 1- 10%

>25 - 50% > 10 - 25%
> 50% > 25 -50% > 50%
 1 2 Periodic Table of the Elements*

1
1 H
1.0079

3 4
2 Li Be
6.94 9.01
Metals
11 12
3 Na Mg
3 4 5 6 7 8 9
22.99 24.31

19 20 21 22 23 24 25 26 27
4 K Ca Sc Ti V Cr Mn Fe Co
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93

37 38 39 40 41 42 43 44 45
5 Rb Sr Y Zr Nb Mo Tc Ru Rh
85.47 87.62 88.91 91.22 92.91 95.94 101.07 102.91

55 56 71 72 73 74 75 76 77
6 Cs Ba Lu Hf Ta W Re Os Ir
132.91 137.34 174.97 178.49 180.95 183.85 186.2 190.2 192.2

87 88 103 104 105 106 107 108 109

7 Fr Ra Lr Rf Db Sg Bh Hs Mt
223 226.03

57 58 59 60 61
La Ce Pr Nd Pm
138.91 140.12 140.91 144.24

89 90 91 92 93
*Molar masses quoted to the number of Ac Th Pa U Np
significant figures given here can be 227.03 232.04 231.04 238.03
regarded as typical of most naturally
occurring samples.
 13 14 15 16 17 18

2
He
Nonmetals 4.00

5 6 7 8 9 10
Metalloids B C N O F Ne
10.81 12.01 14.01 16.00 19.00 20.18

13 14 15 16 17 18
Al Si P S Cl Ar
10 11 12
26.98 28.09 30.97 32.06 35.45 39.95

28 29 30 31 32 33 34 35 36
Ni Cu Zn Ga Ge As Se Br Kr
58.71 63.54 65.37 69.72 72.59 74.92 78.96 79.91 83.80

46 47 48 49 50 51 52 53 54
Pd Ag Cd In Sn Sb Te I Xe
106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

78 79 80 81 82 83 84 85 86
Pt Au Hg Tl Pb Bi Po At Rn
195.09 196.97 200.59 204.37 207.19 208.98 210 210 222

110 111 112 113 114 115 116 117 118

Ds Rg Cn Uut Fl Uup Lv Uus Uuo

62 63 64 65 66 67 68 69 70
Sm Eu Gd Tb Dy Ho Er Tm Yb Lanthanoids
150.35 151.96 157.25 158.92 162.50 164.93 167.26 168.93 173.04

94 95 96 97 98 99 100 101 102

Pu Am Cm Bk Cf Es Fm Md No Actinoids
DESCRIPTIVE INORGANIC
CHEMISTRY
 SIXTH EDITION
DESCRIPTIVE INORGANIC
CHEMISTRY

Geoff Rayner-Canham
Grenfell Campus, Memorial University
Corner Brook, Newfoundland, Canada

Tina Overton
University of Hull, UK

W. H. Freeman and Company

A Macmillan Higher Education Company
Publisher: Jessica Fiorillo
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Library of Congress Preassigned Control Number: 2013950809

ISBN-13: 978-1-4641-2557-7
ISBN-10: 1-4641-2557-0
© 2014, 2010, 2006, 2003 by W. H. Freeman and Company
All rights reserved

Printed in the United States of America

First printing

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www.whfreeman.com
OVERVIEW

CHAPTER 1 The Electronic Structure of the Atom:

A Review 1
CHAPTER 2 The Structure of the Periodic Table 19
CHAPTER 3 Covalent Bonding and Molecular
Spectroscopy 41
CHAPTER 4 Metallic Bonding and Alloys 85
CHAPTER 5 Ionic Bonding and Solid State Structures 99
CHAPTER 6 Why Compounds Exist—Inorganic
Thermodynamics 125
CHAPTER 7 Solvent Systems and Acid-Base Behavior 153
CHAPTER 8 Oxidation and Reduction 181
CHAPTER 9 Periodic Patterns 211
CHAPTER 10 Hydrogen
CHAPTER 11 The Group 1 Elements: The Alkali Metals 243
CHAPTER 12 The Group 2 Elements: The Alkaline
Earth Metals 289
CHAPTER 13 The Group 13 Elements 311
CHAPTER 14 The Group 14 Elements 335
CHAPTER 15 The Group 15 Elements: The Pnictogens 379
CHAPTER 16 The Group 16 Elements: The Chalcogens 428
CHAPTER 17 The Group 17 Elements: The Halogens 473
CHAPTER 18 The Group 18 Elements: The Noble Gases 507
CHAPTER 19 Transition Metal Complexes 519
CHAPTER 20 The 3d Transition Metals 559
CHAPTER 21 The 4d and 5d Transition Metals 607
CHAPTER 22 The Group 12 Elements 633
CHAPTER 23 Organometallic Chemistry 645
CHAPTER 24 The Rare Earth, Actinoid, and
Postactinoid Elements [On the Web]
www.whfreeman.com/descriptive6e 691w
Appendices A-1
Index I-1
v
CONTENTS
What Is Descriptive Inorganic Chemistry? xiii 3.5 The Valence-Bond Concept 50
Preface xv 3.6 Introduction to Molecular Orbitals 53
Acknowledgments xxi 3.7 Molecular Orbitals for Period 1
Dedication xxiii Diatomic Molecules 55
3.8 Molecular Orbitals for Period 2
CHAPTER 1 Diatomic Molecules 57
The Electronic Structure of 3.9 Molecular Orbitals for Heteronuclear
the Atom: A Review 1 Diatomic Molecules 62
3.10 Network Covalent Substances 64
Context: The Importance of the Lanthanoids 1
3.11 Intermolecular Forces 66
1.1 A Review of the Quantum Model 2
3.12 Molecular Symmetry 70
1.2 Shapes of the Atomic Orbitals 4
3.13 Symmetry and Vibrational
1.3 The Polyelectronic Atom 8
Spectroscopy 76
1.4 Ion Electron Configurations 13
3.14 The Bonding Continuum 80
1.5 Magnetic Properties of Atoms 15
CHAPTER 4
CHAPTER 2 Metallic Bonding and Alloys 85
The Structure of the Periodic Table 19 Context: Metal Matrix Composites 85
Context: Bioinorganic Chemistry 19 4.1 Metallic Bonding 86
2.1 Organization of the Modern 4.2 Bonding Models 87
Periodic Table 20 4.3 Structure of Metals 89
2.2 Existence of the Elements 23 4.4 Unit Cells 92
2.3 Stability of the Elements and Their 4.5 Alloys 93
Isotopes 24 4.6 Nanometal Particles 95
2.4 Classifications of the Elements 28 4.7 Magnetic Properties of Metals 95
2.5 Periodic Properties: Atomic Radius 31
2.6 Periodic Properties: Ionization CHAPTER 5
Energies 35 Ionic Bonding and Solid State
2.7 Periodic Properties: Electron Affinity 37 Structures 99
Context: Superconductivity and Ionic
CHAPTER 3 Compounds 99
Covalent Bonding and Molecular 5.1 The Ionic Model and the Size of Ions 100
Spectroscopy 41 5.2 Polarization and Covalency 102
Context: The Greenhouse Effect 41 5.3 Ionic Crystal Structures 106
3.1 A Brief Review of Lewis Structures 42 5.4 Hydrated Salts 113
3.2 Partial Bond Order 44 5.5 Isostructural Ionic Compounds 114
3.3 Formal Charge 44 5.6 Perovskites 117
3.4 Valence-Shell Electron-Pair 5.7 Spinels 118
Repulsion Rules 45 5.8 Defects and Nonstoichiometry 119
vii
viii Contents

CHAPTER 6 8.6 Redox Equations 188

Why Compounds Exist— 8.7 Quantitative Aspects of
Inorganic Thermodynamics 125 Half-Reactions 192
8.8 Electrode Potentials as
Context: Against Convention: Ionic
Thermodynamic Functions 193
Compounds of Metal Ions 125
8.9 Latimer (Reduction Potential)
6.1 Thermodynamics of the Formation
Diagrams 195
of Compounds 236
8.10 Frost (Oxidation State) Diagrams 197
6.2 Formation of Ionic Compounds 134 U
8.11 Pourbaix (E -pH) Diagrams 200
6.3 Non-Existent Ionic Compounds 137
8.12 Redox Synthesis 204
6.4 Thermodynamics of the Solution
8.13 Biological Aspects 206
Process for Ionic Compounds 139
6.5 Lattice Energies and Comparative
Ion Sizes and Charges 142 CHAPTER 9
6.6 Formation of Covalent Compounds 144 Periodic Patterns 211
6.7 Thermodynamic versus Context: Is the Periodic Table Only
Kinetic Factors 146 Groups and Periods? 211
9.1 Group Trends 212
CHAPTER 7
9.2 Periodic Trends in Bonding 215
Solvent Systems and Acid-Base 9.3 Isoelectronic Series in Covalent
Behavior 153 Compounds 219
Context: Green Solvents for the Future 153 9.4 The (n) Group and (n 1 10)
7.1 Solvents 154 Group Similarities 221
7.2 Brønsted-Lowry Acids 158 9.5 Diagonal Relationships 227
7.3 Trends in Acid-Base Behavior 163 9.6 The “Knight’s Move” Relationship 229
7.4 Acid-Base Reactions of Oxides 168 9.7 The Early Actinoid Relationships
7.5 Lewis Theory 170 with Transition Metals 233
7.6 Pearson Hard-Soft Acid-Base 9.8 The Lanthanoid Relationships 233
Concepts 171 9.9 “Combo” Elements 235
7.7 Application of the HSAB Concept 173 9.10 Biological Aspects 239
7.8 Biological Aspects 176
CHAPTER 10
CHAPTER 8 Hydrogen 243
Oxidation and Reduction 181 Context: Hydrogen Bond—The Real
Context: Unraveling Nature’s Secrets 181 “Special Agent” 243
8.1 Redox Terminology 182 10.1 Isotopes of Hydrogen 244
8.2 Oxidation Number Rules 183 10.2 Nuclear Magnetic Resonance 246
8.3 Determination of Oxidation Numbers 10.3 Properties of Hydrogen 247
from Electronegativities 184 10.4 The Trihydrogen Ion 250
8.4 The Difference Between Oxidation 10.5 Hydrides 252
Number and Formal Charge 186 10.6 Water and Hydrogen Bonding 256
8.5 Periodic Variations of Oxidation 10.7 Clathrates 257
Numbers 187 10.8 Element Reaction Flowchart 260
 Contents ix

CHAPTER 11 12.11 Biological Aspects 305

The Group 1 Elements: 12.12 Element Reaction Flowcharts 307
The Alkali Metals 263
Context: The Sodium Ion–Potassium CHAPTER 13
Ion Balance in Living Cells 263 The Group 13 Elements 311
11.1 Group Trends 265
Context: Aluminum—The Toxic Ion 311
11.2 Features of Alkali Metal
13.1 Group Trends 312
Compounds 266
13.2 Boron 313
11.3 Trends in Alkali Metal Oxides 269
13.3 Borides 315
11.4 Solubility of Alkali Metal Salts 271
13.4 Boranes 316
11.5 Lithium 274
13.5 Boron Halides 320
11.6 Sodium 277 13.6 Aluminum 322
11.7 Sodium Hydroxide 278 13.7 Aluminum Halides 327
11.8 Sodium Chloride 280 13.8 Aluminum Potassium Sulfate 328
11.9 Sodium Carbonate and Sodium 13.9 Aluminides 329
Hydrogen Carbonate 280 13.10 Biological Aspects 330
11.10 Potassium 282 13.11 Element Reaction Flowchart 331
11.11 Potassium Chloride 283
11.12 Ammonium Ion as a
CHAPTER 14
Pseudo–Alkali-Metal Ion 284
The Group 14 Elements 335
11.13 Biological Aspects 285
11.14 Element Reaction Flowcharts 285 Context: Cermets—The Toughest
Materials 335
14.1 Group Trends 336
CHAPTER 12 14.2 Contrasts in the Chemistry of
The Group 2 Elements: The Alkaline Carbon and Silicon 337
Earth Metals 289 14.3 Carbon 339
Context: Calcium and Magnesium—
14.4 Isotopes of Carbon 343
Another Biological Balance 289 14.5 Carbides 344
14.6 Carbon Monoxide 348
12.1 Group Trends 291
14.7 Carbon Dioxide 350
12.2 Features of Alkaline Earth Metal
14.8 Carbonates and Hydrogen
Compounds 292
Carbonates 352
12.3 Trends in Alkaline Earth Metal
14.9 Carbon Sulfides 354
Oxides 296
14.10 Carbon Halides 354
12.4 Beryllium 297
14.11 Methane 356
12.5 Magnesium 298
14.12 Cyanides 357
12.6 Calcium Carbonate 300 14.13 Silicon 358
12.7 Cement 302 14.14 Silicon Dioxide 360
12.8 Calcium Chloride 303 14.15 Silicates 362
12.9 Calcium Sulfate 304 14.16 Aluminosilicates 364
12.10 Calcium Carbide 304 14.17 Silicones 367
x Contents

14.18 Tin and Lead 368 16.4 Oxygen and the Atmosphere 436
14.19 Biological Aspects 371 16.5 Bonding in Covalent Oxygen
14.20 Element Reaction Flowchart 374 Compounds 438
16.6 Trends in Oxide Properties 440
CHAPTER 15 16.7 Hydrogen Oxides 442
The Group 15 Elements: 16.8 Hydroxides 444
The Pnictogens 379 16.9 Allotropes of Sulfur 445
16.10 Overview of Sulfur Chemistry 446
Context: The Essential Phosphorus-
16.11 Hydrogen Sulfide 450
Oxygen Bond 379
16.12 Sulfides 452
15.1 Group Trends 380
16.13 Sulfur Oxides 454
15.2 Contrasts in the Chemistry of
16.14 Sulfites 457
Nitrogen and Phosphorus 381
16.15 Sulfuric Acid 458
15.3 Overview of Nitrogen Chemistry 384
16.16 Sulfates and Hydrogen Sulfates 460
15.4 Nitrogen 386
16.17 Other Oxosulfur Anions 461
15.5 Nitrogen Hydrides 387
16.18 Sulfur Halides 463
15.6 Nitrogen Ions 394
16.19 Sulfur-Nitrogen Compounds 466
15.7 The Ammonium Ion 396
16.20 Selenium 466
15.8 Nitrogen Oxides 397
16.21 Biological Aspects 467
15.9 Nitrogen Halides 402
16.22 Element Reaction Flowchart 468
15.10 Nitrous Acid and Nitrites 402
15.11 Nitric Acid and Nitrates 403 CHAPTER 17
15.12 Overview of Phosphorus
The Group 17 Elements:
Chemistry 407
The Halogens 473
15.13 Phosphorus 408
15.14 Phosphine 411 Context: Experimenting with the
Atmosphere—The Antarctic Ozone Hole 473
15.15 Phosphorus Oxides 411
15.16 Phosphorus Chlorides 412 17.1 Group Trends 475
15.17 Phosphorus Oxoacids and 17.2 Contrasts in the Chemistry of
Phosphates 414 Fluorine and the Other Halogens 476
15.18 The Pnictides 417 17.3 Halides 478
15.19 Biological Aspects 418 17.4 Fluorine 482
15.20 Element Reaction Flowchart 421 17.5 Hydrogen Fluoride and
Hydrofluoric Acid 484
17.6 Overview of Chlorine Chemistry 486
CHAPTER 16
17.7 Chlorine 487
The Group 16 Elements: The
17.8 Hydrochloric Acid 489
Chalcogens 427
17.9 Chlorine Oxides 489
Context: Macular Degeneration 17.10 Chlorine Oxoacids and
and Singlet Oxygen 427 Oxoanions 491
16.1 Group Trends 428 17.11 Interhalogen Compounds and
16.2 Contrasts in the Chemistry of Polyhalide Ions 495
Oxygen and Sulfur 430 17.12 Cyanide Ion as a
16.3 Allotropes of Oxygen 431 Pseudo-halide Ion 498
 Contents xi

17.13 Biological Aspects 499 19.14 Coordination Complexes and

17.14 Element Reaction Flowchart 502 the Hard-Soft Acid-Base (HSAB)
Concept 554
CHAPTER 18
19.15 Biological Aspects 555

The Group 18 Elements:

CHAPTER 20
The Noble Gases 507
The 3d Transition Metals 559
Context: Helium—An Increasingly
Rare Gas 507 Context: Iron Is at the Core of Everything 559
18.1 Group Trends 508 20.1 Overview of the 3d Transition
18.2 Helium 510 Metals 560
18.3 Compounds of Helium, Argon, 20.2 Group 4: Titanium 562
and Krypton 511 20.3 The Vanadium-Chromium-
18.4 Xenon Fluorides 511 Manganese Triad 563
18.5 Xenon Oxides 515 20.4 Group 5: Vanadium 564
18.6 Other Xenon Compounds 516 20.5 Group 6: Chromium 564
18.7 Biological Aspects 516 20.6 Group 7: Manganese 571
18.8 Element Reaction Flowchart 517 20.7 The Iron-Cobalt-Nickel Triad 575
20.8 Group 8: Iron 576
20.9 Group 9: Cobalt 586
CHAPTER 19
20.10 Group 10: Nickel 590
Transition Metal Complexes 519 20.11 Group 11: Copper 592
Context: Platinum Complexes and 20.12 Biological Aspects 598
Cancer Treatment 519 20.13 Element Reaction Flowchart 601
19.1 Transition Metals 521
19.2 Introduction to Transition Metal CHAPTER 21
Complexes 522
The 4d and 5d Transition Metals 607
19.3 Stereochemistries 523
Context: Silver Is a Killer 607
19.4 Isomerism in Transition Metal
Complexes 525 21.1 Comparison of the Transition Metals 609
19.5 Naming Transition Metal 21.2 Features of the Heavy Transition
Complexes 528 Metals 610
19.6 An Overview of Bonding Theories 21.3 Group 4: Zirconium and Hafnium 613
of Transition Metal Compounds 530 21.4 Group 5: Niobium and Tantalum 615
19.7 Crystal Field Theory 532 21.5 Group 6: Molybdenum and
19.8 Successes of Crystal Field Tungsten 617
Theory 538 21.6 Group 7: Technetium, and
19.9 More on Electronic Structure 542 Rhenium 620
19.10 Ligand Field Theory 546 21.7 The Platinum Group Metals 622
19.11 Thermodynamic versus Kinetic 21.8 Group 8: Ruthenium and Osmium 623
Factors 548 21.9 Group 9: Rhodium and Iridium 624
19.12 Synthesis of Coordination 21.10 Group 10: Palladium and Platinum 624
Compounds 549 21.11 Group 11: Silver and Gold 625
19.13 Reaction Mechanisms 550 21.12 Biological Aspects 629
xii Contents

CHAPTER 22 23.17 Fluxionality 680

The Group 12 Elements 633 23.18 Organometallic Complexes in
Industrial Synthesis 681
Context: Zinc Oxide Can Save
23.19 Biological Aspects 686
Your Skin! 633
22.1 Group Trends 635
CHAPTER 24 ON THE WEB
22.2 Zinc and Cadmium 636 www.whfreeman.com/descriptive6e
22.3 Mercury 639 The Rare Earth, Actinoid, and
22.4 Biological Aspects 641 Postactinoid Elements 691w
22.5 Element Reaction Flowchart 643
Context: Uranium: Enriched or Depleted? 691w

CHAPTER 23 24.1 The Group 3 Elements 693w

24.2 The Lanthanoids 694w
Organometallic Chemistry 645
24.3 The Actinoids 696w
Context: The Extreme Toxicity of 24.4 Uranium 700w
Dimethylmercury 645
24.5 The Postactinoid Elements 702w
23.1 Introduction to Organometallic 24.6 Biological Aspects 703w
Compounds 646
23.2 Naming Organometallic
APPENDICES
Compounds 647
Appendix 1 Thermodynamic Properties
23.3 Counting Electrons 648
of Some Selected Inorganic
23.4 Solvents for Organometallic Compounds A-1
Chemistry 649
Appendix 2 Charge Densities of
23.5 Main Group Organometallic Selected Ions A-13
Compounds 650
Appendix 3 Selected Bond Energies A-16
23.6 Organometallic Compounds of
Appendix 4 Ionization Energies of
the Transition Metals 658
Selected Metals A-18
23.7 Transition Metal Carbonyls 662
Appendix 5 Electron Affinities of
23.8 Synthesis and Properties of Selected Nonmetals A-20
Simple Metal Carbonyls 667
Appendix 6 Selected Lattice Energies A-21
23.9 Reactions of Transition Metal
Appendix 7 Selected Hydration
Carbonyls 669
Enthalpies A-22
23.10 Other Carbonyl Compounds 670
Appendix 8 Selected Ionic Radii A-23
23.11 Complexes with Phosphine ON THE WEB www.whfreeman.com/descriptive6e
Ligands 672 Appendix 9 Standard Half-Cell
23.12 Complexes with Alkyl, Alkene, Electrode Potentials
and Alkyne Ligands 673 of Selected Elements A-25w
23.13 Complexes with Allyl and ON THE WEB www.whfreeman.com/descriptive6e
1,3-Butadiene Ligands 676 Appendix 10 Electron Configurations
23.14 Metallocenes 677 of the Elements A-35w
23.15 Complexes with h6-Arene Ligands 679
23.16 Complexes with Cycloheptatriene PHOTO CREDITS C-1
and Cyclooctatetraene Ligands 680 INDEX I-1
What Is Descriptive Inorganic
Chemistry?

D escriptive inorganic chemistry was traditionally concerned with the prop-

erties of the elements and their compounds. Now, in the renaissance of the
subject, the properties are being linked with explanations for the formulas and
structures of compounds together with an understanding of the chemical reac-
tions 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 appli-
cations throughout science and our lives. And it is because of a need for greater
contextualization that we have added more relevance by means of the new
chapter openers: Context.
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, environmental sci-
ence, and other scientific fields. This course can then be followed by a junior or
senior course that focuses on the theoretical principles and the use of spectros-
copy to a greater depth than is covered in a descriptive text. In fact, the theo-
retical course builds nicely on the descriptive background. Without the
descriptive grounding, however, the theory becomes sterile, uninteresting, and
irrelevant.
This book was written to pass on to another generation our fascination with
descriptive inorganic chemistry. Thus, the comments of the readers, both stu-
dents and instructors, will be sincerely appreciated. Our current e-mail
addresses are: grcanham@grenfell.mun.ca and T.L.Overton@hull.ac.uk.

xiii
PREFACE

Descriptive Inorganic chemistry goes beyond academic interest;

it is an important part of our lives.

T he role of inorganic chemistry in our lives is increasing. Thus, the sixth

edition of Descriptive Inorganic Chemistry now has the following
improvements:
Context: Each chapter opens with a Context, an aspect of inorganic chemistry
which impinges on us in one way or another. Each of these contexts is intended
to be thought-provoking and also ties in with an aspect of the chapter content.
Worked Examples: Sprinkled throughout the chapters, we have added Worked
Examples, so that students can see how content relates to principles.
New Discoveries: In addition to some reorganization of content and an
increased use of subheadings, we have added new discoveries to show that
descriptive inorganic chemistry is alive and well as the twenty-first century
progresses.
Predominance Diagrams: To provide a visual display of which species of an
element or ion are present under specific conditions, comparative predomi-
nance diagrams have been added, where appropriate.

Chapter 1: The Electronic Structure of the Atom: A Review

Addition of discussion of f-orbitals.
Chapter 2: The Structure of the Periodic Table
Inclusion of relativistic effects.
Improved discussion of electron affinity patterns.
Chapter 3: Covalent Bonding and Molecular Spectroscopy
VSEPR theory now precedes molecular orbital theory.
Improvement of spectroscopy discussion.
Chapter 4: Metallic Bonding and Alloys
Expansion of discussion on alloys.
Addition of subsection on quasicrystals.
Chapter 5: Ionic Bonding and Solid-State Structures
Consolidation of solid-state structures into this one chapter.
Addition of a section on crystal defects and nonstoichiometric compounds.
Chapter 6: Why Compounds Exist—Inorganic Thermodynamics
Discussion on nonexistent compounds.
New section on lattice energies and comparative ion sizes and charges.
Chapter 7: Solvent Systems and Acid-Bases Behavior
Revised section on acid-base reactions of oxides.

xv
xvi Preface

Chapter 8: Oxidation and Reduction

Improved discussion of Frost diagrams.
Improved discussion of Pourbaix diagrams.
Chapter 9: Periodic Patterns
Revised section on the “knight’s move” relationship.
Revised section on the lanthanoid relationships.
Chapter 10: Hydrogen
New section on the trihydrogen ion.
Chapter 11: The Group 1 Elements: The Alkali Metals
Restructuring of chapter.
Chapter 12: The Group 2 Elements: The Alkaline Earth Metals
Restructuring of chapter.
Chapter 13: The Group 13 Elements
Minor changes.
Chapter 14: The Group 14 Elements
Revised comparison of carbon and silicon.
Additional subsection in carbides on MAX phases.
Chapter 15: The Group 15 Elements: The Pnictogens
Revised comparison of nitrogen and phosphorus.
Additional discussion of nitrogen species such as pentazole.
Chapter 16: The Group 16 Elements: The Chalcogens
Additional subsections on octaoxygen and dihydrogen dioxide.
New section on oxygen and the atmosphere.
Chapter 17: The Group 17 Elements: The Halogens
Restructuring of chapter.
Chapter 18: The Group 18 Elements: The Noble Gases
New section on compounds of helium, argon, and krypton.
New section on other xenon compounds.
Chapter 19: Transition Metal Complexes
More detailed discussion on crystal field theory.
New section on reaction mechanisms.
Chapter 20: The 3d Transition Metals
New section on the V-Cr-Mn triad.
New section on the Fe-Co-Ni triad.
Chapter 21: The 4d and 5d Transition Metals
Restructuring of chapter.
Chapter 22: The Group 12 Elements
Updating of chapter.
Chapter 23: Organometallic Chemistry
Updating of chapter.
Chapter 24: The Rare Earth, Actinoid, and Postactinoid Elements—web
Updating of chapter.
 Preface xvii

ANCILLARY SUPPORT

Student Support Resources

Book Companion Site
The Descriptive Inorganic Chemistry Book Companion Site, www.whfreeman.
com/descriptive6e, contains the following student friendly materials:

■ Chapter 24 Although the lanthanoids, actinoids, and postactinoid

elements are of interest and of increasing importance, as few instructors
cover these elements, the chapter is only available on-line.
■ Appendices 9 and 10 To save space and paper, these lengthy appen-
dices are also available on the Book Companion Site.
■ Video Demos Chemistry is a visual subject, thus over 60 video demos
are on-line to match reactions described in the text. The text has a margin
symbol to identify where there is a corresponding video demo.
■ Laboratory Experiments A series of experimental exercises are
available to enable students to see a selection of the chemical reactions
described in the text.

Student Solutions Manual

The Student Solutions Manual, ISBN: 1-4641-2560-0, contains the answers to
the odd-numbered end-of-chapter questions.
The CourseSmart e-Textbook
The CourseSmart e-Textbook provides the full digital text, along with tools to
take notes, search, and highlight passages. A free app allows access to Cours-
eSmart e-Textbooks and Android and Apple devices, such as the iPad. They can
also be downloaded to your computer and accessed without an Internet con-
nection, removing any limitations for students when it comes to reading digital
text. The CourseSmart e-Textbook can be purchased at www.coursesmart.com.

Instructor Resources
Book Companion Site
The password-protected instructor side of the Book Companion Site contains
the Instructor’s Solutions Manual, with answers to the even-numbered end-of-
chapter questions, as well as all the illustrations and tables in the book, in .jpg
and PowerPoint format.
Correlation of Descriptive Inorganic Chemistry,
6th Edition, with American Chemical Society
Guidelines Committee on Professional Training,
Inorganic Chemistry Supplement 2012

Each topic from the ACS guidelines listed below is followed by the corre-
sponding chapter(s) in Descriptive Inorganic Chemistry, 6th edition, [DIC6]
in brackets.
■ Atomic Structure. Spectra and orbitals, ionization energy, electron affinity,
shielding and effective nuclear charge. [DIC6, Chapter 1]
■ Covalent Molecular Substances. Geometries (symmetry point groups),
valence bond theory (hybridization, s, p, d bonds), molecular orbital theory
(homonuclear and heteronuclear diatomics, multicentered MO, electron-
deficient molecules, p-donor and acceptor ligands). [DIC6, Chapter 3 (and
parts of 13 and 21)]
■ Main Group Elements. Synthesis, structure, physical properties, variations
in bonding motifs, acid-base character, and reactivities of the elements and
their compounds. [DIC6, Chapters 2, 6 through 18, 22]
■ Transition Elements and Coordination Chemistry. Ligands, coordination
number, stereochemistry, bonding motifs, nomenclature; ligand field and
molecular orbital theories, Jahn-Teller effects, magnetic properties, electronic
spectroscopy (term symbols and spectrochemical series), thermodynamic
aspects (formation constants, hydration enthalpies, chelate effect), kinetic
aspects (ligand substitution, electron transfer, fluxional behavior), lan-
thanides, and actinides. [DIC6, Chapters 19, 20, 21, 24]
■ Organometallic Chemistry. Metal carbonyls, hydrocarbon and carbocyclic
ligands, 18-electron rule (saturation and unsaturation), synthesis and proper-
ties, patterns of reactivity (substitution, oxidative-addition and reductive-
elimination, insertion and deinsertion, nucleophilic attack on ligands,
isomerization, stereochemical nonrigidity). [DIC6, Chapter 23]
■ Solid-State Materials. Close packing in metals and metal compounds,
metallic bonding, band theory, magnetic properties, conductivity, semiconduc-
tors, insulators, and defects. [DIC6, Chapters 4 and 5]
■ Special Topics. Catalysis and important industrial processes, bioinorganic
chemistry, condensed materials containing chain, ring, sheet, cage, and net-
work structures, supramolecular structures, nanoscale structures and effects,
surface chemistry, environmental and atmospheric chemistry. [DIC6, Topics
incorporated throughout]

xix
ACKNOWLEDGMENTS

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

have contributed their talents to the six editions of this book. We offer
our sincere gratitude to the editors of the sixth edition, Jessica Fiorillo, Heidi
Bamatter, and Elizabeth Geller; 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 spe-
cial 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: Stephen Anderson at Ramapo
College of New Jersey; Jon J. Barnett at Concordia University Wisconsin; Craig
A. Bayse at Old Dominion University; M. A. Salam Biswas at Tuskegee Uni-
versity; Paul Brandt at North Central College; P. A. Deck at Virginia Tech;
Nancy C. Dopke at Alma College; Anthony L. Fernandez at Merrimack Col-
lege; John Alan Goodwin at Coastal Carolina University; Thomas A. Gray at
The Sage Colleges; Alison G. Hyslop at St. John’s University; Susanne M. Lewis
at Olivet College; James L. Mack at Fort Valley State University; Yuanbing Mao
at University Of Texas–Pan American; Li-June Ming at University of South
Florida; Mahesh Pattabiraman at Western New Mexico University; Jeffrey
Rood at Elizabethtown College; Shawn C. Sendlinger at North Carolina Central
University; Tasneem Ahmed Siddiquee at Tennessee State University; Jay R.
Stork at Lawrence University; Carmen Valdez Gauthier at Florida Southern
College; Yan Waguespack at University of Maryland Eastern Shore; Xin Wen
at California State University, Los Angeles; Kimberly Woznack at California
University of Pennsylvania; Michael J. Zdilla at Temple University.
We acknowledge with thanks the contributions of the reviewers of the fifth
edition: 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
xxi
xxii Acknowledgments

Fritsch at Pepperdine University; Rebecca Roesner at Illinois Wesleyan

University, and Carmen Works at Sonoma College.
And 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 Univer-
sity; 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 Univer-
sity; 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.
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 Univer-
sity; and particularly Joe Takats of the University of Alberta for his comprehen-
sive 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 Uni-
versity; Richard B. Kaner at the University of California, Los Angeles; Richard
H. Langley at Stephen F. Austin State University; James M. Mayer at the Univer-
sity 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 Col-
lege; 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 Dave for his patience throughout this project.
DEDICATION

C hemistry is a human endeavor. New discoveries are the result of the work
of enthusiastic individuals and groups of individuals 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 persons 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 peri-
odic 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 discover-
ing that, upon bombardment with electrons, each element emit-
ted X-rays of characteristic wavelengths. The wavelengths fitted
a formula related by an integer number unique to each element.
We now know that number to be the number of protons. With
the establishment of the atomic number of an element, chem-
ists at last knew the fundamental organization of the periodic
table. Sadly, Moseley was killed at the battle of Gallipoli in the
First World War. Thus, one of the brightest scientific talents of the
twentieth century died at the age of 27. The famous American sci-
entist 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, there was the claim of the discovery
of element 43, and it was named moseleyum; however, the claim
was disproved by the very method that Moseley had pioneered.

xxiii
xxiv 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 ele-
ments and extend the periodic table. The Austrian scientist Lise
Meitner had shared leadership with Otto Hahn of the German
research team working on the synthesis of new elements. They
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, the
physicist Otto Frisch, Meitner realized that an atomic nucleus
could break in two just like a drop of water. No wonder the ele-
ment formed behaved like barium: it was barium! Thus, was born
the concept of nuclear fission. She informed Hahn of her pro-
posal. 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 naming an ele-
ment after her, element 109, meitnerium.

Additional reading
Heilbron, J.L., H.G.J. Moseley, University of California Press, Berkeley, CA, 1974.
Rayner-Canham, M.F., and Rayner-Canham, G.W. Women in Chemistry: Their
Changing Roles from Alchemical Times to the Mid-Twentieth Century, Chemi-
cal Heritage Foundation, Philadelphia, PA, 1998.
Sime, R.L., Lise Meitner: A Life in Physics, University of California Press,
Berkeley, CA, 1996.
Weeks M.E., and Leicester, H.M. Discovery of the Elements, Journal of
Chemical Education, Easton, PA, 7th edition, 1968.
THE ELECTRONIC CHAPTER 1
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 1.1 A Review of the Quantum Model
constituent atoms. Our coverage of inorganic chemistry, therefore, starts with a survey
1.2 Shapes of the Atomic Orbitals
of the quantum (probability) model’s applications to the electron configurations
1.3 The Polyelectronic Atom
of atoms and ions. We will show how these configurations can be used to explain
patterns and trends in common physical properties of atoms. 1.4 Ion Electron Configurations
1.5 Magnetic Properties of Atoms

Context: The Importance of the Lanthanoids

The cover design of this sixth edition of Descriptive Inorganic Chemistry
highlights the lack of recycling of most of the metallic elements. In
particular, very little of the elements from lanthanum to lutetium—
the lanthanoids—is reclaimed. Yet we are depending more and more on
the unique properties of each of these metals to serve vital niche roles in
our electronic-based civilization. For example, hybrid and all-electric
vehicles rely on what are called nickel-metal hydride batteries for the
energy storage. The metal is, in fact, lanthanum, and a hybrid vehicle
battery typically contains between 10 and 15 kilograms of lanthanum.
The hybrid electric motor and generator itself contains neodymium,

GLASS AND MIRRORS

UV CUT GLASS POLISHING POWDER
– Cerium – Cerium
DIESEL FUEL LCD SCREEN
ADDITIVE – Europium
– Cerium – Yttrium
– Lanthanum – Cerium
COMPONENT
HYBRID NiMH SENSORS
BATTERY – Yttrium
– Lanthanum
– Cerium HYBRID ELECTRIC
MOTOR AND
CATALYTIC GENERATOR
CONVERTER – Neodymium
– Cerium – Praseodymium
– Lanthanum 25+ ELECTRIC MOTORS HEADLIGHT GLASS – Dysprosium
– Neodymium – Terbium
THROUGHOUT VEHICLE
– Neodymium
The lanthanoid elements (and yttrium) used in a typical hybrid vehicle.

1
2 CHAPTER 1 / The Electronic Structure of the Atom: A Review

praseodymium, dysprosium, and terbium; each metal performing a vital function.

The figure above shows the wide-ranging use of the lanthanoids (and yttrium)
in a typical hybrid vehicle.
All modern high-performance magnets depend upon alloys containing
neodymium, whether they are tiny magnets in the ear-pieces for audio devices
or giant magnets in the turbines of commercial wind turbines. The brilliance of
color displays for computers and televisions is commonly the result of emission
from europium ions (for red), terbium ions (for green), and cerium ions (for
blue). There are also many medical applications for these elements. For exam-
ple, gadolinium gives a strong image in a magnetic resonance imaging (MRI)
scan. Thus, to see a finer structure of blood vessels (and of tumors), an intrave-
nous injection of a gadolinium(III) compound is administered to a patient
prior to performing an MRI scan.
The common feature of these elements is that, progressing from lanthanum
to lutetium, the 4f orbitals are being filled. Thus, in this chapter, we will not only
review the s, p, and d orbitals which you have encountered in lower level courses,
but also introduce you to the f orbitals.

1.1 A Review of the Quantum Model

The quantum 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 par-
tial differential equation to represent the behavior of an electron around an
atomic nucleus.
The derivation of the 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.

Quantum Numbers
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 inte-
gers: n, l, and ml.
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 exper-
iment 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 direc-
tion. Other investigators proposed that the observation was the result of two
different electronic spin orientations. The atoms possessing an electron with
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