33
As

34
Se

35
Br

36
Kr

51
Sb

52
Te

53
I

54
Xe

83
Bi

84
Po

85

At

86
Rn

115
Uup

116
Lv

117
Uus

118
Uuo

Descriptive
Inorganic Chemistry

69
Tm

70
Yb

71
Lu

101

Md

102
No

103
Lr

Sixth Edition

Geoff Rayner-Canham
Tina Overton

22
23
24
Ti 25 V 26 Cr27
40 Mn 41 Fe 42Co
Zr 43 Nb 44 Mo45

5
B

2

6 He 7
C
N

5

B

6
C

7
N

8
O13

9
10
F14 Ne15

13
28
Al

14
29
Si

15
30
P

16
S31


17
18
Cl32 Ar33

Ni
31

Cu
32
Ge
47

Zn
33
As
48

Ga
34
Se
49

35Ge 36As
Br50 Kr51

Cd
51
Sb

52In

Te

53Sn 54Sb
I
Xe

Al

Si

P

25
26
Mn28 Fe29

27
Co
30

Cu
43Ni 44
Tc46 Ru
47

Zn
45
Rh
48


Ga
46
Pd
49

Ag
50

Ag
72 Tc 73 Ru 74Rh 75Pd 76
79
Hf 75 Ta 76 W77 Re78 Os

Cd
77
80
Ir

In
78
81
Pt

Sn
79
82
Au

80
83

Hg

81
84
Tl

04 105 106 107 108 109
112
Rf 107Db108 Sg109 Bh110 Hs111 Mt

110
113
Ds

111
114
Rg

112
115
Cn

113 114 115
116
Uut 117Fl 118
Uu

Re

Os


Ir

Pt

Au

Bh

Hs

Mt

Ds

Rg

Cn

58
59
60
61
62
61
62
63
64
65
Ce Pm Pr Sm NdEu PmGd Sm

Tb

63
66
Eu
Dy

64
67
Gd
Ho

68
Tb
Er

69
Dy
Tm

70
Ho
Yb

68

69
Tm

0 93 91 94 9295 9396 94

97 95
98
Th Np Pa Pu UAm Np
Cm Pu
Bk Am
Cf

96
99
Cm
Es

97
100
Bk
Fm

98
101
Cf
Md

99 103
100
102
Es LrFm
No

101
Md


< 1%

1 - 10%

< 1%>10 - 25%

Hg

Tl

Uut

1- 10%
>25 - 50% > 10 - 25%
> 50%

Pb
Fl

65

Bi

Uup

66

> 25 -50%


Po

82
83
85Pb 86Bi

Lv

67

At

Rn

Uus

Uuo

71
Er
Lu

> 50%


1

Periodic Table of the Elements*

2


1
H
1.0079

1

2

3
Li
6.94

4
Be
9.01
Metals

3

11
Na
22.99

12
Mg
24.31

4


19
K
39.10

5

3

4

5

6

7

8

9

20
Ca
40.08

21
Sc
44.96

22
Ti

47.88

23
V
50.94

24
Cr
52.00

25
Mn
54.94

26
Fe
55.85

27
Co
58.93

37
Rb
85.47

38
Sr
87.62


39
Y
88.91

40
Zr
91.22

41
Nb
92.91

42
Mo
95.94

43
Tc

44
Ru
101.07

45
Rh
102.91

6

55

Cs
132.91

56
Ba
137.34

71
Lu
174.97

72
Hf
178.49

73
Ta
180.95

74
W
183.85

75
Re
186.2

76
Os
190.2


77
Ir
192.2

7

87
Fr
223

88
Ra
226.03

103
Lr

104
Rf

105
Db

106
Sg

107
Bh


108
Hs

109
Mt

57
La
138.91

58
Ce
140.12

59
Pr
140.91

60
Nd
144.24

61
Pm

89
Ac
227.03

90

Th
232.04

91
Pa
231.04

92
U
238.03

93
Np

*Molar masses quoted to the number of
significant figures given here can be
regarded as typical of most naturally
occurring samples.


13

14

15

16

17


2
He
4.00

Nonmetals

Metalloids

18

5
B
10.81

6
C
12.01

7
N
14.01

8
O
16.00

9
F
19.00


10
Ne
20.18

13
Al
26.98

14
Si
28.09

15
P
30.97

16
S
32.06

17
Cl
35.45

18
Ar
39.95

10


11

12

28
Ni
58.71

29
Cu
63.54

30
Zn
65.37

31
Ga
69.72

32
Ge
72.59

33
As
74.92

34
Se

78.96

35
Br
79.91

36
Kr
83.80

46
Pd
106.4

47
Ag
107.87

48
Cd
112.40

49
In
114.82

50
Sn
118.69


51
Sb
121.75

52
Te
127.60

53
I
126.90

54
Xe
131.30

78
Pt
195.09

79
Au
196.97

80
Hg
200.59

81
Tl

204.37

82
Pb
207.19

83
Bi
208.98

84
Po
210

85
At
210

86
Rn
222

110
Ds

111
Rg

112
Cn


113
Uut

114
Fl

115
Uup

116
Lv

117
Uus

118
Uuo

62
Sm
150.35

63
Eu
151.96

64
Gd
157.25


65
Tb
158.92

66
Dy
162.50

67
Ho
164.93

68
Er
167.26

94
Pu

95
Am

96
Cm

97
Bk

98

Cf

99
Es

100
Fm

69
70
Tm
Yb
168.93 173.04
101
Md

102
No

Lanthanoids

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
Associate Editor: Heidi Bamatter
Associate Director of Marketing: Debbie Clare
Media Acquisitions Editor: Dave Quinn
Photo Editors: Christine Buese, Nicholas A. Ciani
Cover Designer: Vicki Tomaselli
Text Designer: Blake Logan
Project Editor: Elizabeth Geller
Illustrations: Aptara®, Inc.
Production Coordinator: Paul Rohloff
Composition: Aptara®, Inc.
Printing and Binding: RR Donnelley

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
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

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

Appendices
Index

691w
A-1
I-1
v



CONTENTS
What Is Descriptive Inorganic Chemistry?
Preface
Acknowledgments
Dedication

xiii
xv
xxi
xxiii


3.5
3.6
3.7
3.8

CHAPTER 1

The Electronic Structure of
the Atom: A Review
Context: The Importance of the Lanthanoids

1.1
1.2
1.3
1.4
1.5

A Review of the Quantum Model
Shapes of the Atomic Orbitals
The Polyelectronic Atom
Ion Electron Configurations
Magnetic Properties of Atoms

3.9

1
1

2
4

8
13
15

3.10
3.11
3.12
3.13
3.14

The Valence-Bond Concept
Introduction to Molecular Orbitals
Molecular Orbitals for Period 1
Diatomic Molecules
Molecular Orbitals for Period 2
Diatomic Molecules
Molecular Orbitals for Heteronuclear
Diatomic Molecules
Network Covalent Substances
Intermolecular Forces
Molecular Symmetry
Symmetry and Vibrational
Spectroscopy
The Bonding Continuum

50
53
55
57
62

64
66
70
76
80

CHAPTER 4
CHAPTER 2

The Structure of the Periodic Table

19

Context: Bioinorganic Chemistry

19

2.1
2.2
2.3
2.4
2.5
2.6
2.7

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

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

20
23
24
28
31

85

Context: Metal Matrix Composites

85

4.1
4.2
4.3
4.4
4.5
4.6
4.7

86
87
89
92

93
95
95

Metallic Bonding
Bonding Models
Structure of Metals
Unit Cells
Alloys
Nanometal Particles
Magnetic Properties of Metals

CHAPTER 5

35
37

CHAPTER 3

Covalent Bonding and Molecular
Spectroscopy

41

Context: The Greenhouse Effect

41

3.1
3.2

3.3
3.4

42
44
44

A Brief Review of Lewis Structures
Partial Bond Order
Formal Charge
Valence-Shell Electron-Pair
Repulsion Rules

Metallic Bonding and Alloys

45

Ionic Bonding and Solid State
Structures

99

Context: Superconductivity and Ionic
Compounds

99

5.1
5.2
5.3

5.4
5.5
5.6
5.7
5.8

The Ionic Model and the Size of Ions
Polarization and Covalency
Ionic Crystal Structures
Hydrated Salts
Isostructural Ionic Compounds
Perovskites
Spinels
Defects and Nonstoichiometry

100
102
106
113
114
117
118
119
vii


viii

Contents


8.6
8.7

CHAPTER 6

Why Compounds Exist—
Inorganic Thermodynamics

125

Context: Against Convention: Ionic
Compounds of Metal Ions

125

6.1
6.2
6.3
6.4
6.5
6.6
6.7

Thermodynamics of the Formation
of Compounds
Formation of Ionic Compounds
Non-Existent Ionic Compounds
Thermodynamics of the Solution
Process for Ionic Compounds
Lattice Energies and Comparative

Ion Sizes and Charges
Formation of Covalent Compounds
Thermodynamic versus
Kinetic Factors

236
134
137
139
142
144
146

CHAPTER 7

Solvent Systems and Acid-Base
Behavior

153

Context: Green Solvents for the Future

153

7.1
7.2
7.3
7.4
7.5
7.6


154
158
163
168
170

7.7
7.8

Solvents
Brønsted-Lowry Acids
Trends in Acid-Base Behavior
Acid-Base Reactions of Oxides
Lewis Theory
Pearson Hard-Soft Acid-Base
Concepts
Application of the HSAB Concept
Biological Aspects

171
173
176

Redox Equations
Quantitative Aspects of
Half-Reactions
8.8
Electrode Potentials as
Thermodynamic Functions

8.9
Latimer (Reduction Potential)
Diagrams
8.10 Frost (Oxidation State) Diagrams
U
8.11 Pourbaix (E -pH) Diagrams
8.12 Redox Synthesis
8.13 Biological Aspects

188
192
193
195
197
200
204
206

CHAPTER 9

Periodic Patterns
Context: Is the Periodic Table Only
Groups and Periods?

9.1
9.2
9.3

Group Trends
Periodic Trends in Bonding

Isoelectronic Series in Covalent
Compounds
9.4
The (n) Group and (n 1 10)
Group Similarities
9.5
Diagonal Relationships
9.6
The “Knight’s Move” Relationship
9.7
The Early Actinoid Relationships
with Transition Metals
9.8
The Lanthanoid Relationships
9.9
“Combo” Elements
9.10 Biological Aspects

211
211

212
215
219
221
227
229
233
233
235

239

CHAPTER 10

Hydrogen

CHAPTER 8

Oxidation and Reduction
Context: Unraveling Nature’s Secrets

8.1
8.2
8.3
8.4
8.5

181
181

Redox Terminology
182
Oxidation Number Rules
183
Determination of Oxidation Numbers
from Electronegativities
184
The Difference Between Oxidation
Number and Formal Charge
186

Periodic Variations of Oxidation
Numbers
187

243

Context: Hydrogen Bond—The Real
“Special Agent”

243

10.1
10.2
10.3
10.4
10.5
10.6
10.7
10.8

244
246
247
250
252
256
257
260

Isotopes of Hydrogen

Nuclear Magnetic Resonance
Properties of Hydrogen
The Trihydrogen Ion
Hydrides
Water and Hydrogen Bonding
Clathrates
Element Reaction Flowchart


Contents

12.11 Biological Aspects
12.12 Element Reaction Flowcharts

CHAPTER 11

The Group 1 Elements:
The Alkali Metals
Context: The Sodium Ion–Potassium
Ion Balance in Living Cells

11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9

11.10
11.11
11.12
11.13
11.14

Group Trends
Features of Alkali Metal
Compounds
Trends in Alkali Metal Oxides
Solubility of Alkali Metal Salts
Lithium
Sodium
Sodium Hydroxide
Sodium Chloride
Sodium Carbonate and Sodium
Hydrogen Carbonate
Potassium
Potassium Chloride
Ammonium Ion as a
Pseudo–Alkali-Metal Ion
Biological Aspects
Element Reaction Flowcharts

CHAPTER 13

263

265
266

269
271
274
277
278
280
280
282
283
284
285
285

Group Trends
Features of Alkaline Earth Metal
Compounds
12.3 Trends in Alkaline Earth Metal
Oxides
12.4 Beryllium
12.5 Magnesium
12.6 Calcium Carbonate
12.7 Cement
12.8 Calcium Chloride
12.9 Calcium Sulfate
12.10 Calcium Carbide

The Group 13 Elements

289


291
292
296
297
298
300
302
303
304
304

311

Context: Aluminum—The Toxic Ion

311

13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
13.9
13.10
13.11

312

313
315
316
320
322
327
328
329
330
331

Group Trends
Boron
Borides
Boranes
Boron Halides
Aluminum
Aluminum Halides
Aluminum Potassium Sulfate
Aluminides
Biological Aspects
Element Reaction Flowchart

CHAPTER 14

The Group 14 Elements
Context: Cermets—The Toughest
Materials

14.1

14.2

The Group 2 Elements: The Alkaline
Earth Metals
289

12.1
12.2

305
307

263

CHAPTER 12

Context: Calcium and Magnesium—
Another Biological Balance

ix

14.3
14.4
14.5
14.6
14.7
14.8
14.9
14.10
14.11

14.12
14.13
14.14
14.15
14.16
14.17

Group Trends
Contrasts in the Chemistry of
Carbon and Silicon
Carbon
Isotopes of Carbon
Carbides
Carbon Monoxide
Carbon Dioxide
Carbonates and Hydrogen
Carbonates
Carbon Sulfides
Carbon Halides
Methane
Cyanides
Silicon
Silicon Dioxide
Silicates
Aluminosilicates
Silicones

335
335


336
337
339
343
344
348
350
352
354
354
356
357
358
360
362
364
367


x

Contents

14.18 Tin and Lead
14.19 Biological Aspects
14.20 Element Reaction Flowchart

368
371
374


CHAPTER 15

The Group 15 Elements:
The Pnictogens
Context: The Essential PhosphorusOxygen Bond

15.1
15.2
15.3
15.4
15.5
15.6
15.7
15.8
15.9
15.10
15.11
15.12
15.13
15.14
15.15
15.16
15.17
15.18
15.19
15.20

Group Trends
Contrasts in the Chemistry of

Nitrogen and Phosphorus
Overview of Nitrogen Chemistry
Nitrogen
Nitrogen Hydrides
Nitrogen Ions
The Ammonium Ion
Nitrogen Oxides
Nitrogen Halides
Nitrous Acid and Nitrites
Nitric Acid and Nitrates
Overview of Phosphorus
Chemistry
Phosphorus
Phosphine
Phosphorus Oxides
Phosphorus Chlorides
Phosphorus Oxoacids and
Phosphates
The Pnictides
Biological Aspects
Element Reaction Flowchart

379
379

380
381
384
386
387

394
396
397
402
402
403
407
408
411
411
412
414
417
418
421

CHAPTER 16

The Group 16 Elements: The
Chalcogens
Context: Macular Degeneration
and Singlet Oxygen

16.1
16.2
16.3

Group Trends
Contrasts in the Chemistry of
Oxygen and Sulfur

Allotropes of Oxygen

427
427

428
430
431

16.4
16.5
16.6
16.7
16.8
16.9
16.10
16.11
16.12
16.13
16.14
16.15
16.16
16.17
16.18
16.19
16.20
16.21
16.22

Oxygen and the Atmosphere

Bonding in Covalent Oxygen
Compounds
Trends in Oxide Properties
Hydrogen Oxides
Hydroxides
Allotropes of Sulfur
Overview of Sulfur Chemistry
Hydrogen Sulfide
Sulfides
Sulfur Oxides
Sulfites
Sulfuric Acid
Sulfates and Hydrogen Sulfates
Other Oxosulfur Anions
Sulfur Halides
Sulfur-Nitrogen Compounds
Selenium
Biological Aspects
Element Reaction Flowchart

436
438
440
442
444
445
446
450
452
454

457
458
460
461
463
466
466
467
468

CHAPTER 17

The Group 17 Elements:
The Halogens
Context: Experimenting with the
Atmosphere—The Antarctic Ozone Hole

17.1
17.2

Group Trends
Contrasts in the Chemistry of
Fluorine and the Other Halogens
17.3 Halides
17.4 Fluorine
17.5 Hydrogen Fluoride and
Hydrofluoric Acid
17.6 Overview of Chlorine Chemistry
17.7 Chlorine
17.8 Hydrochloric Acid

17.9 Chlorine Oxides
17.10 Chlorine Oxoacids and
Oxoanions
17.11 Interhalogen Compounds and
Polyhalide Ions
17.12 Cyanide Ion as a
Pseudo-halide Ion

473
473

475
476
478
482
484
486
487
489
489
491
495
498


Contents

17.13 Biological Aspects
17.14 Element Reaction Flowchart


499
502

CHAPTER 18

The Group 18 Elements:
The Noble Gases
Context: Helium—An Increasingly
Rare Gas

18.1 Group Trends
18.2 Helium
18.3 Compounds of Helium, Argon,
and Krypton
18.4 Xenon Fluorides
18.5 Xenon Oxides
18.6 Other Xenon Compounds
18.7 Biological Aspects
18.8 Element Reaction Flowchart

507

508
510

20.1

Transition Metal Complexes

519


Context: Platinum Complexes and
Cancer Treatment

519

19.3
19.4
19.5
19.6
19.7
19.8
19.9
19.10
19.11
19.12
19.13

Transition Metals
Introduction to Transition Metal
Complexes
Stereochemistries
Isomerism in Transition Metal
Complexes
Naming Transition Metal
Complexes
An Overview of Bonding Theories
of Transition Metal Compounds
Crystal Field Theory
Successes of Crystal Field

Theory
More on Electronic Structure
Ligand Field Theory
Thermodynamic versus Kinetic
Factors
Synthesis of Coordination
Compounds
Reaction Mechanisms

The 3d Transition Metals
Context: Iron Is at the Core of Everything

511
511
515
516
516
517

554
555

CHAPTER 20

507

CHAPTER 19

19.1
19.2


19.14 Coordination Complexes and
the Hard-Soft Acid-Base (HSAB)
Concept
19.15 Biological Aspects

xi

20.2
20.3
20.4
20.5
20.6
20.7
20.8
20.9
20.10
20.11
20.12
20.13

Overview of the 3d Transition
Metals
Group 4: Titanium
The Vanadium-ChromiumManganese Triad
Group 5: Vanadium
Group 6: Chromium
Group 7: Manganese
The Iron-Cobalt-Nickel Triad
Group 8: Iron

Group 9: Cobalt
Group 10: Nickel
Group 11: Copper
Biological Aspects
Element Reaction Flowchart

559
559

560
562
563
564
564
571
575
576
586
590
592
598
601

521
CHAPTER 21

522
523

The 4d and 5d Transition Metals

Context: Silver Is a Killer

607

525

21.1
21.2

609

528
530
532
538
542
546
548
549
550

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

21.7 The Platinum Group Metals
21.8 Group 8: Ruthenium and Osmium
21.9 Group 9: Rhodium and Iridium
21.10 Group 10: Palladium and Platinum
21.11 Group 11: Silver and Gold
21.12 Biological Aspects

607

610
613
615
617
620
622
623
624
624
625
629


xii

Contents

CHAPTER 22

The Group 12 Elements


633

Context: Zinc Oxide Can Save
Your Skin!

633

22.1
22.2
22.3
22.4
22.5

635
636
639
641
643

Group Trends
Zinc and Cadmium
Mercury
Biological Aspects
Element Reaction Flowchart

CHAPTER 23

Organometallic Chemistry
Context: The Extreme Toxicity of
Dimethylmercury


23.1
23.2
23.3
23.4
23.5
23.6
23.7
23.8
23.9
23.10
23.11
23.12
23.13
23.14
23.15
23.16

Introduction to Organometallic
Compounds
Naming Organometallic
Compounds
Counting Electrons
Solvents for Organometallic
Chemistry
Main Group Organometallic
Compounds
Organometallic Compounds of
the Transition Metals
Transition Metal Carbonyls

Synthesis and Properties of
Simple Metal Carbonyls
Reactions of Transition Metal
Carbonyls
Other Carbonyl Compounds
Complexes with Phosphine
Ligands
Complexes with Alkyl, Alkene,
and Alkyne Ligands
Complexes with Allyl and
1,3-Butadiene Ligands
Metallocenes
Complexes with h6-Arene Ligands
Complexes with Cycloheptatriene
and Cyclooctatetraene Ligands

645
645

646
647
648
649
650
658
662
667
669
670
672


23.17 Fluxionality
23.18 Organometallic Complexes in
Industrial Synthesis
23.19 Biological Aspects

680
681
686

CHAPTER 24 ON THE WEB
www.whfreeman.com/descriptive6e

The Rare Earth, Actinoid, and
Postactinoid Elements

691w

Context: Uranium: Enriched or Depleted?

691w

24.1
24.2
24.3
24.4
24.5
24.6

693w

694w
696w
700w
702w
703w

The Group 3 Elements
The Lanthanoids
The Actinoids
Uranium
The Postactinoid Elements
Biological Aspects

APPENDICES

Appendix 1

Appendix 2
Appendix 3
Appendix 4
Appendix 5
Appendix 6
Appendix 7
Appendix 8

Thermodynamic Properties
of Some Selected Inorganic
Compounds
A-1
Charge Densities of

Selected Ions
A-13
Selected Bond Energies
A-16
Ionization Energies of
Selected Metals
A-18
Electron Affinities of
Selected Nonmetals
A-20
Selected Lattice Energies A-21
Selected Hydration
Enthalpies
A-22
Selected Ionic Radii
A-23

ON THE WEB www.whfreeman.com/descriptive6e

Appendix 9

673

Standard Half-Cell
Electrode Potentials
of Selected Elements

A-25w

ON THE WEB www.whfreeman.com/descriptive6e


676
677
679
680

Appendix 10

Electron Configurations
of the Elements

PHOTO CREDITS
INDEX

A-35w
C-1
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, 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. 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 science, 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 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.
This book was written to pass on to another generation our fascination with
descriptive inorganic chemistry. Thus, the comments of the readers, both students and instructors, will be sincerely appreciated. Our current e-mail
addresses are: and

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 predominance 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

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 appendices 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 CourseSmart e-Textbooks and Android and Apple devices, such as the iPad. They can
also be downloaded to your computer and accessed without an Internet connection, 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-ofchapter questions, as well as all the illustrations and tables in the book, in .jpg
and PowerPoint format.

xvii



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 corresponding 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, electrondeficient 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), lanthanides, and actinides. [DIC6, Chapters 19, 20, 21, 24]
■

■
Organometallic Chemistry. Metal carbonyls, hydrocarbon and carbocyclic

ligands, 18-electron rule (saturation and unsaturation), synthesis and properties, patterns of reactivity (substitution, oxidative-addition and reductiveelimination, 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, semiconductors, 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 network 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 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: 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 University; Paul Brandt at North Central College; P. A. Deck at Virginia Tech;
Nancy C. Dopke at Alma College; Anthony L. Fernandez at Merrimack College; 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 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.
And the contributions of the reviewers of the third edition: Franỗois 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 Dave for his patience throughout this project.