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Descriptive Inorganic Chemistry
Second Edition
James E. House
Kathleen A. House
Illinois Wesleyan University
Bloomington, Illinois
AMSTERDAM • BOSTON • HEIDELBERG • LONDON
NEW YORK • OXFORD • PARIS • SAN DIEGO
SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
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10 11 12 9 8 7 6 5 4 3 2 1
Contents
Preface ................................................................................................. xv
Chapter 1: Where It All Comes From ........................................................... 1
1.1 The Structure of the Earth ........................................................................ 1
1.2 Composition of the Earth’s Crust .............................................................. 4
1.3 Rocks and Minerals ................................................................................. 4
1.4 Weathering ............................................................................................ 5
1.5 Obtaining Metals .................................................................................... 6
1.6 Some Metals Today ............................................................................... 10
1.7 Nonmetallic Inorganic Minerals ............................................................... 12
References for Further Reading ............................................................... 15
Problems .............................................................................................. 15
Chapter 2: Atomic and Molecular Structure .................................................. 17
2.1 Atomic Structure ................................................................................... 17
2.2
2.3
2.4
2.5
2.1.1 Quantum Numbers ........................................................................... 18
2.1.2 Hydrogen-Like Orbitals .................................................................... 21
Properties of Atoms ............................................................................... 23
2.2.1 Electron Configurations .................................................................... 23
2.2.2 Ionization Energy ............................................................................. 26
2.2.3 Electron Affinity .............................................................................. 28
2.2.4 Electronegativity .............................................................................. 29
Molecular Structure ............................................................................... 31
2.3.1 Molecular Orbitals ........................................................................... 32
2.3.2 Orbital Overlap ................................................................................ 35
2.3.3 Polar Molecules ............................................................................... 38
2.3.4 Geometry of Molecules Having Single Bonds ...................................... 40
2.3.5 Valence Shell Electron Pair Repulsion (VSEPR) ................................... 43
Symmetry ............................................................................................ 44
Resonance ............................................................................................ 51
References for Further Reading ............................................................... 57
Problems .............................................................................................. 57
Chapter 3: Ionic Bonding , Crystals, and Intermolecular Forces .......................... 63
3.1 Ionic Bonds .......................................................................................... 63
3.1.1 Energetics of the Ionic Bond ............................................................. 64
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Contents
3.1.2 Radius Ratio Effects ......................................................................... 68
3.1.3 Crystal Structures ............................................................................. 71
3.2 Intermolecular Interactions ...................................................................... 76
3.2.1 Dipole-Dipole Forces ........................................................................ 76
3.2.2 Dipole-Induced Dipole Forces ............................................................ 77
3.2.3 London Dispersion Forces ................................................................. 78
3.2.4 Hydrogen Bonding ........................................................................... 79
3.2.5 Solubility Parameters ........................................................................ 85
References for Further Reading ............................................................... 88
Problems .............................................................................................. 88
Chapter 4: Reactions and Energy Relationships ............................................. 91
4.1 Thermodynamic Considerations ............................................................... 91
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.1.1 The Boltzmann Distribution Law ........................................................ 91
4.1.2 Reactions and ΔG ............................................................................ 96
4.1.3 Relationship between ΔG and T ......................................................... 98
4.1.4 Bond Enthalpies .............................................................................. 99
Combination Reactions ......................................................................... 103
Decomposition Reactions ...................................................................... 105
Redox Reactions ................................................................................. 107
Hydrolysis Reactions ............................................................................ 108
Replacement Reactions ......................................................................... 109
Metathesis .......................................................................................... 110
Neutralization Reactions ....................................................................... 112
References for Further Reading ............................................................. 114
Problems ............................................................................................ 114
Chapter 5: Acids, Bases, and Nonaqueous Solvents ....................................... 119
5.1 Acid-Base Chemistry ........................................................................... 119
5.1.1 Factors Affecting Acid Strength ....................................................... 122
5.1.2 Factors Affecting Base Strength ....................................................... 125
5.1.3 Molten Salt Protonic Acids .............................................................. 126
5.1.4 Lewis Theory ................................................................................ 127
5.1.5 Hard-Soft Acid-Base Principle (HSAB) ............................................. 130
5.1.6 Applications of the Hard-Soft Interaction Principle (HSIP) ................... 132
5.2 Nonaqueous Solvents ........................................................................... 136
5.2.1 The Solvent Concept ...................................................................... 136
5.2.2 The Coordination Model ................................................................. 139
5.2.3 Liquid Ammonia ............................................................................ 140
5.2.4 Reactions in Liquid Ammonia .......................................................... 141
5.2.5 Liquid Hydrogen Fluoride ............................................................... 144
5.2.6 Liquid Sulfur Dioxide ..................................................................... 145
5.3 Superacids .......................................................................................... 148
References for Further Reading ............................................................. 149
Problems ............................................................................................ 149
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Contents
Chapter 6: Hydrogen ............................................................................. 153
6.1 Elemental and Positive Hydrogen .......................................................... 153
6.2 Occurrence and Properties .................................................................... 158
6.3 Hydrides ............................................................................................ 160
6.3.1 Ionic Hydrides ............................................................................... 160
6.3.2 Interstitial Hydrides ........................................................................ 162
6.3.3 Covalent Hydrides .......................................................................... 163
References for Further Reading ............................................................. 166
Problems ............................................................................................ 167
Chapter 7: The Group IA and IIA Metals ................................................... 169
7.1 General Characteristics ......................................................................... 170
7.2 Oxides and Hydroxides ........................................................................ 175
7.3 Halides ............................................................................................... 178
7.4 Sulfides .............................................................................................. 179
7.5 Nitrides and Phosphides ....................................................................... 180
7.6 Carbides, Cyanides, Cyanamides, and Amides ......................................... 181
7.7 Carbonates, Nitrates, Sulfates, and Phosphates ......................................... 182
7.8 Organic Derivatives ............................................................................. 183
References for Further Reading ............................................................. 186
Problems ............................................................................................ 187
Chapter 8: Boron ................................................................................. 189
8.1 Elemental Boron .................................................................................. 189
8.2 Bonding in Boron Compounds .............................................................. 191
8.3 Boron Compounds ............................................................................... 191
8.3.1 Borides ......................................................................................... 192
8.3.2 Boron Halides ................................................................................ 192
8.3.3 Boron Hydrides ............................................................................. 194
8.3.4 Boron Nitrides ............................................................................... 196
8.3.5 Polyhedral Boranes ......................................................................... 199
References for Further Reading ............................................................. 203
Problems ............................................................................................ 204
Chapter 9: Aluminum, Gallium, Indium, and Thallium ................................... 207
9.1 The Elements ...................................................................................... 207
9.2 Oxides ............................................................................................... 211
9.3 Hydrides ............................................................................................ 214
9.4 Halides ............................................................................................... 215
9.5 Other Compounds ................................................................................ 217
9.6 Organometallic Compounds .................................................................. 219
References for Further Reading ............................................................. 222
Problems ............................................................................................ 222
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Contents
Chapter 10: Carbon .............................................................................. 225
10.1 The Element ..................................................................................... 225
10.2 Industrial Uses of Carbon ................................................................... 229
10.2.1 Advanced Composites ................................................................... 229
10.2.2 Manufactured Carbon .................................................................... 230
10.2.3 Chemical Uses of Carbon .............................................................. 230
10.3 Carbon Compounds ............................................................................ 231
10.3.1 Ionic Carbides .............................................................................. 231
10.3.2 Covalent Carbides ........................................................................ 232
10.3.3 Interstitial Carbides ....................................................................... 233
10.3.4 Oxides of Carbon ......................................................................... 233
10.3.5 Carbon Halides ............................................................................ 239
10.3.6 Carbon Nitrides ............................................................................ 239
10.3.7 Carbon Sulfides ............................................................................ 241
10.4 Fullerenes ......................................................................................... 242
References for Further Reading ............................................................ 243
Problems ........................................................................................... 244
Chapter
11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
Chapter
12.1
12.2
12.3
12.4
11: Silicon, Germanium, Tin, and Lead ........................................... 247
The Elements .................................................................................... 247
Hydrides of the Group IVA Elements ................................................... 251
Oxides of the Group IVA Elements ...................................................... 252
11.3.1 The +2 Oxides ............................................................................. 252
11.3.2 The +4 Oxides ............................................................................. 253
11.3.3 Glass .......................................................................................... 256
Silicates ............................................................................................ 258
Zeolites ............................................................................................ 263
Halides of the Group IVA Elements ..................................................... 265
11.6.1 The +2 Halides ............................................................................ 266
11.6.2 The +4 Halides ............................................................................ 268
Organic Compounds ........................................................................... 269
Miscellaneous Compounds .................................................................. 271
References for Further Reading ............................................................ 273
Problems ........................................................................................... 274
12: Nitrogen ............................................................................ 277
Elemental Nitrogen ............................................................................ 277
Nitrides ............................................................................................ 278
Ammonia and Aquo Compounds ......................................................... 279
Hydrogen Compounds ........................................................................ 280
12.4.1
12.4.2
12.4.3
12.4.4
Ammonia .................................................................................... 280
Hydrazine, N2H4 .......................................................................... 283
Diimine, N2H2 ............................................................................. 284
Hydrogen Azide, HN3 ................................................................... 284
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Contents
12.5 Nitrogen Halides ................................................................................ 286
12.5.1 NX3 Compounds .......................................................................... 286
12.5.2 Difluorodiazine, N2F2 .................................................................... 287
12.5.3 Oxyhalides .................................................................................. 287
12.6 Nitrogen Oxides ................................................................................ 288
12.6.1 Nitrous Oxide, N2O ...................................................................... 288
12.6.2 Nitric Oxide, NO .......................................................................... 289
12.6.3 Dinitrogen Trioxide, N2O3 ............................................................. 290
12.6.4 Nitrogen Dioxide, NO2 and N2O4 ................................................... 291
12.6.5 Dinitrogen Pentoxide, N2O5 ........................................................... 292
12.7 Oxyacids .......................................................................................... 293
12.7.1 Hyponitrous Acid, H2N2O2 ............................................................ 293
12.7.2 Nitrous Acid, HNO2 ..................................................................... 294
12.7.3 Nitric Acid, HNO3 ........................................................................ 295
References for Further Reading ............................................................ 297
Problems ........................................................................................... 297
Chapter
13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
13.9
Chapter
14.1
14.2
14.3
14.4
13: Phosphorus, Arsenic, Antimony, and Bismuth ............................. 301
Occurrence ........................................................................................ 301
Preparation and Properties of the Elements ............................................ 302
Hydrides ........................................................................................... 303
Oxides .............................................................................................. 305
13.4.1 The +3 Oxides ............................................................................. 305
13.4.2 The +5 Oxides ............................................................................. 306
Sulfides ............................................................................................ 307
Halides ............................................................................................. 308
13.6.1 Halides of the Type E2X4 .............................................................. 308
13.6.2 Trihalides .................................................................................... 309
13.6.3 Pentahalides and Oxyhalides .......................................................... 312
Phosphonitrilic Compounds ................................................................. 315
Acids and Their Salts ......................................................................... 317
13.8.1 Phosphorous Acid and Phosphites ................................................... 317
13.8.2 Phosphoric Acids and Phosphates ................................................... 319
Fertilizer Production ........................................................................... 323
References for Further Reading ............................................................ 325
Problems ........................................................................................... 326
14: Oxygen .............................................................................. 329
Elemental Oxygen, O2 ........................................................................ 329
Ozone, O3 ......................................................................................... 331
Preparation of Oxygen ........................................................................ 333
Binary Compounds of Oxygen ............................................................. 333
14.4.1 Ionic Oxides ................................................................................ 333
14.4.2 Covalent Oxides ........................................................................... 335
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Contents
14.4.3 Amphoteric Oxides ....................................................................... 336
14.4.4 Peroxides and Superoxides ............................................................. 337
14.5 Positive Oxygen ................................................................................ 338
References for Further Reading ............................................................ 339
Problems ........................................................................................... 339
Chapter
15.1
15.2
15.3
15.4
15.5
15.6
15.7
15: Sulfur, Selenium, and Tellurium ............................................... 341
Occurrence of Sulfur .......................................................................... 341
Occurrence of Selenium and Tellurium ................................................. 343
Elemental Sulfur ................................................................................ 344
Elemental Selenium and Tellurium ....................................................... 346
Reactions of Elemental Selenium and Tellurium ..................................... 347
Hydrogen Compounds ........................................................................ 348
Oxides of Sulfur, Selenium, and Tellurium ............................................ 350
15.7.1 Dioxides ...................................................................................... 350
15.7.2 Trioxides ..................................................................................... 352
15.8 Halogen Compounds .......................................................................... 353
15.9 Nitrogen Compounds .......................................................................... 356
15.10 Oxyhalides of Sulfur and Selenium ..................................................... 359
15.10.1 Oxidation State +4 .................................................................... 359
15.10.2 Oxidation State +6 .................................................................... 361
15.11 Oxyacids of Sulfur, Selenium, and Tellurium ....................................... 362
15.11.1 Sulfurous Acid and Sulfites ........................................................ 362
15.11.2 Dithionous Acid and Dithionites ................................................. 364
15.11.3 Dithionic Acid and Dithionates ................................................... 365
15.11.4 Peroxydisulfuric Acid and Peroxydisulfates .................................. 365
15.11.5 Oxyacids of Selenium and Tellurium ........................................... 366
15.12 Sulfuric Acid ................................................................................... 367
15.12.1 Preparation of Sulfuric Acid ....................................................... 367
15.12.2 Physical Properties of Sulfuric Acid ............................................ 368
15.12.3 Chemical Properties of Sulfuric Acid ........................................... 369
15.12.4 Uses of Sulfuric Acid ................................................................ 371
References for Further Reading .......................................................... 372
Problems ......................................................................................... 372
Chapter
16.1
16.2
16.3
16: Halogens ........................................................................... 375
Occurrence ........................................................................................ 375
The Elements .................................................................................... 376
Interhalogens ..................................................................................... 378
16.3.1
16.3.2
16.3.3
16.3.4
16.3.5
16.3.6
Type XX′ .................................................................................... 378
Type XX′3 ................................................................................... 380
Type XX′5 ................................................................................... 381
Type XX′7 ................................................................................... 381
Structures .................................................................................... 381
Chemical Properties ...................................................................... 382
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Contents
16.4 Polyatomic Cations and Anions ........................................................... 384
16.4.1 Polyatomic Halogen Cations .......................................................... 384
16.4.2 Interhalogen Cations ..................................................................... 384
16.4.3 Polyatomic Halogen Anions ........................................................... 385
16.5 Hydrogen Halides .............................................................................. 387
16.5.1 Physical Properties ........................................................................ 387
16.5.2 Preparation .................................................................................. 389
16.6 Oxides .............................................................................................. 389
16.6.1 Oxygen Fluorides ......................................................................... 390
16.6.2 Chlorine Oxides ........................................................................... 390
16.6.3 Bromine Oxides ........................................................................... 392
16.6.4 Iodine Oxides .............................................................................. 393
16.6.5 Oxyfluorides of the Heavier Halogens ............................................. 393
16.7 Oxyacids and Oxyanions .................................................................... 394
16.7.1 Hypohalous Acids and Hypohalites ................................................. 394
16.7.2 Halous Acids and Halites ............................................................... 395
16.7.3 Halic Acids and Halates ................................................................ 395
16.7.4 Perhalic Acids and Perhalates ......................................................... 396
References for Further Reading ............................................................ 398
Problems ........................................................................................... 398
Chapter
17.1
17.2
17.3
17.4
17: The Noble Gases ................................................................. 401
The Elements .................................................................................... 401
The Xenon Fluorides .......................................................................... 404
Reactions of Xenon Fluorides .............................................................. 407
Oxyfluorides and Oxides ..................................................................... 409
References for Further Reading ............................................................ 410
Problems .......................................................................................... 411
Chapter 18: The Transition Metals ........................................................... 413
18.1 The Metals ........................................................................................ 413
18.2
18.3
18.4
18.5
18.1.1 Structures of Metals ...................................................................... 416
18.1.2 Alloys ......................................................................................... 420
Oxides .............................................................................................. 424
Halides and Oxyhalides ...................................................................... 430
Miscellaneous Compounds .................................................................. 432
The Lanthanides ................................................................................ 434
References for Further Reading ............................................................ 437
Problems .......................................................................................... 437
Chapter 19: Structure and Bonding in Coordination Compounds ...................... 441
19.1 Types of Ligands and Complexes ........................................................ 441
19.2 Naming Coordination Compounds ........................................................ 444
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Contents
19.3 Isomerism ......................................................................................... 446
19.3.1 Geometrical Isomerism .................................................................. 446
19.3.2 Optical Isomerism ......................................................................... 447
19.3.3 Linkage Isomerism ....................................................................... 448
19.3.4 Ionization Isomerism ..................................................................... 449
19.3.5 Coordination Isomerism ................................................................. 450
19.3.6 Polymerization Isomerism .............................................................. 450
19.3.7 Hydrate Isomerism ........................................................................ 450
19.4 Factors Affecting the Stability of Complexes ......................................... 451
19.4.1 The Nature of the Acid-Base Interaction .......................................... 451
19.4.2 The Chelate Effect ........................................................................ 452
19.4.3 Ring Size and Structure ................................................................. 454
19.5 A Valence Bond Approach to Bonding in Complexes ............................. 455
19.6 Back Donation .................................................................................. 461
19.7 Ligand Field Theory ........................................................................... 464
19.7.1 Octahedral Fields .......................................................................... 465
19.7.2 Tetrahedral, Tetragonal, and Square Planar Fields .............................. 466
19.7.3 Factors Affecting Δ ....................................................................... 469
19.7.4 Ligand Field Stabilization Energy ................................................... 470
19.8 Jahn-Teller Distortion ......................................................................... 473
References for Further Reading ............................................................ 474
Problems ........................................................................................... 475
Chapter 20: Synthesis and Reactions of Coordination Compounds .................... 479
20.1 Synthesis of Coordination Compounds .................................................. 479
20.1.1 Reaction of a Metal Salt with a Ligand ............................................ 479
20.1.2 Ligand Replacement Reactions ....................................................... 481
20.1.3 Reaction of Two Metal Compounds ................................................ 481
20.1.4 Oxidation-Reduction Reactions ....................................................... 482
20.1.5 Partial Decomposition ................................................................... 482
20.1.6 Size and Solubility Relationships .................................................... 483
20.1.7 Reactions of Metal Salts with Amine Salts ....................................... 483
20.2 A Survey of Reaction Types ............................................................... 484
20.2.1 Ligand Substitution ....................................................................... 485
20.2.2 Oxidative Addition (Oxad) Reactions .............................................. 486
20.2.3 Insertion Reactions ....................................................................... 488
20.2.4 Group Transfer Reactions .............................................................. 489
20.2.5 Electron Transfer Reactions ............................................................ 490
20.3 A Closer Look at Substitution Reactions ............................................... 493
20.4 Substitution in Square Planar Complexes .............................................. 496
20.4.1 Mechanisms ................................................................................. 497
20.4.2 The Trans Effect .......................................................................... 499
20.4.3 Causes of the Trans Effect ............................................................. 503
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Contents
20.5 Substitution in Octahedral Complexes ................................................... 505
20.5.1 Classification Based on Rates ......................................................... 505
20.5.2 The Effect of LFSE on Rate of Substitution ..................................... 506
20.5.3 The SN1CB Mechanism ................................................................. 509
References for Further Reading ............................................................ 511
Problems ........................................................................................... 512
Chapter
21.1
21.2
21.3
21.4
21.5
21: Organometallic Compounds .................................................... 517
Structure and Bonding in Metal Alkyls ................................................. 518
Preparation of Organometallic Compounds ............................................ 522
Reactions of Metal Alkyls ................................................................... 525
Cyclopentadienyl Complexes (Metallocenes) .......................................... 528
Metal Carbonyl Complexes ................................................................. 531
21.5.1 Binary Metal Carbonyls ................................................................. 531
21.5.2 Structures of Metal Carbonyls ........................................................ 533
21.5.3 Preparation of Metal Carbonyls ...................................................... 536
21.5.4 Reactions of Metal Carbonyls ......................................................... 537
21.6 Metal Olefin Complexes ..................................................................... 541
21.6.1 Structure and Bonding ................................................................... 541
21.6.2 Preparation of Metal Olefin Complexes ........................................... 544
21.7 Complexes of Benzene and Related Aromatics ....................................... 545
References for Further Reading ............................................................ 546
Problems ........................................................................................... 547
Appendix A: Ground State Electron Configurations of Atoms .......................... 551
Appendix B: Ionization Energies ............................................................... 555
Index ................................................................................................. 559
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xiii
Preface
Inorganic chemistry is a broad and complex field. The underlying principles and theories are
normally dealt with at a rather high level in a course that is normally taught at the senior
level. With the emphasis on these topics, there is little time devoted to the descriptive
chemistry of the elements. Recognition of this situation has led to the inclusion of a course
earlier in the curriculum that deals primarily with the descriptive topics. That course is
usually offered at the sophomore level, and it is this course for which this book is an
intended text.
Students in inorganic chemistry courses should have some appreciation of the naturally
occurring materials that serve as sources of inorganic compounds. With that in mind,
Chapter 1, “Where It All Comes From,” gives a unique introduction to inorganic chemistry
in nature. Throughout the book, reference is made to how inorganic substances are produced
from the basic raw materials.
Although theories of structure and bonding are covered in the advanced course, the concepts
are so useful for predicting chemical properties and behavior that they must be included to
some extent in the descriptive chemistry course. These topics are normally covered in the
general chemistry courses, but based on our experience, some review and extension of these
topics is essential in the sophomore course. As a result, Chapter 2 is devoted to the general
topic of covalent bonding and symmetry of molecules. Chapter 3 is devoted to a discussion
of ionic bonding and the intermolecular forces that are so important for predicting properties
of inorganic materials.
Much of descriptive inorganic chemistry deals with reactions, so Chapter 4 presents a
survey of the most important reaction types and the predictive power of thermodynamics.
The utility of acid-base chemistry in classifying chemical behavior is described in Chapter 5.
The chemistry of the elements follows in Chapters 6–17 based on the periodic table. The
remaining chapters are devoted to the transition metals, coordination chemistry, and
organometallic compounds.
Throughout the book, we have tried to make the text clear and easy to read. Our students
who have used the book have persuaded us that this objective has been met. We have also
xv
Preface
tried to show how many aspects of inorganic chemistry can be predicted from important
ideas such the hard-soft interaction principle. These are some of the issues that formed the
basis our work as we attempted to produce a readable, coherent text.
There is no end to the discussion of what should or should not be included in a text of this
type. We believe that the content provides a sound basis for the study of descriptive
inorganic chemistry given the extreme breadth of the field.
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