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CnNIENIs 1 The Evolving Realm of Inorganic Chemistry Summary 6 1 PART I COORDINATION CHEMISTRY 7 2 An Introduction to Coordination Chemistry 2.1 The Historical Perspective 10 2.2 The History of Coordination Compounds Early Compounds 12 The Blomstrand-Jorgensen Chain Theory The Werner Coordination Theory 15 2.3 The Modern View of Coordination Compounds 18 2.4 An Introduction to the Nomenclature of Coordination Compounds Summary 25 . Problems 26 9 12 13 3 Structures of Coordination Compounds 33 3.1 Stereoisomers 33 3.2 Octahedral Coordination Spheres 37 Compounds with Monodentate Ligands Compounds with Chelating Ligands 3.3 Square Planar Coordination Spheres 3.4 Tetrahedral Coordination Spheres 3.5 Other Coordination Spheres 45 3.6 Structural Isomers 48 Summary 50 Problems 51 37 40 44 45 4 BondingTheories for Coordination Compounds 4.1 Early Bonding Theories 58 The Lewis Acid-Base Definition 58 Crystal Field, Valence-Bond, and Molecular Orbital Theories 4.2 Crystal Field Theory 60 Shapes of 3d Orbitals 60 Octahedral Fields 64 Tetragonally Distorted Octahedral and Square Planar Fields Tetrahedral Fields 68 57 21 59 66 vii
Transcript of CnNIENIs - gralib.hcmuns.edu.vngralib.hcmuns.edu.vn/sachmoi/2005/10-05/SOLID STATE.pdf · CnNIENIs...
CnNIENIs
1 The Evolving Realm of Inorganic ChemistrySummary 6
1
PART I COORDINATION CHEMISTRY 7
2 An Introduction to Coordination Chemistry
2.1 The Historical Perspective 10
2.2 The History of Coordination Compounds
Early Compounds 12
The Blomstrand-Jorgensen Chain Theory
The Werner Coordination Theory 15
2.3 The Modern View of Coordination Compounds 18
2.4 An Introduction to the Nomenclature of Coordination Compounds
Summary 25 .
Problems 26
9
12
13
3 Structures of Coordination Compounds 333.1 Stereoisomers 33
3.2 Octahedral Coordination Spheres 37
Compounds with Monodentate Ligands
Compounds with Chelating Ligands
3.3 Square Planar Coordination Spheres
3.4 Tetrahedral Coordination Spheres
3.5 Other Coordination Spheres 453.6 Structural Isomers 48
Summary 50Problems 51
374044
45
4 BondingTheories for CoordinationCompounds
4.1 Early Bonding Theories 58The Lewis Acid-Base Definition 58
Crystal Field, Valence-Bond, and Molecular Orbital Theories
4.2 Crystal Field Theory 60
Shapes of 3d Orbitals 60Octahedral Fields 64
Tetragonally Distorted Octahedral and Square Planar FieldsTetrahedral Fields 68
57
21
59
66
vii
viii Contents
4.3 Consequences and Applications of Crystal Field Splitting
Crystal Field Splitting Energies versus Pairing Energies
Crystal Field Stabilization Energies 71
Factors Affecting the Magnitude of the Crystal Field Splitting Energies
Magnetic Properties 76
Absorption Spectroscopy and the Colors of Coordination Compounds
Summary 82Problems 84
69
69
72
79
5 Rates and Mechanisms of Reactions of Coordination Compounds
5.1 A Brief Survey of Reaction Types 93
5.2 Labile and Inert Coordination Compounds 97
5.3 Substitution Reactions of Octahedral ComplexesPossible Mechanisms 98
Experimental Complications 101Evidence for Dissociative Mechanisms 102
Explanation of Inert versus Labile Complexes
5.4 Redox, or Electron-Transfer, Reactions 111
Outer-Sphere Mechanisms / 111Inner-Sphere Mechanisms 113
5.5 Substitution Reactions in Square Planar Complexes: The KineticTrans Effect 115
Summary 118Problems 119
93
98
107
6 Applications of Coordination Compounds 127
6.1 Applications of Mono dentate Complexes 127
6.2 Two Keys to the Stability of Transition Metal ComplexesHard and Soft Acids and Bases 130
The Chelate Effect 131
6.3 Applications of Multi dentate Complexes 133
6.4 Chelating Agents as Detergent Builders 136
6.5 Bioinorganic Applications of Coordination Chemistry
Oxygen Transport 138
Therapeutic Chelating Agents for Heavy Metals
Platinum Antitumor Agents 143
Summary 144Problems 145
130
137
140
PART" SOLID-STATE CHEMISTRY 151
7 Solid-State Structures 153
7.1 Types of Crystals 153Ionic Crystals 153
Contents ix
Metallic Crystals 155
Covalent Network Crystals 155
Atomic-Molecular Crystals 156
7.2 A-Type Crystal Lattices 157
Space Lattices and Unit Cells
A-Type Lattices 158
7.3 ABn-Type Crystal Lattices 167Cubic, Octahedral, and Tetrahedral HolesRadius Ratios 169
Ionic Radii 171
AB Structures 172
AB2 Structures 178
7.4 Structures Involving Polyatomic Molecules and Ions7.5 Defect Structures 182
7.6 Spinel Structures: Connecting Crystal Field Effectswith Solid-State Structures 182
Summary 185Problems 185
157
168
.180
8 SoLid-State Energetics 193
8.1 Lattice Energy: A Theoretical Evaluation
8.2 Lattice Energy: Thermodynamic CyclesElectron Affinities 203
Heats of Formation for Unknown CompoundsThermochemical Radii 206
8.3 Lattice Energies and Ionic Radii: Connecting Crystal Field Effects
with Solid-State Energetics 206
Summary 209Problems 210
193
200
204
PART III DESCRIPTIVE CHEMISTRY
OF THE REPRESENTATIVE ELEMENTS 215
9 BuiLdinga Ne.tworkof Ideas to Make Senseof the PeriodicTabLe9.1 The Periodic Law 218
Effective Nuclear ChargeAtomic Radii 223
Ionization Energy 224
Electron Affinity 225
Electronegativity 227
9.2 The Uniqueness Principle 228The Small Size of the First Elements 228
The Increased Likelihood of Pi Bonding in the First Elements
The Lack of Availability of d Orbitals in the First Elements
217
220
229
230
x Contents
9.3 The Diagonal Effect 231904 The Inert-Pair Effect 233
9.5 Metal, Nonmetal, and Metalloid Regions
Summary 235Problems 237
235
10 Hydrogenand Hydrides 243
10.1 The Origin of the Elements (and of Us!) 243
10.2 Discovery, Preparation, and Uses of Hydrogen
10.3 Isotopes of Hydrogen 248
lOA Radioactive Processes Involving Hydrogen 251
Alpha and Beta Decay, Nuclear Fission, and DeuteriumTritium 253
246
10.5 Hydrides and the NetworkCovalent Hydrides 255Ionic Hydrides 256
Metallic Hydrides 25710.6 The Role of Hydrogen in VariousAlternative Energy Sources
The Hydrogen Economy 258Nuclear Fusion 260
Summary 260Problems 261
254
11 Oxygen,AqueousSolutions, and the Acid-Base Characterof Oxides
and Hydroxides 267
11.1 Oxygen 267
Discovery 267
Occurrence, Preparation, Properties, and Uses
11.2 Water and Aqueous Solutions 271The Structure of the Water Molecule
Ice and Liquid Water 272
Solubility of Substances in WaterSelf-Ionization of Water 277
11.3 The Acid-Base Character of Oxides and Hydroxides
in Aqueous Solution 278
Oxides: General Expectations from the Network 278
Oxides in Aqueous Solution (Acidic and Basic Anhydrides)
The E-O-H Unit in Aqueous Solution 282An Addition to the Network 283
11.4 The Relative Strengths ofOxoacids and Hydroacids
in Aqueous Solution 285Ox()acids 285
Nomenclature ofOxoacids and Corresponding Salts (Optional)
Hydroacids 288
269
271
274
251
258
279
285
Contents xi
11.5 Ozone 289
11.6 The Greenhouse Effect and Global Warming
Summary 295Problems 296
291
12 Group 1A:The ALkaliMetaLs 303
12.1 Discovery and Isolation of the Elements 303
12.2 Fundamental Properties and the Network 306
Hydrides, Oxides, Hydroxides, and Halides 306
Application of the Uniqueness Principle and Diagonal Effect12.3 Reduction Potentials and the Network 310
12.4 Peroxides and Superoxides 317Peroxides 317
Superoxides 321
12.5 Reactions and Compounds of Practical Importance
12.6 Selected Topic in Depth: Metal-Ammonia Solutions
Summary 325Problems 326
308
321
322
13 Group 2A: The ALkaLine-EarthMetaLs 33113.1 Discovery and Isolation of the Elements
Calcium, Barium, and Strontium 333
Magnesium 333
Beryllium 334Radium 334
13.2 Fundamental Properties and the Network 336
Hydrides, Oxides, Hydroxides, and Halides 338
Uniqueness of Beryllium and Diagonal Relationship to Aluminum
13.3 Reactions and Compounds of Practical Importance 341
Beryllium Disease 341Radiochemical Uses 342
Metallurgical Uses 342
Fireworks and X Rays 343Hard Water 344
13.4 Selected Topic in Depth: The Commercial Uses of Calcium
Compounds 345CaCO3 (Limestone) 345
CaO (Qyicklime) and Ca(OHh (Slaked Lime)
Summary 349Problems 350
331
339
348
14 The Group 3A ELements 35514.1 Discovery and Isolation of the Elements
Boron 355
Aluminum 356
355
xii Contents
Gallium 357
Indium and Thallium 358
14.2 Fundamental Properties and the Network 359
Hydrides, Oxides, Hydroxides, and Halides 361
14.3 Structural Aspects of Boron Chemistry 365
Allotropes 365Borides 366
Borates 368
14.4 Aluminum, Gallium, Indium, and Thallium: Reactions and Compounds of
Practical Importance 369
Aluminum Metal and AlloysAlums 371
Alumina 372
Gallium, Indium, and Thallium Compounds 372
14.5 Selected Topic in Depth: Electron-Deficient Compounds
Summary 380Problems 382
369
15 The Group4A Elements 38715.1 Discovery and Isolation of the Elements
Carbon, Tin, and Lead 388Silicon 390
387
Germanium 390
15.2 Fundamental Properties and the Network
Hydrides 392
Oxides and HydroxidesHalides 395
15.3 An Eighth Component of the Interconnected Network:
In-in Bonding Involving Elements of the Secondand Third Periods 396
15.4 Reactions and Compounds of Practical Importance
Diamond, Graphite, and the Graphenes 399Tin Disease 405
Radiochemical Uses 406
Carbon Compounds 407
Lead Compounds and Toxicology15.5 Silicates, Silica, and Aluminosilicates
Silicates and Silica 410
Aluminosilicates 413
15.6 Selected Topics in Depth: Semiconductors and GlassSemiconductors 415
391
394
408
410
Glass 418
Summary 419Problems 421
373
399
415
Contents xiii
16 Group SA:The Pnicogens 427
16.1 Discovery and Isolation of the Elements
Antimony and Arsenic 428
Phosphorus 429Bismuth 429
Nitrogen 430
16.2 Fundamental Properties and the Network
The Uniqueness Principle 430
pn-dn Bonding Involving Elements of the Secondand Third Periods 432
Other Network Components
Hydrides 434Oxides and Oxoacids
Halides 437
16.3 A Survey of Nitrogen Oxidation States 438
Nitrogen (-3) Compounds: Nitrides and Ammonia
Nitrogen (-2): Hydrazine, N2H4 440
Nitrogen (-1): Hydroxylamine, NH2OH
Nitrogen (+1): Nitrous Oxide, N2O 442
Nitrogen (+2): Nitric Oxide, NO 443
Nitrogen (+3): Dinitrogen Trioxide, N2O3, and Nitrous Acid, HNO2
Nitrogen (+4): Nitrogen Dioxide, NO2 445
Nitrogen (+5): DinitrogenPentoxide, N2Os, and Nitric Acid, HNO,
16.4 Reactions and Compounds of Practical Importance 447
Nitrogen Fixation 447Nitrates and Nitrites 449
Nitrogen Air Bags 450
Matches and Phossy Jaw
Phosphates 452
16.5 Selected Topic in Depth: Photochemical Smog
Summary 460Problems 461
427
430
434
435
438
441
445
446
451
454
17 SuLfur,SeLenium, TeLLurium,and PoLonium
17.1 Discovery and Isolation of the ElementsSulfur 468
Tellurium and Selenium (Earth and Moon)
Polonium 469
17.2 Fundamental Properties and the Network
Hydrides 472Oxides and Oxoacids
467
467
469
470
473
Halides 475
17.3 Allotropes and Compounds Involving Element-Element Bonds
Allotropes 477
Polycations and Anions
477
478
xiv Contents
Catenated Halides and Hydrides 479
Catenated Oxoacids and Corresponding Salts17.4 Sulfur Nitrides 481
17.5 Reactions and Compounds of Practical ImportanceSodium-Sulfur Batteries 483
Photoelectric Uses of Selenium and Tellurium
Sulfuric Acid 485
17.6 Selected Topic in Depth: Acid Rain
Summary 488Problems 490
480
483
484
485
18 Group 7A:The Halogens 49518.1 Discovery and Isolation of the Elements
Chlorine 495
Iodine 497
Bromine 497
Fluorine 498
Astatine 499
18.2 Fundamental Properties and the Network
Hydrides 502Halides 504
Oxides 505
18.3 Oxoacids and Their Salts 506
Hypohalous Acids, HOX, and Hypohalites, OX-
Halous Acids, HOXO, and Halites, XO2 508
Halic Acids, HOXO2, and Halates, XO3 508
Perhalic Acids, HOXO3, and Perhalates, XO4
18.4 Neutral and Ionic Interhalogens 510
18.5 Reactions and Compounds of Practical ImportanceFluoridation 514
Chlorination 516
Bleaches 516
Bromides 517
18.6 Selected Topic in Depth: Chlorofluorocarbons (CFCs)-A Threat to the
Ozone Layer 517
Summary 521Problems 523
495
499
506
509
514
19 Group8A: The Noble Gases 52919.1 Discovery and Isolation of the Elements
Argon 530Helium 531
Krypton, Neon, and Xenon 532Radon 532
19.2 Fundamental Properties and the Network
529
533
19.3 Compounds of Noble Gases
History 535Fluorides 536
Structures 538
Other Compounds 539
19.4 Physical Properties and Elements of Practical Importance
19.5 Selected Topic in Depth: Radon as a Carcinogen 542
Summary 543Problems 545
535
A Wordabout Sources 549
Credit References 555
Lists of Figures,Tables, Formulas,and Constants 557
Index 561
Contents xv
540
