Inorganic Chemistry

Inorganic Chemistry......Page 4
Copyright Page......Page 5
Contents......Page 6
Preface......Page 12
PART 1 Structure of Atoms and Molecules......Page 16
1.1 Some Early Experiments in Atomic Physics......Page 18
1.2 The Nature of Light......Page 22
1.3 The Bohr Model......Page 26
1.4 Particle-Wave Duality......Page 30
1.5 Electronic Properties of Atoms......Page 32
1.6 Nuclear Binding Energy......Page 37
1.7 Nuclear Stability......Page 39
1.8 Types of Nuclear Decay......Page 40
1.9 Predicting Decay Modes......Page 44
2.1 The Postulates......Page 50
2.2 The Hydrogen Atom......Page 59
2.3 The Helium Atom......Page 64
2.4 Slater Wave Functions......Page 66
2.5 Electron Configurations......Page 67
2.6 Spectroscopic States......Page 71
3.1 The Basic Ideas of Molecular Orbital Methods......Page 80
3.2 The H[sub(2)][sup(+)] and H[sub(2)] Molecules......Page 88
3.3 Diatomic Molecules of Second-Row Elements......Page 91
3.4 Photoelectron Spectroscopy......Page 98
3.5 Heteronuclear Diatomic Molecules......Page 99
3.6 Electronegativity......Page 102
3.7 Spectroscopic States for Molecules......Page 106
4.1 Structures of Molecules Having Single Bonds......Page 110
4.2 Resonance and Formal Charge......Page 120
4.3 Complex Structures—A Preview of Coming Attractions......Page 132
4.4 Electron-Deficient Molecules......Page 140
4.5 Structures Having Unsaturated Rings......Page 142
4.6 Bond Energies......Page 144
5.1 Symmetry Elements......Page 152
5.2 Orbital Symmetry......Page 160
5.3 A Brief Look at Group Theory......Page 163
5.4 Construction of Molecular Orbitals......Page 168
5.5 Orbitals and Angles......Page 173
5.6 Simple Calculations Using the Hückel Method......Page 176
PART 2 Condensed Phases......Page 192
6.1 Dipole Moments......Page 194
6.2 Dipole-Dipole Forces......Page 199
6.3 Dipole-Induced Dipole Forces......Page 201
6.4 London (Dispersion) Forces......Page 202
6.5 The van der Waals Equation......Page 206
6.6 Hydrogen Bonding......Page 208
6.7 Cohesion Energy and Solubility Parameters......Page 218
7.1 Energetics of Crystal Formation......Page 226
7.2 Madelung Constants......Page 231
7.3 The Kapustinskii Equation......Page 234
7.4 Ionic Sizes and Crystal Environments......Page 235
7.5 Crystal Structures......Page 239
7.6 Solubility of Ionic Compounds......Page 244
7.7 Proton and Electron Affinities......Page 249
7.8 Structures of Metals......Page 252
7.9 Defects in Crystals......Page 255
7.10 Phase Transitions in Solids......Page 258
7.11 Heat Capacity......Page 260
7.12 Hardness of Solids......Page 263
8.1 Characteristics of Solid-State Reactions......Page 270
8.2 Kinetic Models for Reactions in Solids......Page 273
8.3 Thermal Methods of Analysis......Page 281
8.4 Effects of Pressure......Page 282
8.5 Reactions in Some Solid Inorganic Compounds......Page 285
8.6 Phase Transitions......Page 287
8.7 Reactions at Interfaces......Page 291
8.8 Diffusion in Solids......Page 292
8.9 Sintering......Page 295
8.10 Drift and Conductivity......Page 297
PART 3 Acids, Bases, and Solvents......Page 302
9.1 Arrhenius Theory......Page 304
9.2 Brønsted-Lowry Theory......Page 307
9.3 Factors Affecting Strength of Acids and Bases......Page 311
9.4 Acid-Base Character of Oxides......Page 316
9.5 Proton Affinities......Page 317
9.6 Lewis Theory......Page 320
9.7 Catalytic Behavior of Acids and Bases......Page 324
9.8 The Hard-Soft Interaction Principle (HSIP)......Page 328
9.9 Electronic Polarizabilities......Page 338
9.10 The Drago Four-Parameter Equation......Page 339
10.1 Some Common Nonaqueous Solvents......Page 346
10.2 The Solvent Concept......Page 347
10.4 The Coordination Model......Page 350
10.5 Chemistry in Liquid Ammonia......Page 351
10.6 Liquid Hydrogen Fluoride......Page 357
10.7 Liquid Sulfur Dioxide......Page 360
10.8 Superacids......Page 364
PART 4 Chemistry of the Elements......Page 368
11.1 The Metallic Elements......Page 370
11.2 Band Theory......Page 371
11.3 Group IA and IIA Metals......Page 374
11.4 Zintl Phases......Page 382
11.5 Aluminum and Beryllium......Page 385
11.6 The First-Row Transition Metals......Page 387
11.7 Second- and Third-Row Transition Metals......Page 389
11.8 Alloys......Page 391
11.9 Chemistry of Transition Metals......Page 394
11.10 The Lanthanides......Page 402
CHAPTER 12 Organometallic Compounds of the Main Group Elements......Page 410
12.1 Preparation of Organometallic Compounds......Page 411
12.2 Organometallic Compounds of Group IA Metals......Page 413
12.3 Organometallic Compounds of Group IIA Metals......Page 415
12.4 Organometallic Compounds of Group IIIA Metals......Page 418
12.5 Organometallic Compounds of Group IVA Metals......Page 423
12.6 Organometallic Compounds of Group VA Elements......Page 424
12.7 Organometallic Compounds of Zn, Cd, and Hg......Page 425
13.1 Hydrogen......Page 430
13.2 Boron......Page 437
13.3 Oxygen......Page 448
13.4 Carbon......Page 459
14.1 The Group IVA Elements......Page 478
14.2 Nitrogen......Page 495
14.3 Phosphorus, Arsenic, Antimony, and Bismuth......Page 512
15.1 Sulfur, Selenium, and Tellurium......Page 538
15.2 The Halogens......Page 560
15.3 The Noble Gases......Page 579
PART 5 Chemistry of Coordination Compounds......Page 590
16.1 Structures of Coordination Compounds......Page 592
16.2 Metal-Ligand Bonds......Page 597
16.3 Naming Coordination Compounds......Page 598
16.4 Isomerism......Page 600
16.5 A Simple Valence Bond Description of Coordinate Bonds......Page 607
16.6 Magnetism......Page 612
16.8 Complexes of Second- and Third-Row Metals......Page 614
16.9 The 18-Electron Rule......Page 616
16.10 Back Donation......Page 619
16.11 Complexes of Dinitrogen, Dioxygen, and Dihydrogen......Page 624
17.1 Splitting of d Orbital Energies in Octahedral Fields......Page 632
17.2 Splitting of d Orbital Energies in Fields of Other Symmetry......Page 636
17.3 Factors Affecting Δ......Page 640
17.4 Consequences of Crystal Field Splitting......Page 642
17.5 Jahn-Teller Distortion......Page 645
17.6 Spectral Bands......Page 646
17.7 Molecular Orbitals in Complexes......Page 648
18.1 Splitting of Spectroscopic States......Page 660
18.2 Orgel Diagrams......Page 665
18.3 Racah Parameters and Quantitative Methods......Page 667
18.4 The Nephelauxetic Effect......Page 670
18.5 Tanabe-Sugano Diagrams......Page 673
18.6 The Lever Method......Page 677
18.7 Jørgensen's Method......Page 680
18.8 Charge Transfer Absorption......Page 681
19.1 Composition of Complexes in Solution......Page 686
19.2 Job's Method of Continuous Variations......Page 688
19.3 Equilibria Involving Complexes......Page 690
19.4 Distribution Diagrams......Page 696
19.5 Factors Affecting the Stability of Complexes......Page 700
20.1 Synthesis of Coordination Compounds......Page 710
20.2 Substitution Reactions in Octahedral Complexes......Page 716
20.3 Ligand Field Effects......Page 723
20.4 Acid-Catalyzed Reactions of Complexes......Page 727
20.5 Base-Catalyzed Reactions of Complexes......Page 728
20.6 The Compensation Effect......Page 730
20.7 Linkage Isomerization......Page 731
20.8 Substitution in Square Planar Complexes......Page 734
20.9 The Trans Effect......Page 736
20.10 Electron Transfer Reactions......Page 740
20.11 Reactions in Solid Coordination Compounds......Page 743
21.1 Binary Metal Carbonyls......Page 754
21.2 Structures of Metal Carbonyls......Page 757
21.3 Bonding of Carbon Monoxide to Metals......Page 759
21.4 Preparation of Metal Carbonyls......Page 762
21.5 Reactions of Metal Carbonyls......Page 763
21.6 Structure and Bonding in Metal Alkene Complexes......Page 769
21.7 Preparation of Metal Alkene Complexes......Page 775
21.8 Chemistry of Cyclopentadienyl and Related Complexes......Page 776
21.9 Bonding in Ferrocene......Page 779
21.10 Reactions of Ferrocene and Other Metallocenes......Page 782
21.11 Complexes of Benzene and Related Aromatics......Page 785
21.12 Compounds Containing Metal-Metal Bonds......Page 788
CHAPTER 22 Coordination Compounds in Catalysis and Biochemistry......Page 794
22.1 Elementary Steps in Catalysis Processes......Page 795
22.2 Homogeneous Catalysis......Page 807
22.3 Bioinorganic Chemistry......Page 817
Appendix A: Ionization Energies......Page 832
Appendix B: Character Tables for Selected Point Groups......Page 836
A......Page 842
B......Page 843
C......Page 845
D......Page 848
E......Page 849
G......Page 850
H......Page 851
I......Page 852
K......Page 853
L......Page 854
M......Page 855
N......Page 856
O......Page 857
P......Page 858
R......Page 859
S......Page 860
T......Page 863
X......Page 864
Z......Page 865