Inorganic Chemistry (eBook)

Front Cover 1
Inorganic Chemistry 4
Copyright Page 5
Contents 6
Preface 12
PART 1 Structure of Atoms and Molecules 16
CHAPTER 1 Light, Electrons, and Nuclei 18
1.1 Some Early Experiments in Atomic Physics 18
1.2 The Nature of Light 22
1.3 The Bohr Model 26
1.4 Particle-Wave Duality 30
1.5 Electronic Properties of Atoms 32
1.6 Nuclear Binding Energy 37
1.7 Nuclear Stability 39
1.8 Types of Nuclear Decay 40
1.9 Predicting Decay Modes 44
CHAPTER 2 Basic Quantum Mechanics and Atomic Structure 50
2.1 The Postulates 50
2.2 The Hydrogen Atom 59
2.3 The Helium Atom 64
2.4 Slater Wave Functions 66
2.5 Electron Configurations 67
2.6 Spectroscopic States 71
CHAPTER 3 Covalent Bonding in Diatomic Molecules 80
3.1 The Basic Ideas of Molecular Orbital Methods 80
3.2 The H[sub(2)][sup(+)] and H[sub(2)] Molecules 88
3.3 Diatomic Molecules of Second-Row Elements 91
3.4 Photoelectron Spectroscopy 98
3.5 Heteronuclear Diatomic Molecules 99
3.6 Electronegativity 102
3.7 Spectroscopic States for Molecules 106
CHAPTER 4 A Survey of Inorganic Structures and Bonding 110
4.1 Structures of Molecules Having Single Bonds 110
4.2 Resonance and Formal Charge 120
4.3 Complex Structures—A Preview of Coming Attractions 132
4.4 Electron-Deficient Molecules 140
4.5 Structures Having Unsaturated Rings 142
4.6 Bond Energies 144
CHAPTER 5 Symmetry and Molecular Orbitals 152
5.1 Symmetry Elements 152
5.2 Orbital Symmetry 160
5.3 A Brief Look at Group Theory 163
5.4 Construction of Molecular Orbitals 168
5.5 Orbitals and Angles 173
5.6 Simple Calculations Using the Hückel Method 176
PART 2 Condensed Phases 192
CHAPTER 6 Dipole Moments and Intermolecular Interactions 194
6.1 Dipole Moments 194
6.2 Dipole-Dipole Forces 199
6.3 Dipole-Induced Dipole Forces 201
6.4 London (Dispersion) Forces 202
6.5 The van der Waals Equation 206
6.6 Hydrogen Bonding 208
6.7 Cohesion Energy and Solubility Parameters 218
CHAPTER 7 Ionic Bonding and Structures of Solids 226
7.1 Energetics of Crystal Formation 226
7.2 Madelung Constants 231
7.3 The Kapustinskii Equation 234
7.4 Ionic Sizes and Crystal Environments 235
7.5 Crystal Structures 239
7.6 Solubility of Ionic Compounds 244
7.7 Proton and Electron Affinities 249
7.8 Structures of Metals 252
7.9 Defects in Crystals 255
7.10 Phase Transitions in Solids 258
7.11 Heat Capacity 260
7.12 Hardness of Solids 263
CHAPTER 8 Dynamic Processes in Inorganic Solids 270
8.1 Characteristics of Solid-State Reactions 270
8.2 Kinetic Models for Reactions in Solids 273
8.3 Thermal Methods of Analysis 281
8.4 Effects of Pressure 282
8.5 Reactions in Some Solid Inorganic Compounds 285
8.6 Phase Transitions 287
8.7 Reactions at Interfaces 291
8.8 Diffusion in Solids 292
8.9 Sintering 295
8.10 Drift and Conductivity 297
PART 3 Acids, Bases, and Solvents 302
CHAPTER 9 Acid-Base Chemistry 304
9.1 Arrhenius Theory 304
9.2 Brønsted-Lowry Theory 307
9.3 Factors Affecting Strength of Acids and Bases 311
9.4 Acid-Base Character of Oxides 316
9.5 Proton Affinities 317
9.6 Lewis Theory 320
9.7 Catalytic Behavior of Acids and Bases 324
9.8 The Hard-Soft Interaction Principle (HSIP) 328
9.9 Electronic Polarizabilities 338
9.10 The Drago Four-Parameter Equation 339
CHAPTER 10 Chemistry in Nonaqueous Solvents 346
10.1 Some Common Nonaqueous Solvents 346
10.2 The Solvent Concept 347
10.3 Amphoteric Behavior 350
10.4 The Coordination Model 350
10.5 Chemistry in Liquid Ammonia 351
10.6 Liquid Hydrogen Fluoride 357
10.7 Liquid Sulfur Dioxide 360
10.8 Superacids 364
PART 4 Chemistry of the Elements 368
CHAPTER 11 Chemistry of Metallic Elements 370
11.1 The Metallic Elements 370
11.2 Band Theory 371
11.3 Group IA and IIA Metals 374
11.4 Zintl Phases 382
11.5 Aluminum and Beryllium 385
11.6 The First-Row Transition Metals 387
11.7 Second- and Third-Row Transition Metals 389
11.8 Alloys 391
11.9 Chemistry of Transition Metals 394
11.10 The Lanthanides 402
CHAPTER 12 Organometallic Compounds of the Main Group Elements 410
12.1 Preparation of Organometallic Compounds 411
12.2 Organometallic Compounds of Group IA Metals 413
12.3 Organometallic Compounds of Group IIA Metals 415
12.4 Organometallic Compounds of Group IIIA Metals 418
12.5 Organometallic Compounds of Group IVA Metals 423
12.6 Organometallic Compounds of Group VA Elements 424
12.7 Organometallic Compounds of Zn, Cd, and Hg 425
CHAPTER 13 Chemistry of Nonmetallic Elements I. Hydrogen, Boron, Oxygen and Carbon 430
13.1 Hydrogen 430
13.2 Boron 437
13.3 Oxygen 448
13.4 Carbon 459
CHAPTER 14 Chemistry of Nonmetallic Elements II. Groups IVA and VA 478
14.1 The Group IVA Elements 478
14.2 Nitrogen 495
14.3 Phosphorus, Arsenic, Antimony, and Bismuth 512
CHAPTER 15 Chemistry of Nonmetallic Elements III. Groups VIA to VIIIA 538
15.1 Sulfur, Selenium, and Tellurium 538
15.2 The Halogens 560
15.3 The Noble Gases 579
PART 5 Chemistry of Coordination Compounds 590
CHAPTER 16 Introduction to Coordination Chemistry 592
16.1 Structures of Coordination Compounds 592
16.2 Metal-Ligand Bonds 597
16.3 Naming Coordination Compounds 598
16.4 Isomerism 600
16.5 A Simple Valence Bond Description of Coordinate Bonds 607
16.6 Magnetism 612
16.7 A Survey of Complexes of First-Row Metals 614
16.8 Complexes of Second- and Third-Row Metals 614
16.9 The 18-Electron Rule 616
16.10 Back Donation 619
16.11 Complexes of Dinitrogen, Dioxygen, and Dihydrogen 624
CHAPTER 17 Ligand Fields and Molecular Orbitals 632
17.1 Splitting of d Orbital Energies in Octahedral Fields 632
17.2 Splitting of d Orbital Energies in Fields of Other Symmetry 636
17.3 Factors Affecting & #916
17.4 Consequences of Crystal Field Splitting 642
17.5 Jahn-Teller Distortion 645
17.6 Spectral Bands 646
17.7 Molecular Orbitals in Complexes 648
CHAPTER 18 Interpretation of Spectra 660
18.1 Splitting of Spectroscopic States 660
18.2 Orgel Diagrams 665
18.3 Racah Parameters and Quantitative Methods 667
18.4 The Nephelauxetic Effect 670
18.5 Tanabe-Sugano Diagrams 673
18.6 The Lever Method 677
18.7 Jørgensen's Method 680
18.8 Charge Transfer Absorption 681
CHAPTER 19 Composition and Stability of Complexes 686
19.1 Composition of Complexes in Solution 686
19.2 Job's Method of Continuous Variations 688
19.3 Equilibria Involving Complexes 690
19.4 Distribution Diagrams 696
19.5 Factors Affecting the Stability of Complexes 700
CHAPTER 20 Synthesis and Reactions of Coordination Compounds 710
20.1 Synthesis of Coordination Compounds 710
20.2 Substitution Reactions in Octahedral Complexes 716
20.3 Ligand Field Effects 723
20.4 Acid-Catalyzed Reactions of Complexes 727
20.5 Base-Catalyzed Reactions of Complexes 728
20.6 The Compensation Effect 730
20.7 Linkage Isomerization 731
20.8 Substitution in Square Planar Complexes 734
20.9 The Trans Effect 736
20.10 Electron Transfer Reactions 740
20.11 Reactions in Solid Coordination Compounds 743
CHAPTER 21 Complexes Containing Metal-Carbon and Metal-Metal Bonds 754
21.1 Binary Metal Carbonyls 754
21.2 Structures of Metal Carbonyls 757
21.3 Bonding of Carbon Monoxide to Metals 759
21.4 Preparation of Metal Carbonyls 762
21.5 Reactions of Metal Carbonyls 763
21.6 Structure and Bonding in Metal Alkene Complexes 769
21.7 Preparation of Metal Alkene Complexes 775
21.8 Chemistry of Cyclopentadienyl and Related Complexes 776
21.9 Bonding in Ferrocene 779
21.10 Reactions of Ferrocene and Other Metallocenes 782
21.11 Complexes of Benzene and Related Aromatics 785
21.12 Compounds Containing Metal-Metal Bonds 788
CHAPTER 22 Coordination Compounds in Catalysis and Biochemistry 794
22.1 Elementary Steps in Catalysis Processes 795
22.2 Homogeneous Catalysis 807
22.3 Bioinorganic Chemistry 817
Appendix A: Ionization Energies 832
Appendix B: Character Tables for Selected Point Groups 836
Index 842
A 842
B 843
C 845
D 848
E 849
F 850
G 850
H 851
I 852
J 853
K 853
L 854
M 855
N 856
O 857
P 858
Q 859
R 859
S 860
T 863
U 864
V 864
W 864
X 864
Y 865
Z 865