Inorganic Chemistry Book

	List of Tables	xii
	Preface	xv
Part 1	Inorganic Ions and Simple Molecules in Chemistry and in Our Environment	1
Chapter 1	Periodic Trends in Fundamental Properties of Atoms and Simple Ions	3
1.1	Why Study Inorganic Chemistry?	3
1.2	The Periodic Table	5
1.3	Quantum Mechanics: Waves/Particles	7
1.4	Electrons in Atoms: Angular Part of the Electronic Wave Function	10
1.5	Radial Part of the Wave Function	15
1.6	Shielding and Slater's Rules	18
1.7	Characteristic Valence Electron Configurations	21
1.8	Valence Electron Configurations, Charges, and Oxidation Numbers of Ions	27
1.9	Types of Atomic Radii, Their Periodic Trends, and Reasons for the Trends	30
1.10	Periodic Trends in Electronegativities of Atoms and Their Explanation	36
1.11	Relativistic Effects on Orbitals	39
1.12	Predicting the Chemistry of Superheavy Elements	41
Chapter 2	Monoatomic Ions and Their Acid-Base Reactivity	55
2.1	Hydration of Cations	55
2.2	Acidity of Cations	56
2.3	Classification of Cations by Acidity Category	61
2.4	Halides that Fail to Undergo Hydrolysis: Oxo Cations	67
2.5	Hydration and Hydrolysis of Monoatomic Nonmetal Anions	68
2.6	Predominance Diagrams for Anions: Partially Protonated Anions	73
2.7	Acidic Nonmetal Hydrides and Basic Metal Oxides	74
2.8	Nomenclature	79
Chapter 3	Polyatomic Ions and Their Acid-Base Properties With Applications to Environmental Chemistry and Analytical Chemistry	89
3.1	Covalent Bond Types and Periodicity of Bond Energies	89
3.2	Covalent Bonding to Ions: The Lewis Acid-Base Concept and Complex Ions	98
3.3	Lewis Structures, Coordination Numbers, and Fluoro Anions	101
3.4	The Shapes of p-Block Molecules and Complex Ions	105
3.5	Formulas of Oxo Anions	111
3.6	Basicity of Oxo Anions	116
3.7	Protonation of Oxo Anions: Hydroxo Anions and Oxo Acids	120
3.8	Most Common Forms of the Elements in Natural Waters	125
3.9	Nomenclature of Fluoro and Oxo Anions and Acids	129
3.10	Lewis Structures and Oxidation Numbers	132
Chapter 4	Ionic Solids and Precipitation Reactions of Hydrated Ions With Applications to Analytical Chemistry, Organic Chemistry, and Water Chemistry	149
4.1	Solubility Rules for Salts of Oxo and Fluoro Anions	149
4.2	Thermodynamics and Solubility Rules for Salts	154
4.3	Entropy and Precipitation: The Structure of Hydrated Ions	157
4.4	Nonacidic Cations, Nonbasic Anions, and the Structure of Liquid Water	161
4.5	Enthalpy and Precipitation: The Importance of Lattice Energies	162
4.6	Ionic Solids: Coulombic Attractions and Lattice Energies	164
4.7	Radius Ratios and Lattice Types	167
4.8	Stability of Lattices and the Solubility Rules	171
4.9	Writing and Interpreting Net Ionic Equations	173
4.10	Nonaqueous Solvents for ionic or Ionizable Compounds	175
Chapter 5	Trends in Coordination Equilibria With Applications to Biochemistry, Environmental Chemistry, Geochemistry, and Medicinal Chemistry	191
5.1	Classification of Ligands	191
5.2	Chelate and Macrocyclic Effects	197
5.3	The Hard and Soft Acid-Base Principle	198
5.4	Relative and Borderline Hardness and Softness	201
5.5	The HSAB Principle and Polar Covalent Bonding	204
5.6	The Need for Two Parameters: Softness and Strength	206
5.7	Applications of HSAB: Solubility of Halides and Chalcogenides	207
5.8	Applications of HSAB: The Qualitative Analysis Scheme for Metal Ions	209
5.9	Applications of HSAB: The Geochemical Classification and Differentiation of the Elements	212
5.10	Metal ions in Biochemistry	215
5.11	Applications of HSAB: Biological Functions and Toxicology of the Elements	220
5.12	Applications of HSAB and Cholation: Medicinal Chemistry	225
Chapter 6	Principles of Oxidation-Reduction Reactivity With Applications to Chemical Safety, Environmental Chemistry, and Industrial Chemistry	243
6.1	Standard Reduction Potentials and Their Diagrammatic Representation	243
6.2	Explosives, Flammable Compounds, and the Handling of Strong Reducing Agents	254
6.3	Redox Predominance Diagrams: Construction; Species that Disproportionate; Nonstanmdard Conditions	261
6.4	Charge-Transfer Spectra and Marginal Redox Stability	264
6.5	Periodicity in the Activity of Metals and the Reduction of Metal Ions	266
6.6	Hard and Soft Acids and Bases and Redox Chemistry	270
6.7	Redox Chemistry of the Nonmetals	273
6.8	Industrial Processes for Extracting Elements from Their Ores	276
6.9	Effects of Concentration and pH on Redox Chemistry: Pourbaix Diagrams	287
6.10	pH Effects on Redox Chemistry: The Synthesis of Oxo Anions and Acids and Corrosion of Metals	297
Chapter 7	Thermochemical Analyses of Reactivity Trends	315
7.1	Thermochemical Analysis of Redox Reactions: Born-Haber Cycle	315
7.2	Thermochemical Analysis of the Activity Series of the Elements	323
7.3	Significance of Atomization Energies in Redox Chemistry	325
7.4	Periodicity and Significance of Ionization Energies and Electron Affinities	327
7.5	Polar Covalent Bond Energies and Pauling Electronegativities	331
7.6	Effects of Changing Substituents and Oxidation Numbers on Electronegativities	337
7.7	Definitions of Electronegativity and Hardness Related to Ionization Energies and Electron Affinities	339
7.8	Thermodynamics of the Lewis Acis-Lewis Base Interaction: Drago's E, C, and T Parameters	341
Chapter 8	Introduction to Transition Metal complexes With Applications to Biochemistry	357
8.1	Introduction	357
8.2	The Crystal Field Theory	359
8.3	High- and Low-Spin Electron Configurations: Magnetic Properties	362
8.4	Electronic Absorption Spectra of Complex Ions	365
8.5	The Spectrochemical Series of Ligands and the Effects of Covalency	369
8.6	Thermodynamic and Structural Consequences of Crystal Field Effects	374
8.7	Crystal Field Splitting in Complexes of Other Geometries	380
8.8	Geometric Preferences: Rates and Mechanisms of Ligand Exchange	387
8.9	Syntheses of d-Block Complexes	391
8.10	Bioinorganic Chemistry and Crystal Field Theory: Heme and Hemoglobin	395
8.11	Nomenclature of Coordination and Organometallic Compounds	398
Part II	Inorganic Molecules and Materials: Theory and Applications	417
Chapter 9	Symmetry With Applications to Art, Environmental Chemistry and Organic Chemistry	419
9.1	Symmetry Operations and Elements	419
9.2	Molecular Point Groups	425
9.3	Elementary Applications of Symmetry: Molecular Polarity, Chirality, and Fluxionality	430
9.4	Character Tables for Symmetry Point Groups	438
9.5	Applications of Symmetry: Infrared and Raman Spectra	443
Chapter 10	Molecular Orbital Theory With Applications to Organic Chemistry and materials Science	459
10.1	Molecular Orbital Theory for Homonuclear Diatomic Molecules	459
10.2	Bond Energies and Lengths, Spectroscopy, and Orbital Mixing in Homonuclear Diatomic Molecules	468
10.3	Heteroatomic Diatomic Molecules and Ions	476
10.4	Molecular Ionization Energies, Electron Affinities, Electronegativities, and Hardness	483
10.5	Molecular Orbital Theory for Linear Molecules	485
10.6	Molecular Orbital Theory for Cyclic Molecules: Generator Orbitals	492
10.7	Orbital Symmetry Rules for Concerted Reactions	498
10.8	Molecular Orbitals for D[subscript nh] Molecules	501
10.9	Molecular Orbitals for Three-Dimensional Molecules in Higher Order Point Groups	505
10.10	Molecular Orbitals for Cluster Compounds	510
10.11	Molecular Orbitals for Metals	513
Chapter 11	Organometallic Chemistry of the d-Block Elements With Applications to Industrial Chemistry, Organic Chemistry, Biochemistry and Environmental Chemistry	531
11.1	Organometallic Compounds of the d-Block Metals: The 18-Electron Rule	531
11.2	Mononuclear Metal Carbonyls and Related Organometallics	534
11.3	Metal Complexes of [pi]-Donor Ligands	539
11.4	Other Ligands Forming One [sigma] Bond in Organometallics: Dinuclear and Polynuclear Organometallics	548
11.5	Bridging Ligands: Alkynes and Carbonyls	556
11.6	Ligands Forming Two or More Bonds to a Metal or Metals: The Isolobal Analogy	559
11.7	Reaction Types of d-Block Organometallic Compounds	563
11.8	Catalytic Cycles	573
11.9	Organometallic Catalysis in Biochemistry and Environmental Chemistry	581
Chapter 12	The Elements and Their Physical Properties With Applications to Materials Science	595
12.1	Interunit Forces and Physical Properties	595
12.2	Physical Properties, Allotropes, and Uses of the Nonmetallic Elements	599
12.3	Metals and Alloys	611
12.4	Magnetism, Electrical Conductivity, and Semiconduction	617
12.5	Homopolyatomic Anions and Cations of the Elements: Metal Complexes	624
12.6	Heterogeneous Catalysis by Metals	631
12.7	Metallic Chains, Sheets, and Clusters	635
Chapter 13	Oxides of the Elements With Applications to Geochemistry, Environmental Chemistry, and Materials Science	657
13.1	Physical States and Structures of the Fluorides and Oxides of the Elements	657
13.2	Covalent Oxides: Periodic Trends in Structure and Physical State	667
13.3	Acidity, Solubility, Practical Uses, and Environmental Chemistry of Volatile Oxides and Oxo Acids	673
13.4	Close Packed Anions, Metal Oxides, and Electrical Conductivity of Solid Ionic Compounds	685
13.5	Spinels, Perovskites, High-Temperature Superconductors, and Cooperative Magnetic Properties in Mixed-Metal Oxides	691
13.6	Polysilicates: Basic Structural Types, Uses, and Chemistry	697
13.7	Aluminosilicates	705
13.8	Oligomeric Polyoxometallate Anions of Other p- and d-Block Elements: Selected Structures and Uses	711
Chapter 14	The Halides, Nitrides, and Sulfides of the Elements With Applications to Materials Science and Biochemistry	729
14.1	Structural Features of Halides	729
14.2	Physical States and Physical Properties of Halides	738
14.3	Methods of Synthesis of Halides	741
14.4	Reactions and Uses of Halides	744
14.5	Catenated and Cluster Halides	748
14.6	More Complex Oxygen Derivatives: Oxo Halides, Silicones, Inorganic Esters, Alkoxides	754
14.7	Nitrides and Carbides of the Elements	761
14.8	Sulfides, Selenides, Tellurides, and Arsenides of the Elements	767
14.9	Relationships among Ionic, Covalent, and Metallic Bonding	775
Chapter 15	Hydrides, Alkyls, and Aryls of the Elements With Applications to Materials Science and Organic Chemistry	789
15.1	Classification of Hydrides: Hydrides of Metals	789
15.2	Electron-Precise and Electron-Rich Molecular Hydrides	792
15.3	Electron-Deficient Molecular Hydrides	799
15.4	Syntheses of the Hydrides and Hydride Anions of the Elements	804
15.5	Reactions and Uses of the Hydrides	807
15.6	Alkyls and Aryls of the Elements: Classification and Structures	810
15.7	Methods of Synthesis of Alkyls and Aryls	816
15.8	Reactions and Uses of the Alkyls and Aryls	820
15.9	Catenated Alkyls and Aryls of the p-Block	823
15.10	Multiply Bonded and Divalent Alkyls and Aryls of the Heavier p-Block Elements	828
Chapter 16	Inorganic Reaction Mechanisms With Applications to Materials Science, Organic Chemistry, Environmental Chemistry, and Biochemistry	839
16.1	Rate Laws and Stoichiometric Reaction Mechanisms for Ligand Substitution Reactions	840
16.2	Intimate Mechanisms for Ligand Substitution Reactions	846
16.3	Entering Group, Leaving Group, and Metal Effects on Ligand Substitution Rates	851
16.4	Spectator Ligand Effects on Ligand Substitution Rates	853
16.5	Classification of Redox Reaction Mechanisms	857
16.6	Outer-Sphere Electron-Transfer Processes	858
16.7	One-Electron Inner-Sphere and Long-Range Electron-Transfer Processes	861
16.8	Two-Electron Inner-Sphere Electron-Transfer Processes	868
Chapter 17	Advanced Topics: Excited Electronic States, Photochemistry, and Activated Molecules With Applications to Materials Science, Atmospheric Chemistry, and Biochemistry	879
17.1	Electronic States and Term Symbols	879
17.2	Electronic States for Diatomic Molecules and Their Consequences	885
17.3	Electronic States for Octahedral Complexes	887
17.4	Tanabe-Sugano Diagrams and Spectra of d-Block Complexes	889
17.5	Luminescence, Lasers, and Spin-Orbit Coupling	898
17.6	Photochemically Assisted Substitution and Redox Processes	901
17.7	Chlorophyll and Photosynthesis	905
17.8	Biochemical Oxygen Transport and Activation	906
17.9	Biochemical Nitrogen Activation	913
Appendix A	Discovery Laboratory Experiments for Part I	927
A.1	Some Reactions of Cations	928
A.2	Nonaqueous Reactions of Metal Ions and Compounds	929
A.3	Some Reactions of Oxo Anions	931
A.4	Reaction of Anions with Cations	932
A.5	Competitive Precipitation and Complexation Reactions	933
A.6	Periodicity in the Activity (Electromotive) Series of Metals	935
A.7	The Widely Varying Colors of d-Block Metal Complexes	938
Appendix B	Character Tables	940
	Answers to Selected Exercises	949
	Index	969