Inorganic Chemistry

This concise textbook meets several objectives. First, the topics included were selected in order to provide essential information in the major areas of inorganic chemistry (molecular structure, acid-base chemistry, coordination chemistry, ligand field theory, solid state chemistry, etc.). These topics form the basis for competency in inorganic chemistry at a level commensurate with the one semester course taught at most colleges and universities. The second objective has been to stress fundamental principles in the discussion of several topics. For example, the hard-soft interaction principle is employed in discussion of acid-base chemistry, stability of complexes, solubility, and predicting reaction products. Third, the presentation of topics is made with an effort to be clear and concise so that the book is portable and user friendly. This book presents in convenient form a readable account of the essentials of inorganic chemistry that can serve as both as a textbook for a one semester course upper level course and as a guide for self study. Figures, tables, and end-of-chapter problems round out this pedagogically rich, thematically balanced text for advanced undergraduate and graduate level students. • Concise coverage maximizes student understanding and minimizes the inclusion of details students are unlikely to use. • Discussion of elements begins with survey chapters focused on the main groups, while later chapters cover the elements in greater detail. • Each chapter opens with narrative introductions and includes figures, tables, and end-of-chapter problem sets. 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 Δ 640 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 Inorganic Chemistry provides essential information in the major areas of inorganic chemistry. The author emphasizes fundamental principles—including molecular structure, acid-base chemistry, coordination chemistry, ligand field theory, and solid state chemistry — and presents topics in a clear, concise manner. Concise coverage maximizes student understanding and minimizes the inclusion of details students are unlikely to use. The discussion of elements begins with survey chapters focused on the main groups, while later chapters cover the elements in greater detail. Each chapter opens with narrative introductions and includes figures, tables, and end-of-chapter problem sets. This text is ideal for advanced undergraduate and graduate-level students enrolled in the inorganic chemistry course. The text may also be suitable for biochemistry, medicinal chemistry, and other professionals who wish to learn more about this subject are. Concise coverage maximizes student understanding and minimizes the inclusion of details students are unlikely to use. Discussion of elements begins with survey chapters focused on the main groups, while later chapters cover the elements in greater detail. Each chapter opens with narrative introductions and includes figures, tables, and end-of-chapter problem sets. "Inorganic chemistry is a broad, rapidly developing field that includes theoretical, physical, and synthetic topics. If organic chemistry is defined as the chemistry of hydrocarbon compounds and their derivatives, then inorganic chemistry can be described as the chemistry of "everything else." This includes all of the remaining elements in the periodic table as well as carbon, which plays a major role in many inorganic compounds." "Written for the one-semester inorganic chemistry course, this textbook provides essential information for upper-level undergraduate and graduate students and for individuals pursuing self-study. The author presents the major areas of inorganic chemistry in a clear, concise manner and incorporates pedagogy that reflects his extensive experience teaching the course."--Jacket