Discover the foundational principles of inorganic chemistry with this intuitively organized new edition of a celebrated textbook
In the newly revised Second Edition of Principles of Inorganic Chemistry, experienced researcher and chemist Dr. Brian W. Pfennig delivers an accessible and engaging exploration of inorganic chemistry perfect for sophomore-level students. This redesigned book retains all of the rigor of the first edition but reorganizes it to assist readers with learning and retention. In-depth boxed sections include original mathematical derivations for more advanced students, while topics like atomic and molecular term symbols, symmetry coordinates in vibrational spectroscopy, polyatomic MO theory, band theory, and Tanabe-Sugano diagrams are all covered.
Readers will find many worked examples throughout the text, as well as numerous unanswered problems at varying levels of difficulty. Informative, colorful illustrations also help to highlight and explain the concepts discussed within.
The new edition includes an increased emphasis on the comparison of the strengths and weaknesses of different chemical models, the interconnectedness of valence bond theory and molecular orbital theory, as well as a more thorough discussion of the atoms in molecules topological model.
Readers will also find: - A thorough introduction to and treatment of group theory, with an emphasis on its applications to chemical bonding and spectroscopy - A comprehensive exploration of chemical bonding that compares and contrasts the traditional classification of ionic, covalent, and metallic bonding - In-depth examinations of atomic and molecular orbitals and a nuanced discussion of the interrelationship between VBT, MOT, and band theory - A section on the relationship between a molecule’s structure and bonding and its chemical reactivity
With its in-depth boxed discussions, this textbook is also ideal for senior undergraduate and first-year graduate students in inorganic chemistry, Principles of Inorganic Chemistry is a must-have resource for anyone seeking a principles-based approach with theoretical depth. Furthermore, it will be useful for students of physical chemistry, materials science, and chemical physics.
Table of Contents
Preface to the Second Edition xv
Acknowledgments xvii
About the Companion Website xix
Chapter 1The Structure of Matter 1
1.1 Science as an Art Form 1
1.2 Atomism 5
1.3 The Anatomy of an Atom 8
1.4 The Periodic Table of the Elements 14
1.5 The Nucleus 17
1.6 Nuclear Reactions 20
1.7 Radioactive Decay and the Band of Stability 23
1.8 The Shell Model of the Nucleus 29
1.9 The Origin of the Elements 32
1.9.1 The Big Bang 32
1.9.2 Big Bang Nucleosynthesis 32
1.9.3 Stellar Nucleosynthesis 33
1.9.4 The s-Process and the r-Process 37
Exercises 39
Bibliography 41
Chapter 2The Structure of the Atom 43
2.1 The Wave-Like Properties of Light 43
2.2 The Electromagnetic Spectrum 44
2.3 The Interference of Waves 45
2.4 The Line Spectrum of Hydrogen 48
2.5 Energy Levels in Atoms 51
2.6 The Bohr Model of the Atom 54
2.6.1 In-Depth: Derivation of the Bohr Model of the Atom 56
2.7 The Wave-Like Properties of Matter 60
2.8 Circular Standing Waves and the Quantization of Angular Momentum 62
2.9 The Classical Wave Equation 64
2.10 The Particle in a Box Model 65
2.10.1 In-Depth: The Quantum Mechanical Behavior of Nanoparticles 67
2.11 The Heisenberg Uncertainty Principle 68
2.12 The Schrödinger Equation 70
2.13 The Hydrogen Atom 74
2.13.1 The Radial Wave Functions 76
2.13.2 The Angular Wave Functions 79
2.14 The Spin Quantum Number 83
2.15 The Topological Atom 85
2.15.1 In-Depth: Atomic Units 87
Exercises 88
Bibliography 90
Chapter 3The Periodicity of the Elements 91
3.1 Introduction 91
3.2 Hydrogenic Orbitals in Polyelectronic Atoms 92
3.2.1 In-Depth: The Helium Atom 94
3.3 The Quantum Structure of the Periodic Table 95
3.4 Electron Configurations 98
3.5 Shielding and Effective Nuclear Charges 102
3.6 Ionization Energy 104
3.7 Electron Affinity 109
3.8 Theoretical Radii 111
3.8.1 In-Depth: How the Radius Affects Other Properties 114
3.9 Polarizability 116
3.10 The Metal-Nonmetal Staircase 118
3.11 Global Hardness 120
3.12 Electronegativity 121
3.13 The Uniqueness Principle 124
3.14 Diagonal Properties 125
3.15 Relativistic Effects 126
3.16 The Inert-Pair Effect 128
Exercises 129
Bibliography 131
Chapter 4 An Introduction to Chemical Bonding 133
4.1 The Definition of a Chemical Bond 133
4.2 The Thermodynamic Driving Force for Bond Formation 134
4.3 Lewis Structures and Formal Charges 138
4.3.1 Rules for Drawing Lewis Structures 140
4.4 Covalent Bond Lengths and Bond Dissociation Energies 143
4.5 Resonance 144
4.6 Electronegativity and Polar Covalent Bonding 147
4.7 Types of Chemical Bonds - The Triangle of Bonding 148
4.8 Atoms in Molecules 153
Exercises 159
Bibliography 160
Chapter 5 Molecular Geometry 163
5.1 X-Ray Crystallography and the Determination of Molecular Geometry 163
5.2 Linnett’S Double Quartet Theory 165
5.3 Valence-Shell Electron Pair Repulsion Theory 170
5.3.1 Rules for Determining the Geometry of a Molecule Using VSEPD Theory 171
5.4 The Ligand Close-Packing Model 183
5.5 A Comparison of the VSEPR and LCP Models 187
Exercises 188
Bibliography 190
Chapter 6 Symmetry and Spectroscopy 191
6.1 Symmetry Elements and Symmetry Operations 191
6.1.1 Identity, E 193
6.1.2 Proper Rotation, Cn 193
6.1.3 Reflection, σ 195
6.1.4 Inversion, i 196
6.1.5 Improper Rotation, Sn 196
6.2 Symmetry Groups 199
6.3 Molecular Point Groups 203
6.3.1 In-Depth: Dipole Moments 208
6.4 Representations of Symmetry Operations 210
6.5 Character Tables 217
6.5.1 Irreducible Representations and Characters 217
6.5.2 Degenerate Representations 218
6.5.3 Rules Regarding Irreducible Representations 219
6.5.4 Conjugate Matrices and Classes 220
6.5.5 Mulliken Symbols 222
6.6 Direct Products 224
6.7 Reducible Representations and the Great Orthogonality Theorem 229
6.8 Molecular Spectroscopy and the Selection Rules 234
6.8.1 Infrared Spectroscopy 236
6.8.2 Raman Spectroscopy 240
6.8.3 A Summary of the Selection Rules for Vibrational Spectroscopy 241
6.8.4 In-Depth: Resonance Raman Spectroscopy 241
6.9 Determining the Symmetries of the Normal Modes of Vibration 243
6.10 Determining a Molecule’s Likely Geometry from Its Spectroscopy 249
6.11 Generating Symmetry Coordinates Using the Projection Operator Method 252
Exercises 263
Bibliography 269
Chapter 7 Structure and Bonding in Molecules 271
7.1 Molecules as Unique Entities 271
7.2 Valence Bond Theory 272
7.2.1 Diatomic Molecules 272
7.2.2 In-Depth: A Mathematical Treatment of VBT 273
7.2.3 Polyatomic Atoms and Hybridization 275
7.2.4 Variable Hybridization 281
7.2.5 Bent’s Rule 283
7.2.6 Hypervalent Molecules 286
7.2.7 Sigma and pi Bonding 288
7.2.8 Transition Metal Compounds 289
7.2.9 Limitations of Valence Bond Theory 293
7.3 Molecular Orbital Theory 293
7.3.1 Homonuclear Diatomics 293
7.3.2 In-Depth: A Mathematical Treatment of MOT 294
7.3.3 Mixing 302
7.3.4 Heteronuclear Diatomics 307
7.3.5 The Covalent to Ionic Transition in MOT 310
7.3.6 Polyatomic Molecules: H3- and H3+ 312
7.3.7 Correlation Diagrams and the Prediction of Molecular Geometry 316
7.3.8 A Brief Introduction to the Jahn-Teller Effect 318
7.3.9 AHn Molecules and Walsh Diagrams 320
7.3.10 In-Depth: Pearson’s Symmetry Rules for Predicting the Structures of AHn Molecules 332
7.3.11 Polyatomic Molecules Having pi Orbitals 334
7.3.12 In-Depth: Pearson’s Symmetry Rules for Predicting the Structures of AXn Molecules 340
7.3.13 pi Molecular Orbitals and Hückel Theory 342
7.3.14 Combining VB Concepts into MO Diagrams 346
7.3.15 Hypercoordinated Molecules 349
7.3.16 MO Diagrams for Transition Metal Compounds 352
7.3.17 Metal-Metal Bonding 356
7.3.18 Three-Centered, Two-Electron Bonding in Diborane 358
7.4 The Complementarity of VBT and MOT 363
Exercises 365
Bibliography 367
Chapter 8 Structure and Bonding in Solids 369
8.1 Crystal Structures 369
8.1.1 The 14 Bravais Lattices 373
8.1.2 Closest-Packed Structures 377
8.1.3 The 32 Crystallographic Point Groups and 230 Space Groups 381
8.1.4 The Determination of Crystal Structures 386
8.1.5 The Bragg Diffraction Law 386
8.1.6 Miller Planes and Indexing Powder Patterns 387
8.1.7 In-Depth: Quasicrystals 392
8.2 Metallic Bonding 393
8.2.1 The Free Electron Model of Metallic Bonding 395
8.2.2 Band Theory of Solids 399
8.2.3 Conductivity in Solids 407
8.2.4 In-Depth: the p-n Junction and n-p-n Bipolar Junction Transistor 418
8.3 Ionic Bonding 421
8.3.1 In-Depth: High-Temperature Superconductors 429
8.3.2 Lattice Enthalpies and the Born-Haber Cycle 430
8.3.3 Ionic Radii and Pauling’s Rules 436
8.3.4 In-Depth: the Silicates 449
8.3.5 Defects in Crystals 450
8.4 Types of Crystalline Solids 453
8.4.1 Intermediate Types of Bonding in Solids 457
Exercises 465
Bibliography 475
Chapter 9 Chemical Structure and Reactivity 477
9.1 Acid-Base Chemistry 478
9.1.1 Definitions of Acids and Bases 478
9.1.2 Measuring the Strengths of Acids and Bases 485
9.1.3 Factors Affecting the Strengths of Acids and Bases 489
9.1.4 Pearson’s Hard-Soft Acid-Base Theory 495
9.1.5 The Relationship Between HSAB Theory and FMO Theory 497
9.2 Redox Chemistry 499
9.2.1 The Relationship Between Acid-Base and Redox Chemistry 499
9.2.2 Rationalizing Trends in Standard Reduction Potentials 500
9.2.3 Quantum Structure Property Relationships 505
9.2.4 The Drago-Wayland Parameters 507
9.3 A Generalized View of Chemical Reactivity 509
Exercises 515
Bibliography 519
Chapter 10 Coordination Chemistry 521
10.1 An Overview of Coordination Chemistry 522
10.1.1 The Historical Development of Coordination Chemistry 523
10.1.2 Types of Ligands and Proper Nomenclature 525
10.1.3 Stability Constants 527
10.1.4 Isomers 531
10.1.5 Common Coordination Geometries 534
10.1.6 In-Depth: Five-Coordinate Compounds 537
10.1.7 The Shapes of the d-Orbitals 540
10.2 Models of Bonding in Coordination Compounds 541
10.2.1 Crystal Field Theory 541
10.2.2 Ligand Field Theory 555
10.2.3 Quantitative Measures of LF Strength 562
10.3 Electronic Spectroscopy of Coordination Compounds 572
10.3.1 Term Symbols 572
10.3.2 Tanabe-Sugano Diagrams 578
10.3.3 Electronic Absorptions and the Selection Rules 584
10.3.4 Using Tanabe-Sugano Diagrams to Interpret or Predict Electronic Spectra 587
10.3.5 The Effect of Reduced Symmetry on Electronic Transitions 593
10.3.6 The Jahn-Teller Effect 594
10.3.7 Charge Transfer Transitions 596
10.3.8 Magnetic Properties of Coordination Compounds 598
10.3.9 Diamagnetism 601
10.3.10 Paramagnetism 602
10.3.11 Antiferromagnetism 602
10.3.12 Ferromagnetism 603
10.3.13 Ferrimagnetism 604
Exercises 605
Bibliography 610
Chapter 11 Reactions of Coordination Compounds 613
11.1 An Introduction to Kinetics and Reaction Coordinate Diagrams 613
11.1.1 Zero-Order Reactions 614
11.1.2 First-Order Reactions (Irreversible) 615
11.1.3 First-Order Reactions (Reversible and Coming to Equilibrium) 616
11.1.4 Simple Second-Order Reactions (Irreversible) 617
11.1.5 Complex Second-Order Reactions (Reversible and Coming to Equilibrium) 617
11.1.6 Complex Second-Order Reactions (Irreversible) 618
11.1.7 Pseudo First-Order Reactions 618
11.1.8 Consecutive First-Order Reactions and the Steady-State Approximation 619
11.1.9 Competing Mechanisms 619
11.1.10 Summary of the Common Rate Laws 620
11.1.11The Arrhenius Equation 620
11.1.12 Activation Parameters 621
11.2 Octahedral Substitution Reactions 623
11.2.1 Associative (A) Mechanisms 624
11.2.2 Interchange (I) Mechanisms 624
11.2.3 Dissociative (D) Mechanisms 625
11.2.4 Acid and Base Catalysis 628
11.2.5 Ligand Field Activation Energies 629
11.3 Square Planar Substitution Reactions 631
11.3.1 The Trans Effect 635
11.3.2 The Effects of the Leaving Group and the Nucleophile 637
11.3.3 MOT and Square Planar Substitution 638
11.4 Electron Transfer Reactions 640
11.4.1 Outer-Sphere Electron Transfer 641
11.4.2 The Franck-Condon Principle 641
11.4.3 Marcus Theory 645
11.4.4 Inner-Sphere Electron Transfer 648
11.4.5 Mixed-Valence Compounds 652
Exercises 655
Bibliography 657
Chapter 12 Organometallic Chemistry 659
12.1 Introduction to Organometallic Chemistry 659
12.2 Electron Counting and the 18-Electron Rule 660
12.3 Carbonyl Ligands 663
12.4 Nitrosyl Ligands 668
12.5 Hydride and Dihydrogen Ligands 670
12.6 Phosphine Ligands 672
12.7 Ethylene and Related Ligands 674
12.8 Cyclopentadiene and Related Ligands 678
12.9 Carbenes, Carbynes, and Carbidos 682
Exercises 684
Bibliography 687
Chapter 13 Reactions of Organometallic Compounds 689
13.1 Some General Principles 689
13.2 Organometallic Reactions Involving Changes at the Metal 690
13.2.1 Ligand Substitution Reactions 690
13.2.2 Oxidative Addition and Reductive Elimination 692
13.3 Organometallic Reactions Involving Changes at the Ligand 705
13.3.1 Insertion and Elimination Reactions 705
13.3.2 Nucleophilic Attack on the Ligands 709
13.3.3 Electrophilic Attack on the Ligands 710
13.4 Metathesis Reactions 711
13.4.1 π-Bond Metathesis 711
13.4.2 Ziegler-Natta Polymerization of Alkenes 712
13.4.3 σ-Bond Metathesis 713
13.5 A Summary of Organometallic Reaction Mechanisms 714
13.6 Organometallic Catalytic Cycles 714
13.6.1 Catalytic Hydrogenation 716
13.6.2 Hydroformylation 717
13.6.3 The Wacker-Smidt Process 719
13.6.4 The Monsanto Acetic Acid Process 720
13.6.5 Palladium-Catalyzed Cross-Coupling Mechanisms 721
13.7 The Isolobal Analogy and the Relationship to Main Group Chemistry 725
13.8 Closing Remarks 728
Exercises 729
Bibliography 732
Appendix: A Derivation of the Classical Wave Equation 733
Bibliography 734
Appendix: B Derivation of the Schrödinger Equation 735
Appendix: C Postulates of Quantum Mechanics 739
Bibliography 741
Appendix: D Atomic Term Symbols and Spin-Orbit Coupling 743
Extracting Term Symbols Using Russell-Saunders Coupling 744
Extracting Term Symbols Using jj Coupling 747
Correlation Between RS (LS) Coupling and jj Coupling 749
Appendix: E Character Tables 751
Bibliography 763
Appendix: F Direct Product Tables 765
Bibliography 769
Appendix: G Reducing Representations by the Process of Diagonalization 771
Appendix: H Correlation Tables 775
Bibliography 781
Appendix: I The Harmonic Oscillator Model 783
Bibliography 786
Appendix: J Molecular Term Symbols 787
Bibliography 789
Appendix: K The 230 Space Groups 791
Bibliography 795
Index 797
