ISBN-13: 9781119650324 / Angielski / Miękka / 2022 / 832 str.
ISBN-13: 9781119650324 / Angielski / Miękka / 2022 / 832 str.
ContentsPreface to the Second Edition xvAcknowledgments xviiAbout the Companion Website xixChapter 1 The Structure of Matter 11.1 Science as an Art Form 11.2 Atomism 51.3 The Anatomy of an Atom 81.4 The Periodic Table of the Elements 141.5 The Nucleus 171.6 Nuclear Reactions 201.7 Radioactive Decay and the Band of Stability 231.8 The Shell Model of the Nucleus 291.9 The Origin of the Elements 321.9.1 The Big Bang 321.9.2 Big Bang Nucleosynthesis 321.9.3 Stellar Nucleosynthesis 331.9.4 The s-Process and the r-Process 37Exercises 39Bibliography 41Chapter 2 The Structure of the Atom 432.1 The Wave-Like Properties of Light 432.2 The Electromagnetic Spectrum 442.3 The Interference of Waves 452.4 The Line Spectrum of Hydrogen 482.5 Energy Levels in Atoms 512.6 The Bohr Model of the Atom 542.6.1 In-Depth: Derivation of the Bohr Model of the Atom 562.7 The Wave-Like Properties of Matter 602.8 Circular Standing Waves and the Quantization of Angular Momentum 622.9 The Classical Wave Equation 642.10 The Particle in a Box Model 652.10.1 In-Depth: The Quantum Mechanical Behavior of Nanoparticles 672.11 The Heisenberg Uncertainty Principle 682.12 The Schrödinger Equation 702.13 The Hydrogen Atom 742.13.1 The Radial Wave Functions 762.13.2 The Angular Wave Functions 792.14 The Spin Quantum Number 832.15 The Topological Atom 852.15.1 In-Depth: Atomic Units 87Exercises 88Bibliography 90Chapter 3 The Periodicity of the Elements 913.1 Introduction 913.2 Hydrogenic Orbitals in Polyelectronic Atoms 923.2.1 In-Depth: The Helium Atom 943.3 The Quantum Structure of the Periodic Table 953.4 Electron Configurations 983.5 Shielding and Effective Nuclear Charges 1023.6 Ionization Energy 1043.7 Electron Affinity 1093.8 Theoretical Radii 1113.8.1 In-Depth: How the Radius Affects Other Properties 1143.9 Polarizability 1163.10 The Metal-Nonmetal Staircase 1183.11 Global Hardness 1203.12 Electronegativity 1213.13 The Uniqueness Principle 1243.14 Diagonal Properties 1253.15 Relativistic Effects 1263.16 The Inert-Pair Effect 128Exercises 129Bibliography 131Chapter 4 An Introduction to Chemical Bonding 1334.1 The Definition of a Chemical Bond 1334.2 The Thermodynamic Driving Force for Bond Formation 1344.3 Lewis Structures and Formal Charges 1384.3.1 Rules for Drawing Lewis Structures 1404.4 Covalent Bond Lengths and Bond Dissociation Energies 1434.5 Resonance 1444.6 Electronegativity and Polar Covalent Bonding 1474.7 Types of Chemical Bonds--The Triangle of Bonding 1484.8 Atoms in Molecules 153Exercises 159Bibliography 160Chapter 5 Molecular Geometry 1635.1 X-Ray Crystallography and the Determination of Molecular Geometry 1635.2 Linnett'S Double Quartet Theory 1655.3 Valence-Shell Electron Pair Repulsion Theory 1705.3.1 Rules for Determining the Geometry of a Molecule Using VSEPD Theory 1715.4 The Ligand Close-Packing Model 1835.5 A Comparison of the VSEPR and LCP Models 187Exercises 188Bibliography 190Chapter 6 Symmetry and Spectroscopy 1916.1 Symmetry Elements and Symmetry Operations 1916.1.1 Identity, E 1936.1.2 Proper Rotation, Cn 1936.1.3 Reflection, sigma 1956.1.4 Inversion, i 1966.1.5 Improper Rotation, Sn 1966.2 Symmetry Groups 1996.3 Molecular Point Groups 2036.3.1 In-Depth: Dipole Moments 2086.4 Representations of Symmetry Operations 2106.5 Character Tables 2176.5.1 Irreducible Representations and Characters 2176.5.2 Degenerate Representations 2186.5.3 Rules Regarding Irreducible Representations 2196.5.4 Conjugate Matrices and Classes 2206.5.5 Mulliken Symbols 2226.6 Direct Products 2246.7 Reducible Representations and the Great Orthogonality Theorem 2296.8 Molecular Spectroscopy and the Selection Rules 2346.8.1 Infrared Spectroscopy 2366.8.2 Raman Spectroscopy 2406.8.3 A Summary of the Selection Rules for Vibrational Spectroscopy 2416.8.4 In-Depth: Resonance Raman Spectroscopy 2416.9 Determining the Symmetries of the Normal Modes of Vibration 2436.10 Determining a Molecule's Likely Geometry from Its Spectroscopy 2496.11 Generating Symmetry Coordinates Using the Projection Operator Method 252Exercises 263Bibliography 269Chapter 7 Structure and Bonding in Molecules 2717.1 Molecules as Unique Entities 2717.2 Valence Bond Theory 2727.2.1 Diatomic Molecules 2727.2.2 In-Depth: A Mathematical Treatment of VBT 2737.2.3 Polyatomic Atoms and Hybridization 2757.2.4 Variable Hybridization 2817.2.5 Bent's Rule 2837.2.6 Hypervalent Molecules 2867.2.7 Sigma and pi Bonding 2887.2.8 Transition Metal Compounds 2897.2.9 Limitations of Valence Bond Theory 2937.3 Molecular Orbital Theory 2937.3.1 Homonuclear Diatomics 2937.3.2 In-Depth: A Mathematical Treatment of MOT 2947.3.3 Mixing 3027.3.4 Heteronuclear Diatomics 3077.3.5 The Covalent to Ionic Transition in MOT 3107.3.6 Polyatomic Molecules: H3¯. and H3¯+ 3127.3.7 Correlation Diagrams and the Prediction of Molecular Geometry 3167.3.8 A Brief Introduction to the Jahn-Teller Effect 3187.3.9 AHn Molecules and Walsh Diagrams 3207.3.10 In-Depth: Pearson's Symmetry Rules for Predicting the Structures of AHn Molecules 3327.3.11 Polyatomic Molecules Having pi Orbitals 3347.3.12 In-Depth: Pearson's Symmetry Rules for Predicting the Structures of AXn Molecules 3407.3.13 pi Molecular Orbitals and Hückel Theory 3427.3.14 Combining VB Concepts into MO Diagrams 3467.3.15 Hypercoordinated Molecules 3497.3.16 MO Diagrams for Transition Metal Compounds 3527.3.17 Metal-Metal Bonding 3567.3.18 Three-Centered, Two-Electron Bonding in Diborane 3587.4 The Complementarity of VBT and MOT 363Exercises 365Bibliography 367Chapter 8 Structure and Bonding in Solids 3698.1 Crystal Structures 3698.1.1 The 14 Bravais Lattices 3738.1.2 Closest-Packed Structures 3778.1.3 The 32 Crystallographic Point Groups and 230 Space Groups 3818.1.4 The Determination of Crystal Structures 3868.1.5 The Bragg Diffraction Law 3868.1.6 Miller Planes and Indexing Powder Patterns 3878.1.7 In-Depth: Quasicrystals 3928.2 Metallic Bonding 3938.2.1 The Free Electron Model of Metallic Bonding 3958.2.2 Band Theory of Solids 3998.2.3 Conductivity in Solids 4078.2.4 In-Depth: the p-n Junction and n-p-n Bipolar Junction Transistor 4188.3 Ionic Bonding 4218.3.1 In-Depth: High-Temperature Superconductors 4298.3.2 Lattice Enthalpies and the Born-Haber Cycle 4308.3.3 Ionic Radii and Pauling's Rules 4368.3.4 In-Depth: the Silicates 4498.3.5 Defects in Crystals 4508.4 Types of Crystalline Solids 4538.4.1 Intermediate Types of Bonding in Solids 457Exercises 465Bibliography 475Chapter 9 Chemical Structure and Reactivity 4779.1 Acid-Base Chemistry 4789.1.1 Definitions of Acids and Bases 4789.1.2 Measuring the Strengths of Acids and Bases 4859.1.3 Factors Affecting the Strengths of Acids and Bases 4899.1.4 Pearson's Hard-Soft Acid-Base Theory 4959.1.5 The Relationship Between HSAB Theory and FMO Theory 4979.2 Redox Chemistry 4999.2.1 The Relationship Between Acid-Base and Redox Chemistry 4999.2.2 Rationalizing Trends in Standard Reduction Potentials 5009.2.3 Quantum Structure Property Relationships 5059.2.4 The Drago-Wayland Parameters 5079.3 A Generalized View of Chemical Reactivity 509Exercises 515Bibliography 519Chapter 10 Coordination Chemistry 52110.1 An Overview of Coordination Chemistry 52210.1.1 The Historical Development of Coordination Chemistry 52310.1.2 Types of Ligands and Proper Nomenclature 52510.1.3 Stability Constants 52710.1.4 Isomers 53110.1.5 Common Coordination Geometries 53410.1.6 In-Depth: Five-Coordinate Compounds 53710.1.7 The Shapes of the d-Orbitals 54010.2 Models of Bonding in Coordination Compounds 54110.2.1 Crystal Field Theory 54110.2.2 Ligand Field Theory 55510.2.3 Quantitative Measures of LF Strength 56210.3 Electronic Spectroscopy of Coordination Compounds 57210.3.1 Term Symbols 57210.3.2 Tanabe-Sugano Diagrams 57810.3.3 Electronic Absorptions and the Selection Rules 58410.3.4 Using Tanabe-Sugano Diagrams to Interpret or Predict Electronic Spectra 58710.3.5 The Effect of Reduced Symmetry on Electronic Transitions 59310.3.6 The Jahn-Teller Effect 59410.3.7 Charge Transfer Transitions 59610.3.8 Magnetic Properties of Coordination Compounds 59810.3.9 Diamagnetism 60110.3.10 Paramagnetism 60210.3.11 Antiferromagnetism 60210.3.12 Ferromagnetism 60310.3.13 Ferrimagnetism 604Exercises 605Bibliography 610Chapter 11 Reactions of Coordination Compounds 61311.1 An Introduction to Kinetics and Reaction Coordinate Diagrams 61311.1.1 Zero-Order Reactions 61411.1.2 First-Order Reactions (Irreversible) 61511.1.3 First-Order Reactions (Reversible and Coming to Equilibrium) 61611.1.4 Simple Second-Order Reactions (Irreversible) 61711.1.5 Complex Second-Order Reactions (Reversible and Coming to Equilibrium) 61711.1.6 Complex Second-Order Reactions (Irreversible) 61811.1.7 Pseudo First-Order Reactions 61811.1.8 Consecutive First-Order Reactions and the Steady-State Approximation 61911.1.9 Competing Mechanisms 61911.1.10 Summary of the Common Rate Laws 62011.1.11 The Arrhenius Equation 62011.1.12 Activation Parameters 62111.2 Octahedral Substitution Reactions 62311.2.1 Associative (A) Mechanisms 62411.2.2 Interchange (I) Mechanisms 62411.2.3 Dissociative (D) Mechanisms 62511.2.4 Acid and Base Catalysis 62811.2.5 Ligand Field Activation Energies 62911.3 Square Planar Substitution Reactions 63111.3.1 The Trans Effect 63511.3.2 The Effects of the Leaving Group and the Nucleophile 63711.3.3 MOT and Square Planar Substitution 63811.4 Electron Transfer Reactions 64011.4.1 Outer-Sphere Electron Transfer 64111.4.2 The Franck-Condon Principle 64111.4.3 Marcus Theory 64511.4.4 Inner-Sphere Electron Transfer 64811.4.5 Mixed-Valence Compounds 652Exercises 655Bibliography 657Chapter 12 Organometallic Chemistry 65912.1 Introduction to Organometallic Chemistry 65912.2 Electron Counting and the 18-Electron Rule 66012.3 Carbonyl Ligands 66312.4 Nitrosyl Ligands 66812.5 Hydride and Dihydrogen Ligands 67012.6 Phosphine Ligands 67212.7 Ethylene and Related Ligands 67412.8 Cyclopentadiene and Related Ligands 67812.9 Carbenes, Carbynes, and Carbidos 682Exercises 684Bibliography 687Chapter 13 Reactions of Organometallic Compounds 68913.1 Some General Principles 68913.2 Organometallic Reactions Involving Changes at the Metal 69013.2.1 Ligand Substitution Reactions 69013.2.2 Oxidative Addition and Reductive Elimination 69213.3 Organometallic Reactions Involving Changes at the Ligand 70513.3.1 Insertion and Elimination Reactions 70513.3.2 Nucleophilic Attack on the Ligands 70913.3.3 Electrophilic Attack on the Ligands 71013.4 Metathesis Reactions 71113.4.1 pi-Bond Metathesis 71113.4.2 Ziegler-Natta Polymerization of Alkenes 71213.4.3 sigma-Bond Metathesis 71313.5 A Summary of Organometallic Reaction Mechanisms 71413.6 Organometallic Catalytic Cycles 71413.6.1 Catalytic Hydrogenation 71613.6.2 Hydroformylation 71713.6.3 The Wacker-Smidt Process 71913.6.4 The Monsanto Acetic Acid Process 72013.6.5 Palladium-Catalyzed Cross-Coupling Mechanisms 72113.7 The Isolobal Analogy and the Relationship to Main Group Chemistry 72513.8 Closing Remarks 728Exercises 729Bibliography 732Appendix: A Derivation of the Classical Wave Equation 733Bibliography 734Appendix: B Derivation of the Schrödinger Equation 735Appendix: C Postulates of Quantum Mechanics 739Bibliography 741Appendix: D Atomic Term Symbols and Spin-Orbit Coupling 743Extracting Term Symbols Using Russell-Saunders Coupling 744Extracting Term Symbols Using jj Coupling 747Correlation Between RS (LS) Coupling and jj Coupling 749Appendix: E Character Tables 751Bibliography 763Appendix: F Direct Product Tables 765Bibliography 769Appendix: G Reducing Representations by the Process of Diagonalization 771Appendix: H Correlation Tables 775Bibliography 781Appendix: I The Harmonic Oscillator Model 783Bibliography 786Appendix: J Molecular Term Symbols 787Bibliography 789Appendix: K The 230 Space Groups 791Bibliography 795Index 797
Brian W. Pfennig, PhD, has 25 years of experience teaching advanced general chemistry, inorganic chemistry, and organometallic photochemistry at colleges including Franklin and Marshall, Haverford, Vassar, and Ursinus.
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