Elementary Physical Chemistry

This Book Is Designed For A One-semester Course, For Undergraduates, Not Necessarily Chemistry Majors, Who Need To Know Something About Physical Chemistry. The Emphasis Is Not On Mathematical Rigor, But Subtleties And Conceptual Difficulties Are Not Hidden. It Covers The Essential Topics In Physical Chemistry, Including The State Of Matter, Thermodynamics, Chemical Kinetics, Phase And Chemical Equilibria, Introduction To Quantum Theory, And Molecular Spectroscopy. Supplementary Materials Are Available Upon Request For All Instructors Who Adopt This Book As A Course Text. Please Send Your Request To Sales@wspc.com. Contents 10 Preface 8 Chapter 1 State of Matter. Properties of Gases 16 1.1. State of Matter 16 1.2. Description of Some States of Matter 17 1.3. Units 17 1.4. Ideal or Perfect Gas Law 18 1.5. Evaluation of the Gas Constant, R 18 1.6. Mixtures of Gases 19 1.7. The Kinetic Theory of Gases 20 1.8. Molecular Collisions 22 1.9. Diffusion of Gases. Graham’s Law 23 1.10. Molecular Basis of Graham’s Law 24 1.11. Real Gases 25 Chapter 2 The First Law of Thermodynamics 26 2.1. Classification 26 2.2. System and Surrounding 27 2.3. Work and Heat 27 2.4. Measurement of Work 28 2.5. Reversible Process 29 2.6. Measurement of Heat 29 2.7. Internal Energy 30 Convention about signs 30 2.8. Exact and Inexact Differentials 31 2.9. Relation of ΔU to qV (q at constant volume) 32 2.10. Heat Capacity 33 2.11. Enthalpy Changes in Chemical Reactions 33 2.12. Standard Enthalpy 33 2.13. Variation of Enthalpy with Temperature 34 Chapter 3 The Second Law of Thermodynamics 35 3.1. Statements of the Second Law 36 3.2. Carnot Cycle 37 3.3. Engine Efficiency 37 3.3.1. Reversible Process 39 3.3.2. Irreversible Process 40 3.3.3. General Changes in Entropy 41 3.3.4. Isolated Systems 42 3.4. Determination of Entropy 42 3.4.1. Entropy change in Phase Transitions (solid–liquid, liquid–vapor, solid–vapor) 42 3.4.2. Entropy change in (Ideal) Gas Expansion 43 Chapter 4 The Third Law of Thermodynamics 44 4.1. Standard Entropy 45 4.2. Molecular Interpretation of Entropy 45 4.3. The Surroundings 46 4.4. The Entropy of the Surroundings 47 Chapter 5 The Free Energy Functions 48 5.1. The Gibbs Free Energy 48 5.2. Free Energy Changes in Chemical Reactions 50 5.3. Variation of G with T and P 52 5.4. Generalization of the Free Energy. Activity 52 5.5. Partial Molar, Molal Quantities 53 5.6. The Chemical Potential 54 5.7. Relation of ΔGo to the Equilibrium Constant, K 55 5.8. Variation of K with T 56 Chapter 6 Phase and Chemical Equilibria 58 6.1. Phase Equilibrium 58 6.1.1. The Phase Rule 58 6.1.2. The Clapeyron Equation 59 6.2. Chemical Equilibrium. Mixtures 61 6.2.1. Ideal Solutions. Raoult’s Law 61 6.2.2. Ideal Dilute Solutions. Henry’s Law 62 6.2.3. Colligative Properties 64 6.2.4. Elevation of Boiling Point. Depression of Freezing Point 64 6.2.5. Osmotic Pressure 67 6.2.6. Chemical Reaction Equilibria 69 6.2.7. Elements of Electrochemistry. Electrochemical Cells 71 6.2.8. Half-Reactions. Redox Reactions 72 6.2.9. Cells at Equilibrium 73 Chapter 7 Chemical Kinetics 75 7.1. The Rates of Reactions 75 7.2. Order of Reaction 76 7.3. Units of the Reaction Rate Constant, k 77 7.4. Determination of the Rate Law 78 7.4.1. Isolation Method 78 7.4.2. Initial Rate Method 78 7.5. Integrated Rate Law 79 7.5.1. First-Order Reaction 79 7.6. Half-Lives 81 7.7. Other Reaction Orders 82 7.7.1. Zero-Order Reactions 82 7.7.2. Third-Order Reactions 82 7.8. Concentration of Products 83 7.9. Temperature-Dependent Reaction Rates. The Arrhenius Equation 84 7.10. Reaction Rate Theories 85 7.10.1. Collision Theory 86 7.10.2. Activated Complex Theory 87 7.11. Rate Law Mechanisms 88 7.12. The Steady State Approximation 89 7.13. The Rate-Determining Step (or Equilibrium) Approximation 91 7.14. Unimolecular Reactions 92 7.14.1. The Lindemann Mechanism 92 7.15. Chain Reactions 94 Chapter 8 Introduction to Quantum Theory 97 8.1. Historical Development 97 8.2. Failure of Classical Theories 98 8.2.1. Black-Body Radiation 98 8.2.2. Photo-Electric Effect 99 8.2.3. Heat Capacity of Solids 100 8.2.4. Wave or Particle? 101 8.3. The Rutherford Atom 101 8.4. The Bohr Theory of the Hydrogen Atom 103 8.5. Louis de Broglie 104 8.6. The Schr ̈odinger Equation 107 8.7. Summary and Conclusions 108 8.8. Schr ̈odinger’s Cat 109 Chapter 9 Applications of Quantum Theory 112 9.1. Translational Motion. Particle-in-a-Box 112 9.2. Hydrogenic Atoms (H, He+, Li2+, etc.) 113 9.3. One-Electron Wave-Functions 114 9.4. Ionization Energy 114 9.5. Shells and Subshells 114 9.6. Shapes of Orbitals 115 Radial Distribution Function 115 9.7. Electron Spin 116 9.8. Structure, Transitions and Selection Rules 117 9.9. Many-Electron Atoms 117 9.10. Pauli Exclusion Principle 117 9.11. Selection Rules for Spectroscopic Transitions 118 Chapter 10 Quantum Theory. The Chemical Bond 119 10.1. Valence Bond Theory 120 10.2. Polyatomic Molecules 122 10.3. Molecular Orbital Theory 123 10.4. Bonding and Anti-bonding Orbitals 124 10.5. Bond Order 126 10.6. Polar Covalent Molecules 127 10.7. Structure of Polyatomic Molecules 128 10.8. Normalization. Normal Constants 128 10.9. Normalization Molecules (MO) 128 Chapter 11 Elements of Molecular Spectroscopy 130 11.1. Vibration–Rotation Spectra of Diatomic Molecules 130 11.2. Rotational Selection Rules 130 11.3. Vibrational Selection Rules 131 11.4. Further Requirements 131 11.5. Pure Rotational Spectra 132 11.6. Vibration–Rotation Spectra 132 Chapter 12 Elements of Intermolecular Forces 135 12.1. Types of Intermolecular Forces 135 12.1.1. Electrostatic Forces 135 12.1.1.1. Ion–Ion Forces 135 12.1.1.2. Ion-Dipole Forces 135 12.1.1.3. Dipole–Dipole Forces 135 12.1.2. van der Waals Forces 136 12.1.2.1. Orientation Forces 136 12.1.2.2. Induction Forces 136 12.1.2.3. London Dispersion Forces 137 12.2. Hydrogen Bonding 137 12.3. Intermolecular Forces and Liquid Properties 138 12.4. Properties of Liquids 139 12.5. Classification of Solids by Types of Intermolecular Forces 140 Appendix A Homework Problem Sets 142 Problem Set I. Chapter 1 142 Problem Set II. Chapter 2 143 Problem Set III. Chapters 3, 4, 5 144 Problem Set IV. Chapter 6 145 Problem Set V. Chapter 7 147 Problem Set VI. Chapters 8, 9 149 Problem Set VII. Chapters 10, 11, 12 150 Appendix B Thermodynamic Data 152 Appendix C Standard Reduction Potentials 154 Index 156 9814299669,9789814299664 World Scientific 2010 Suitable for undergraduates, not necessarily chemistry majors, who need to know something about physical chemistry, this book covers the essential topics in physical chemistry, including the state of matter, thermodynamics, chemical kinetics, phase and chemical equilibria, introduction to quantum theory, and molecular spectroscopy.