Chemical Kinetics and Reaction Dynamics

Preface 1. Elementary 1.1. Rate of Reaction 1.2. Rate Constant 1.3. Order and Molecularity 1.4. Rate Equations 1.5. Half-life of a Reaction 1.6. Zero Order Reactions 1.7. First Order Reactions 1.8. Radioactive Decay as a First Order Phenomenon 1.9. Second Order Reactions 1.10. Third Order Reactions 1.11. Determination of Order of Reaction 1.12. Experimental Methods of Chemical Kinetics Exercises 2. Temperature Effect on Reaction Rate 2.1. Derivation of Arrhenius Equation 2.2. Experimental Determination of Energy of Activation and Arrhenius Factor 2.3. Potential Energy Surface 2.4. Significance of Energy of Activation Exercises 3. Complex Reactions 3.1. Reversible Reactions 3.2. Parallel Reactions 3.3. Consecutive Reactions 3.4. Steady-State Treatment 3.5. Chain Reactions Reactions Exercises 4. Theories of Reaction Rate 4.1. Equilibrium and Rate of Reaction 4.2. Partition Functions and Statistical Mechanics of Chemical Equilibrium 4.3. Partition Functions and Activated Complex 4.4. Collision Theory 4.5. Transition State Theory 4.6. Unimolecular Reactions and the Collision Theory 4.7. Kinetic and Thermodynamic Control 4.8. Hammond’s Postulate 4.9. Probing of the Transition State Exercises 5. Kinetics of Some Special Reactions 5.1. Kinetics of Photochemical Reactions 5.2. Oscillatory Reactions 5.3. Kinetics of Polymerization 5.4. Kinetics of Solid State Reactions 5.5. Electron Transfer Reactions Exercises 6. Kinetics of Catalyzed Reactions 6.1. Catalysis 6.2. Theories of Catalysis 6.3. Characteristics of Catalytic Reactions 6.4. Mechanism of Catalysis 6.5. Activation Energies of Catalyzed Reactions 6.6. Acid Base Catalysis 6.7. Enzyme Catalysis 6.8. Influence of pH 6.9. Heterogeneous Catalysis 6.10. Micellar Catalysis 6.11. Phase Transfer Catalysis 6.12. Kinetics of Inhibition Exercises 7. Fast Reactions 7.1. Introduction 7.2. Flow Techniques 7.3. Relaxation Method 7.4. Shock Tubes 7.5. Flash Photolysis 7.6. ESR Spectroscopic Technique 7.7. NMR Spectroscopic Techniques Exercises 8. Reactions in Solutions 8.1. Introduction 8.2. Theory of Absolute Reaction Rate 8.3. Influence of Internal Pressure 8.4. Influence of Solvation 8.5. Reactions between Ions 8.6. Entropy Change 8.7. Influence of Ionic Strength (Salt Effect) 8.8. Secondary Salt Effect 8.9. Reactions between the Dipoles 8.10. Kinetic Isotope Effect 8.11. Solvent Isotope Effect 8.12. Hemmett Equation 8.13. Linear Free Energy Relationship 8.14. The Taft Equation 8.15. Compensation Effect Exercises 9. Reaction Dynamics 9.1. Molecular Reaction Dynamics 9.2. Microscopic-Macroscopic Relation 9.3. Reaction Rate and Rate Constant 9.4. Distribution of Velocities of Molecules 9.5. Rate of Reaction for Collisions with a Distribution of Relative Speeds 9.6. Collision Cross Sections 9.7. Activation Energy 9.8. Potential Energy Surface 9.9. Classical Trajectory Calculations 9.10. Potential Energy Surface and Classical Dynamics 9.11. Disposal of Excess Energy 9.12. Influence of Rotational Energy 9.13. Experimental Chemical Dynamics Suggested Readings Index