Chemical Kinetics and Transport

ISBN-13: 9781461591009 / Angielski / Miękka / 2012 / 368 str.

Peter Jordan

Opis

This book began as a program of self-education. While teaching under- graduate physical chemistry, I became progressively more dissatisfied with my approach to chemical kinetics. The solution to my problem was to write a detailed set of lecture notes which covered more material, in greater depth, than could be presented in undergraduate physical chemistry. These notes are the foundation upon which this book is built. My background led me to view chemical kinetics as closely related to transport phenomena. While the relationship of these topics is well known, it is often ignored, except for brief discussions of irreversible thermody- namics. In fact, the physics underlying such apparently dissimilar processes as reaction and energy transfer is not so very different. The intermolecular potential is to transport what the potential-energy surface is to reactivity. Instead of beginning the sections devoted to chemical kinetics with a discussion of various theories, I have chosen to treat phenomenology and mechanism first. In this way the essential unity of kinetic arguments, whether applied to gas-phase or solution-phase reaction, can be emphasized. Theories of rate constants and of chemical dynamics are treated last, so that their strengths and weaknesses may be more clearly highlighted. The book is designed for students in their senior year or first year of graduate school. A year of undergraduate physical chemistry is essential preparation. While further exposure to chemical thermodynamics, statistical thermodynamics, or molecular spectroscopy is an asset, it is not necessary.

Spis treści

1. Kinetic Theory of Gases—Equilibrium.- 1.1. Introduction.- 1.2. The Maxwell-Boltzmann Distribution of Velocities.- 1.3. Determination of Pressure.- 1.4. Properties of the Maxwell Distribution.- 1.5. The Molecular Flux and Effusion of Gases.- Problems.- General References.- 2. Kinetic Theory of Gases—Transport.- 2.1. Introduction.- 2.2. Mean Free Path.- 2.3. Collision Frequency.- 2.4. Macroscopic Equations of Transport.- 2.5. Solution of the Transport Equations.- 2.6. Kinetic Theory of Transport and Postulate of Local Equilibrium.- 2.7. Simplified Transport Theory: Dilute Hard-Sphere Gas.- 2.8. Comparison with Experiment.- Appendix. Coordinate Transformation by Jacobian Method.- Problems.- General References.- 3. Electrolytic Conduction and Diffusion.- 3.1. Introduction.- 3.2. Ionic Conduction in Solution—a Review.- 3.3. Nernst-Einstein Relation.- 3.4. Electrolyte Diffusion.- 3.5. Stokes’ Law and the Microscopic Interpretation of ?0.- 3.6. The Mobility of H+ and OH- in Water.- 3.7. The Concentration Dependence of ?.- 3.8. The Wien Effects.- Problems.- General References.- 4. Determination of Rate Laws.- 4.1. Introduction.- 4.2. Stoichiometry, Rate Law, and Mechanism.- 4.3. Elementary Rate Laws and the Principle of Mass Action.- 4.4. Reaction Order and Molecularity.- 4.5. The Principle of Detailed Balance.- 4.6. Experimental Methods for Determining Rate Laws.- 4.7. Integrated Rate Laws—First Order.- 4.8. Isolation Methods.- 4.9. Relaxation Methods.- 4.10. Determination of Rate Law from Data—Two Examples.- 4.11. Temperature Dependence of Rate Constants.- Appendix. Linear Least-Squares Analysis.- Problems.- General References.- 5. Stationary State Mechanisms.- 5.1. Introduction.- 5.2. Consecutive Reactions—First Order.- 5.3. Consecutive Reactions—Arbitrary Order.- 5.4. Unimolecular Decomposition—Gases.- 5.5. Radical Recombination—Gases.- 5.6. Complex Mechanisms—Gaseous Chain Reactions.- 5.7. Simple Mechanisms—Solution.- 5.8. Complex Mechanisms—Solution.- 5.9. Homogeneous Catalysis.- 5.10. Enzyme Catalysis.- 5.11. Heterogeneous Catalysis.- Appendix A. Matrix Solution to the Coupled Rate Equation (5.2).- Appendix B. Approximations to ?+ and ?-.- Problems.- General References.- 6. Photochemistry.- 6.1. Introduction.- 6.2. Measurement of Intensity.- 6.3. Spectroscopic Review.- 6.4. Primary Processes.- 6.5. Secondary Processes.- 6.6. Chemiluminescence.- 6.7. Orbital Symmetry Correlations: Woodward-Hoffman Rules.- 6.8. Laser Activation.- 6.9. Laser-Controlled Isotope Separation.- Problems.- General References.- 7. Nonstationary State Mechanisms.- 7.1. Introduction.- 7.2. Thermal Explosion.- 7.3. Population Explosion—Autocatalysis.- 7.4. The Lotka Problem: Chemical Oscillations.- 7.5. The Belousov-Zhabotinskii Reaction.- 7.6. Other Oscillating Systems.- 7.7. Multiple Stationary States: The NO2-N2O4 Reaction.- Problems.- General References.- 8. Single-Collision Chemistry.- 8.1. Introduction.- 8.2. Reaction Cross Section: Relation to the Rate Constant.- 8.3. Scattering Measurements—Molecular Beams.- 8.4. Reaction Cross Section: Hard-Sphere Model.- 8.5. Reaction Cross Section : Ion-Molecule Systems.- 8.6. Reaction Cross Section : Atom-Molecule Systems.- 8.7. Product Distribution Analysis.- 8.8. Direct, Forward-Peaked—The Ar+ + D2 System.- 8.9. Recoil—The D + Cl2 System.- 8.10. Collision Complexes—The O + Br2 System.- 8.11. State Selection Experiments.- Problems.- General References.- 9. Theories of Reaction Rates.- 9.1. Introduction.- 9.2. Potential-Energy Surfaces.- 9.3. Activated Complex Theory.- 9.4. Model Calculations of k2(T).- 9.5. The Kinetic Isotope Effect.- 9.6. Unimolecular Reaction—General Features.- 9.7. Unimolecular Reaction—RRKM Theory.- 9.8. Critique of RRKM Theory—Isomerization of Methyl Isocyanide.- 9.9. Thermodynamic Analogy.- 9.10. Gas-Phase Reactions.- 9.11. Solution Reactions.- 9.12. Primary Salt Effect.- 9.13. Diffusion-Limited Kinetics—Debye Theory.- Appendix A. Statistical Thermodynamics.- Appendix B. Evaluation of k? in RRKM Theory.- Problems.- General References.- 10. A Dynamical Model for Chemical Reaction.- 10.1. Introduction.- 10.2. Kinetic Energy of a Triatomic System.- 10.3. Model for Inelastic Collision.- 10.4. Effects Due to More Complex Potential-Energy Surfaces.- 10.5. Model for Thermoneutral Chemical Reaction.- 10.6. Exoergic Reactions.- 10.7. Endoergic Reactions.- 10.8. Noncollinear Geometries.- 10.9. Realistic Scattering Calculations.- Problems.- General References.- Physical Constants.