Chemical Kinetics and Reaction Mechanisms: McGraw-Hill Series In Advanced Chemistry

This book covers chemical kinetics from the working chemists' point of view. Competing books present a more theoretical presentation of kinetics. This book is a "how to" book for designing experiments, analyzing, and critiquing them. Chemical Kinetics and Reaction Mechanisms also prepares chemists to devise experiments to test different hypotheses. A diskette that helps students solve end-of-chapter problems is packaged with each text. Front cover Series Title page Date-line About the author CONTENTS Preface 1 Reactions and Reaction Rates 1.1 Reaction Mechanisms 1.2 Net Reactions and Reaction Rates 1.3 Elementary Reactions and Reaction Mechanisms 1.4 The Order of a Rate Law 1.5 Factors Influencing Reaction Rates 1.6 Practical Kinetics 1.7 Pitfalls 1.8 Stoichiometric Equations, Elementary Reactions, Mechanisms, and Molecularity Problems References Bibliography 2 Reactions with a Simple Kinetic Form 2.1 First-Order Reactions 2.2 Second-Order Kinetics, $v=k[A]^2$ 2.3 Second-Order Kinetics, $v=k[A][B]$ 2.4 Use of Physical Properties with Kinetic Data 2.5 Methods When the Infinity Reading ("End Point") is Unknown 2.6 Reactions that are Zeroth-Order or a Fractional Order with Respect to a Single Concentration 2.7 Rate Expressions and the Method of Flooding 2.8 The Experimental Determination of Reaction Orders 2.9 Reactions with a Complex Dependence on a Single Concentration Variable 2.10 Product-Catalyzed Reactions 2.11 Methods of Data Analysis Problems References 3 Reversible and Concurrent Reactions 3.1 Reversible First-Order Reactions 3.2 Opposing Reactions of Higher Order 3.3 Concentration-Jump Methods for Opposing Reactions 3.4 Exchange Reactions 3.5 Parallel and Concurrent Reactions 3.6 Concurrent Reactions of Mixtures Problems References 4 Consecutive Reactions; the Steady-State and Other Approximations 4.1 Consecutive First-Order Reactions 4.2 Dual Solutions in Consecutive Reactions 4.3 A Series Reaction with a Reversible Step 4.4 The Steady-State Approximation 4.5 The Rate-Controlling Step 4.6 The Prior-Equilibrium and Improved Steady-State Approximations 4.7 Catalyzed and Enzyme-Catalyzed Reactions 4.8 Racemization and Reaction Problems References 5 Complex Mechanisms—Intermediates and Numerical Solutions 5.1 Identification of the Intermediate 5.2 The Reactivity of Intermediates 5.3 Kinetic Probes and Radical Clocks 5.4 Other Tests for Reaction Intermediates 5.5 Numerical Simulations Problems References 6 Deduction of Reaction Mechanisms 6.1 The Transition State 6.2 Mechanistic Interpretation of Rate Laws 6.3 Equivalent Kinetic Expressions 6.4 Kinetically Indistinguishable Schemes 6.5 pH-Rate Profiles and Downward Bends 6.6 pH-Rate Profiles and Upward Bends 6.7 Complexation Equilibria Problems References 7 Transition State Theory and Microscopic Reversibility 7.1 Temperature Effects 7.2 The Heat Capacity of Activation 7.3 Composite Rate Constants 7.4 The Isokinetic Relationship 7.5 Pressure Effects and the Volume of Activation 7.6 The Chemical Interpretation of Activation Parameters 7.7 Transition State Theory 7.8 Forward and Reverse Rate Constants and the Principle of Microscopic Reversibility Problems References 8 Chain Reactions and Oscillating Reactions 8.1 Characteristics of Chain Reactions 8.2 The Decomposition of Acetaldehyde 8.3 Autoxidation of an Organochromium Complex 8.4 Oxidation of Phosphorous Acid by Peroxodisulfate Ions 8.5 Well-Behaved Chain Reactions 8.6 Further Features of Chain Mechanisms 8.7 Branching Chain Reactions 8.8 Oscillating Reactions Problems References 9 Reactions in Solution 9.1 The Nature of Reactions in a Solvent 9.2 Diffusion-Controlled Reactions 9.3 Applications of Transition State Theory 9.4 Solvent Effects on Polar and Ionic Reactions 9.5 Salt Effects on Second-Order Ionic Reactions 9.6 Salt Effects on Other Reaction Orders 9.7 Salt Effects and Reaction Mechanisms 9.8 Kinetic Isotope Effects Problems References 10 Extrakinetic Probes of Mechanism 10.1 Linear Free Energy Relations (LFER) 10.2 The Hammett Correlation 10.3 The Taft Equation 10.4 The Swain-Scott and Edwards Equations 10.5 Acid-Base Catalysis 10.6 The Bronsted Catalysis Law 10.7 Mechanisms of Acid-Base Catalyzed Reactions 10.8 The Reactivity-Selectivity Principle and the Isoselectivity Rule 10.9 The Intrinsic Barrier and Hammond's Postulate 10.10 The Marcus Equations for Electron Transfer 10.11 Applications of the Marcus Equation Problems References 11 Reactions at Extreme Rates 11.1 Survey of Methods for Very Fast Reactions 11.2 Flow Methods for Rapid Reactions 11.3 Chemical Relaxation Methods 11.4 Kinetic Equations for Chemical Relaxation 11.5 NMR Line Shape Analysis 11.6 Flash and Laser Photolysis 11.7 Picosecond and Femtosecond Methods 11.8 Pulse Radiolysis Problems References A Concluding Assignment Answers to Numerical Problems Index Back cover 1. Reactions And Reaction Rates -- 2. Reactions With A Simple Kinetic Form -- 3. Reversible And Concurrent Reactions -- 4. Consecutive Reactions: The Steady-state And Other Approximations -- 5. Complex Mechanisms -- Intermediates And Numerical Solutions -- 6. Deduction Of Reaction Mechanisms -- 7. Transition State Theory And Microscopic Reversibility -- 8. Chain Reactions And Oscillating Reactions -- 9. Reactions In Solution -- 10. Extrakinetic Probes Of Mechanism -- 11. Reactions At Extreme Rates. James H. Espenson. Includes Bibliographical References And Index. Covering chemical kinetics from the working chemist's point of view, this book aims to prepare chemists to devise experiments to test different hypothesis. A number of examples from research literature have been included