Chemical Kinetics and Reaction Dynamics,9780486453347

Chemical Kinetics and Reaction Dynamics

by
ISBN13: 9780486453347
ISBN10: 0486453340
Format: Paperback
Pub. Date: 2006-11-17
Publisher(s): Dover Publications
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Summary

This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications. The author is the Peter J. W. Debye Professor of Chemistry at Cornell University.

Table of Contents

Preface xi
Introduction: A User's Guide to Chemical Kinetics and Reaction Dynamics xiii
Errata xvii
Kinetic Theory of Gases
1(33)
Introduction
1(1)
Pressure of an Ideal Gas
2(2)
Temperature and Energy
4(1)
Distributions, Mean Values, and Distribution Functions
5(3)
The Maxwell Distribution of Speeds
8(9)
The Velocity Distribution Must Be an Even Function of v
8(1)
The Velocity Distributions Are Independent and Uncorrelated
9(1)
<v2> Should Agree with the Ideal Gas Law
9(2)
The Distribution Depends Only on the Speed
11(4)
Experimental Measurement of the Maxwell Distribution of Speeds
15(2)
Energy Distributions
17(2)
Collisions: Mean Free Path and Collision Number
19(5)
Summary
24(1)
Appendix 1.1 The Functional Form of the Velocity Distribution
25(1)
Appendix 1.2 Spherical Coordinates
26(1)
Appendix 1.3 The Error Function and Co-Error Function
27(1)
Appendix 1.4 The Center-of-Mass Frame
28(6)
Suggested Readings
30(1)
Problems
31(3)
The Rates of Chemical Reactions
34(57)
Introduction
34(1)
Empirical Observations: Measurement of Reaction Rates
35(1)
Rates of Reactions: Differential and Integrated Rate Laws
35(16)
First-Order Reactions
37(3)
Second-Order Reactions
40(4)
Pseudo-First-Order Reactions
44(3)
Higher-Order Reactions
47(1)
Temperature Dependence of Rate Constants
48(3)
Reaction Mechanisms
51(12)
Opposing Reactions, Equilibrium
52(2)
Parallel Reactions
54(2)
Consecutive Reactions and the Steady-State Approximation
56(4)
Unimolecular Decomposition: The Lindemann Mechanism
60(3)
Homogeneous Catalysis
63(9)
Acid-Base Catalysis
63(1)
Enzyme Catalysis
64(6)
Autocatalysis
70(2)
Free Radical Reactions: Chains and Branched Chains
72(5)
H2 + Br2
72(1)
Rice-Herzfeld Mechanism
73(1)
Branched Chain Reactions: Explosions
74(3)
Determining Mechanisms from Rate Laws
77(4)
Summary
81(10)
Suggested Readings
83(1)
Problems
83(8)
Theories of Chemical Reactions
91(25)
Introduction
91(1)
Potential Energy Surfaces
92(3)
Collision Theory
95(7)
Simple Collision Theory
95(4)
Modified Simple Collision Theory
99(3)
Activated Complex Theory (ACT)
102(7)
Thermodynamic Interpretation of ACT
109(1)
Summary
109(7)
Suggested Readings
111(1)
Problems
111(5)
Transport Properties
116(28)
Introduction
116(1)
The Functional Form of the Transport Equations
117(2)
The Microscopic Basis for the Transport Laws
119(5)
Simplifying Assumptions
119(1)
The Molecular Flux
120(2)
The Vertical Distance between Collisions
122(1)
The General Flux Equation
122(2)
Thermal Conductivity
124(3)
Viscosity
127(4)
Diffusion
131(2)
Time-Dependent Transport
133(5)
Summary
138(1)
Appendix 4.1 The Poiseuille Formula
139(5)
Suggested Readings
141(1)
Problems
141(3)
Reactions in Liquid Solutions
144(27)
Introduction
144(1)
The Cage Effect, Friction, and Diffusion Control
145(7)
The Cage Effect
145(1)
The Langevin Equation
145(3)
A Simple Model for Diffusion Control
148(1)
The Diffusion-Controlled Rate Constant
148(4)
Reactions of Charged Species in Solution: Ionic Strength and Electron Transfer
152(7)
Reaction Rates and Ionic Strength
153(2)
Electron Transfer Reactions: Marcus Theory
155(4)
Experimental Techniques
159(5)
The Temperature Jump Technique
159(2)
Ultrafast Laser Techniques
161(3)
Summary
164(1)
Appendix 5.1 The Langevin Equation and the Mean Squared Displacement
165(2)
Appendix 5.2 Diffusion with an Electrostatic Potential
167(4)
Suggested Readings
169(1)
Problems
169(2)
Reactions at Solid Surfaces
171(33)
Introduction
171(3)
Adsorption and Desorption
174(5)
The Langmuir Isotherm
176(1)
Competitive Adsorption
177(1)
Heats of Adsorption
178(1)
Reactions at Surfaces: Catalysis
179(4)
Unimolecular Surface Reactions
179(1)
Bimolecular Surface Reactions
180(1)
Activated Complex Theory of Surface Reactions
181(1)
The Nature of Surface Catalytic Sites
182(1)
Surface Diffusion
183(2)
Advanced Topics in Surface Reactions
185(9)
Temperature-Programmed Desorption
185(2)
Modulated Molecular Beam Methods
187(7)
Summary
194(2)
Appendix 6.1 Integral Transforms
196(8)
Suggested Readings
198(1)
Problems
198(6)
Photochemistry
204(53)
Introduction
204(1)
Absorption and Emission of Light
205(4)
Photophysical Processes
209(12)
Fluorescence and Quenching
209(3)
Intramolecular Vibrational Energy Redistribution
212(3)
Internal Conversion, Intersystem Crossing, and Phosphorescence
215(3)
Photodissociation
218(3)
Atmospheric Chemistry
221(4)
Photodissociation Dynamics
225(20)
The Pump-Probe Technique
226(2)
Laser-Induced Fluorescence
228(1)
Multiphoton Ionization
229(2)
Unimolecular Dissociation
231(8)
Photofragment Angular Distributions
239(5)
Photochemistry on Short Time Scales
244(1)
Summary
245(12)
Suggested Readings
248(1)
Problems
249(8)
Molecular Reaction Dynamics
257(58)
Introduction
257(1)
A Molecular Dynamics Example
258(2)
Molecular Collisions---A Detailed Look
260(3)
Molecular Scattering
263(18)
The Center-of-Mass Frame---Newton Diagrams
264(6)
Reactive Scattering: Differential Cross Section for F + D2
270(3)
Elastic Collisions
273(5)
Inelastic Collisions
278(3)
Potential Energy Surfaces
281(8)
Trajectory Calculations by Classical Mechanics
283(3)
Semiclassical Calculations
286(3)
Molecular Energy Transfer
289(13)
Translational Energy Transfer
289(3)
Vibrational Energy Transfer
292(4)
Rotational Energy Transfer
296(1)
Electronic Energy Transfer
297(5)
Molecular Reaction Dynamics---Some Examples
302(5)
Reactive Collisions: Orientation
302(2)
Reactive Collisions: Bond-Selective Chemistry
304(1)
Potential Energy Surfaces from Spectroscopic Information: van der Waals Complexes
305(2)
Summary
307(8)
Suggested Readings
309(1)
Problems
310(5)
Answers and Solutions to Selected Problems 315(4)
Index 319

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