Chemical Kinetics and Dynamics,9780137371235

Chemical Kinetics and Dynamics

by ; ;
Edition: 2nd
ISBN13: 9780137371235
ISBN10: 0137371233
Format: Paperback
Pub. Date: 1998-08-10
Publisher(s): Pearson
List Price: $217.39

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Summary

Presents a balanced presentation of the macroscopic view of empirical kinetics and the microscopic molecular viewpoint of chemical dynamics.Stressing interconnections between phenomenological chemical kinetics and molecular reaction dynamics, the book discusses reactions in gas phase, liquids, and at surfaces; molecular potential surfaces; gas-gas and gas-surface theories applied to reactive collisions. It features applications to atmospheric chemistry, combustion, and chemical lasers as well as multiple methods for solving kinetic equations. It also addresses topics not found in other books: Information theory, Stochastic simulation, and Sensitivity analysis. The second edition ofChemical Kinetics and Dynamicshas been revised to include the latest information as well as new topics, such as heterogeneous reactions in atmospheric chemistry, reactant product imaging, and molecular dynamics of H + H2. It provides an experimental observation of the transition state ("Femtochemistry"); new treatment of stratospheric chemistry, including heterogeneous processes, balance among catalytic cycles, environmental consequences, and policy implications as well as current database information on NIST kinetics as well as JPL evaluations.A valuable resource on kinetics for professional atmospheric kineticists and chemical engineers.

Table of Contents

Preface Chapter 1 Basic Concepts of Kinetics
1(21)
1.1 Definition of the Rate of a Chemical Reaction
1(2)
1.2 Order and Molecularity of a reaction
3(3)
1.3 Integrated Reaction Rate Laws
6(7)
1.4 Determination of Reaction Order:Reaction Half-Lives
13(1)
1.5 Temperature Dependence of Rate Constants:The Arhenius Equation
14(3)
1.6 Reaction Mechanisms, Molecular Dynamics, and the Road Ahead
17(1)
References
18(1)
Bibliography
18(1)
Problems
19(3)
Chapter 2 Complex Reactions
22(65)
2.1 Exact Analytic Solutions for Complex Reactions
22(15)
2.2 Approximation Methods
37(4)
2.3 Example of a Complex Reaction Mechanism:The Hydrogen + Halogen Reaction
41(6)
2.4 Laplace Transform Method
47(5)
2.5 Determinant (Matrix) Methods
52(3)
2.6 Numerical Methods
55(11)
2.7 Stochastic Methods
66(6)
References
72(2)
Bibliography
74(1)
Appendix 2.1 The Laplace Transform
74(2)
Appendix 2.2 Numerical Algorithms for Differential Equations
76(1)
Appendix 2.3 Stochastic Numerical Simulation of Chemical Reacions
77(2)
Problems
79(8)
Chapter 3 Kinetic Measurements
87(37)
3.1 Introduction
87(2)
3.2 Techniques of Kinetic Measurements
89(16)
3.3 Treatment of Kinetic Data
105(15)
References
120(1)
Problems
121(3)
Chapter 4 Reactions in Solution
124(23)
4.1 General Properties of Reactions in Solution
124(1)
4.2 Phenomenological Theory of Reaction Rates
125(5)
4.3 Difusion-Limited Rate Constant
130(2)
4.4 Slow Reactions
132(1)
4.5 Effect of Ionic Strength on Reaction Between Ions
133(3)
4.6 Linear Free-Energy Relationships
136(4)
4.7 Relaxation Methods for Fast Reactions
140(3)
References
143(1)
Bibliography
143(1)
Problems
144(3)
Chapter 5 Catalysis
147(24)
5.1 Catalysis and Equilibrium
147(1)
5.2 Homogeneous Catalysis
148(3)
5.3 Autocatalysis and Oscillating Reactions
151(8)
5.4 Enzyme-Catalyzed Reactions
159(4)
5.5 Heterogenous Catalysis and Gas-Surface Reactions
163(4)
References
167(1)
Problems
168(3)
Chapter 6 The Transition from the Macroscopic to the Microscopic Level
171(8)
6.1 Relation between Cross Section and Rate Coefficient
171(3)
6.2 Internal States of the Reactants and Products
174(1)
6.3 Microscopic Reversibility and Detailed Balancing
174(1)
6.4 The Microscopic-Macroscopic Connection
175(2)
References
177(1)
Bibliography
178(1)
Problems
178(1)
Chapter 7 Potential Energy Surfaces
179(38)
7.1 Long-range Potentials
180(3)
7.2 Empirical Intermolecular Potentials
183(1)
7.3 Molecular Bonding Potentials
184(3)
7.4 Internal Coordinates and Normal Modes of Vibration
187(3)
7.5 Potential Energy Ssurfaces
190(1)
7.6 Ab Initio Calculation of Potential Energy Surfaces
191(5)
7.7 Analytic Potential Energy Funtions
196(8)
7.8 Experimental Determination of Potential Energy Surface
204(2)
7.9 Details of the Reaction Path
206(1)
7.10 Potential Energy Surfaces of Electronically Excited Molecules
207(4)
References
211(2)
Bibliography
213(2)
Problems
215(2)
Chapter 8 Dynamics of Bimolecular Collisions
217(38)
8.1 Simple Collision Models
217(5)
8.2 Two-body Classical Scattering
222(9)
8.3 Complex Scattering Processes
231(18)
Problems
249(1)
Bibliography
250(5)
Chapter 9 Experimental Chemical Dynamics
255(32)
9.1 Molecular Beam Scattering
255(8)
9.2 State-Resolved Spectroscopic Techniques
263(3)
9.3 Molecular Dynamics of the H + H(2) Reaction
266(2)
9.4 State-to-state Kinetics of tge F + H(2) Reaction
268(8)
9.5 Warning:Information Overload!
276(1)
References
276(2)
Problems
278(4)
Appendix The Master Equation
282(4)
References
286(1)
Chapter 10 Statistical Approach to Reaction Dynamics: Transition State Theory
287(37)
10.1 Motion on the Potential Surface
287(2)
10.2 Basic Postulates and Deivation of Transition State theory
289(5)
10.3 Dynamical Derivation of Transition State Theory
294(3)
10.4 Quantum Mechanical Effects in Transition State Theory
297(3)
10.5 Thermodynamic Formulation of Transition State Theory
300(2)
10.6 Applications of Transition State Theory
302(8)
10.7 Microcanonical Transition State Theory
310(2)
10.8 Variational Transition State Theory
312(2)
10.9 Experimental Observation of the Transition State Region
314(2)
10.10 Critique of Transition State Theory
316(3)
References
319(1)
Bibliography
320(1)
Problems
321(3)
Chapter 11 Unimolecular Reaction Dynamics
324(66)
11.1 Formation of Energized Molecules
326(3)
11.2 Sum and Density of States
329(5)
11.3 Lindemann-Hinshelwood Theory of Thermal Unimolecular Reactions
334(4)
11.4 Statistical Energy-dependent Rate Constant K(E)
388(2)
11.5 RRK Theory
340(3)
11.6 RRKM Theory
343(6)
11.7 Application of RRKM Theory to Thermal Activation
349(2)
11.8 Measurement of k(E)
351(5)
11.9 Intermolecular Energy Transfer
356(3)
11.10 Product Energy Partitioning
359(3)
11.11 Apparent and Intrinsic non-RRKM Behavior
362(3)
11.12 Classical Mechanical Description of Intramolecular Motion and Unimolecular Decomposition
365(2)
11.13 Infrared Multiple-Photon Excitation
367(7)
11.14 Mode Specificity
374(3)
References
377(5)
Bibliography
382(1)
Problems
383(7)
Chapter 12 Dynamics Beyodn the Gas Phase
390(34)
12.1 Transition State Theory of Solution Reactions
390(12)
12.2 Kramer's Theory and Friction
402(5)
12.3 Gas-Surface Reaction Dynamics
407(13)
References
420(1)
Bibliography
421(13)
Problems
422(2)
Chapter 13 Information-Theoretical Approach to State-to-state Dynamics
424(29)
13.1 Introduction
424(1)
13.2 The Maximal-Entropy Postulate
424(8)
13.3 Surprisal Analyis and Synthesis:Product State Distributtion in Exothermic Reactions
432(5)
13.4 Information-Theoretical Analysis of Energy Transfer Processes
437(12)
13.5 Conclusion
449(1)
References
449(2)
Bibliography
451(1)
Problems
452(1)
Chapter 14 Kinetics of Multicomponent Systems: Combustion Chemistry
453(17)
14.1 Introduction
453(1)
14.2 The Hydrogen-Oxygen Reaction, an Explosive Combustion Process
453(6)
14.3 The Methane Combustion Process
459(10)
References
469(1)
Chapter 15 Kinetics of Multicomponent Systems: Atmospheric Chemistry
470(29)
15.1 Physical Structure of the Atmosphere
470(2)
15.2 Chemical Composition of the Atmosphere
472(1)
15.3 Photochemistry in the Atmosphere
472(4)
15.4 Catalytic Cycles Involving Stratospheric Ozone
476(12)
15.5 Modeling Studies of the Atmosphere
488(1)
15.6 Atmospheric Measurements
489(2)
15.7 Current Understanding of Atmospheric Kinetics
491(2)
15.8 Conclusion
493(1)
References
494(1)
Bibliography
494(1)
Problems
495(4)
Appendix 1 Quantum Statistical Mechanics 499(1)
Appendix 2 Classical Statistical Mechanics 500(7)
Appendix 3 Data Bases in Chemical Kinetics 507(2)
Index 509

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