Relaxation kinetics - 1st Edition - ISBN: 9780120929504, 9780323156998

Relaxation kinetics

1st Edition

Authors: Claude Bernasconi
eBook ISBN: 9780323156998
Imprint: Academic Press
Published Date: 28th January 1976
Page Count: 300
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Description

Relaxation Kinetics focuses on the theory of relaxation kinetics (also known as chemical relaxation) and the experimental techniques used in the study of fast reactions. Topics covered include relaxation times in single-step, two-step, and multistep systems; small perturbations; and relaxation amplitudes in single-step and multistep systems. Chemical relaxation in complex systems is also described, and a complete solution of the relaxation equation is presented. This book is comprised of 16 chapters divided into two sections and begins with an overview of the basic principles of chemical relaxation, including the linearization of rate equations, relaxation times, and transient and stationary relaxation methods. The following chapters explore relaxation times in single-step, two-step, and multistep systems, as well as relaxation amplitudes in single-step and multistep systems. The possibility of linearization of a rate equation for ""small"" perturbations is then considered, along with the derivation of the complete relaxation equation. The next chapter discusses transient relaxation techniques and explains how the data are analyzed for the stationary techniques when dealing with the specific techniques. The second section is devoted to experimental techniques such as the temperature-jump method, the electric field-jump method, and the concentration-jump method. Ultrasonic techniques and stationary electric field methods are also described. This monograph will be a valuable resource for chemists and physicists.

Table of Contents


Preface

Acknowledgments

Part I Theory of Chemical Relaxation

Chapter 1 Basic Principles

1.1 Linearization of Rate Equations

1.2 Relaxation Time

1.3 Transient and Stationary Relaxation Methods

Problems

Chapter 2 Relaxation Times in Single-Step Systems

2.1 The A + B ≅ C System

2.2 Other Single-Step Systems

Problems

References

Chapter 3 Relaxation Times in Two-Step Systems

3.1 General Considerations Regarding Multistep Systems

3.2 The A + B ≅ C ≅ D System

3.3 Some Other Two-Step Systems

Problems

References

Chapter 4 Relaxation Times in Common Multistep Systems

4.1 General System. Castellan's Treatment

4.2 The A + B ≅ C ≅ D ≅ E (+ F) System

4.3 The E + S ≅ ES ≅ EP ≅ P + E System (Enzyme Reactions)

4.4 Cyclic Reaction Schemes

4.5 Miscellaneous Multistep Schemes. Two Calculated Examples from Organic Chemistry

Problems

References

Chapter 5 What is a Small Perturbation?

5.1 Conditions for Linearization in the A + B ≅ C System

5.2 Other Systems

Problems

References

Chapter 6 Relaxation Amplitudes in Single-Step Systems

6.1 The Extent of Equilibrium Displacement

6.2 Determination of ΔH from Relaxation Amplitudes

6.3 Determination of K from Relaxation Amplitudes

Problems

References

Chapter 7 Relaxation Amplitudes in Multistep Systems

7.1 Two-Step Systems with Rapid Equilibration of One Step

7.2 Normal Modes of Reactions

7.3 Applications of Normal Mode Analysis

Problems

References

Chapter 8 Complete Solution of the Relaxation Equation

8.1 Derivation of the Complete Relaxation Equation

8.2 Transient and Forced Solutions as Special Cases of the Complete Solution

8.3 Complete Solution for Some Common Step Functions (Transient Relaxation Methods)

8.4 Forced Solution for Oscillating Forcing Function (Stationary Relaxation Methods)

Problems

Reference

Chapter 9 Evaluation of Relaxation Times from Experimental Relaxation Curves

9.1 One Relaxation Time

9.2 Two or More Relaxation Times

9.3 Mean Relaxation Times

Problems

References

Chapter 10 Chemical Relaxation in Complex Systems

10.1 Binding of Small Molecules to Multiunit Enzymes

10.2 Cooperative Conformational Transitions of Linear Biopolymers (Helix-Coil Transition of Polypeptides)

10.3 Cooperative Binding of Small Molecules to Linear Biopolymers

10.4 Molecular Aggregation Phenomena. Micelle Formation

References

Part II Experimental Techniques and Applications

Chapter 11 The Temperature-Jump Method

11.1 The Temperature Pulse

11.2 Detection of Concentration Changes

11.3 The Combination Stopped-Flow-Temperature-Jump Apparatus

11.4 Temperature-Jump Equipment and Its Operation; Commercial Products

11.5 Applications of the Temperature-Jump Method

Problems

References

Chapter 12 Pressure-Jump Methods

12.1 Principles and Apparatus

12.2 Shock Wave Apparatus

12.3 Applications

Problems

References

Chapter 13 The Electric Field-Jump Method

13.1 Principles

13.2 Experimental Techniques

13.3 Applications

Problem

References

Chapter 14 The Concentration-Jump Method

14.1 Principles

14.2 The Stopped-Flow Technique

14.3 Applications

References

Chapter 15 Ultrasonic Techniques

15.1 Principles

15.2 General Experimental Considerations and Treatment of Data

15.3 Experimental Methods

15.4 Applications of the Ultrasonic Methods

Problems

References

Chapter 16 Stationary Electric Field Methods

16.1 Principles and Experimental Techniques

16.2 Applications

References

Index

Details

No. of pages:
300
Language:
English
Copyright:
© Academic Press 1976
Published:
Imprint:
Academic Press
eBook ISBN:
9780323156998

About the Author

Claude Bernasconi