Thermodynamics and Fluctuations Far From Equilibrium

by Ross, John; Berry, R. Stephen (CON)

• ISBN13: 9783540745549
• ISBN10: 3540745548
• Format: Hardcover
• Copyright: 2008-03-05
• Publisher: Springer Verlag

Summary

"This book deals with the formulation of the thermodynamics of chemical and other systems far from equilibrium, including connections to fluctuations. It contains applications to non-equilibrium stationary states and approaches to such states, systems with multiple stationary states, stability and equi-stability conditions, reaction diffusion systems, transport properties, and electrochemical systems. The theoretical treatment is complemented by experimental results to substantiate the formulation. Dissipation and efficiency are analyzed in autonomous and externally forced reactions, including several biochemical systems."--BOOK JACKET.

Table of Contents

Thermodynamics and Fluctuations Far from Equilibrium
Introduction to Part I	p. 3
Some Basic Concepts and Definitions	p. 4
Elementary Thermodynamics and Kinetics	p. 7
References	p. 10
Thermodynamics Far from Equilibrium: Linear and Nonlinear One-Variable Systems	p. 11
Linear One-Variable Systems	p. 11
Nonlinear One-Variable Systems	p. 12
Dissipation	p. 15
Connection of the Thermodynamic Theory with Stochastic Theory	p. 16
Relative Stability of Multiple Stationary Stable States	p. 18
Reactions with Different Stoichiometries	p. 20
References	p. 21
Thermodynamic State Function for Single and Multivariable Systems	p. 23
Introduction	p. 23
Linear Multi-Variable Systems	p. 25
Nonlinear Multi-Variable Systems	p. 29
References	p. 32
Continuation of Deterministic Approach for Multivariable Systems	p. 33
References	p. 39
Thermodynamic and Stochastic Theory of Reaction-Diffusion Systems	p. 41
Reaction-Diffusion Systems with Two Intermediates	p. 44
Linear Reaction Systems	p. 45
Non-Linear Reaction Mechanisms	p. 47
Relative Stability of Two Stable Stationary States of a Reaction-Diffusion System	p. 49
Calculation of Relative Stability in a Two-Variable Example, the Selkov Model	p. 52
References	p. 58
Stability and Relative Stability of Multiple Stationary States Related to Fluctuations	p. 59
References	p. 64
Experiments on Relative Stability in Kinetic Systems with Multiple Stationary States	p. 65
Multi-Variable Systems	p. 65
Single-Variable Systems: Experiments on Optical Bistability	p. 68
References	p. 71
Thermodynamic and Stochastic Theory of Transport Processes	p. 73
Introduction	p. 73
Linear Transport Processes	p. 75
Linear Diffusion	p. 75
Linear Thermal Conduction	p. 77
Linear Viscous Flow	p. 79
Nonlinear One-Variable Transport Processes	p. 82
Coupled Transport Processes: An Approach to Thermodynamics and Fluctuations in Hydrodynamics	p. 83
Lorenz Equations and an Interesting Experiment	p. 83
Rayleigh Scattering in a Fluid in a Temperature Gradient	p. 87
Thermodynamic and Stochastic Theory of Electrical Circuits	p. 87
References	p. 87
Thermodynamic and Stochastic Theory for Non-Ideal Systems	p. 89
Introduction	p. 89
A Simple Example	p. 90
References	p. 93
Electrochemical Experiments in Systems Far from Equilibrium	p. 95
Introduction	p. 95
Measurement of Electrochemical Potentials in Non-Equilibrium Stationary States	p. 95
Kinetic and Thermodynamic Information Derived from Electrochemical Measurements	p. 97
References	p. 100
Theory of Determination of Thermodynamic and Stochastic Potentials from Macroscopic Measurements	p. 101
Introduction	p. 101
Change of Chemical System into Coupled Chemical and Electrochemical System	p. 102
Determination of the Stochastic Potential [phi] in Coupled Chemical and Electrochemical Systems	p. 104
Determination of the Stochastic Potential in Chemical Systems with Imposed Fluxes	p. 105
Suggestions for Experimental Tests of the Master Equation	p. 107
References	p. 108
Dissipation and Efficiency in Autonomous and Externally Forced Reactions, Including Several Biochemical Systems
Dissipation in Irreversible Processes	p. 113
Introduction	p. 113
Exact Solution for Thermal Conduction	p. 113
Newton's Law of Cooling	p. 113
Fourier Equation	p. 114
Exact Solution for Chemical Reactions	p. 116
Invalidity of the Principle of Minimum Entropy Production	p. 118
Invalidity of the 'Principle of Maximum Entropy Production'	p. 119
Editorial	p. 119
References	p. 119
Efficiency of Irreversible Processes	p. 121
Introduction	p. 121
Power and Efficiency of Heat Engines	p. 122
References	p. 129
Finite-Time Thermodynamics	p. 131
Introduction and Background	p. 131
Constructing Generalized Potentials	p. 133
Examples: Systems with Finite Rates of Heat Exchange	p. 134
Some More Realistic Applications: Improving Energy Efficiency by Optimal Control	p. 137
Optimization of a More Realistic System: The Otto Cycle	p. 139
Another Example: Distillation	p. 141
Choices of Objectives and Differences of Extrema	p. 144
References	p. 146
Reduction of Dissipation in Heat Engines by Periodic Changes of External Constraints	p. 147
Introduction	p. 147
A Simple Example	p. 147
Some Calculations and Experiments	p. 152
Calculations	p. 152
Experiments	p. 157
References	p. 158
Dissipation and Efficiency in Biochemical Reactions	p. 159
Introduction	p. 159
An Introduction to Oscillatory Reactions	p. 159
An Oscillatory Reaction with Constant Input of Reactants	p. 163
References	p. 168
Three Applications of Chapter 16	p. 169
Thermodynamic Efficiency in Pumped Biochemical Reactions	p. 169
Thermodynamic Efficiency of a Proton Pump	p. 172
Experiments on Efficiency in the Forced Oscillatory Horse-Radish Peroxidase Reaction	p. 174
References	p. 179
Stochastic Theory and Fluctuations in Systems Far from Equilibrium, Including Disordered Systems
Fluctuation-Dissipation Relations	p. 183
References	p. 188
Fluctuations in Limit Cycle Oscillators	p. 191
References	p. 195
Disordered Kinetic Systems	p. 197
References	p. 202
Index	p. 205
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