Thermodynamics and Fluctuations Far From Equilibrium

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  • Format: Hardcover
  • Copyright: 2008-03-05
  • Publisher: Springer Verlag

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"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 Ip. 3
Some Basic Concepts and Definitionsp. 4
Elementary Thermodynamics and Kineticsp. 7
Referencesp. 10
Thermodynamics Far from Equilibrium: Linear and Nonlinear One-Variable Systemsp. 11
Linear One-Variable Systemsp. 11
Nonlinear One-Variable Systemsp. 12
Dissipationp. 15
Connection of the Thermodynamic Theory with Stochastic Theoryp. 16
Relative Stability of Multiple Stationary Stable Statesp. 18
Reactions with Different Stoichiometriesp. 20
Referencesp. 21
Thermodynamic State Function for Single and Multivariable Systemsp. 23
Introductionp. 23
Linear Multi-Variable Systemsp. 25
Nonlinear Multi-Variable Systemsp. 29
Referencesp. 32
Continuation of Deterministic Approach for Multivariable Systemsp. 33
Referencesp. 39
Thermodynamic and Stochastic Theory of Reaction-Diffusion Systemsp. 41
Reaction-Diffusion Systems with Two Intermediatesp. 44
Linear Reaction Systemsp. 45
Non-Linear Reaction Mechanismsp. 47
Relative Stability of Two Stable Stationary States of a Reaction-Diffusion Systemp. 49
Calculation of Relative Stability in a Two-Variable Example, the Selkov Modelp. 52
Referencesp. 58
Stability and Relative Stability of Multiple Stationary States Related to Fluctuationsp. 59
Referencesp. 64
Experiments on Relative Stability in Kinetic Systems with Multiple Stationary Statesp. 65
Multi-Variable Systemsp. 65
Single-Variable Systems: Experiments on Optical Bistabilityp. 68
Referencesp. 71
Thermodynamic and Stochastic Theory of Transport Processesp. 73
Introductionp. 73
Linear Transport Processesp. 75
Linear Diffusionp. 75
Linear Thermal Conductionp. 77
Linear Viscous Flowp. 79
Nonlinear One-Variable Transport Processesp. 82
Coupled Transport Processes: An Approach to Thermodynamics and Fluctuations in Hydrodynamicsp. 83
Lorenz Equations and an Interesting Experimentp. 83
Rayleigh Scattering in a Fluid in a Temperature Gradientp. 87
Thermodynamic and Stochastic Theory of Electrical Circuitsp. 87
Referencesp. 87
Thermodynamic and Stochastic Theory for Non-Ideal Systemsp. 89
Introductionp. 89
A Simple Examplep. 90
Referencesp. 93
Electrochemical Experiments in Systems Far from Equilibriump. 95
Introductionp. 95
Measurement of Electrochemical Potentials in Non-Equilibrium Stationary Statesp. 95
Kinetic and Thermodynamic Information Derived from Electrochemical Measurementsp. 97
Referencesp. 100
Theory of Determination of Thermodynamic and Stochastic Potentials from Macroscopic Measurementsp. 101
Introductionp. 101
Change of Chemical System into Coupled Chemical and Electrochemical Systemp. 102
Determination of the Stochastic Potential [phi] in Coupled Chemical and Electrochemical Systemsp. 104
Determination of the Stochastic Potential in Chemical Systems with Imposed Fluxesp. 105
Suggestions for Experimental Tests of the Master Equationp. 107
Referencesp. 108
Dissipation and Efficiency in Autonomous and Externally Forced Reactions, Including Several Biochemical Systems
Dissipation in Irreversible Processesp. 113
Introductionp. 113
Exact Solution for Thermal Conductionp. 113
Newton's Law of Coolingp. 113
Fourier Equationp. 114
Exact Solution for Chemical Reactionsp. 116
Invalidity of the Principle of Minimum Entropy Productionp. 118
Invalidity of the 'Principle of Maximum Entropy Production'p. 119
Editorialp. 119
Referencesp. 119
Efficiency of Irreversible Processesp. 121
Introductionp. 121
Power and Efficiency of Heat Enginesp. 122
Referencesp. 129
Finite-Time Thermodynamicsp. 131
Introduction and Backgroundp. 131
Constructing Generalized Potentialsp. 133
Examples: Systems with Finite Rates of Heat Exchangep. 134
Some More Realistic Applications: Improving Energy Efficiency by Optimal Controlp. 137
Optimization of a More Realistic System: The Otto Cyclep. 139
Another Example: Distillationp. 141
Choices of Objectives and Differences of Extremap. 144
Referencesp. 146
Reduction of Dissipation in Heat Engines by Periodic Changes of External Constraintsp. 147
Introductionp. 147
A Simple Examplep. 147
Some Calculations and Experimentsp. 152
Calculationsp. 152
Experimentsp. 157
Referencesp. 158
Dissipation and Efficiency in Biochemical Reactionsp. 159
Introductionp. 159
An Introduction to Oscillatory Reactionsp. 159
An Oscillatory Reaction with Constant Input of Reactantsp. 163
Referencesp. 168
Three Applications of Chapter 16p. 169
Thermodynamic Efficiency in Pumped Biochemical Reactionsp. 169
Thermodynamic Efficiency of a Proton Pumpp. 172
Experiments on Efficiency in the Forced Oscillatory Horse-Radish Peroxidase Reactionp. 174
Referencesp. 179
Stochastic Theory and Fluctuations in Systems Far from Equilibrium, Including Disordered Systems
Fluctuation-Dissipation Relationsp. 183
Referencesp. 188
Fluctuations in Limit Cycle Oscillatorsp. 191
Referencesp. 195
Disordered Kinetic Systemsp. 197
Referencesp. 202
Indexp. 205
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