Thermodynamics and Fluctuations far from Equilibrium / Edition 1

Thermodynamics and Fluctuations far from Equilibrium / Edition 1

by John Ross
     
 

ISBN-10: 3540745548

ISBN-13: 9783540745549

Pub. Date: 02/29/2008

Publisher: Springer Berlin Heidelberg

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

Overview

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.

Product Details

ISBN-13:
9783540745549
Publisher:
Springer Berlin Heidelberg
Publication date:
02/29/2008
Series:
Springer Series in Chemical Physics, #90
Edition description:
2008
Pages:
209
Product dimensions:
6.40(w) x 9.30(h) x 0.80(d)

Table of Contents


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

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