Thermodynamics and fluctuations far from equilibrium

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Searching... PSZ JB	30000010199047	QC311 R67 2008	Open Access Book	Book	Searching... Unknown
Searching... PSZ JB	30000003499021	QC311 R67 2008	Open Access Book	Book	Searching... Unknown

Thermodynamics is one of the foundations of science. The subject has been developed for systems at equilibrium for the past 150 years. The story is di?erent for systems not at equilibrium, either time-dependent systems or systems in non-equilibrium stationary states; here much less has been done, even though the need for this subject has much wider applicability. We have been interested in, and studied, systems far from equilibrium for 40 years and present here some aspects of theory and experiments on three topics: Part I deals with formulation of thermodynamics of systems far from equilibrium, including connections to ?uctuations, with applications to n- equilibrium stationary states and approaches to such states, systems with multiple stationary states, reaction di?usion systems, transport properties, andelectrochemicalsystems. Experimentsto substantiatethe formulationare also given. In Part II, dissipation and e?ciency in autonomous and externally forced reactions, including several biochemical systems, are explained. Part III explains stochastic theory and ?uctuations in systems far from equilibrium, ?uctuation-dissipation relations, including disordered systems. We concentrate on a coherent presentation of our work and make conn- tions to related or alternative approaches by other investigators. There is no attempt of a literature survey of this ?eld. We hope that this book will help and interest chemists, physicists, b- chemists, and chemical and mechanical engineers. Sooner or later, we expect this book to be introduced into graduate studies and then into undergraduate studies, and hope that the book will serve the purpose.

Part I Thermodynamics and Fluctuations Far from Equilibrium
1 Introduction to Part I	p. 3
1.1 Some Basic Concepts and Definitions	p. 4
1.2 Elementary Thermodynamics and Kinetics	p. 7
References	p. 10
2 Thermodynamics Far from Equilibrium: Linear and Nonlinear One-Variable Systems	p. 11
2.1 Linear One-Variable Systems	p. 11
2.2 Nonlinear One-Variable Systems	p. 12
2.3 Dissipation	p. 15
2.4 Connection of the Thermodynamic Theory with Stochastic Theory	p. 16
2.5 Relative Stability of Multiple Stationary Stable States	p. 18
2.6 Reactions with Different Stoichiometries	p. 20
References	p. 21
3 Thermodynamic State Function for Single and Multivariable Systems	p. 23
3.1 Introduction	p. 23
3.2 Linear Multi-Variable Systems	p. 25
3.3 Nonlinear Multi-Variable Systems	p. 29
References	p. 32
4 Continuation of Deterministic Approach for Multivariable Systems	p. 33
References	p. 39
5 Thermodynamic and Stochastic Theory of Reaction-Diffusion Systems	p. 41
5.1 Reaction-Diffusion Systems with Two Intermediates	p. 44
5.1.1 Linear Reaction Systems	p. 45
5.1.2 Non-Linear Reaction Mechanisms	p. 47
5.1.3 Relative Stability of Two Stable Stationary States of a Reaction-Diffusion System	p. 49
5.1.4 Calculation of Relative Stability in a Two-Variable Example, the Selkov Model	p. 52
References	p. 58
6 Stability and Relative Stability of Multiple Stationary States Related to Fluctuations	p. 59
References	p. 64
7 Experiments on Relative Stability in Kinetic Systems with Multiple Stationary States	p. 65
7.1 Multi-Variable Systems	p. 65
7.2 Single-Variable Systems: Experiments on Optical Bistability	p. 68
References	p. 71
8 Thermodynamic and Stochastic Theory of Transport Processes	p. 73
8.1 Introduction	p. 73
8.2 Linear Transport Processes	p. 75
8.2.1 Linear Diffusion	p. 75
8.2.2 Linear Thermal Conduction	p. 77
8.2.3 Linear Viscous Flow	p. 79
8.3 Nonlinear One-Variable Transport Processes	p. 82
8.4 Coupled Transport Processes: An Approach to Thermodynamics and Fluctuations in Hydrodynamics	p. 83
8.4.1 Lorenz Equations and an Interesting Experiment	p. 83
8.4.2 Rayleigh Scattering in a Fluid in a Temperature Gradient	p. 87
8.5 Thermodynamic and Stochastic Theory of Electrical Circuits	p. 87
References	p. 87
9 Thermodynamic and Stochastic Theory for Non-Ideal Systems	p. 89
9.1 Introduction	p. 89
9.2 A Simple Example	p. 90
References	p. 93
10 Electrochemical Experiments in Systems Far from Equilibrium	p. 95
10.1 Introduction	p. 95
10.2 Measurement of Electrochemical Potentials in Non-Equilibrium Stationary States	p. 95
10.3 Kinetic and Thermodynamic Information Derived from Electrochemical Measurements	p. 97
References	p. 100
11 Theory of Determination of Thermodynamic and Stochastic Potentials from Macroscopic Measurements	p. 101
11.1 Introduction	p. 101
11.2 Change of Chemical System into Coupled Chemical and Electrochemical System	p. 102
11.3 Determination of the Stochastic Potential [phi] in Coupled Chemical and Electrochemical Systems	p. 104
11.4 Determination of the Stochastic Potential in Chemical Systems with Imposed Fluxes	p. 105
11.5 Suggestions for Experimental Tests of the Master Equation	p. 107
References	p. 108
Part II Dissipation and Efficiency in Autonomous and Externally Forced Reactions, Including Several Biochemical Systems
12 Dissipation in Irreversible Processes	p. 113
12.1 Introduction	p. 113
12.2 Exact Solution for Thermal Conduction	p. 113
12.2.1 Newton's Law of Cooling	p. 113
12.2.2 Fourier Equation	p. 114
12.3 Exact Solution for Chemical Reactions	p. 116
12.4 Invalidity of the Principle of Minimum Entropy Production	p. 118
12.5 Invalidity of the 'Principle of Maximum Entropy Production'	p. 119
12.6 Editorial	p. 119
References	p. 119
13 Efficiency of Irreversible Processes	p. 121
13.1 Introduction	p. 121
13.2 Power and Efficiency of Heat Engines	p. 122
References	p. 129
14 Finite-Time Thermodynamics	p. 131
14.1 Introduction and Background	p. 131
14.2 Constructing Generalized Potentials	p. 133
14.3 Examples: Systems with Finite Rates of Heat Exchange	p. 134
14.4 Some More Realistic Applications: Improving Energy Efficiency by Optimal Control	p. 137
14.5 Optimization of a More Realistic System: The Otto Cycle	p. 139
14.6 Another Example: Distillation	p. 141
14.7 Choices of Objectives and Differences of Extrema	p. 144
References	p. 146
15 Reduction of Dissipation in Heat Engines by Periodic Changes of External Constraints	p. 147
15.1 Introduction	p. 147
15.2 A Simple Example	p. 147
15.3 Some Calculations and Experiments	p. 152
15.3.1 Calculations	p. 152
15.3.2 Experiments	p. 157
References	p. 158
16 Dissipation and Efficiency in Biochemical Reactions	p. 159
16.1 Introduction	p. 159
16.2 An Introduction to Oscillatory Reactions	p. 159
16.3 An Oscillatory Reaction with Constant Input of Reactants	p. 163
References	p. 168
17 Three Applications of Chapter 16	p. 169
17.1 Thermodynamic Efficiency in Pumped Biochemical Reactions	p. 169
17.2 Thermodynamic Efficiency of a Proton Pump	p. 172
17.3 Experiments on Efficiency in the Forced Oscillatory Horse-Radish Peroxidase Reaction	p. 174
References	p. 179
Part III Stochastic Theory and Fluctuations in Systems Far from Equilibrium, Including Disordered Systems
18 Fluctuation-Dissipation Relations	p. 183
References	p. 188
19 Fluctuations in Limit Cycle Oscillators	p. 191
References	p. 195
20 Disordered Kinetic Systems	p. 197
References	p. 202
Index	p. 205

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