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.
Table des matières
Thermodynamics and Fluctuations Far from Equilibrium.- to Part I.- Thermodynamics Far from Equilibrium: Linear and Nonlinear One-Variable Systems.- Thermodynamic State Function for Single and Multivariable Systems.- Continuation of Deterministic Approach for Multivariable Systems.- Thermodynamic and Stochastic Theory of Reaction–Diffusion Systems.- Stability and Relative Stability of Multiple Stationary States Related to Fluctuations.- Experiments on Relative Stability in Kinetic Systems with Multiple Stationary States.- Thermodynamic and Stochastic Theory of Transport Processes.- Thermodynamic and Stochastic Theory for Non-Ideal Systems.- Electrochemical Experiments in Systems Far from Equilibrium.- Theory of Determination of Thermodynamic and Stochastic Potentials from Macroscopic Measurements.- Dissipation and Efficiency in Autonomous and Externally Forced Reactions, Including Several Biochemical Systems.- Dissipation in Irreversible Processes.- Efficiency of Irreversible Processes.- Finite-Time Thermodynamics.- Reduction of Dissipation in Heat Engines by Periodic Changes of External Constraints.- Dissipation and Efficiency in Biochemical Reactions.- Three Applications of Chapter 16.- Stochastic Theory and Fluctuations in Systems Far from Equilibrium, Including Disordered Systems.- Fluctuation–Dissipation Relations.- Fluctuations in Limit Cycle Oscillators.- Disordered Kinetic Systems.