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Entropy 2010, 12(10), 2199-2243; doi:10.3390/e12102199

Thermodynamics and Fluctuations Far From Equilibrium

Department of Chemistry, Stanford University, Stanford, CA 94305, USA
Bioprocess Engineering Group, IIM-CSIC, Eduardo Cabello 6, Vigo, 36208, Spain
Author to whom correspondence should be addressed.
Received: 21 September 2010 / Revised: 14 October 2010 / Accepted: 18 October 2010 / Published: 21 October 2010
(This article belongs to the Special Issue Nonequilibrium Thermodynamics)
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We review a coherent mesoscopic presentation of thermodynamics and fluctuations far from and near equilibrium, applicable to chemical reactions, energy transfer and transport processes, and electrochemical systems. Both uniform and spatially dependent systems are considered. The focus is on processes leading to and in non‑equilibrium stationary states; on systems with multiple stationary states; and on issues of relative stability of such states. We establish thermodynamic state functions, dependent on the irreversible processes, with simple physical interpretations that yield the work available from these processes and the fluctuations. A variety of experiments are cited that substantiate the theory. The following topics are included: one-variable systems, linear and nonlinear; connection of thermodynamic theory with stochastic theory; multivariable systems; relative stability of different phases; coupled transport processes; experimental determination of thermodynamic and stochastic potentials; dissipation in irreversible processes and nonexistence of extremum theorems; efficiency of oscillatory reactions, including biochemical systems; and fluctuation-dissipation relations. View Full-Text
Keywords: nonequilibrium thermodynamics; irreversible thermodynamics; stochastic processes; diffusion in chemical reaction kinetics; chemical reactions nonequilibrium thermodynamics; irreversible thermodynamics; stochastic processes; diffusion in chemical reaction kinetics; chemical reactions

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This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Ross, J.; Villaverde, A.F. Thermodynamics and Fluctuations Far From Equilibrium. Entropy 2010, 12, 2199-2243.

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