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On the relationship between dissipation and the rate of spontaneous entropy production from linear irreversible thermodynamics
Authors:Stephen R. Williams  Debra J. Searles
Affiliation:1. Research School of Chemistry, Australian National University, CanberraACT0200, Australia;2. Australian Institute of Bioengineering and Nanotechnology and School of Chemistry and Molecular Biosciences, The University of Queensland, BrisbaneQLD4072, Australia
Abstract:
When systems are far from equilibrium, the temperature, the entropy and the thermodynamic entropy production are not defined and the Gibbs entropy does not provide useful information about the physical properties of a system. Furthermore, far from equilibrium, or if the dissipative field changes in time, the spontaneous entropy production of linear irreversible thermodynamics becomes irrelevant. In 2000 we introduced a definition for the dissipation function and showed that for systems of arbitrary size, arbitrarily near or far from equilibrium, the time integral of the ensemble average of this quantity can never decrease. In the low-field limit, its ensemble average becomes equal to the spontaneous entropy production of linear irreversible thermodynamics. We discuss how these quantities are related and why one should use dissipation rather than entropy or entropy production for non-equilibrium systems.
Keywords:fluctuation theorem  linear irreversible thermodynamics  non-equilibrium  statistical mechanics  dissipation
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