On the relationship between dissipation and the rate of spontaneous entropy production from linear irreversible thermodynamics

Williams, Stephen R.; Searles, Debra J.; Evans, Denis J.

doi:10.1080/08927022.2013.843175

Cited by 7 publications

(3 citation statements)

References 31 publications

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“…A central issue in nonequilibrium physics is whether thermodynamics can be extended to systems far from equilibrium [1][2][3][4][5][6]. Such a theory would be a macroscopic description employing a small number of variables, capable of predicting the final state of a system following removal of some constraint [7].…”

Section: Introductionmentioning

confidence: 99%

Failure of steady-state thermodynamics in nonuniform driven lattice gases

Dickman

2014

Phys. Rev. E

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To be useful, steady-state thermodynamics (SST) must be self-consistent and have predictive value. Consistency of SST was recently verified for driven lattice gases under global weak exchange. Here I verify consistency of SST under local (pointwise) exchange, but only in the limit of a vanishing exchange rate; for a finite exchange rate the coexisting systems have different chemical potentials. I consider the lattice gas with nearest-neighbor exclusion on the square lattice, with nearest-neighbor hopping, and with hopping to both nearest and next-nearest neighbors. I show that SST does not predict the coexisting densities under a nonuniform drive or in the presence of a nonuniform density provoked by a hard wall or nonuniform transition rates. The steady-state chemical potential profile is, moreover, nonuniform at coexistence, contrary to the basic principles of thermodynamics. Finally, I discuss examples of a pair of systems possessing identical steady states but which do not coexist when placed in contact. The results of these studies confirm the validity of SST for coexistence between spatially uniform systems but cast serious doubt on its consistency and predictive value in systems with a finite rate of particle exchange between coexisting regions exhibiting a nonuniform particle density.

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Section: Introductionmentioning

confidence: 99%

Failure of steady-state thermodynamics in nonuniform driven lattice gases

Dickman

2014

Phys. Rev. E

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“…A central issue in nonequilibrium physics is whether thermodynamics can be extended to systems far from equilibrium, in particular, to steady states [1][2][3][4][5][6][7][8][9][10][11][12]. A key thermodynamic concept is phase coexistence; indeed, one of the principal applications of equilibrium thermodynamics is the prediction of phase coexistence based upon knowledge of the isolated phases.…”

Section: Introductionmentioning

confidence: 99%

Phase coexistence far from equilibrium

Dickman

2016

New J. Phys.

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Investigation of simple far-from-equilibrium systems exhibiting phase separation leads to the conclusion that phase coexistence is not well defined in this context. This is because the properties of the coexisting nonequilibrium systems depend on how they are placed in contact, as verified in the driven lattice gas with attractive interactions, and in the two-temperature lattice gas, under (a) weak global exchange between uniform systems, and (b) phase-separated (nonuniform) systems. Thus, far from equilibrium, the notions of universality of phase coexistence (i.e., independence of how systems exchange particles and/or energy), and of phases with intrinsic properties (independent of their environment) are lost.

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“…Furthermore, our approach unambiguously defines † For T-mixing systems, time integrals of transient time-correlation functions of zero-mean physical phase functions converge to finite values in the long time limit. [5] Thus, lim the temperature appearing in the inequality, as discussed below. Our proof is based on the laws of classical mechanics and the axiom of causality.…”

Section: Clausius' Equality For Quasi-static Processes and The Gibbs mentioning

confidence: 99%

A Derivation of the Gibbs Equation and the Determination of Change in Gibbs Entropy from Calorimetry

2016

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In this paper, we give a succinct derivation of the fundamental equation of classical equilibrium thermodynamics, namely the Gibbs equation. This derivation builds on our equilibrium relaxation theorem for systems in contact with a heat reservoir. We reinforce the comments made over a century ago, pointing out that Clausius' strict inequality for a system of interest is within Clausius' set of definitions, logically undefined. Using a specific definition of temperature that we have recently introduced and which is valid for both reversible and irreversible processes, we can define a property that we call the change in calorimetric entropy for these processes. We then demonstrate the instantaneous equivalence of the change in calorimetric entropy, which is defined using heat transfer and our definition of temperature, and the change in Gibbs entropy, which is defined in terms of the full N-particle phase space distribution function. The result shows that the change in Gibbs entropy can be expressed in terms of physical quantities.

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On the relationship between dissipation and the rate of spontaneous entropy production from linear irreversible thermodynamics

Cited by 7 publications

References 31 publications

Failure of steady-state thermodynamics in nonuniform driven lattice gases

Failure of steady-state thermodynamics in nonuniform driven lattice gases

Phase coexistence far from equilibrium

A Derivation of the Gibbs Equation and the Determination of Change in Gibbs Entropy from Calorimetry

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