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Physical Review E
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Physical Review E
Article . 2012 . Peer-reviewed
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Article . 2011
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Nonequilibrium thermodynamics. III. Generalization of Maxwell, Clausius-Clapeyron, and response-function relations, and the Prigogine-Defay ratio for systems in internal equilibrium

Authors: Gujrati, P. D.; Aung, P. P.;

Nonequilibrium thermodynamics. III. Generalization of Maxwell, Clausius-Clapeyron, and response-function relations, and the Prigogine-Defay ratio for systems in internal equilibrium

Abstract

We follow the consequences of internal equilibrium in non-equilibrium systems that has been introduced recently [Phys. Rev. E 81, 051130 (2010)] to obtain the generalization of Maxwell's relation and the Clausius-Clapeyron relation that are normally given for equilibrium systems. The use of Jacobians allow for a more compact way to address the generalized Maxwell relations; the latter are available for any number of internal variables. The Clausius-Clapeyron relation in the subspace of observables show not only the non-equilibrium modification but also the modification due to internal variables that play a dominant role in glasses. Real systems do not directly turn into glasses (GL) that are frozen structures from the supercooled liquid state L; there is an intermediate state (gL) where the internal variables are not frozen. Thus, there is no single glass transition. A system possess several kinds of glass transitions, some conventional (L \rightarrow gL; gL\rightarrow GL) in which the state change continuously and the transition mimics a continuous or second order transition, and some apparent (L\rightarrow gL; L\rightarrow GL) in which the free energies are discontinuous so that the transition appears as a zeroth order transition, as discussed in the text. We evaluate the Prigogine-Defay ratio �� in the subspace of the observables at these transitions. We find that it is normally different from 1, except at the conventional transition L\rightarrow gL, where ��=1 regardless of the number of internal variables.

42 pages, 3 figures, citations corrected

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Keywords

Statistical Mechanics (cond-mat.stat-mech), Entropy, FOS: Physical sciences, Mathematical Physics (math-ph), Models, Theoretical, 80, 82, Models, Chemical, Thermodynamics, Computer Simulation, Glass, Condensed Matter - Statistical Mechanics, Mathematical Physics

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
6
Average
Average
Average
Green
bronze