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 nonequilibrium systems that has been introduced recently [Gujrati, Phys. Rev. E 81, 051130 (2010) and Gujrati, Phys. Rev. E 85, 041128 (2012).] to obtain the generalization of the Maxwell relation and the Clausius-Clapeyron relation that are normally given for equilibrium systems. The use of Jacobians allows for a more compact way to address the generalized Maxwell relations in the presence of internal variables. The Clausius-Clapeyron relation in the subspace of observables shows not only the nonequilibrium modification but also the modification due to internal variables that play a dominant role in glasses to which we apply the above relations. 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. A system possesses several kinds of glass transitions, some conventional (L→gL; gL→GL) in which the state changes continuously and the transition mimics a continuous or second-order transition, and some apparent (L→gL; L→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 Π in the subspace of the observables at these transitions. We find that it is normally different from 1, except at the conventional transition L→gL, where Π=1.