Non-equilibrium configurational Prigogine–Defay ratio

Abstract

Classically, the Prigogine–Defay (PD) ratio involves differences in isobaric heat capacity, isothermal compressibility, and isobaric thermal expansion coefficient between a super-cooled liquid and the corresponding glass at the glass transition. However, determining such differences by extrapolation of coefficients that have been measured for super-cooled liquid and glassy state, respectively, poses the problem that it does not exactly take into account the non-equilibrium character of the glass transition. In this paper, we assess this question by taking into account the time dependence of configurational contributions to the three thermodynamic coefficients in the glass transition range upon varying temperature and/or pressure. Macroscopic non-equilibrium thermodynamics is applied to obtain a generalised form of the PD ratio. The classical PD ratio can then be taken as a particular case of this generalisation. Under some assumptions, the configurational PD ratio (CPD ratio) can be expressed in terms of fictive temperature and fictive pressure which, hence, provides another possibility to experimentally verify this formalism.