Abstract
A critical analysis for the arguments in support of, and against, the traditional approach to thermodynamics of vitreous state is provided. In this approach one presumes that there is a continuous variation of the entropy in the glass-liquid transition temperature range, or a “continuous entropy approach” towards 0 K which produces a positive value of the entropy at T → 0 K. I find that arguments given against this traditional approach use a different understanding of the thermodynamics of glass transition on cooling a liquid, because it suggests a discontinuity or “entropy loss approach” in the variation of entropy in the glass-liquid transition range. That is based on: (1) an unjustifiable use of the classical Boltzmann statistics for interpreting the value of entropy at absolute zero; (2) the rejection of thermodynamic analysis of systems with broken ergodicity, even though the possibility of analogous analysis was proposed already by Gibbs; (3) the possibility of a finite change in entropy of a system without absorption or release of heat; and, (4) describing the thermodynamic properties of glasses in the framework of functions, instead of functionals. The last one is necessary because for glasses the entropy and enthalpy are not functions of the state, but functionals, as defined by Gibbs’ in his classification.
Highlights
The possibility of calculating the thermodynamic functions for substances in and out of equilibrium states has been debated for almost 100 years, especially because the entropy of some solids, e.g., crystals of CO, N2 O, glassy state of glycerol, glucose, etc., at T → 0 K were much greater than zero, and that violates the Third Law of Thermodynamics
Explanations of positive values of entropy at absolute zero for crystals led to the development of molecular structural models, the first given by Pauling [2]
S0 = 0, at T → 0 K, or S0 > 0, at T → 0 K. These points are: (1) the impossibility of using classical reasons. These points are related to the justification of the eligibility of the concepts, of the terms (Boltzmann) statistics to justify the Third Law of Thermodynamics, (2) the possibility of applying and the models used, and their relevance to the entropy continuity or entropy decrease through the thermodynamics to non-ergodic systems, (3) the impossibility of a finite change in entropy of a liquid-glass transition range. or
Summary
The possibility of calculating the thermodynamic functions for substances in and out of equilibrium states has been debated for almost 100 years, especially because the entropy of some solids, e.g., crystals of CO, N2 O, glassy state of glycerol, glucose, etc., at T → 0 K were much greater than zero, and that violates the Third Law of Thermodynamics. These points are: (1) the impossibility of using classical reasons These points are related to the justification of the eligibility of the concepts, of the terms (Boltzmann) statistics to justify the Third Law of Thermodynamics, (2) the possibility of applying and the models used, and their relevance to the entropy continuity or entropy decrease through the thermodynamics to non-ergodic systems, (3) the impossibility of a finite change in entropy of a liquid-glass transition range. Before discussing their significance further, it is necessary to briefly recall some features of the vitreous state and their history and analysis
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