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Entropy 2018, 20(3), 187; https://doi.org/10.3390/e20030187

On the Possibility of Calculating Entropy, Free Energy, and Enthalpy of Vitreous Substances

Saint-Petersburg National Research University of Information Technologies, Mechanics and Optics (ITMO University), 4 Birzhevaya linia, 199034 St. Petersburg, Russia
Received: 26 January 2018 / Revised: 23 February 2018 / Accepted: 8 March 2018 / Published: 11 March 2018
(This article belongs to the Special Issue Residual Entropy and Nonequilibrium States)
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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. View Full-Text
Keywords: entropy; statistical physics; thermodynamics of the vitreous state; third law of thermodynamics; glass transition; structure of glasses entropy; statistical physics; thermodynamics of the vitreous state; third law of thermodynamics; glass transition; structure of glasses
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Nemilov, S.V. On the Possibility of Calculating Entropy, Free Energy, and Enthalpy of Vitreous Substances. Entropy 2018, 20, 187.

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