Heat capacity, enthalpy fluctuations, and configurational entropy in broken ergodic systems

John C. Mauro, Roger J. Loucks, Sabyasachi Sen

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52 Scopus citations

Abstract

A common assumption in the glass science community is that the entropy of a glass can be calculated by integration of measured heat capacity curves through the glass transition. Such integration assumes that glass is an equilibrium material and that the glass transition is a reversible process. However, as a nonequilibrium and nonergodic material, the equations from equilibrium thermodynamics are not directly applicable to the glassy state. Here we investigate the connection between heat capacity and configurational entropy in broken ergodic systems such as glass. We show that it is not possible, in general, to calculate the entropy of a glass from heat capacity curves alone, since additional information must be known related to the details of microscopic fluctuations. Our analysis demonstrates that a time-average formalism is essential to account correctly for the experimentally observed dependence of thermodynamic properties on observation time, e.g., in specific heat spectroscopy. This result serves as experimental and theoretical proof for the nonexistence of residual glass entropy at absolute zero temperature. Example measurements are shown for Corning code 7059 glass.

Original languageEnglish (US)
Article number164503
JournalJournal of Chemical Physics
Volume133
Issue number16
DOIs
StatePublished - Oct 28 2010

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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