Residual Entropy of Glasses and the Third Law Expression

Abstract

The third law of thermodynamics dictates that the entropy of materials becomes zero as temperature ($T$) approaches zero. Contrarily, glass and other similar materials exhibit nonzero entropy at $T=0$, which contradicts the third law. For over a century, it has been a common practice to evade this problem by regarding glass as nonequilibrium. However, this treatment causes many inconsistencies in thermodynamics theory. This paper provides resolutions to these inconsistencies and provides a rigorous expression of the third law without any exception. To seek the entropy origin, the anthropomorphic feature of entropy must be resolved. Because entropy can be uniquely determined only when thermodynamic coordinates (TCs) are specified, we have to know which are TCs. This requires the reconsideration of the definition of equilibrium for solids in an unambiguous way, which does not depend on the solid structure. On this basis, it is deduced that TCs of solids are the equilibrium positions of atoms. TCs comprise a thermodynamic space, on which a unique value can be assigned to the entropy. For solids, equilibrium states are specified by discrete points in the thermodynamic space, which define atom configurations. Among various atom configurations, only one is thermally activated at sufficiently low temperatures, and others are called frozen configuration, which do not contribute to the temperature dependence of entropy in that region. The rigorous statement of the third law has been established by expressing that the entropy associated with the active configuration vanishes at $T=0$. Residual entropy arises when the entropy is evaluated on an extended space including the frozen configurations, which were previously active at high temperatures. The reconciliation of the two different views is explained through several debates on the glass transition.

Figures (2)

• Figure 1: Distinction between metastable stable (a) and frozen state (b). (c) is the stable state.
• Figure 2: Glass transition represented in the configuration space $K$ versus $T$: (a) heating process starting from the glass state, for which $S_{\rm gl}^{\mathscr A}(0)=0$, (b) cooling process starting from the liquid state at a reference temperature $T_{m}+$, at which the entropy is $S_{\rm li}^{\mathscr B}(T_{m}+)$. The cooling process consists of many cooling and heating steps between $T_{g}+$ and $T_{1}$. The thick dashed line with an arrow indicates an irreversible process, and the thick solid lines with arrows indicate reversible processes.