论文标题
眼镜的残留熵和第三定律表达式
Residual Entropy of Glasses and the Third Law Expression
论文作者
论文摘要
热力学的第三定律表明，随着温度（$ t $）接近零，材料的熵变为零。相反，玻璃和其他类似材料在$ t = 0 $时表现出非零熵，这与第三定律相矛盾。一个多世纪以来，人们普遍避免将这个问题视为非平衡。但是，这种治疗方法在热力学理论中导致许多不一致。本文为这些不一致提供了决议，并在没有任何例外的情况下对第三定律提供了严格的表达。为了寻求熵起源，必须解决熵的拟人化特征。由于只有在指定热力学坐标（TC）时才能唯一确定熵，因此我们必须知道哪些是TC。这就需要重新考虑以明确的方式对固体平衡的定义，这不取决于固体结构。在此基础上，推断出固体的TC是原子的平衡位置。 TCS组成了热力学空间，可以在该空间上将唯一值分配给熵。对于固体，平衡状态由定义原子构型的热力学空间中的离散点指定。在各种原子构型中，只有一种在足够低的温度下热活化，而其他原子构型被称为冷冻构型，这不影响该区域熵的温度依赖性。通过表达与活动配置相关的熵在$ t = 0 $中消失的熵来确定第三定律的严格声明。当在包括冷冻构型（以前在高温下活跃的冷冻构型）评估熵时，会出现残留熵。通过有关玻璃过渡的几次辩论来解释了两种不同观点的和解。
The third law of thermodynamics dictates that the entropy of materials becomes zero as temperature ($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.
