Beyond Onsager–Casimir Relations: Shared Dependence of Phenomenological Coefficients on State Variables,The Journal of Physical Chemistry Letters

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Beyond Onsager–Casimir Relations: Shared Dependence of Phenomenological Coefficients on State Variables
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-12-01 00:00:00 , DOI: 10.1021/acs.jpclett.8b03281
Václav Klika ₁ , Andrew L. Krause ₂

Affiliation

Phenomenological coefficients in linear nonequilibrium thermodynamics have been considered to be independent, apart from restrictions due to the Onsager–Casimir reciprocal relations and the requirement to have non-negative entropy production. Recently, it has been shown that functional constraints between these coefficients may hold, restricting their dependence on state variables, especially in the case of coupled phenomena. Here we demonstrate that such restrictions require only mild assumptions on the system of interest and are, in fact, much more constraining than previously reported. Such constraints vastly reduce the set of plausible models for constitutive relations and allow for simpler experimental determinations of dependencies in coupled systems. These results may also clarify inconsistencies in the literature regarding constitutive models used that do not obey these thermodynamic constraints.

中文翻译：

超越Onsager-Casimir关系：现象学系数对状态变量的共同依赖

线性非平衡热力学中的现象学系数被认为是独立的，除了由于Onsager-Casimir倒数关系和要求具有非负熵产生的限制之外。最近，已经显示出这些系数之间的函数约束可能成立，从而限制了它们对状态变量的依赖，特别是在耦合现象的情况下。在这里，我们证明了这样的限制只需要对感兴趣的系统进行温和的假设，并且实际上比以前的报道有更多的约束。这样的约束极大地减少了本构关系的合理模型集，并允许对耦合系统中的依存关系进行更简单的实验确定。

更新日期：2018-12-01

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