Abstract Originally derived by Walther Nernst more than a century ago, the Nernst equation for the open-circuit voltage is a cornerstone in the analysis of electrochemical systems. Unfortunately, the assumptions behind its derivation are often overlooked in the literature, leading to incorrect forms of the equation when applied to complex systems (for example, those with ion-exchange membranes or involving mixed potentials). Such flaws can be avoided by applying a correct thermodynamic derivation independently of the form in which the electrochemical reactions are written. The proper derivation of the Nernst equation becomes important, for instance, in modeling of vanadium redox flow batteries or zinc-air batteries. The rigorous path towards the Nernst equation derivation starts in non-equilibrium thermodynamics.

中文翻译：

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开路电压来自非平衡热力学

摘要 开路电压的 Nernst 方程最初由 Walther Nernst 在一个多世纪前推导出来，是电化学系统分析的基石。不幸的是，其推导背后的假设在文献中经常被忽视，导致当应用于复杂系统（例如，那些具有离子交换膜或涉及混合电位的系统）时方程的形式不正确。这些缺陷可以通过应用正确的热力学推导来避免，而与电化学反应的书写形式无关。能斯特方程的正确推导变得很重要，例如，在钒氧化还原液流电池或锌空气电池的建模中。推导能斯特方程的严格路径始于非平衡热力学。