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介观电化学反应的随机热力学
肖铁军*,周匀
作者单位E-mail
肖铁军* 贵州师范学院, 贵州省纳米材料模拟与计算重点实验室, 贵州省科学云大数据开发及其产业应用协同创新中心, 贵阳 550018 tjxiao@gznc.edu.cn 
周匀 贵州师范学院, 贵州省纳米材料模拟与计算重点实验室, 贵州省科学云大数据开发及其产业应用协同创新中心, 贵阳 550018  
摘要:
关键词:  
DOI:10.1063/1674-0068/31/cjcp1705110
分类号:
基金项目:
Stochastic Thermodynamics of Mesoscopic Electrochemical Reactions
Tie-jun Xiao*,Yun Zhou
Abstract:
In this work, we discussed the stochastic thermodynamics of mesoscopic electron transfer reactions between ions and electrodes. With a relationship between the reaction rate constant and the electrode potential, we find that the heat dissipation βq equals to the dynamic irreversibility of the reaction system minus an internal entropy change term. The total entropy change Δst is defined as the summation of the system entropy change Δs and the heat dissipation βq such that Δsts+βq. Even though the heat dissipation depends linearly on the electrode potential, the total entropy change is found to satisfy the fluctuation theorem <(e)st>=1, and hence a second law-like inequality reads <Δst>≥0. Our study provides a practical methodology for the stochastic thermodynamics of electrochemical reactions, which may find applications in biochemical and electrochemical reaction systems.
Key words:  Mesoscopic chemical reaction  Electron transfer  Electrode potential  Entropy production  Fluctuation theorem