Stochastic Thermodynamics of Mesoscopic Electrochemical Reactions

介观电化学反应的随机热力学（英文）

In this work, we discussed the stochastic thermodynamics of mesoscopic electron transfer reactions between ions and electrodes. With a relationship between the reaction rate con- stant 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 en- tropy change Ast is defined as the summation of the system entropy change As and the heat dissipation/βq such that △st=△s＋βq. Even though the heat dissipation depends linearly on the electrode potential, the total entropy change is found to satisfy the fluctuation theo- rem 〈e-△st 〉=1, and hence a second law-like inequality reads （△st）≥0. Our study provides a practical methodology for the stochastic thermodynamics of electrochemical reactions, which may find applications in biochemical and electrochemical reaction systems.