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 ...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.展开更多
基金supported by the National Natural Science Foundation of China(No.21403041 and No.21503048)the Startup Packages from Guizhou Education University
文摘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.
