Stochastic Thermodynamics of Mesoscopic Electrochemical Reactions

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 Δst=Δs+βq. Even though the heat dissipation depends linearly on the electrode potential, the total entropy change is found to satisfy the fluctuation theorem ⟨e−Δst⟩=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.