Fluctuational self-consistency of the theory of the elementary act of electrochemical reactions in the neighbourhood of the equilibrium state

摘要

The analysis of the theory of the elementary act of electrochemical reactions in relation to the fluctuation-dissipation theorem shows that in the neighbourhood of the equilibrium state the fluctuational self-consistency of the theory holds if an integral number of electrons is transferred in the elementary reaction act. The fluctuational self-consistency must also exist for the electrode processes with partial charge transfer. However, this requirement results in a non-zero correlation between fluctuations of the electrochemical reaction rate and the fluctuations of the number of electrons involved in the elementary act.