FLUCTUATIONAL SELF-CONSISTENCY OF THE THEORY OF THE ELEMENTARY ACT OFELECTROCHEMICAL REACTIONS IN THE NEIGHBORHOOD OF THE EQUILIBRIUM STATE

The analysis of the theory of the elementary act of electrochemical re actions in relation to the fluctuation-dissipation theorem shows that in the neighbourhood of the equilibrium state the fluctuational self-c onsistency of the theory holds if an integral number of electrons is t ransferred in the elementary reaction act. The fluctuational self-cons istency must also exist for the electrode processes with partial charg e transfer. However, this requirement results in a non-zero correlatio n between fluctuations of the electrochemical reaction rate and the fl uctuations of the number of electrons involved in the elementary act. (C) 1998 Elsevier Science S.A. All rights reserved.