Frumkin correction: Microscopic view

Approaches to perfecting analysis of psi-prime effects, based on modeling the reaction layer of electrochemical reactions and allowing for real molecular structure of reactants and products, are considered. Conditions of applicability of the traditional slow-discharge theory relations to systems with reactants of complicated structure are analyzed in a wide overvoltage interval. Special attention is paid to the problem of accounting for nonuniformity of charge distributions in particles of reactants and products. It is shown that it becomes essential to account for the dielectricity of the effective cavity used for modeling the particles, provided the particles are sufficiently large.