The effect of charge distribution within Cr(III) and Eu(III) aquacomplexes on the kinetics of simple electron-transfer reactions at electrodes is considered. The construction of corrected Tafel plots using noninteger effective charges for the reactant and product estimated on the basis of quantum-chemical data was shown to be more reasonable than the traditional approach in which integer charges are assumed. The potential distribution near the electrode has been estimated both by the Gouy-Chapman model and from Monte Carlo simulations for 1-1 supporting electrolytes. Kinetic parameters obtained using the two approaches are compared.