1. The effect of the double layer structure on the kinetics of electrode processes is due, in the general case, to three factors: (a) variation of the effective potential difference between the electrode and the particle under discharge; (b) variation of ion concentrations (in particular for hydrogen ions) in the layer surrounding the electrode, as compared to the bulk of the solution; (c) variation of sorbtivity, which is especially important for processes preceded by a chemical reaction. The effect of these factors on polarographic waves of different natures is shown. 2. Reduction waves of organic substances consuming protons in, the potential-determining step represent processes preceded by fast protonation. It is shown that in the majority of cases protonation preceding electron transfer takes place on the electrode surface and involves adsorbed particles, i.e. it occurs under conditions of maximum effect on the double layer structure and on factors accounting for the adsorption on the electrode. 3. It is shown that the rate of preceding reactions in the surface layer is considerably higher than in the bulk of the solution, thus “surface” kinetic waves, for example, preceded by protonation may be observed even at pH's higher by 7—8 units than the p K A value of the acid under discharge. 4. It is shown that in comparing the E 1/2's of irreversible waves of organic compounds, not only pH, but also the ionic strenght, buffer capacity and the nature of buffer and indifferent electrolyte components, as well as the possible effect on E 1/2 of the electrode products formed, are to be taken into account when determining the E 1/2 value. 5. Investigation of the effect of ionic strenght on polarographic waves often allows the nature of the particle under discharge and the mechanisim of the electrode process to be judjed.