Direct current polarography in the presence of alternating voltages. II. Irreversible systems

Abstract

The superposition of a small alternating voltage on the normal D.C. voltage applied at the dropping mercury electrode (D.M.E.) results in the case of irreversible systems in a marked displacement of the entire D.C. wave, in contradistinction to those cases known to be reversible. Such a displacement has been interpreted in terms of an ionic picture. The cases examined were ZnO₂^--, Fe⁺⁺, Ni⁺⁺, Sb⁺⁺⁺ in the presence of varying concentrations of Cl^-, and Cd⁺⁺ in the presence of varying concentrations of cyclohexanol. The effect of frequency was investigated.