Application of chronopotentiometry and derivative chronopotentiometry with an alternating current to the study of a slow charge transfer in a surface confined redox system

General analytical expressions for the potential–time (E–t) and derivative–potential ((dt/dE)–E) curves of a electroactive monolayer exhibiting a quasi-reversible behaviour, corresponding to the application of an alternating current time function of the form I(t) = I0 cos(ωt), are presented. The use of this programmed current gives rise to singular and characteristic electrochemical responses. The alternating current also allows to obtain cathodic or both anodic and cathodic responses depending on whether the depletion of the adsorbed species was complete or not, and without using more than one applied current. Moreover, in this last case, it is possible to distinguish a reversible or an irreversible process by means of a simple visualisation of the E–t or (dt/dE)–E curves. Easy methods for estimating thermodynamic and kinetic parameters of the electroactive film are proposed and experimentally tested and compared with those previously obtained by using Cyclic Voltammetry.