REVERSE DIFFERENTIAL-PULSE VOLTAMMETRY AND POLAROGRAPHY

In this paper we obtain the analytical solution for the reverse differ ential pulse (RDP) technique for a slow electronic transfer process, s tarting from expressions obtained previously for the faradaic response to a triple potential pulse, The solutions are valid for the planar a pproximations of a static mercury drop electrode and of a dropping mer cury electrode, An irreversible reduction process gives rise in the RD P technique to the appearance of two peaks, one at more negative poten tials than the normal reduction potential, E degrees, and the other at more positive potentials than E degrees. From half-width peak and pea k potential measurements, it is possible to evaluate approximately the kinetic and thermodynamic parameters corresponding to the electronic transfer, such as the transfer coefficient, alpha, the normal reductio n potential, E degrees, and the apparent heterogeneous rate constant, k(s). The solutions are checked against experimental examples of well- known processes.