Steady State Reciprocal Derivative Chronopotentiometry with Programmed Currents at Microelectrodes

Equations corresponding to the application of Reciprocal Derivative Chronopotentiometry with programmed currents to spherical and disk microelectrodes under steady state conditions have been deduced. Traditional stationary dt/dE vs. E curves for a current time function of the form I(t)=I₀t^u, u>0, and the new dI/dE vs. E curves, which do not depend on the particular characteristics of the applied programmed current I(t) are shown for any degree of reversibility of the electrode process. The evolution from transient to steady state for both derivative techniques has been analyzed. Criteria for characterizing reversible and totally irreversible stationary derivative curves, together with easy methods for determining thermodynamic and kinetic parameters of the charge transfer process from the measure of peak parameters are proposed. The validity of the theoretical predictions has been experimentally tested with hexachloroiridate(IV) reversible oxidation and with iron(III) irreversible reduction in aqueous media.