Theoretical study of irreversible electrode reactions with Henry adsorption using symmetrical cyclic reciprocal derivative chronopotentiometry

Cyclic reciprocal derivative chronopotentiometry (CRDCP) with successive symmetrical programmed currents applied has been extended to describe irreversible electrode reactions where Henry adsorption occurs at the electrode/solution interface. The numerical simulated (dt/dE)–E curves are sensitive to electrode reactions coupled with adsorption processes. Effects of parameters on (dt/dE)–E curves presented in this work involve adsorption constants (KOx and KRed) and kinetic parameters (ks0 and α). Characteristic parameters of (dt/dE)–E curves depend on the adsorption strength markedly and afford effective criteria to determine different cases. The characteristic behavior of (dt/dE)–E curves with successive currents applied give distinct descriptions between two limiting cases – the “surface nature” and “diffusion character”. Comparisons are made with reversible charge transfer reaction with Henry adsorption and uncomplicated, irreversible electrode reaction.