Electrochemical Faradaic Spectroscopy

Abstract

Abstract For the purpose of simplification of the electrochemical study under conditions of square‐wave voltammetry (SWV), a simplified form of potential modulation is proposed by replacing the staircase potential ramp with a constant potential. The resulting potential modulation, which could be considered as a pulse form of a chronoamperometric experiment (i. e., square‐wave chronoamperometry), is provisionally termed as electrochemical faradaic spectroscopy, considering the fact that the main tool in the kinetic analysis is the frequency of the potential pulses applied. The proposed technique is illustrated with theoretical analysis of a simple, kinetically controlled electrode reaction of a dissolved redox couple and experimentally verified with the Eu 3+ (aq)/Eu 2+ (aq) redox couple at a mercury electrode. The square‐wave chronoamperometry exhibits unique features of the response absent in both conventional SWV and chronoamperometry, widening the range of accessible electrode kinetics.