Sweep voltammetry with a semi-circular potential waveform: Electrode kinetics

We introduce a sensitive, novel way to determine the standard electrochemical rate constant, k(o), through the application of a semi-circular potential wave at a microdisc electrode. A one-electron reduction reaction is investigated and simulated for varying rate constants. It is shown that the voltammograms of a semi-circular potential wave exhibit significantly greater sensitivity to the changes in electrode kinetics compared to the conventional linear potential wave. A reprogramming of a commercial potentiostat can yield a one order magnitude greater sensitivity and can be used to determine the rate constant of a system under investigation.