Double-pulse chronoamperometry using short times for the kinetic study of simple quasi-reversible electrochemical reactions at low overpotentials

摘要

This work presents a simple and fast way to determinate the standard heterogeneous rate constant (k(0)) of simple quasi-reversible electrochemical reactions based on the short time double-pulse chronoamperometry at low overpotentials. The value of k(0) was determined for the faradaic reaction involving redox couples of iron complexes on a commercial glassy carbon electrode. The errors involved in this type of analysis were evaluated by finite difference numerical simulations, and accurate determinations of k(0) values have proved to be possible at short times in the case where the charge transfer is considerably hindered in comparison to the mass-transfer of the electroactive species. A very good correspondence was observed between the experimental findings and the theoretical analysis involving the finite difference numerical simulation.