Non-linear frequency response analysis of the kinetics of electrochemical reactions: a case study – ferrocyanide oxidation kinetics

Abstract

In general, electrochemical (EC) systems are non-linear, which means they respond nonlinearly to a frequency-dependent periodic input perturbation of high amplitude imposed around a steady-state. In addition, the kinetics of EC reactions are quite complex and different rivalling model presentations can be formulated for certain EC reaction. While standard electrochemical methods (steady-state and electrochemical impedance spectroscopy) showed low sensitivity towards the model discrimination, non-linear frequency response analysis (NLFRA) of EC kinetics can appear advantageous for this purpose. In this work, NLFRA is applied in experimental and theoretical study of ferrocyanide oxidation as a model EC reaction.