Nonlinear Frequency Response Analysis of the Ferrocyanide Oxidation Kinetics. Part I. A Theoretical Analysis

Abstract

In this work, a nonlinear frequency response (NLFR) analysis was used for a first time in a theoretical study of nonlinear behavior of electrochemical (EC) ferrocyanide oxidation as a simple model reaction. Analytical expressions of the first- and second-order frequency response functions (FRFs) are derived. The first-order FRF is equivalent to the EC admittance and contains information about the linear behavior of the system, whereas the second-order FRF contains additional nonlinear information. The influence of different parameters, such as the heterogeneous rate constant, solution resistance, double-layer capacitance, diffusion coefficients of the reacting species, and electrode rotation rate on the characteristics of the first- and second-order FRFs was checked and discussed. It was found that the second-order FRF is more sensitive to the changes of the studied parameters than the first-order FRF. Experimental verification of the NLFR analysis of EC ferrocyanide oxidation is presented in Part II of this work.