Chemical information from electroanalytical data. Part 1—Determination of system parameters for quasi‐reversible electron transfer reactions from cyclic voltammetric test data and data for the reduction of cerium (IV) bis(octaethylporphyrinate)

Values of the peak potential, the peak current function and the peak potential difference are extracted from simulated cyclic voltammograms of a quasi‐reversible electron transfer reaction. Variations of the feature values are described by empirical functions of the model parameters α (transfer coefficient) and ψ′ (dimensionless form of the heterogeneous electron transfer rate constant k s ) using multiple linear regression. These functions are used to determine the system parameters α and k s from test data sets of feature values. The predictive power of the features is discussed. It is shown that several features can be used simultaneously in the analysis. Also, α, k s , the formal potential E 0 and the diffusion coefficient D can be estimated simultaneously. Experimental data from the metal‐centered one‐electron reduction of cerium (IV) bis(octaethylporphyrinate), Ce(OEP) 2 , are analyzed using the technique, and values of the system parameters for this electrochemical reaction are determined.