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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)
Author(s) -
Scharbert Bernd,
Speiser Bernd
Publication year - 1989
Publication title -
journal of chemometrics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.47
H-Index - 92
eISSN - 1099-128X
pISSN - 0886-9383
DOI - 10.1002/cem.1180030108
Subject(s) - dimensionless quantity , cerium , electron transfer , chemistry , electrochemistry , diffusion , analytical chemistry (journal) , cyclic voltammetry , linear regression , thermodynamics , electrode , inorganic chemistry , mathematics , chromatography , statistics , physics
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.