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Computer elimination of voltammogram deformations by catalytic reaction to improve their signal for quantitative analysis. Determination of catalytic rate constant
Author(s) -
Rievaj Miroslav,
Korgová Elena,
Mesároš Štefan,
Bustin Dušan
Publication year - 1994
Publication title -
electroanalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.574
H-Index - 128
eISSN - 1521-4109
pISSN - 1040-0397
DOI - 10.1002/elan.1140060212
Subject(s) - catalysis , reaction rate constant , chemistry , symmetrization , signal (programming language) , constant (computer programming) , interference (communication) , analytical chemistry (journal) , electrode , reaction rate , inorganic chemistry , kinetics , physics , chromatography , mathematical analysis , organic chemistry , electrical engineering , mathematics , computer science , channel (broadcasting) , quantum mechanics , programming language , engineering
Abstract Chemical reactions coupled with the electrode process lead to the change of shape and/or height of the measured voltammogram, thus complicating its application in quantitative analysis. This article describes a fractional differintegration procedure which corrects voltammograms for interference by catalytic reactions while simultaneously providing a value for the catalytic rate constants. A peocedure is proposed which utilizes the change of the shape of a reversible charge transfer voltammogram caused by slow and moderately fast catalytic reaction to the elimination of its influence on the analytical signal. It is based upon computer symmetrization of the voltammogram by fractional differentiation of the optimized order and the following correction of the signal. The procedure also enables an advantageous determination of the catalytic reaction rate constant. Since the height of the symmetrized signal is more sensitive to the catalytic process than the height of the original voltammogram, it is of special importance for lower rate constant values. Both elimination of catalytic influence and the determination of rate constant were tested with the Ti(III) NH 2 OH catalytic system.