Theory of reverse scan square-wave voltammetry influenced by the kinetics of reactant adsorption |
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Authors: | Milivoj Lovrić Šebojka Komorsky-Lovrić |
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Affiliation: | (1) Department of Environmental Engineering, Engineering Faculty, Mersin University, Mersin, 33360, Turkey |
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Abstract: | A model of electrode reaction complicated by slow adsorption of the reactant is developed for square-wave voltammetry with inverse scan direction. The relationship between the dimensionless net peak current and the logarithm of dimensionless rate constant of adsorption is a curve with a minimum and a maximum. For this reason the ratio of real net peak current and the square-root of frequency is a non-linear function of the logarithm of frequency and exhibits either a maximum or a minimum. The frequency of extreme serves for the estimation of the rate constant: log(k ads /D 1/2 ) = log(k* ads )crit + 0.5 log f crit , where (k* ads ) crit is a critical dimensionless rate constant of adsorption. Square-wave voltammetry is sensitive to the kinetics of adsorption if k ads < 102 cm s−1 ![MediaObjects/11532_2010_34_Fig1_HTML.jpg](/content/101J97567275P045/MediaObjects/11532_2010_34_Fig1_HTML.jpg) |
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