Micellar accelerated reduction of ethylenediaminetetraacetatocobaltate(III) by 1-benzyl-1,4-dihydronicotinamide.

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The electrostatic and hydrophobic effects of ionic micelles on the reduction of ethylenediaminetetraacetato cobaltate(III) ([Co(edta)]−) by 1-benzyl-1,4-dihydronicotinamide (BNAH) were investigated with dodecyltrimethylammonium chloride (DTAC) and/or sodium dodecyl sulfate (SDS). Cationic DTAC accelerated the reduction of [Co(edta)]−, while anionic SDS retarded the reaction. The micellar effects of DTAC on the present reaction at 30°C were kinetically analyzed by using the ion-exchange model and the Berezin's approach: the evaluated rate constant, (1.0±0.1–1.1±0.4)×10−4 mol−1 dm3 s−1, for the micellar-phase reaction was ten times smaller than that, 1.46×10−3 mol−1 dm3 s−1, for the aqueous-phase one. This fact was well-explained by the electron-transfer rate constant calculated with the experimentally determined redox potentials of BNAH and [Co(edta)]−. The cationic DTAC micelles, however, resulted in considerably larger value (3.58×10−3 mol−1 dm3 s−1) of overall reaction rate constant than that (1.46×10−3 mol−1 dm3 s−1) of nonmicellar one, because the apparent concentrations of the reactants in the micellar phase increased remarkably by condensation of BNAH and [Co(edta)]− to the micelles through the hydrophobic interaction and the electrostatic interaction, respectively.
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