Os(VIII)/Ru(III) Catalysed Oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-Valine by Ag(III) Periodate Complex in Aqueous Alkaline Medium: A Comparative Kinetic Study |
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Authors: | Shweta J Malode Nagaraj P Shetti Sharanappa T Nandibewoor |
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Affiliation: | (1) P.G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580003, India; |
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Abstract: | Abstract The kinetics of osmium(VIII) (Os(VIII)) and ruthenium(III) (Ru(III)) catalysed oxidation of l-valine (l-val) by diperiodatoargentate(III) (DPA) in aqueous alkaline medium at 25 °C and a constant ionic strength of 0.006 mol dm−3 was studied spectrophotometrically. The stoichiometry is the same in both the catalysed reactions, i.e., l-val]:DPA] = 1:1. The reaction is of first order in Os(VIII)], Ru(III)], and DPA] and has less than unit order in l-val] and negative fractional order in OH−]. Added periodate had no effect on rate of reaction. The products were identified by spot test and characterized by spectral
studies. The catalytic constant (K
C) was also calculated for both catalysed reactions at different temperatures. The activation parameters with respect to slow
step of the mechanisms were computed and discussed and thermodynamic quantities were also determined. It has been observed
that the catalytic efficiency for the present reaction is in the order of Os(VIII) > Ru(III). The probable active species
of catalyst and oxidant have been identified. |
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