• S T Nandibewoor

      Articles written in Journal of Chemical Sciences

    • Osmium (VIII)-mediated oxidation of arsenic (III)/antimony (III) by 1-equivalent oxidants

      S R Kampli S T Nandibewoor

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      Os(VIII) catalysis of oxidation of As(III)/Sb(III) by 1-equivalent oxidants like Ce(IV) and Mn(III) in acid medium is studied. A multistep mechanism involving the intervention of the intermediate oxidation states of osmium is found to apply. Specific rates of different steps in the mechanism are estimated and used to calculate reaction rates which are in reasonable agreement with those of experiment.

    • Mechanistic study of ruthenium (III) catalysed oxidation of L-lysine by diperiodatoargentate (III) in aqueous alkaline medium

      R R Hosamani S T Nandibewoor

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      The kinetics of Ru(III) catalysed oxidation of L-lysine by diperiodatoargentate (III) (DPA) in alkaline medium at 298 K and a constant ionic strength of 0.50 mol dm-3 was studied spectrophotometrically. The oxidation products are aldehyde (5-aminopentanal) and Ag (I). The stoichiometry is i.e. [L-lysine] : [DPA] = 1 : 1. The reaction is of first order in [Ru(III)] and [DPA] and is less than unit order in both [L-lys] and [alkali]. Addition of periodate had a retarding effect on the reaction. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)-L-lysine complex, which further reacts with one molecule of monoperiodatoargentate(III) (MPA) in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test, IR, GC-MS studies. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.

    • Mechanistic investigation on the oxidation of kinetin by Ag(III) periodate complex in aqueous alkaline media: A kinetic approach

      S D Lamani A M Tatagar S T Nandibewoor

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      The oxidation of amino acid, kinetin (KNT) by diperiodatoargentate(III) (DPA) in alkaline medium at a constant ionic strength of 0.5 mol dm-3 was studied spectrophtometrically. The reaction between KNT and DPA in alkaline medium exhibits 1 : 3 stoichiometry (KNT : DPA). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidences, a mechanism involving the monoperiodatoargentate(III) (MPA) as the reactive oxidant species has been proposed. The products, furon-2-methanol and para-nitro-purine were identified by spot test and characterized by spectral studies. The rate constants and associated activation parameters for the proposed mechanism as well as the thermodynamic quantities for different equilibrium steps are reported and discussed.

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