• Sharanappa T Nandibewoor

      Articles written in Journal of Chemical Sciences

    • Kinetic, mechanistic and spectral investigation of ruthenium (III)-catalysed oxidation of atenolol by alkaline permanganate (stopped-flow technique)

      Rahamatalla M Mulla Gurubasavaraj C Hiremath Sharanappa T Nandibewoor

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      Kinetics of ruthenium (III) catalyzed oxidation of atenolol by permanganate in alkaline medium at constant ionic strength of 0.30 mol dm3 has been studied spectrophotometrically using a rapid kinetic accessory. Reaction between permanganate and atenolol in alkaline medium exhibits 1 : 8 stoichiometry (atenolol : KMnO4). The reaction shows first-order dependence on [permanganate] and [ruthenium (III)] and apparently less than unit order on both atenolol and alkali concentrations. Reaction rate decreases with increase in ionic strength and increases with decreasing dielectric constant of the medium. Initial addition of reaction products does not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The active species of ruthenium (III) is understood as [Ru(H2O)5OH]2+. The reaction constants involved in the different steps of mechanism are calculated. Activation parameters with respect to the slow step of the mechanism are computed and discussed and thermodynamic quantities are also calculated.

    • Mechanistic aspects of Os(VIII) catalysed oxidation of loop diuretic drug furosemide by Ag(III) periodate complex in aqueous alkaline medium

      Shweta J Malode Nagaraj P Shetti Sharanappa T Nandibewoor

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      The kinetics of oxidation of a loop diuretic drug furosemide (Fur) by diperiodatoargentate(III) (DPA) has been investigated in the presence of osmium(VIII) (Os(VIII)) used as homogeneous catalyst in alkaline medium at a constant ionic strength of 0.20mol dm-3 spectrophotometrically attached with HI-TECH SFA-12 stopped flow accessory. The stoichiometry was 1:2 (Fur:DPA). The order of the reaction with respect to [DPA] was unity while the order with respect to [Fur] was less than unity over the concentration range studied. The rate increased with an increase in [OH−] and decreased with an increase in [IO$^−_4$]. The order with respect to [Os(VIII)] was unity. The oxidation products were identified as 2-(4-carboxy-2-oxo-but-3-enylamino)-4-chloro-5-sulfamoyl-benzoic acid and Ag(I). A suitable mechanism was proposed. The reaction constants involved in the different steps of the reaction mechanism were calculated. Kinetic experiments suggest that [Ag(H2IO6)(H2O)2] is the reactive silver(III) species and [OsO4(OH)2]2− is the reactive Os(VIII) species.

    • Kinetics and mechanism of oxidation of L-leucine by alkaline diperiodatocuprate(III)—A free radical intervention, deamination and decarboxylation

      Keerti M Naik Sharanappa T Nandibewoor

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      The kinetics of oxidation of L-leucine by diperiodatocuprate (III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10mol dm-3 was studied spectrophotometrically. The reaction between L-leucine and DPC in alkaline medium exhibits 1:4 stoichiometry (L-leucine: DPC). The reaction is of first order in [DPC] and has less than unit order in both [L-leucine] and [alkali]. However, the order in [Lleucine] and [alkali] changes from first order to zero order as their concentration increase. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreased the rate. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate (III) - L-leucine complex, which decomposed slowly in a rate-determining step followed by other fast steps to give the products. The main oxidative products were identified by spot test and GC-MS. The reaction constants involved in the different steps of the mechanism were calculated.

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