The kinetics of ruthenium(III) catalysed oxidation of L-Proline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically using a rapid kinetic accessory. The reaction between permanganate and L-Proline in alkaline medium exhibits 2:1 stoichiometry (KMnO4: L-Proline). The reaction shows first order dependence on [permanganate] and [ruthenium(III)] and apparent less than unit order dependence each in L-Proline and alkali concentrations. Reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Initial addition of reaction products did not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect to the slow step of the mechanism and discussed.
The kinetics of Ru I I I catalyzed reduction of hexacyanoferrate(III) [Fe(CN) 6 ] 3) , by atenolol in alkaline medium at constant ionic strength (0.80 mol dm )3 ) has been studied spectrophotometrically, using a rapid kinetic accessory. The reaction between atenolol and [Fe(CN) 6 ] 3) in alkaline medium exhibits 1:2 stoichiometry [atenolol:Fe(CN) 63) ]. The reaction showed first order kinetics in [Fe(CN) 6 ] 3) concentration and apparent less than unit order dependence, each in atenolol and alkali concentrations. Effect of added products, ionic strength and dielectric constant of the reaction medium have been investigated. A retarding effect was observed by one of the products i.e., hexacyanoferrate(II). The main products were identified by i.r., n.m.r., fluorimetric and mass spectral studies. A mechanism involving the formation of a complex between the atenolol and the hydroxylated species of ruthenium(III) has been proposed. The active species of oxidant and catalyst were [Fe(CN) 6 ] 3) and [Ru (H 2 O) 5 OH] 2+ , respectively. The reaction constants involved in the mechanism were evaluated. The activation parameters were computed with respect to the slow step of the mechanism, and discussed.
The kinetics of oxidation of L-proline by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10 mol dm-3was studied spectrophotometrically. The reaction between DPC and L-proline in alkaline medium exhibits 2:1 stoichiometry (DPC: L-Proline). The reaction is of first order in [DPC], less than unit order in [L-proline] and [alkali]. Periodate has no effect on the rate of reaction. The reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Effect of added products and ionic strength of the reaction medium have been investigated. The main products were identified by spot test and I.R spectra. A mechanism involving the DPC as the reactive species of the oxidant and a complex formation with L-proline has been proposed. The reaction constants involved in the different steps of mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also calculated.
The kinetics of oxidation of gabapentin (Neurontin) (GP) by diperiodatonickelate(IV) (DPN) in aqueous alkaline medium was studied spectrophotometrically. The reaction is first order with respect to [DPN] and is an apparent less than unit order, each in [GP] and [alkali] under the experimental conditions. Reaction rate increases with increase in ionic strength and in solvent polarity of the medium. Addition of reaction products has no effect on the reaction rate. A mechanism involving the formation of a complex between the oxidant and substrate has been proposed. The products are identified by spot test, IR and NMR studies. The reaction constants involved in the mechanism were evaluated. There is a good agreement between the observed and calculated rate constants under varying experimental conditions. The activation parameters with respect to the slow step of scheme were evaluated and discussed.
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