The oxidation of antimony(III) by cerium (IV) has been studied spectrometrically (stopped flow technique) in aqueous sulphuric acid medium. A minute amount of manganese(II) (10 -5 mol dm -3 ) is sufficient to enhance the slow reaction between antimony(III) and cerium(IV). The stoichiometry is 1:2, i.e. one mole of antimony(III) requires two moles of cerium(IV). The reaction is first order in both cerium(IV) and manganese(II) concentrations. The order with respect to antimony(III) concentration is less than unity (ca 0.3). Increase in sulphuric acid concentration decreases the reaction rate. The added sulphate and bisulphate decreases the rate of reaction. The added products cerium(III) and antimony(V) did not have any significant effect on the reaction rate. The active species of oxidant, substrate and catalyst are Ce(SO 4 ) 2 , [Sb(OH)(HSO 4 )] + and [Mn(H 2 O) 4 ] 2+ , respectively. The activation parameters were determined with respect to the slow step. Possible mechanisms are proposed and reaction constants involved have been determined.

The kinetics of oxidation of the anti-ulcer drug, ranitidine hydrochloride (RNH) by diperiodatocuprate(III) (DPC) in alkaline medium was studied spectrophotometrically. The reaction exhibits 1:2 stoichiometry (ranitidine: DPC). The reaction is of first order in [DPC] and has less than unit order in [RNH] and negative fractional order in [alkali]. The involvement of free radicals was observed in the reaction. The oxidation has been found to proceed via a DPC-ranitidine complex, which decomposes slowly in a rate-determining step followed by other fast steps to give the products, which were identified as ranitidine sulfoxide by spot test and spectroscopic studies.

The kinetics of ruthenium(III) catalyzed oxidation of atenolol by diperiodatocuprate(III) in aqueous alkaline medium at a constant ionic strength of I = 0.10 M has been studied spectrophotometrically at 27°C. The reaction between diperiodatocuprate(III) and atenolol in alkaline medium in presence of ruthe nium(III) exhibits 2 : 1 stoichiometry (atenolol: diperiodatocuprate(III)). The main products were identified by spot test, IR, NMR, and LC MS. The reaction is of first order in DPC concentrations and has less than unit order in both ATN and alkali concentrations. The order in ruthenium(III) was unity. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown to proceed via a ruthenium(III)-atenolol complex, which reacts with monoperiodatocuprate(III) in a rate determining step followed by other fast steps to give the products. Probable mechanism is proposed and discussed. The activation parameters with respect to the slow step of the mechanism and thermodynamic quantities were determined and discussed.

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