Oxidation of paracetamol by N-chloro-p-toluene sulfonamide (Chloramine-T) in aqueous acid perchlorate medium: A kinetic and mechanistic pathway

780-787Kinetics and mechanism of oxidation of paracetamol by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. Accounting for all such observations, a plausible reaction mechanism has been suggested. The activation parameters such as energy and entropy of activation have been calculated to be (58.63 ± 0.91) kJ mol−1 and (−88.75 ± 4.54) J K−1 mol−1 respectively employing Eyring equation. The stoichiometry of the reaction has been observed to be two moles of the oxidant for a mole of the substrate. The rate of the reaction is retarded by toluene- p-sulfonamide as well as hydrogen ion concentration. The oxidation product of paracetamol has been spectrally confirmed to be quinine oxime. To further support our proposed mechanism, density functional theory (DFT) computations at M06-2X/6-31G(d,p) level of theory have been performed, showing that activation energy barriers predict the same reactivity trend as shown by the kinetic experiments

Kinetics and mechanism of electron transfer reaction: Oxidation of sulfanilic acid by hexachloroiridate(IV) in acid medium

1074-1079The kinetics of oxidation of sulfanilic acid by [IrCl6]2- in acid medium has been studied. The reaction is overall second order being first order with respect to each reactant. However, rate is retarded by hydrogen ion concentration. Various proposals have been suggested on the basis of reactivity of Ir(IV) species. The activation parameters such as energy and entropy of activation calculated by Eyring equation are found to be 59.99±0.93 kJ mol-1 and -106.44±2.2 J K-1 mol-1 respectively. The oxidation product, 2-keto-azoxy- benzene-4,4′-disulfonic acid has been confirmed spectrally

Kinetics and mechanism of electron transfer reactions : Ruthenium(III) catalyzed oxidation of butanone by peroxomonosulphate in acid aqueous medium - Discrimination between keto-enol tautomerism

Department of Chemistry, University of Rajasthan, Jaipur-302 004, Rajasthan, India Manuscript received 22 February 2011, accepted 28 July 2011 Kinetics of oxidation of cyclohexanone by peroxomonosulphate has been studied in acid perchlorate medium. The kinetic rate laws based on the proposed mechanisms are similar. This reaction is second order in nature. A plausible reaction mechanism has been suggested. The preferred mode of electron transfer is via keto and not by enol form of the ketones and thus keto-enol tautomerism does not play any role. Activation parameters such as energy and entropy of activation have been calculated