Mechanistic aspects of uncatalyzed and ruthenium(III) catalyzed oxidation of dl-ornithine by copper(III) periodate complex in aqueous alkaline medium: A comparative kinetic study

Abstract

The oxidation of dl-ornithine monohydrochloride (OMH) by diperiodatocuprate(III) (DPC) has been investigated both in the absence and presence of ruthenium(III) catalyst in aqueous alkaline medium at a constant ionic strength of 0.20 mol dm −3 spectrophotometrically. The stiochiometry was same in both the cases, i.e., [OMH]/[DPC] = 1:4. In both the catalyzed and uncatalyzed reactions, the order of the reaction with respect to [DPC] was unity while the order with respect to [OMH] was < 1 over the concentration range studied. The rate increased with an increase in [OH −] and decreased with an increase in [IO 4 −] in both cases. The order with respect to [Ru(III)] was unity. The reaction rates revealed that Ru(III) catalyzed reaction was about eight-fold faster than the uncatalyzed reaction. The oxidation products were identified by spectral analysis. Suitable mechanisms were proposed. The reaction constants involved in the different steps of the reaction mechanisms were calculated for both cases. The catalytic constant ( K C) was also calculated for catalyzed reaction at different temperatures. The activation parameters with respect to slow step of the mechanism and also the thermodynamic quantities were determined. Kinetic experiments suggest that [Cu(H 2IO 6)(H 2O) 2] is the reactive copper(III) species and [Ru(H 2O) 5OH] 2+ is the reactive Ru(III) species.