화학공학소재연구정보센터
Catalysis Letters, Vol.122, No.1-2, 144-154, 2008
Osmium(VIII)/ruthenium(III) catalysed oxidation of L-lysine by diperiodatocuprate(III) in aqueous alkaline medium: A comparative mechanistic approach by stopped flow technique
The kinetics of osmium(VIII) and ruthenium(III) catalysed oxidation of L-lysine (L-lys) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.15 mol dm(-3) was studied spectrophotometrically. The reaction between L-lys and DPC in alkaline medium exhibits 1:2 stoichiometry in both catalysed reaction (L-lys: DPC). The reaction is first order in [DPC] and has less than unit order both in [L-lys] and [alkali]. Increase in periodate concentration decreases the rate. Intervention of free radicals was observed in the reaction. The main products were identified by spot test, IR and GC-MS studies. Probable mechanisms are proposed and discussed. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. It has been observed that the catalytic efficiency for the present reaction is in the order of Os(VIII) > Ru(III). The active species of catalyst and oxidant have been identified.