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Mechanistic studies of ruthenium(III)-catalyzed oxidation of DL-methionine by hexacyanoferrate(III) in an alkaline medium
Abstract:The kinetics and mechanism of ruthenium(III) catalyzed oxidation of dl-methionine by alkaline hexacyanoferrate(III) (HCF(III)) in an alkaline medium were studied spectrophotometrically at 30±0.1°C. The reaction was first-order-dependent each on [HCF(III)] and [ruthenium(III)] and fractional-order-dependent on [alkali]. The rate of the reaction was found to be decreased with the increase in [methionine]. The main product of oxidation was methionine sulfone nitrile (3-(methylsulfonyl)propanenitrile) and it was identified and confirmed by FT-IR and mass spectral studies. Further, no effect of added reaction product was observed. A plausible mechanism was proposed involving complexation between methionine and ruthenium(III) species, [Ru(H2O)5OH]2+. Thermodynamic parameters for the reaction, E a and Δ S #, were computed using linear least squares method and are found to be 65.83±1.03 kJ/mol and?249.58±3.35 J/K mol, respectively.

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Keywords:oxidation of   smallcaps smallerCapital"  >dl-methionine  hexacyanoferrate(III)  ruthenium(III)  mechanism
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