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Title: Kinetics of oxidation of crotonic acid by sodium N-chloro-p-toluenesulphonamide in the presence of Pd(II) and Os(VIII) as homogeneous catalysts
Authors: Ashish
Singh, Ajaya Kumar
Singh, Ashok Kumar
Singh, Bharat
Issue Date: Aug-2004
Publisher: NISCAIR-CSIR, India
IPC Code: Int. Cl. 7 B01J 23/44; B01J 27/185; C07B 33/00
Abstract: The kinetics of Pd (II) and Os(VIII) catalysed oxidation of crotonic acid (CA) by chloramine-T (CAT) in perchloric acid have been investigated. The reactions are zero order in [chloramine-T] and first order each in both [Pd(II)] and [Os(VIII)], while first order in [CA] at lower concentrations tending towards zero order at its higher concentrations. Positive effect of added [Clˉ] and zero effect of added p-toluenesulphonamide (PTS ) have been observed in Pd (II) catalysed reaction, while in Os(VIII) catalysed reaction negative effect of PTS on rate of reaction has been observed. Negligible effect of change in [H+] and ionic strength of the medium, and rate decrease with decrease in dielectric constant of the medium have been observed in both Pd(II) and Os(VIII) catalysed reactions. The catalytic efficiency is in the order, Pd (II) > Os(VIII). The products of oxidation in both reactions are acetaldehyde and glyoxylic acid. Activation parameters have been computed and mechanistic steps, consistent with the kinetic results, reaction stoichiometry and product analysis for both catalysed reactions have been discussed.
Page(s): 1645-1653
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.43A(08) [August 2004]

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