14.
Kinetics and Mechanism of Chloramine-T Oxidation of Glycolic Acid
Catalysed by Pd(II) Complex in Alkaline Medium
ABHISHEK KUMAR AND R.A. SINGH*
*Department of Chemistry, Chemical Kinetics Research
Laboratory, T.D.P.G. College, Jaunpur - 222 002 (U.P.), India
E-mail :
rasinghtdc@rediffmail.com
Abstract.
The kinetics of chloramine-T (CAT) oxidation of
glycolic acid (GA) using alkaline solution of palladous chloride
complex as homogeneous catalyst has been investigated at 308 K.
A 1 : 1 stoichiometry has been observed. The reaction shows
first-order kinetics at lower [CAT] but at its higher
concentration first-order tends to zero order. A first-order
dependence of the reaction on both [GA] and [Pd(II)] was
observed. An increase in the concentration of OH– ions increased
the reaction rate, while addition of chloride ions decreased the
rate of reaction. Added p-toluene sulphonamide (reduction
product of chloramine-T) did not influence the reaction rate
while zero effect of variation of ionic strength of the medium
was observed. The overall activation parameters have been
calculated from the Arrhenius plot. Mechanistic steps are
suggested and the rate law derived was found in agreement with
the observed kinetic results, stoichiometry and the reaction
products.
Keywords : Kinetics, Oxidation, Chloramine-T, Glycolic acid,
Pd(II) chloride, Mechanism.
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