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Abstract
The kinetics of oxidation of uronic acids (UAs), d-glucuronic acid and d-galacturonic acid, by sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) and sodium N-bromobenzenesulfonamide or bromamine-B (BAB) in alkaline medium at 30°C have been investigated and the rate law, rate=k [OX] [UA] [HO−] where [OX]˭[BAT] or [BAB] was observed. The product p-toluenesulfonamide (PTS) or benzenesulfonamide (BSA) and ionic strength have no influence on the rate. The rate decreased when the dielectric constant (ϵ) of the medium was decreased. The rate increased in D2O medium. Proton inventory studies were made in D2O–H2O mixtures. Effect of temperature was studied and from the Arrhenius plots, activation parameters were computed. A mechanism involving the formation of enediol anion, which reacts with positive bromine of the bromamine in the rate-limiting step is suggested.
ACKNOWLEDGMENTS
VS gratefully acknowledges the award of Teacher fellowship by the UGC, New Delhi. KSR thanks the Council of Scientific and Industrial Research (No. 01 (1458) /97 EMR II), New Delhi, for financial support.