C. Srinivasan, K. Pitchumani
1982
Citations
0
Influential Citations
13
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The kinetics of oxidation of (phenylthio)acetic acid and several (para-substituted phenylthio)acetic acids by chloramine T has been studied in alkaline medium (pH 10.06). A first-order dependence in chloramine T and (phenylthio)acetic acid and a near inverse first-order dependence in hydroxide ion has been observed. The oxidation rate considerably decreases with increase of pH. The reaction exhibits positive salt effect and added p-toluenesulfonamide increases the rate. The oxidation process has been shown to proceed via two paths, the major path involving N-chloro-p-toluenesulfonamide as the main oxidizing species and the other involving hypochlorite ion. Studies with (para-substituted phenylthio)acetic acids show an excellent correlation of the rate constants with σ constants. The reaction exhibits a reaction constant ρ of −2.46 at 308 K (r=0.998, s=0.05, confidence limit on ρ±0.15). The activation parameters and isokinetic temperature have been determined.