Kinetics and mechanism of the oxidation of (substituted phenylthio)acetic acids by chloramine T.

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概要

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• 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 <I>p</I>-toluenesulfonamide increases the rate. The oxidation process has been shown to proceed <I>via</I> two paths, the major path involving <I>N</I>-chloro-<I>p</I>-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 (<I>r</I>=0.998, <I>s</I>=0.05, confidence limit on ρ±0.15). The activation parameters and isokinetic temperature have been determined.

• 公益社団法人 日本化学会の論文

著者

• Pitchumani Kasi

  School Of Chemistry Madurai Kamaraj University

• Srinivasan Chockalingam

  School of Chemistry, Madurai Kamaraj University

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• Kinetics and mechanism of the oxidation of (substituted phenylthio)acetic acids by chloramine T.

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