Open AccessKinetics and mechanism of the oxidation of polyhydric alcohols by dihydroxyditelluratoargentate(III) in alkaline medium
Author(s) -
Shan Ji,
Shuying Huo,
Shigang Shen,
Hanwen Sun
Publication year - 2005
Publication title -
journal of the serbian chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.227
H-Index - 45
eISSN - 1820-7421
pISSN - 0352-5139
DOI - 10.2298/jsc0504592s
Subject(s) - chemistry , kinetics , reaction rate constant , salt (chemistry) , electron transfer , rate equation , radical , first order , reaction rate , reaction mechanism , inorganic chemistry , catalysis , organic chemistry , physics , mathematics , quantum mechanics
The kinetics of oxidation of 1,2-propanediol and 1,2,3-propanetriol by dihydroxyditelluratoargentate(III) (DDA) were studied spectrophotometrically between 298.2 K and 313.2 K in alkaline medium. The reaction rate showed first order dependence on DDA and 1 < nap < 2 order on the reductant. It was found that the pseudo-first order rate constant kobs increased with increasing concentration of OH-1 and decreasing concentration of TeO42-. There is a negative salt effect and no free radicals were detected. In view of this, the dihydroxymonotelluratoargentate(III) species is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed and the rate equations derived from the mechanism can explain all the experimental results. The activation parameters, as well as the rate constants of the rate-determining step were calculated.