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Journal of Chemical Sciences
Volume 135, 2023
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Arunachalam Sarathi
Articles written in Journal of Chemical Sciences
Volume 122 Issue 3 May 2010 pp 335-340 Full Papers
Ponnusamy Sami Natarajan Mariselvi Kandasamy Venkateshwari Arunachalam Sarathi Kasi Rajasekaran
Rates of electron transfer reaction of thioglycolic acid with vanadium(V) substituted Keggintype heteropolyanion, [PVVVVW10O40]5-, in acetate-acetic acid buffers have been measured spectrophotometrically at 25°C. The order of the reaction with respect to substrate and oxidant is unity. The reaction shows simple second order kinetics at constant pH. The rate of the reaction increases with increase of pH of the medium. The mono-anion HSCH2COO- and di-anion -SCH2COO- are found to be the reactive species. Rate constants for mono-anion and di-anion are evaluated from rate law derived from the mechanism. By applying Rehm-Weller relationship, self exchange rate constant for the -SCH2COO-/S$^{\bullet}$ CH2COO- couple was evaluated as $3.3 \times 10^3$ dm3 mol-1 s-1 at 25°C.
Volume 135, 2023
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