Chatterjee, Debabrata and Jaiswal, Namita and Sarkar, Papiya (2015) Ru(EDTA) mediated partial reduction of O2 by H2S. Dalton Transactions, 44. pp. 7613-7617.

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An effective procedure for selective reduction of O2 to H2O2 exploring the use of hydrogen sulfide, an obnoxious industrial pollutant as reductant is reported herein. The reduction of [RuIII(EDTA)pz]− (EDTA4− = ethylenediaminetetraacetate; pz = pyrazine) by hydrogen sulfide resulting in the formation of a red [RuII(EDTA)pz]2− complex (λmax = 462 nm) has been studied spectrophotometrically and kinetically using both rapid scan and stopped-flow techniques. The time course of the reaction was followed as a function of [HS−]i, pH (5.5–8.5), and temperature. Alkali metal ions were found to have a positive influence (K+ > Na+ > Li+) on the reaction rate. Kinetic data and activation parameters are interpreted in terms of a mechanism (admittedly speculative) involving outer-sphere electron transfer between the reaction partners. Reaction of the red [RuII(EDTA)pz]2− complex with molecular oxygen regenerates the [RuIII(EDTA)pz]− species in the reacting system along with the formation of H2O2, a partially reduced product of dioxygen (O2) reduction. A detailed reaction mechanism in agreement with the spectral and kinetic data is presented.

Item Type: Article
Subjects: Chemistry
Depositing User: Dr. Sarita Ghosh
Date Deposited: 19 Sep 2016 10:41
Last Modified: 10 Jul 2017 07:44

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