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Kinetics of the outer-sphere oxidation of thiourea by heteropoly-α2-17-tungsto-1-vanadodiphosphate anion

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Abstract

Kinetics of the oxidation of thiourea (tu) by heteropoly-α2-17-tungsto-1-vanadodiphosphate anion, α2-[P2VVW17O62]7−, have been studied spectrophotometrically in aqueous acidic medium at 25 °C. At low pH (2.4–3.0), the neutral form of tu is the only reactive species. At higher pH (4.2–4.9), both neutral and deprotonated forms of tu participate in the reaction. The observed mixed-order kinetics suggest two parallel reactions: one in which the order in [tu] is unity, and a second in which it is two. In both cases, the order in [α2-[P2VVW17O62]7−] is unity. Based on the kinetic studies, a mechanism is proposed, in which a second-order proton-coupled electron transfer involving NH2CSNH2 and α2-[P2VVW17O62]7− proceeds through a sequential electron transfer, followed by proton transfer such that the reaction is an “activation-controlled” outer-sphere electron transfer process. By applying the Marcus equation, the self-exchange rate constants for the couples \({\text{NH}}_{2} {\text{CSNH}}_{2}^{ \cdot + }\)/NH2CSNH2 and α2-[P2VVW17O62]7−/α2-[P2VIVW17O62]8− were evaluated.

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Acknowledgements

The authors P.S and K.S thank University Grants Commission, New Delhi, India, for the award of major research project (F.No. 42-349/2013(SR)) and financial assistance. We also thank Sophisticated Analytical Instrumentation Facility, CECRI Karaikudi, for EPR facilities and Managing Board, Virudhunagar Hindu Nadars’ Senthikumara Nadar College, Virudhunagar, for infrastructural facilities.

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  1. Postgraduate Department of Chemistry, V.H.N. Senthikumara Nadar College (Autonomous), Virudhunagar, 626001, India

    Thangamariyappan Shanmugaprabha, Karuppaiah Selvakumar, Murugesan Vairalakshmi, Kasi Rajasekaran & Ponnusamy Sami

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  1. Thangamariyappan Shanmugaprabha
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  2. Karuppaiah Selvakumar
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Correspondence to Ponnusamy Sami.

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Shanmugaprabha, T., Selvakumar, K., Vairalakshmi, M. et al. Kinetics of the outer-sphere oxidation of thiourea by heteropoly-α2-17-tungsto-1-vanadodiphosphate anion. Transit Met Chem 42, 95–103 (2017). https://doi.org/10.1007/s11243-016-0111-y

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