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Activation-controlled outer-sphere electron transfer reactions: reduction of heteropoly 11-tungstovanadophosphate and heteropoly 10-tungstodivanado phosphate by thiourea in aqueous acid medium

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Abstract

The kinetics of reduction of heteropoly 11-tungstovanadophosphate, [PVVW11O40]4−, (HPA1) and heteropoly 10-tungstodivanadophosphate, [PVVVVW10O40]5−, (HPA2) by thiourea has been investigated in HClO4/phthalate/acetate buffer solutions spectrophotometrically at 25 °C in aqueous medium. The stoichiometry of the reaction is 1:1 in both cases. The HPAs are converted into the corresponding one-electron reduced heteropoly blues, namely, [PVIVW11O40]5− and [PVIVVVW10O40]6−, and thiourea is oxidised to formamidine disulphide. The reaction shows first-order dependence in both [HPA] and [thiourea] at constant pH. The rate–pH profile shows the participation of both the neutral and deprotonated forms of thiourea in the reaction. The reaction proceeds through an outer sphere electron transfer mechanism in which activation-controlled electron transfer is the rate-determining step. Self-exchange rate constants for the couples [PVVW11O40]4−/[PVIVW11O40]5−, [PVVVVW10O40]5−/[PVIVVVW10O40]6− and H2NCSNH2/H2NCS·+NH2 have been evaluated by Marcus theory.

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Acknowledgments

The authors P.S and K.R thank University Grants Commission, New Delhi, India for the financial assistance in the form of major research project. The authors thank Managing Board, Virudhunagar Hindu Nadars’ Senthikumara Nadar College, Virudhunagar for infrastructural facilities. The authors also thank National Institute of Technology, Trichy for providing HPLC facilities.

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  1. Postgraduate Department of Chemistry, VHNSN College, Virudhunagar, 626001, India

    Ponnusamy Sami, Natarajan Mariselvi, Kandasamy Venkateshwari, Murugesan Vairalakshmi, Arunachalam Sarathi & Kasi Rajasekaran

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  1. Ponnusamy Sami
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  2. Natarajan Mariselvi
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  3. Kandasamy Venkateshwari
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  4. Murugesan Vairalakshmi
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  5. Arunachalam Sarathi
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  6. Kasi Rajasekaran
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Correspondence to Kasi Rajasekaran.

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Sami, P., Mariselvi, N., Venkateshwari, K. et al. Activation-controlled outer-sphere electron transfer reactions: reduction of heteropoly 11-tungstovanadophosphate and heteropoly 10-tungstodivanado phosphate by thiourea in aqueous acid medium. Transition Met Chem 35, 563–570 (2010). https://doi.org/10.1007/s11243-010-9364-z

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