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Vol. 27 No. 4 (2015): Vol 27 Issue 4

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Dynamics of Electron Transfer Reaction of Trioxosulfate(IV) Ion with Dinuclear Iron(III)-Salen Complex in Perchloric Acid Medium

https://doi.org/10.14233/ajchem.2015.17629
Simeon Atiga
Coordination Chemistry and Inorganic Pharmaceutical Unit, Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, Enugu State, Nigeria
Pius O. Ukoha
Coordination Chemistry and Inorganic Pharmaceutical Unit, Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, Enugu State, Nigeria
Oguejiofo T. Ujam
Coordination Chemistry and Inorganic Pharmaceutical Unit, Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, Enugu State, Nigeria

Corresponding Author(s) : Oguejiofo T. Ujam

oguejiofo.ujam@unn.edu.ng

Asian Journal of Chemistry, Vol. 27 No. 4 (2015): Vol 27 Issue 4

Abstract

The kinetics of oxidation of trioxosulfate(IV) ion, SO32-, by [(Fe(salen))2adi], was investigated in aqueous perchloric acid medium. Stoichiometric results indicate that one mole [(Fe(salen))2adi] was reduced per two moles SO32- oxidized. Under pseudo-first order conditions of SO32- being above 20-fold excess of concentration of the oxidant, observed rates were invariant with respect to increase in concentration. Pseudo-first order rate constants were within (1.68 ± 0.003) × 103 s-1 implying zeroth order dependence of rate on [SO32-] and first order dependence on concentration of the oxidant. The rate of reaction increased with increase in [H+], was unaffected by change in ionic strength and decreased with increase in dielectric constant of the reaction medium. Addition of small amounts of AcO- and Mg2+ ions did not catalyze the reaction. A least squares fit of rate against [H+] was linear (r2 = 0.986) and with intercept indicating that oxidation of SO32- followed two parallel paths. The reaction was analyzed on the basis of a proton-coupled outer-sphere electron transfer mechanism.

Keywords

Kinetics Dithionite Electron transfer reduction Mechanism Dinuclear iron(III)
Atiga, S., O. Ukoha, P., & T. Ujam, O. (2015). Dynamics of Electron Transfer Reaction of Trioxosulfate(IV) Ion with Dinuclear Iron(III)-Salen Complex in Perchloric Acid Medium. Asian Journal of Chemistry, 27(4), 1274–1278. https://doi.org/10.14233/ajchem.2015.17629
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