Abstract
The oxidation of the tetrakisoxalatouranate(IV) ion by the hexacyanoferrate(III) ion was studied in an oxalate buffer medium. The reaction was first order in both UIV(C2O4)44– and Fe(CN)63–, and a second order rate constant of k2av = (5.46 ± 0.04) × 10–2 M−1 s−1 at 34.9 °C was obtained. The reaction is inversely proportional to [H+] and a pKa of 5.99 was found for the deprotonation of UIV(C2O4)3(H2O)22−. Activation parameters have been obtained by application of the Eyring equation. Minimum excess concentrations of UIV(C2O4)44– over Fe(CN)63– for the kinetic study under pseudo-order conditions were evaluated following literature guidelines and also compared to results from a direct second order treatment of data. Contradictory to general beliefs, a fivefold excess of UIV(C2O4)44– was found to be sufficient for a pseudo-order kinetic treatment. The need to obtain results from traditional approximation methods, for example utilizing the linearized Eyring equation to obtain activation enthalpies (∆H#) and entropies (∆S#), was demonstrated not to be required anymore as modern computational capabilities utilizing least square fitting programs allows ∆H# and ∆S# to be obtained directly from temperature and rate constant data utilising the exponential Eyring equation easily and more accurately. A reaction mechanism for the reaction is proposed.
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Acknowledgements
The authors acknowledge the Central Research Fund of the University of the Free State, Bloemfontein, South Africa and the South African National Research Foundation Grant 105725 (EF) for funding.
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GJvZ: Investigation. EF: Investigation, writing, editing. CRD: Investigation, Writing, review, editing, project admin. SSB: Conceptualisation, methodology, review, editing, supervision. JCS: Conceptualization, methodology, review, editing, project admin supervision.
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Dennis, C.R., van Zyl, G.J., Fourie, E. et al. A kinetic study of the oxidation of the tetrakisoxalatouranate(IV) ion by the hexacyanoferrate(III) ion in an oxalate buffer medium. Reac Kinet Mech Cat 132, 599–615 (2021). https://doi.org/10.1007/s11144-021-01938-5
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DOI: https://doi.org/10.1007/s11144-021-01938-5