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A kinetic study of the oxidation of the tetrakisoxalatouranate(IV) ion by the octacyanotungstate(V) and the octacyanomolybdate(V) ions in an acidic oxalate buffer medium

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Abstract

The oxidation of the tetrakisoxalatouranate(IV) ion by the octacyanometalate(V) ion of tungsten and molybdenum was studied in an oxalate buffer medium. The reaction was first order in both UIV(C2O4)44− and M(CN)83− (M = W, Mo), and a second order rate constant of k2 = 0.032 ± 0.002 M−1s−1 at pH 4.27 and 24.8 °C was found for the W(CN)83− reaction. For the Mo(CN)83− reaction the second order rate constant is k2 = 16.9 ± 0.1 M−1s−1 at pH 4.77 and 25.3 °C. The reactions are inversely proportional to [H+] and an equilibrium constant of Ka ≈ 1.3 × 10–6 M−1 (pKa ≈ 5.89) at 25 °C was found for the deprotonation of UIV(C2O4)3(H2O)22−. Activation parameters have been obtained by a least squares fit of temperature data directly to the Eyring equation.

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Acknowledgements

The authors acknowledge the Central Research Fund of the University of the Free State, Bloemfontein, South Africa.

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  1. Chemistry Department, University of the Free State, P.O. Box 339, Bloemfontein, 9300, Republic of South Africa

    C. Robert Dennis, Gideon J. van Zyl, Eleanor Fourie, Stephen S. Basson & Jannie C. Swarts

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  2. Gideon J. van Zyl
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  3. Eleanor Fourie
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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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Correspondence to C. Robert Dennis.

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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 octacyanotungstate(V) and the octacyanomolybdate(V) ions in an acidic oxalate buffer medium. Reac Kinet Mech Cat 134, 615–627 (2021). https://doi.org/10.1007/s11144-021-02109-2

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