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The oxidation of the uranium(IV)tetrachloride by the octacyanotungstate(V) and the octacyanomolybdate(V) ions in perchloric acid medium: A kinetic study

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Abstract

The oxidation of the uranium tetrachloride (UCl4) by the octacyanometalate(V) ion of tungsten and molybdenum was studied in a perchloric acid medium at an ionic strength of 1.5 M (NaClO4). The reaction was first order in both UIV(H2O)84+ and MV(CN)83– (M = W, Mo). A second order rate constant of k2 = 0.111 ± 0.002 M−1s−1 at [H+] = 0.932 M and 15.0 °C was found for the W(CN)83– reaction and for the Mo(CN)83– reaction, k2 = 32.9 ± 0.9 M−1s−1 at [H+] = 1.008 M and 29.7 °C. The reactions are proportional to [H+]–2 and an equilibrium constant of Ka2 ≈ 1.18 × 10−3 M−1 (pKa ≈ 6.7) at µ = 1.5 M was found for the deprotonation of UIV(H2O)84+. 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 for financial assistance.

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

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

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GJvZ: Investigation. EF: Investigation, writing, editing. CRD: Investigation, writing, review, editing, project admin. SSB: Conceptualisation, review, editing, supervision. JCS: Conceptualisation, methodology, review, editing, project admin supervision.

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Correspondence to C. Robert Dennis.

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Robert Dennis, C., van Zyl, G.J., Fourie, E. et al. The oxidation of the uranium(IV)tetrachloride by the octacyanotungstate(V) and the octacyanomolybdate(V) ions in perchloric acid medium: A kinetic study. Reac Kinet Mech Cat 135, 2915–2927 (2022). https://doi.org/10.1007/s11144-022-02297-5

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