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Potentiometric Investigation of Fluoride Complexes of Zirconium(IV) and Hafnium(IV) in 1 M (H,Na)ClO4 Medium Using a Fluoride Ion Selective Electrode

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Abstract

The stability constants of zirconium(IV) and hafnium(IV) fluoride complexes in 1 M (H,Na)ClO4 medium were measured potentiometrically at 293 K for the first time using a fluoride ion selective electrode (F-ISE). This technique has been recommended by IUPAC as the best tool for studying fluoride complexes. A number of precautions were taken to ensure the stabilization of zirconium or hafnium in 1 M (H,Na)ClO4 medium and to prevent the formation of polynuclear hydroxo complexes. The formation of only mononuclear complexes was indicated. The average log values of the overall stability constants of zirconium(IV)-fluoride complexes, β1, β2, β3 and β4 were computed by varying the concentration of metal ion and were found to be 8.49 ± 0.11, 15.76 ± 0.15, 21.57 ± 0.10, and 26.68 ± 0.16, respectively, whereas the corresponding values for hafnium(IV)-fluoride complexes were 8.22 ± 0.06, 15.48 ± 0.15, 21.76 ± 0.14, and 27.42 ± 0.15, respectively. The thermodynamic stability constant, β1∘, calculated for these complexes follows the same trend as expected from the linear correlation based on the Brown Sylva Ellies (BSE) model for metal-fluoride complexes provided the effective charge on Zr is taken as +4.1 instead of the formal charge of +4. Without considering this adjustment of formal charge, an attempt has also been made to explain the trend in β1∘ values of group(IV) metal-fluoride complexes based on electronegativity values. A good linear correlation was obtained that could explain the ability of these group(IV) ions to form different fluoride complexes with varying number of fluoride ions.

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Authors and Affiliations

  1. Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India

    R. M. Sawant, U. K. Thakur & K. L. Ramakumar

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  1. R. M. Sawant
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  2. U. K. Thakur
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  3. K. L. Ramakumar
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Correspondence to R. M. Sawant.

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Sawant, R.M., Thakur, U.K. & Ramakumar, K.L. Potentiometric Investigation of Fluoride Complexes of Zirconium(IV) and Hafnium(IV) in 1 M (H,Na)ClO4 Medium Using a Fluoride Ion Selective Electrode. J Solution Chem 34, 113–135 (2005). https://doi.org/10.1007/s10953-005-2693-4

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  • DOI: https://doi.org/10.1007/s10953-005-2693-4

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