A critical review on the stability constants of the fluoride complexes of actinides in aqueous solution and their correlation with fundamental properties of the ions |
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Authors: | N K Chaudhuri R M Sawant D D Sood |
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Institution: | (1) Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, 400085 Mumbai, India |
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Abstract: | Literature data on the stability constants of the fluoride complexes of the actinides in different oxidation states have been
compiled. In order to have a reasonable inter-comparison, the stability constant (β1) values obtained in diverse ionic strength media are converted to so called thermodynamic stability constants, β
1
0
using the DAVIES equation (a modification of Debye-Huckel equation). A correlation of the β
1
0
values with the fundamental properties of the actinide ions using various models available in the literature has been attempted.
Using the values of inonic radii and best available values of the stability constants of a large number of metal ions from
recent compilations a comparative study of the various models or relations available in the literature has been tried. For
metal ions in general, the semi-empirical relation recently developed by BROWN, SYLVA and ELLIS (BSE equation)_gives the best
correlation. In an attempt to accommodate the unusual trend in the stability constants of the tetravalent actinides a modification
in a parameter of the BSE equation has been proposed. Good agreement between the theoretically calculated and experimentally
determined values for actinides in different oxidation states is obtained in most of the cases. Further improvements in theoretical
relation as well as experimental data are required for better correlation. |
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Keywords: | |
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