EXAFS study of the speciation of protactinium(V) in aqueous hydrofluoric acid solutions.
The speciation of protactinium(V) in hydrofluoric acid (HF) solutions was studied using X-ray absorption spectroscopy. Extended X-ray absorption fine structure measurements were performed on an aqueous solution of 0.05 M protactinium(V) with various HF concentrations ranging from 0.5 to 27 M in order to probe the protactinium coordination sphere with respect to the identity and number of coordinating ligands. The resulting fits to the spectra suggest the presence of an eight-coordinate homoleptic fluoro complex in highly concentrated fluoride solutions (27 M), with equilibrium between seven- and eight-coordinate fluoro complexes at moderate acidities, and in more dilute solutions, results indicate that one water molecule is likely to replace a fluoride in the first coordination sphere, at a distance of 2.54-2.57 Å. Comparisons of this chemistry with group V metals, niobium and tantalum, are presented, and the potential implications for these results on the hydrolytic behavior of protactinium in aqueous systems are discussed.
Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Stéphanie M
SM
De Sio
Richard E
RE
Wilson