The infra-red spectra of uranium species in carbon tetrachloride solutions of uranium (VI), dibutyl phosphoric acid and Tri-n-octyl phosphine oxide

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Abstract

Comparisons of the infra-red spectra of uranyl dibutyl phosphate polymer [UO2(DBP)2]n, tri-n-octyl phosphine oxide (TOPO), and dibutyl phosphoric acid (HDBP), for both the separate reagents and in combination in carbon tetrachloride, are consistent with the formation of UO2(DBP)2· 2TOPO, UO2(DBP)2HDBP·TOPO and UO2(DBP)2·2HDBP. The data imply that extraction of UO2+2 from aqueous solutions by combinations of tri-n-octyl phosphine oxide and dibutyl phosphoric acid dimer may be represented by the equations UO22+ + 2(HDBP)2 + TOPOUO2(DBP)2·HDBP·TOPO + 12(HDBP)2 + 2H+UO22 + (HDBP)2 + 2TOPOUO2(DBP)22TOPO + 2H+.

Considerable hydrogen bonding between TOPO and HDBP occurs when these reagents are together in solution. The evidence for previously-postulated structural formulae for the uranium species is not conclusive, but the data are consistent with the equivalence of three DBP ligands in uranium species containing HDBP.

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      The extraction equilibria and the speciation in organic phase are particularly important to understand the origin of the selectivity and the mass transfer of uranium(VI) from phosphoric acid into the extraction solvent. Slope analysis method [11–13], UV spectroscopy [14], infrared spectroscopy [15,16], small angle X-ray and neutron scattering as well as static and dynamical light scattering measurements [17] were mostly used to study the speciation of uranium(VI) in D2EHPA/TOPO. Conversely, no paper concerns the use of Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS) to investigate the speciation of uranium(VI) in extraction solvents contacted with concentrated phosphoric acid.

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