RESUMEN
In this work, we studied the extraction systems for the separation f-elements based on the tetradentate N,O-donor ligand di(N-ethyl-4-ethylanilide) 2,2'-dipyridyl-6,6'-dicarboxylic acid (L). The organic phase of these systems was perspective fluorine-containing organic solvents-metanitrobenzotrifluoride (F-3), ionic liquid C4mimNTf2 (IL), and their mixture. The increase of Am(III) selectivity in the presence of Ln(III) in cases of the diluent mixture was shown. The mechanism of the f-element complexation leading to the improved properties of the extraction systems was studied by UV-visible, Raman-spectroscopy, XRD-study, and density functional theory calculations.
RESUMEN
A new phosphine oxide ligand demonstrates high selectivity for the Am-Cm pair with SF = 2.9-3.5 and the Am-Eu pair with SF = 7.3-8.5 in a range of 0.1-3 M nitric acid. Thermodynamic measurements show that the entropy factor is responsible for selectivity observed in the extraction experiment. The most prevalent complexes of all three metal ions were (Ph2PyPO)2M(NO3)3. According to their DFT modelling, the M-N distances for the Cm ion were larger than those for Am, so the last ion enters deeper into the pseudo-cavity of the ligand, which causes the observed selectivity.
RESUMEN
N,N'-Dialkyl-N,N'-diaryl-1,10-phenanthroline-2,9-dicarboxamides (IV) were predicted (DFT simulation) and then were proved experimentally to be efficient donor ligands with high and unusual selectivity for the extraction separation of lanthanides. Distribution coefficients D of lanthanide cations in two-phase aqueous solution-polar organic solvent decrease with increasing Ln(3+) atomic number. The selectivity factors SFLn1/Ln2 for adjacent lanthanide ions were found to be about 3.