Ionic Liquid as a N,O-Donor Ligand-Based Extraction System Modifier: Establishing the Mechanism of Am(III)-Selectivity Increasing.

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.

Spectroscopy of structurally disordered hydrated iron fluoridotitanate in the regions of vibrational and electronic excitations.

Raman and optical absorption spectra of disordered hydrated iron fluoridotitanate (HITF) single crystal were studied. Temperature transformations of the Raman spectra indicate independent ordering processes of the [TiF6]2- and [Fe(H2O)6]2+ complexes below the structural phase transition. The absorption spectrum in the near-infrared and visible ranges includes transitions from the high spin ground state 5T2 of Fe2+ ion to the excited 5E state and a set of excited triplets. Analysis by Tanabe-Sugano method gives crystal field Dq = 490 cm-1 and Racah parameters B = 340 cm-1 and C = 1904 cm-1. Considerable decrease of B parameter as compared to the free ion value indicates a decrease of interelectron repulsion in the disordered neighborhood of Fe2+ ions.