Comparing extraction, synergism and separation of lanthanoids using acidic and neutral compounds in chloroform and one ionic liquid: Is the latter always ``better``?
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2014-01-01
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Abstract
The complexation properties of a pyrazolone derivative, 3-methyl-1-phenyl-4-(4-trifluoromethylbenzoyl)-pyrazol-5-one (HL), in chloroform were examined and it was found that it possesses improved complexation ability in comparison with 4-benzoyl, 4-(4-methylbenzoyl) and 4-(4-fluorobenzoyl) derivatives. Mixed ligand chelate extractions of trivalent lanthanoids (La, Nd, Eu, Ho and Lu) with HL and 5,11,17,23-tetra-tert-butyl-25,26,27- tris(dimethylphosphinoylpropoxy)-28-hydroxy-calix[4]arene (S1) or 5,11,17,23-tetra-tert-butyl-25,27-bis(dimethylphosphinoylpropoxy)-26, 28-dihydroxy-calix[4]arene (S2) as synergistic agents were also carried out in chloride medium at constant ionic strength μ = 0.1 and CHCl3 as organic phase. The interactions between the extractants in deuterochloroform were studied by 1H, 13C, and 31P NMR. The composition of the extracted species was established as LnL3· HL (L- represents HL anion) with HL as a single extractant, and as LnL3·S in the presence of the phosphorus-containing calix[4]arene. On the basis of the experimental data, the values of the equilibrium constants were calculated. The influence of the number of PO groups of tert-butyl-calix[4]arene on the extraction process was discussed. The synergistic enhancement and separation factors between metals were evaluated. Finally, the extraction of La(iii) and Eu(iii) ions was performed by using an ionic liquid, 1-butyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide, as a solvent and varying the type of ligands. By comparison to CHCl3, the ionic liquid offers increased distribution ratios, at the expense of a levelling off of the separation factors. Reasons for such a phenomenon are discussed. © the Partner Organisations 2014.