By coupling EXAFS, UV-vis spectroscopy, and molecular dynamics and quantum mechanical calculations, we studied the competitive complexation of uranyl cations with nitrate and chloride ions in a water immiscible ionic liquid (IL), C(4)mimTf(2)N (C(4)mim(+): 1-butyl-3-methyl-imidazolium; Tf(2)N(-) = (CF(3)SO(2))(2)N)(-): bis(trifluoromethylsulfonyl)imide). Both nitrate and chloride are stronger ligands for uranyl than the IL Tf(2)N(-) or triflate anions and when those anions are simultaneously present, neither the limiting complex UO(2)(NO(3))(3)(-) nor UO(2)Cl(4)(2-) alone could be observed. At a U/NO(3)/Cl ratio of 1/2/2, the dominant species is likely UO(2)Cl(NO(3))(2)(-). When chloride is in excess over uranyl with different nitrate concentrations (U/NO(3)/Cl ratio of 1/2/6, 1/4/4, and 1/12/4) the solution contains a mixture of UO(2)Cl(4)(2-) and UO(2)Cl(3)(NO(3))(2-) species. Furthermore, it is shown that the experimental protocol for introducing these anions to the solution (either as uranyl counterion, as added salt, or as IL component) influences the UV-vis spectra, pointing to the formation of different kinetically equilibrated complexes in the IL.
We have studied the extraction of four HA acids (HNO(3), HReO(4), HClO(4), HCl) to a hydrophobic ionic liquid (IL) 1-butyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)amide (BMI(+) Tf(2)N(-)) at room temperature, in a wide range of acidic concentrations in water. The effect of tributylphosphate (TBP) as co-solvent is investigated. According to experimental observations, water dragging to the IL phase increases with added TBP and/or acids. Acid extraction is found to be weak, however, for the four acids except for concentrated HNO(3) (>3 M). Molecular dynamics simulations on model biphasic systems show that TBP is not surface active, but well dissolved in the IL. They also reveal the importance of HA acid model (either totally or half dissociated) and of the TBP content on acid extraction to the IL. Furthermore, they show that "the proton" can be extracted by TBP (H(3)O(+)(TBP)(3)"complex") without its A(-) conjugated base, via a cation transfer mechanism (BMI(+) transfer to water). Experiments and simulations show that TBP plays an important role in the mutual solubility between water and ionic liquid, by different amounts, depending on the HA acid. On the other hand, both approaches indicate that a HTf(2)N containing aqueous solution completely mixes with the [BMI][Tf(2)N] IL that contains the same Tf(2)N(-) anion.
The extraction of uranyl from acidic (HNO(3)) aqueous solutions toward an ionic liquid phase, C(1)-C(4)-imTf(2)N (1-methyl,3-butylimidazolium Tf(2)N), has been investigated as a function of initial acid concentration and ligand concentration for two different extracting moieties: a classical malonamide, N,N'-dimethyl-N,N'-dibutylmalonamide (DMDBMA) and a functionalized IL composed of the Tf(2)N(-) anion and an imidazolium cation on which a malonamide pattern has been grafted (FIL-MA). The extraction mechanism, as demonstrated through the influence of added C(1)-C(4)-imCl or added LiTf(2)N in the aqueous phase, is slightly different between the DMDBMA and FIL-MA extracting agents. Modeling of the extraction data evidences a double extraction mechanism, with cation exchange of UO(2)(2+)versus 2 H(+) for DMDBMA or versus C(1)-C(4) -im(+) and H(+) for FIL-MA at low acidic values, and through anion exchange of [UO(2)(NO(3))(3)](-)versus Tf(2)N(-) for both ligands at high HNO(3) concentrations. The FIL-MA molecule is more efficient than its classical DMDBMA parent.
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