Reactivity Towards Europium(III) of the Radiolysis Products of the Ionic Liquid 1‐Methyl‐3‐butyl‐1H‐imidazolium Bis[(trifluoromethyl)sulfonyl]amide (C4‐mimTf2N) and Effect of Water: A TRLFS (Time‐Resolved Laser‐Induced Fluorescence Spectroscopy) Preliminary Study

Billard, Isabelle; Georg, Sylvia

doi:10.1002/hlca.200900140

Cited by 20 publications

(11 citation statements)

References 21 publications

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“…For all the IL solutions, the remaining water content has been checked by IR (Bruker, Equinox 55, quartz cuvette, 1 cm pathway) at the end of the measurements, by comparison with the IR spectra of the three pure ILs before and after degassing. In agreement with previous works, , the water peak is present in the 5200–5350 cm –1 range for the three ILs. For the degassed samples, no significant amount of water could be detected.…”

Section: Methodssupporting

confidence: 93%

“…The temperature was controlled at T = (18 ± 0.5) °C. Previous trials have shown that the Teflon caps are tight enough to prevent water from entering the IL samples, even for a long period of time (up to months) . UV–visible absorption spectra were recorded taking either pure acetonitrile or the corresponding pure degassed ILs as a reference for samples in acetonitrile or in ILs, respectively.…”

Section: Methodsmentioning

confidence: 99%

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Perrhenate Complexation by Uranyl in Traditional Solvents and in Ionic Liquids: A Joint Molecular Dynamics/Spectroscopic Study

et al. 2012

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The complexation of perrhenate (ReO(4)(-)) anions by the uranyl (UO(2)(2+)) cation has been investigated by joint molecular dynamics simulations and spectroscopic (UV-vis, TRLFS, and EXAFS) studies in aqueous solution, acetonitrile, and three ionic liquids (ILs), namely, [Bmi][Tf(2)N], [Me(3)BuN][Tf(2)N], and [Bu(3)MeN][Tf(2)N] that are based on the same Tf(2)N(-) anion (bis(trifluoromethylsulfonyl)imide) and either Bmi(+) (1-butyl,3-methylimidazolium), Me(3)BuN(+), or Bu(3)MeN(+) cations. They show that ReO(4)(-) behaves as a weak ligand in aqueous solution and as a strong ligand in acetonitrile and in the ILs. According to MD simulations in aqueous solution, the UO(2)(ReO(4))(2) complex quickly dissociates to form UO(2)(H(2)O)(5)(2+), while in acetonitrile, a stable UO(2)(ReO(4))(5)(3-) species forms from dissociated ions. In the ILs, the UO(2)(ReO(4))(n)(2-n) complexes (n = 1 to 5) remained stable along the dynamics, and to assess their relative stabilities, we computed the free energy profiles for stepwise ReO(4)(-) complexation to uranyl. In the two studied ILs, complexation is favored, leading to the UO(2)(ReO(4))(5)(3-) species in [Bmi][Tf(2)N] and to UO(2)(ReO(4))(4)(2-) in [Bu(3)MeN][Tf(2)N]. Furthermore, in both acetonitrile and [Bmi][Tf(2)N] solutions, MD and PMF simulations support the formation of dimeric uranyl complexes [UO(2)(ReO(4))(4)](2)(4-) with two bridging ReO(4)(-) ligands. The simulation results are qualitatively consistent with spectroscopic observations in the different solvents, without firmly concluding, however, on the precise composition and structure of the complexes in the solutions.

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Section: Methodssupporting

confidence: 93%

Section: Methodsmentioning

confidence: 99%

Perrhenate Complexation by Uranyl in Traditional Solvents and in Ionic Liquids: A Joint Molecular Dynamics/Spectroscopic Study

et al. 2012

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“…ILs unavoidably absorb H 2 O from the atmosphere and their average water content is about 200 ppm as purchased. Thus, ILs were dried under vacuum following a previously published procedure [38] prior to sample preparation. Due to their hydrophobicity, they can be dried to very low final water contents (20 ppm) prior to mixing.…”

Section: Experimental Section Reagentsmentioning

confidence: 99%

Modulating the Solubilities of Ionic Liquid Components in Aqueous–Ionic Liquid Biphasic Systems: A Q‐NMR Investigation

2015

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Aqueous-ionic liquid (A-IL) biphasic systems have been examined in terms of deuterated water, acid, and IL cation and anion mutual solubilities in the upper (water-rich, in mole fraction) and lower phase of aqueous/IL biphasic systems at ambient temperature. The biphasic mixtures were composed of deuterated acids of various concentrations (mainly DCl, DNO(3), and DClO(4) from 10(-2) to 10(-4) M) and five ionic liquids of the imidazolium family with a hydrophobic anion (CF(3)SO(2))(2) N(-), that is, [C1 Cn im][Tf(2)N], (n=2, 4, 6, 8 and 10). The analytical techniques applied were (1) H NMR, (19) F NMR, Karl-Fischer titration, pH potentiometry for IL cations and anions, and water and acid determination. The effects of the ionic strength (μ=0.1 M NaCl and NaNO(3) as well as μ=0.1 M, 0.2 M and 0.4 M NaClO(4), according to the investigated acid), the nature of the IL cation, and the nature of the mineral acid on the solubilities of the (D(2)O, D(+), Tf(2)N(-), C1 Cn im(+)) entities in the lower or upper phases were determined. The addition of sodium perchlorate was found to enhance the Tf(2)N(-) solubility while inhibiting the solubility of the ionic liquid cation. Differences in IL cation and anion solubilities of up to 42 mM were evidenced. The consequences for the characterization of the aqueous biphasic system, the solvent extraction process of the metal ions, and the ecological impact of the ILs are discussed.

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“…) was purchased from Solvionic, Verniolle, France (purity: 99.5%) and dried in vacuum at a raised temperature of 60 ¡ 1 uC prior to use, according to a previously published procedure. 19 Europium nitrate hexahydrate was obtained from Riedel-de Haen and HNO 3 was from Merck (conc. 65%).…”

Section: Introductionmentioning

confidence: 99%

Kinetics of metal extraction in ionic liquids: Eu3+/HNO3//TODGA/[C1C4im][Tf2N] as a case study

et al. 2013

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The kinetics of metal transfer in the system Eu 3+ /HNO 3 //TODGA/[C 1 C 4 im][Tf 2 N], where TODGA is N,N,N9,N9-tetraoctyl diglycolamide, is shown to depend on the chemical conditions (nitric acid and TODGA concentrations) and the time needed to reach equilibrium which may vary from less than 10 min to more than 4 h. At [HNO 3 ] = 4 M, a detailed kinetic study is performed for two different concentrations of TODGA. It is shown that the time required for water and acid solubilisation in the IL phase is very short, as is the time for IL solubilisation in the aqueous phase. By contrast, the extraction of Eu(III) takes more than 100 min to be completed and depends on the TODGA concentration. On the basis of these experimental facts, a simple kinetic model is proposed which is able to account for the data.

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Reactivity Towards Europium(III) of the Radiolysis Products of the Ionic Liquid 1‐Methyl‐3‐butyl‐1H‐imidazolium Bis[(trifluoromethyl)sulfonyl]amide (C₄‐mimTf₂N) and Effect of Water: A TRLFS (Time‐Resolved Laser‐Induced Fluorescence Spectroscopy) Preliminary Study

Cited by 20 publications

References 21 publications

Perrhenate Complexation by Uranyl in Traditional Solvents and in Ionic Liquids: A Joint Molecular Dynamics/Spectroscopic Study

Perrhenate Complexation by Uranyl in Traditional Solvents and in Ionic Liquids: A Joint Molecular Dynamics/Spectroscopic Study

Modulating the Solubilities of Ionic Liquid Components in Aqueous–Ionic Liquid Biphasic Systems: A Q‐NMR Investigation

Kinetics of metal extraction in ionic liquids: Eu3+/HNO3//TODGA/[C1C4im][Tf2N] as a case study

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