Extraction of Eu(III) and Am(III) by 1-phenyl-3-methyl-4-acetylpyrazol-5-one (HPMAP) and tri-n-octylphosphine oxide (TOPO) in a room-temperature ionic liquid

Gujar, Rajesh B.; Sengupta, Arijit; Murali, M. S.; Mohapatra, P. Κ.

doi:10.1080/01496395.2017.1282966

Cited by 10 publications

(4 citation statements)

References 47 publications

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“…When PHMAP (Chart 42) was mixed with TOPO, the D values for Am(III) and Eu(III) increased by three orders of magnitude in xylene (from D M o 0.01 to B7) and five in [C 8 mim][NTf 2 ] (up to D Eu = 214). 236 The importance of a phosphine oxide moiety in the synergist molecule was highlighted when the amide groups of a series of DGAs and malonamides were subsequently substituted with this group. Each successive substitution led to an increase in the extraction efficiency of Ln(III).…”

Section: Other Carbonylsmentioning

confidence: 99%

Ligands for f-element extraction used in the nuclear fuel cycle

2017

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Liquid-liquid extraction is the major technique being applied for the partitioning of f-elements from nuclear waste. In this review, the recent developments in ligand design, optimization and extraction properties are summarised for the main classes of extractants (organophosphorus ligands, diamides and N-heterocycles), with a focus on the separation of actinides and lanthanides. Structural modifications, pre-organisation and different solvent systems, as key factors for the fine-tuning of the extraction properties, are discussed. From this review, it appears that small modifications of the structure of the ligand, the pre-organising platform or the solvent can have significant impact on the extraction (and separation) of metal ions. Interest in the combinations of ligands for the extraction processes is growing, since they provide improvements over individual ligands. Similarly, unconventional approaches are being pursued to develop more efficient and greener processes.

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Section: Other Carbonylsmentioning

confidence: 99%

Ligands for f-element extraction used in the nuclear fuel cycle

2017

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“…β-diketones are a class of ligands having high potential in complexation and liquid–liquid extraction of f -block elements, due to the formation of six-membered stable chelates on complexation . β-Diketones can lead to keto–enol tautomerism by participation of the α-Hs present therein .…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Insight into the Ionic Liquid-Mediated Complexation of Trivalent Lanthanides with β-Diketone and Its Fluorinated Analogue

Nagar,

Srivastava,

Sengupta

et al. 2024

Inorg. Chem.

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A multitechnique approach with theoretical insights has been employed to understand the complexation of trivalent lanthanides with two β-diketones, viz. 1phenyl-1,3-butanedione (L 1 ) and 4,4,4-trifluoro-1-phenyl-1,3-butanedione (L 2 ), in an ionic liquid (C 6 mim•NTf 2 ). UV−vis spectral analysis of complexation using Nd 3+ revealed the predominance of ML 2 + and ML 4 − species. The stability constants for the PB complexes were higher (β 2 ∼ 10.45 ± 0.05, β 4 ∼ 15.51 ± 0.05) than those for the TPB (β 2 ∼ 7.56 ± 0.05, β 4 ∼ 13.19 ± 0.06). The photoluminescence titration using Eu 3+ corroborated the same observations with slightly higher stability constants, probably due to the higher ionic potential of Eu 3+ . The more asymmetric (A L2 ML4 ∼ 5.2) Eu-L 2 complex was found to contain one water molecule in the primary coordination sphere of Eu 3+ with more covalency of the Eu 3+ -O bond (Ω 2 L1 = 8.5 × 10 −20 , Ω 4 L1 = 1.3 × 10 −20 ) compared to the less asymmetric Eu-L 1 complex (A L1 ML4 ∼ 3.5) with two water molecules having less Eu−O covalency (Judd-Offelt parameters:Liquid−liquid extraction studies involving Nd 3+ and Eu 3+ revealed the formation of the ML 4− complex following an 'anion exchange' mechanism. The shift of the enol peak from 1176 to 1138 cm −1 on the complexation of the β-diketones with Eu 3+ was confirmed from the FTIR spectra. 1 H NMR titration of the β-diketones with La(NTf 2 ) 3 evidenced the participation of α-H of the β-diketones and protons at C 2 , C 4 , and C 5 positions of the methylimidazolium ring. For the ML 2 complex, 4 donor O atoms are suggested to coordinate to the trivalent lanthanides with bond distances of 2.3297−2.411 Å for La− O, 2.206−2.236 Å for Eu−O, and 2.217−2.268 Å for Nd−O, respectively, while for the ML 4 complex, 8 donor O atoms were coordinated with bond lengths of 2.506−2.559 Å for La−O, 2.367−2.447 Å for Eu−O, and 2.408−2.476 Å for Nd−O. The Nd 3+ ion was higher by 9.7 kcal•mol −1 than that of the La 3+ ion for the 1:4 complex. The complexation energy with L1 was quite higher than that with L2 for both 1:2 and 1:4 complexes. Using cyclic voltammetry, the redox behavior of trivalent lanthanides Eu and Gd with β-diketonate in ionic liquid medium was probed and their redox energetic and kinetic parameters were determined.

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“…Also in the IL extraction, the possible use of TOPO has been energetically investigated. [7][8][9][10][11][12][13][14] However, Liu et al made mention in their literature 15 that the use of TOPO on the IL extraction resulted in the formation of an "undesirable" third phase.…”

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confidence: 99%

Formation of Minimal Third Phase in Ionic Liquid Extraction System with Trioctylphosphine Oxide and Its Possible Application to Extraction Concentration

2018

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The third-phase formation behavior in ionic liquid (IL) extraction system using trioctylphosphine oxide (TOPO) was investigated. In the use of a relatively less-lipophilic IL, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (CmimTfN), the third phase was formed between the aqueous phase and the IL phase. The third phase seems to have a relatively high lipophilicity compared to the IL phase. The main components of the third phase were suggested as being (HO)TOPO, IL anion (TfN), IL cation (Cmim) and free TOPO. In addition, the third phase showed an extraction concentration ability for the Fe(III)-thiocyanato complex.

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Extraction of Eu(III) and Am(III) by 1-phenyl-3-methyl-4-acetylpyrazol-5-one (HPMAP) and tri-n-octylphosphine oxide (TOPO) in a room-temperature ionic liquid

Cited by 10 publications

References 47 publications

Ligands for f-element extraction used in the nuclear fuel cycle

Ligands for f-element extraction used in the nuclear fuel cycle

Experimental and Theoretical Insight into the Ionic Liquid-Mediated Complexation of Trivalent Lanthanides with β-Diketone and Its Fluorinated Analogue

Formation of Minimal Third Phase in Ionic Liquid Extraction System with Trioctylphosphine Oxide and Its Possible Application to Extraction Concentration

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