Dependence of Extraction Properties of 2,6-Dicarboxypyridine Diamides on Extractant Structure

Alyapyshev, M. Yu.; Бабаин, В. А.; Ткаченко, Л. И.; Eliseev, I. I.; Didenko, A. V.; Petrov, M. L.

doi:10.1080/07366299.2011.581049

Cited by 79 publications

(48 citation statements)

References 14 publications

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“…The study of protonation of all diamides V except 3 in the gas phase showed three minima on the potential energy surface, which correspond to the protonated forms. The structures corresponding to these minima for N,Ndiethyl-N,N -diphenylpyridine-2,6-dicarboxamide 2 with the best extraction properties [9,10] are presented in Fig. 3.…”

Section: Protonation Of Pyridinedicarboxylic Acid Diamides Vmentioning

confidence: 98%

“…In solutions with a high concentration of nitric acid Ln(III) and An(III) with V form 1:1 complexes, which are extracted from aqueous solutions to the organic phase. [10] We calculated the structures of complexes [LEu 3+ ] and [LAm 3+ ] without anionic ligands (complexes 14-19 for ligands 3, 4, and 10), which are shown in Figs. 6-8.…”

Section: Structures Of Complexes [Lm] 3+ (M = Eu Am) With Diamides 3mentioning

confidence: 99%

“…In particular, diamides V containing one alkyl and one aryl substituent at the amide nitrogens extract actinides and lanthanides to polar organic solvents (phenyltrifluoromethylsulfone, m-nitrobenzotrifluoride, or diethylene glycol bis-(tetrafluoropropyl) ether) from solutions in 6 M nitric acid. [9,10] The partition coefficients that characterize the extraction efficiency increase with acidity, that is, for the Am(III) extraction they increase from 0.1 to 10, while for the extraction of Eu(III) they increase from 0.01 to 1.5 from 1 M HNO 3 to 6 M HNO 3 . The separation factor SF Am/Eu attains 6-10 for various diamides V. Tetraalkyl diamides V well extract Th(IV) and U(VI) from nitric acid media, but the extraction of trivalent lanthanides and actinides is poor.…”

Section: Introductionmentioning

confidence: 98%

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Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Ustynyuk

Gloriozov

Kalmykov

et al. 2014

Solvent Extraction and Ion Exchange

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This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln 3+ ) and 5f-elements (actinides, An 3+ ) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln 3+ and An 3+ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu 3+ /Am 3+ model pair cations (SF Am/Eu ) in extraction experiments on a semi-quantitative level. The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM] 3+ , (H 2 O) n M(NO 3 ) 3 (n = 3, 4), and LM(NO 3 ) 3 (M = Eu, Am).Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln 3+ and An 3+ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An 3+ and Ln 3+ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N ,N -tetraalkyl diamides ("effect of anomalous aryl strengthening"). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An 3+ /Ln 3 separation selectivity in the series of dipicolinic acid diamides.

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Section: Protonation Of Pyridinedicarboxylic Acid Diamides Vmentioning

confidence: 98%

Section: Structures Of Complexes [Lm] 3+ (M = Eu Am) With Diamides 3mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Ustynyuk

Gloriozov

Kalmykov

et al. 2014

Solvent Extraction and Ion Exchange

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show abstract

“…For instance, the solvent extraction of americium and europium with a 0.2 mol/L solution of , -diethyl-, -di(para-ethyl-phenyl) dipicolinamide(Et(pEtPh)DPA) in meta-nitrobenzotrifluoride(F-3) has been investigated. It was shown that the distribution ratios were over 100 [14]. The , -diethyl-, -ditolyldipicolinamide derivative (EtTDPA) has also shown great promise in its ability to extract actinides such as americium from acidic aqueous solutions [15].…”

Section: Introductionmentioning

confidence: 99%

Solvent extraction of uranium(VI) by a dipicolinamide using a room-temperature ionic liquid

et al. 2014

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Room-temperature ionic liquids (RTILs) have recently received increasing attention as solvent alternatives for possible application in spent fuel reprocessing, particularly in the extraction of metal ions from high-level radioactive aqueous waste, due to their unique physical and chemical properties. Herein, the solvent extraction of the uranyl ions (UO 2 2+ ) was performed using , -The effects of vortexing time, phase ratio and the concentration dependence of Et (p) TDPA, nitric acid and sodium nitrate on the extraction were studied in detail. The extraction mechanism was deduced based on the slope analysis and UV-vis measurement. The distribution ratio of U from 3 mol/L nitric acid by 0.3 mol/L EtTDPA/C 4 mimPF 6 is found to be almost 100. Conventional log-log plot analysis of the extraction equilibrium data suggests that the ions are extracted as a complex in 2 : 3 ratio of UO 2 2+ to extractant, and the extraction most likely occurs by a cationexchange mode since the concentration of C 4 mim + in the aqueous phase increases linearly with the percent extraction of UO 2 2+ evidenced by UV-vis measurement. This work promises to provide new efficient media based on RTILs for separation of uranium from the radioactive aqueous waste.

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“…1). Although extraction properties of diamides of heterocyclic acids (pyridine-2,6-dicarboxylic, 2,2 0 -bipyridine-6,6 0 -dicarboxylic and 1,10-phenantroline-2,9-dicarboxylic) towards actinides and lanthanides are well described the literature, [12][13][14] the data on their radiolytic stability is limited by those for the diamides of pyridine-2,6-dicarboxylic acid. 15,16 The ligand (1) have earlier demonstrated high selectivity for separation of neighboring pairs of rare earth elements (REE), 17 and the ligand (2) have demonstrated high selectivity for separation Am/Eu pair.…”

Section: Introductionmentioning

confidence: 99%

Testing a simple approach for theoretical evaluation of radiolysis products in extraction systems. A case of N,O-donor ligands for Am/Eu separation

et al. 2017

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Dependence of Extraction Properties of 2,6-Dicarboxypyridine Diamides on Extractant Structure

Cited by 79 publications

References 14 publications

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

Solvent extraction of uranium(VI) by a dipicolinamide using a room-temperature ionic liquid

Testing a simple approach for theoretical evaluation of radiolysis products in extraction systems. A case of N,O-donor ligands for Am/Eu separation

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