Extraction of Am and Rare-Earth Elements from Nitric Acid Solutions with Ethyl Bis(diphenylphosphinylmethyl)phosphinate

Extraction of HNO₃ and microamounts of Am, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO₃ solutions with solutions of ethyl bis(diphenylphosphinylmethyl)phosphinate in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the effective extraction constants of HNO₃ and Am were calculated. With increasing number of phosphoryl groups in the extractant molecule, the extraction of Am(III) and rare-earth elements from HNO₃ solutions increases.     

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

Extraction of microamounts of U(VI), Th(IV), Sc(III), and Ln(III) from HNO₃ solutions with solutions of bis(diphenylphosphinylethyl)phosphinic acid in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the effect of the inorganic anion and organic diluent on the extraction of rare-earth elements was examined. An increase in the number of phosphoryl groups in the extractant molecule and replacement of ethylene bridges between the phosphorus atoms by methylene bridges enhance the extraction of metal ions from nitric acid solutions.__________Translated from Radiokhimiya, Vol. 47, No. 3, 2005, pp. 252–256.Original Russian Text Copyright © 2005 by Turanov, Karandashev, Ragulin.     

Extraction of Am(III) and Rare-Earth Elements from Nitric Acid Solutions with (Diphenylphosphinylmethyl)phenylphosphinic Acid

Extraction of microamounts of Am, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu nitrates from aqueous HNO₃ with solutions of (diphenylphosphinylmethyl)phenylphosphinic acid in dichloroethane was studied. The stoichiometry of the extractable complexes was determined. Synergistic enhancement of the extraction of rare-earth elements in the presence of tetraphenylmethylenediphosphine dioxide was revealed.     

Extraction of Am(III) and Lanthanides from Nitric Acid Solutions with Polyfunctional Organophosphorus Acids

Extraction of microamounts of Am, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu nitrates from aqueous HNO₃ with solutions of (diphenylphosphinylmethyl)phenylphosphinic, (di-p-tolylphosphinylmethyl)phenylphosphinic, (di-p-anisylphosphinylmethyl)phenylphosphinic, and (dioctylphosphinylmethyl)phenylphosphinic acids and of butyl hydrogen (diphenylphosphinylmethyl)phosphonate in toluene was studied. The metal : extractant ratio in the extractable species was determined.     

Extraction of Am(III) and Rare-Earth Elements from Nitric Acid Solutions with Dibutyl Diphenylphosphinylmethylphosphonate

Extraction of HNO₃ and trace amounts of Am, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu nitrates from aqueous HNO₃ with solutions of dibutyl diphenylphosphinylmethylphosphonate in dichloroethane was studied. The stoichiometry of the extractable solvates was determined, and the apparent extraction constants were calculated.     

Extraction of Am(III) and Eu(III) from Nitric Acid Solutions with Bidentate Neutral Organophosphorus Compounds

Extraction of HNO₃ and microamounts of Am and Eu from nitric acid solutions with solutions of bidentate butyl (phosphorylmethyl)phenylphosphinates R₂P(O)CH₂P(O)Ph(OBu) [R = octyl (I), phenyl (II), p-tolyl (III), p-anisyl (IV)] in 1,2-dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the apparent extraction constants were calculated. The extractive power of the reagents studied toward HNO₃ increases in the order II < III < IV < I, and toward Am(III), in the order I < II < III < IV.     

Extraction Properties of Butyl Bis(dibutoxyphosphinylmethyl)phosphinate in Nitric Acid Solutions

The extraction of HNO₃ and microamounts of U(VI), Th(IV), Sc(III), REE(III), and Am(III) nitrates from HNO₃ solutions with solutions of butyl bis(dibutoxyphosphinylmethyl)phosphinate in organic diluents was studied. The stoichiometry of the extractable complexes was determined, and the apparent extraction constants were calculated. The capability of the extractant to recover the examined elements from nitric acid solutions grows with an increase in the number of phosphoryl groups in its molecule. The recovery of the metal ions into the organic phase becomes more efficient in going to more polar organic diluents.     

Separation of REE(III) and Am(III) by Extraction with Compounds of Zirconium and Dibutyl Phosphoric Acid from Solutions of Nitric and Hydrochloric Acids

Radiochemistry - The behavior of rare-earth elements (REE) and americium during their extraction with compounds of zirconium and dibutyl phosphoric acid (DBPA) in various solvents from solutions of...     

Extraction of U(VI), Th(IV), and REE(III) from Nitric Acid Solutions with Bis[(diphenylphosphoryl)acetamido]alkanes

Radiochemistry - It was found that combining two bidentate fragments Ph2P(O)CH2C(O)NAlk– in the same molecule via an amide atom with an alkylene bridge leads to a noticeable increase in the...     

Uranium(IV) Complexes Formed in Extraction with Tributyl Phosphate from Nitric Acid Solutions

Speciation of U(IV) in tributyl phosphate (TBP) solutions prepared by extraction of U(IV) from 2 M HNO₃ was studied. The electronic spectra showed that in the solutions containing from 3 to 60% TBP a mixture of disolvate U(NO₃)₄(TBP)₂ and hydrates with hypothetical formula (TBP) _m ...[U(NO₃) _k · (H₂O) _n ]^(4-k)+ (k = 3 or 4) is formed. Within the 70-100% concentration range, the hexanitrate complex (TBP) _n ...2H₅O₂(H₂O) _p ⁺...[U(NO₃)₆]^{2 -} also appears. In undiluted TBP, as the concentration of uranyl nitrate increases, first the hexanitrate complex and then hydrated complexes of U(IV) gradually disappear. At uranium concentration more than 300 g l^-1, only U(IV) tetranitrate disolvate exists in the organic phase.     

Extraction of Americium(III) from Nitric Acid Solutions with Neat Diphenyl(dibutylcarbamoylmethyl)phosphine Oxide in the Presence of Metal Salts

Extraction of Am(III) from nitric acid solutions with a liquid complex of diphenyl(dibutylcarbamoylmethyl)phosphine oxide (Ph₂Bu₂) with nitric acid as influenced by concentration of Al, Ca, Na, Ni, Co, Cr, Fe, Zr, and Mo nitrates was studied. Nonextractable (Al, Ca, Na) and poorly extractable (Ni, Co, Cr) nitrates at their widely varied concentration do not interfere with the exhaustive extraction of americium from 3 M HNO3. These salts facilitate both formation of the extraction-active liquid phase on contact of Ph₂Bu₂ with 1 M HNO₃ and exhaustive extraction of americium from the acid. Extraction of Fe(III) at its widely varied concentration insignificantly interferes with extraction of americium, but this effect increases with increasing acidity and phase contact time. Americium is extracted with a powdered reagent from 0.1 M HNO₃ when liquid extractant is not formed in the visible amounts. In extraction of americium from weakly acidic solutions in the presence of salts the solid reagent, apparently, partially transforms into the liquid extractant, and two different extraction mechanisms are operative. It was shown that the neat liquid complex of Ph₂Bu₂ with HNO₃ can be used for exhaustive extraction of americium from high-level saline wastes from plants for processing nuclear fuel.     

Extraction of REE(III), U(VI), and Th(IV) from Nitric Acid Solutions with Carbamoylmethylphosphine Oxides in the Presence of Bis[(trifluoromethyl)sulfonyl]imide Ions

Extraction of microamounts of REE(III), U(VI), and Th(IV) with solutions of carbamoylmethylphosphine oxides (CMPOs) in organic diluents from aqueous HNO₃ solutions containing lithium bis[(trifluoromethyl) sulfonyl]imide (LiTf₂N) was studied. The efficiency of the REE(III), U(VI), and Th(IV) extraction from nitric acid solutions with CMPO solutions considerably increases in the presence of Tf₂N^– ions in the aqueous phase. The stoichiometry of the extractable complexes was determined, and the influence of the structure of the CMPO molecule, kind of organic diluent, and aqueous phase composition on the efficiency of the U(VI), Th(IV), and REE(III) extraction into the organic phase was considered.     

Extraction of Rare-Earth Elements from Nitric Acid Solutions with Ethylenediphosphine Dioxides

Extraction of microamounts of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu from HNO₃ aqueous solutions with ethylenediphosphine dioxides in organic diluents was studied. The effect of the dioxide structure on its extractive power and selectivity was considered. The stoichiometry of extractable solvates was determined.     

Extraction of REE(III), U(VI), and Th(IV) from Nitric Acid Solutions with Carbamoylmethylphosphine Oxides in the Presence of Dinonylnaphthalenesulfonic Acid

The extraction of REE(III), U(VI), and Th(IV) from nitric acid solutions with solutions of carbamoylmethylphosphine oxides (CMPOs) considerably increases in the presence of dinonylnaphthalenesulfonic acid. The stoichiometry of the extractable complexes was determined, and the influence of the aqueous phase composition, kind of organic diluent, and CMPO structure on the efficiency of the extraction of the metal ions was analyzed.     

Extraction of REE(III), U(VI), and Th(IV) from Nitric Acid Solutions with Diphenyl(dibutylcarbamoylmethyl)phosphine Oxide in the Presence of Quaternary Ammonium Bis[(trifluoromethyl)sulfonyl]imides

Radiochemistry - The extraction of REE(III), U(VI), and Th(IV) from nitric acid solutions with solutions of diphenyl(dibutylcarbamoylmethyl)phosphine oxide considerably increases in the presence of...     

Extraction of Rare-Earth Elements and Americium from Nitric Acid Solutions with Polyphosphine Oxides

Extraction of HNO₃ and microamounts of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Am from solutions of NH₄NO₃ and HNO₃ with solutions of polyphosphine oxides containing o-oxyphenylenemethylene fragments in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the apparent extraction constants were calculated. As the number of phosphoryl groups in the extractant molecule is increased, the extraction of cerium-group lanthanides increases and that of yttrium-group lanthanides decreases.     

Extraction of Am(III), U(VI), and Pu(IV) from HCl Solutions with Diphenyl(dibutylcarbamoylmethyl)phosphine Oxide

Extraction of Am(III), U(VI), and Pu(IV) from HCl solutions with solutions of diphenyl(dibutylcarbamoylmethyl)phosphine oxide in dichloroethane and m-nitrobenzotrifluoride was studied. The curves of the Am(III) and U(VI) extraction as a function of the acid concentration pass through a minimum at [HCl] = 1 M, followed by a steep ascent at the acid concentration increased further. The logarithmic dependences of the distribution factors on the extractant concentration are nonlinear, with the slope of the upper portions close to 2 for Am(III) and 1 for U(VI). Pu(IV) is extracted noticeably worse than U(VI). A significant anomalous aryl strengthening effect is observed in HCl solutions.     

Uranyl and Thorium(IV) Sorption from Dilute Nitric Acid Solutions with Dodecavanadic Acid

Sorption of uranyl on dodecavanadic acid proceeds by the ion-exchange mechanism at relatively low metal concentrations in the range (0.8-2.0) ×10^{- 3} M. Sorption of Th(IV) is practically pH-independent over the pH range 1.5-2.5, but depends significantly on the initial Th(IV) concentration. The maximal capacities of DDVA for uranyl and Th(IV) remarkably differ from each other (9 and 6.3 mg-equiv g^{- 1}, respectively). The uranyl compound formed on contacting DDVA with concentrated uranyl nitrate solution was identified by X-ray diffraction as UO₂(VO₃)₂·nH₂O.     

Solid-Phase Extraction of Eu(III) and Am(III) with Synergistic Mixtures of Extractants

Solid-phase extraction (SPE) of Eu(III) and Am(III) in systems containing a chelating agent and a neutral electron-donor compound was studied. In the systems 1-phenyl-3-methyl-4-benzoylpyrazol-5-one-tetraphenylmethylenediphosphine dioxide and 1-phenyl-3-methyl-4-benzoylpyrazol-5-one-trioctylphosphine oxide, the distribution factors of Eu(III) and Am(III) showed a synergistic effect owing to adduct formation.     

Features of Pu(IV) and Np(IV) Extraction from Nitric Acid Solutions of Uranyl Nitrate with 30% TBP

The extraction of Pu(IV) and Np(IV) from nitric acid solutions containing high concentrations of uranyl nitrate with 30% TBP in hydrocarbon diluent was studied. It was found that, as the Pu(IV) and Np(IV) concentration grows from tens milligrams to several grams at fixed uranyl nitrate (100 g l^-1 and higher) and nitric acid concentrations in the aqueous phase, the distribution coefficients of actinides(IV) increase (for Np to a greater extent than for Pu). This trend becomes more pronounced at higher temperatures. Correlation equations describing this effect are suggested.