STUDIES ON U-Th SEPARATION USING TRI-sec-BUTYL PHOSPHATE

In this work, the extraction of Am(III), U(VI), Th(IV) and Fe(III) by P,P′-di(2-ethylhexyl) methylene- (H₂DEH[MDP]), ethylene- (H₂DEH[EDP]), and butylene- (H₂DEH[BuDP]) diphosphonic acids dissolved in the monomerizing diluent 1-decanol has been investigated. A comparison of the acid dependencies with those observed in o-xylene has revealed a number of novel features which have been ascribed to extraction of metal nitrates through a solvation mechanism made possible by facile transfer of nitrate ions into the 1-decanol phase. The use of 1-decanol as the diluent gives rise to strong suppression of metal extraction, which increases along the series Fe(III)2DEH[MDP]2DEH[EDP]≤H₂DEH[BuDP]. The extractant dependencies of U(VI) and Th(IV) have slopes equal to 2 with all extractants. Those for Am(III) and Fe(III) exhibit variable slopes with limiting values of 1 at the lowest and 3 at the highest extractant concentrations. From the combined information provided by the acid and extractant dependencies, stoichiometries and probable structures for complexes formed in the organic phase have been proposed. The data obtained in this work suggest a simple route for actinide stripping from diphosphonic acid extractants loaded in nonpolar diluents.     

HYDROGEN BONDING IN AGGREGATES OF DIALKYL-SUBSTITUTED DLPHOSPHONIC ACIDS AND MONOFUNCTIONAL ANALOGUES∗

ABSTRACT

Hydrogen bonding of dialkyl-substituted diphosphonic acids in nonpolar (toluene and CC1₄) and alcohol (1-decanol) solutions is examined. The compounds are monomeric in 1-decanol and dimeric or higher in nonpolar organic diluents. Infrared spectroscopy and molecular mechanics calculations suggest that the dimers of P,P'-di(2-ethylhexyl) methanediphosphonic acid (H₂DEH[MDP]) and its straight-chain isomer, P.P'-dioctyl methanediphosphonic acid (H₂DO[MDP]), adopt rigid highly hydrogen-bonded structures such as C or D. The homologous P.P'-di(2-ethylhexyl) ethane- and butanediphosphonic acids, H₂DEH[EDP] and H₂DEH[BuDP], respectively, adopt structures that are also intermolecularly hydrogen-bonded but more flexible. The effect on the P=0 stretching vibration of increasing 1-decanol concentration in the solvent differs for these compounds. In the case of H₂DEH[MDP]and H₂DO[MDP], the frequency remains constant until all CC1₄ has been replaced by the alcohol, then the P=0 stretching frequency shifts to a lower energy. In the case of H₂DEH[EDP] and H₂DEH[BuDP], a gradual shift to higher energy occurs as the alcohol concentration increases. The magnitude of the difference in the P=0     

METAL EXTRACTION BY ALKYL SUBSTITUTED DIPHOSPHONIC ACIDS. PART 4 P,P′-DI(2-ETHYLHEXYL) BUTANEDIPHOSPHONIC ACID

ABSTRACT

As part of an ongoing investigation of the properties of dialkyl substituted diphosphonic acids as solvent extraction reagents for metal cations, we have studied the extraction of alkaline earth cations, Fe(III) and representative actinides (Am(III), U(VI) and Th(IV)) at tracer-level concentration by o-xylene solutions of P,P′-di(2-ethylhexyl) butanediphosphonic acid, H₂DEH[BuDP]. The extractant and acid dependencies of these metal ions exhibited significant differences from those of the previously investigated analogous extractants in which the two phosphonate groups are separated by a methylene or an ethylene bridge. The aggregation of H₂DEH[BuDP] was investigated in toluene at 25° C by vapor pressure osmometry. H₂DEH[BuDP] was found to exist predominantly as a trimeric species in the 0.1-0.005 molal concentration range. Osmometric measurements and infrared spectra indicate that Ca(II) is extracted into H₂DEH[BuDP] solutions with little disruption of the structure of the extractant. Iron(III) causes significant deprotonation of the ligand and dramatically changes the apparent aggregation number. A comparison of the extraction of Ca(II), Am(III) and Fe(III) by H₂DEH[BuDP] with data obtained using bis(2-ethylhexyl) phosphoric acid (HDEHP) or 2-ethylhexyl 2-ethylhexylphosphonic acid (HEH[EHP]) as the extractant indicates that H₂DEH[BuDP] has characteristics similar to these monofunctional analogs. Infrared spectra of the Ca(II) and Fe(III) salts of H₂DEH[BuDP] show a shift of both v_asym (POO?) and v_sym (POO?) to lower frequencies relative to their values in the sodium salt. This indicates a symmetrical interaction between the metal ion and the phosphonate groups through chelate and/or bridging interactions.     

EXTRACTION OF ALKALINE EARTH AND ACTINIDE CATIONS BY MIXTURES OF DI(2-ETHYLHEXYL) ALKYLENEDIPHOSPHONIC ACIDS AND NEUTRAL SYNERGISTS

ABSTRACT

The synergistic extraction of alkaline earth (Ca²⁺, Sr²⁺, Ba²⁺ and Ra²⁺) and actinide (Am³⁺, UO₂ ²⁺ and Th⁴⁺) cations from aqueous nitric acid solutions by mixtures of P,P^′-di(2-ethylhexyl) methylene-(H₂DEH[MDP]), ethylene-(H₂DEH[EDP]), and butylene-(H₂DEH[BuDP]) diphosphonic acids and neutral extractants in o-xylene has been investigated. The cis-syn-cis and cis-anti-cis stereoisomers of dicyclohexano-18-crown-6 (DCH18C6), the unsubstituted 21-crown-7 (21C7) and dicyclohexano-21-crown-7 (DCH21C7) were used as neutral synergists of the crown ether type. For Am(III) synergistic effects were also investigated using neutral organophosphorus esters, such as, tri-n-butylphosphate (TBP), diamyl amylphosphonate (DA[AP]) and tri-n-octylphosphine oxide (TOPO) as co-extractants. In all systems investigated, no synergistic extraction enhancement was observed for actinide ions. For the alkaline earth cations, synergistic effects were only observed when mixtures of H₂DEH[EDP] or H₂DEH-[BuDP] with DCH18C6 were used to extract Sr²⁺, Ba²⁺ and Ra²⁺. No synergistic effects were observed for the extraction of alkaline earth cations by H₂DEH[MDP] or for the extraction of Ca²⁺ by any of the diphosphonic acids studied. The synergistic effects obtained with DCH18C6 were significantly higher for the cis-syn-cis than for the cis-anti-cis stereoisomer.     

SANS STUDY OF AGGREGATION OF THE COMPLEXES FORMED BY SELECTED METAL CATIONS AND P,P'-DI(2-ETHYLHEXYL) ETHANE- AND BUTANE-DIPHOSPHONIC ACIDS∗

ABSTRACT

The aggregation of several metal complexes formed during solvent extraction with P,P'-di(2-ethylhexyl) ethanediphosphonic acid, H₂DEH[EDP], and by P,P'-di(2-ethylhexyl) butanediphosphorac acid, H₂DEH[BuDP], in deuterated toluene, has been investigated by small angle neutron scattering (SANS). With H₂DEH[EDP], the extraction of Ca(II), La(IH) and U(VT) does not disrupt the cyclic hexameric structure of the ligand in solution. Fe(III) and Th(IV) complexes of H₂DEH[EDP], on the other hand, exhibit a very modest tendency to aggregate but only at very high metal loading in the organic phase. With H₂DEH[BuDP], the extraction of Ca(H), La(III), U(VI) and Th(IV) is not accompanied by significant aggregation of the metal complexes The Fe(HI)-H₂DEH[BuDP] complexes, however, form long cylindrical aggregates similar to those previously observed with P,P'di(2-ethylhexyl) methanediphosphonic acid, H₂DEH[MDP]. The aggregation behavior of the various metal-extractant species is discussed in light of the information obtained from earlier solvent extraction, vapor pressure osmometry, and infrared spectroscopy studies.     

AGGREGATION OF COMPLEXES FORMED IN THE EXTRACTION OF SELECTED METAL CATIONS BY P,P'-DI(2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID*

ABSTRACT

The aggregation of several metal complexes formed during solvent extraction with P,P'-di(2-ethylhexyl) methanediphosphonic acid, H₂DEH[MDP], in deuterated toluene, has been investigated by small angle neutron scattering (SANS). The SANS results show that the Ca(II)-, Al(ni)-, La(III)- and Nd(III)-H₂DEH[MDP] compounds exhibit little or no tendency to aggregate. Uranyl complexes of H₂DEH[MDP] at high metal loading form small aggregates with an aggregation number of approximately 14. This behavior is in sharp contrast with the Th(IV)-H₂DEH[MDP] system which forms large aggregates in the organic phase under high metal loading conditions. The aggregation behavior of the various metal-H₂DEH[MDP] compounds is discussed in light of the information obtained from earlier solvent extraction, vapor pressure osmometry, and infrared spectroscopy studies.     

ACIDS. PART 1. P,P"-DI(2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID

ABSTRACT

Two novel extractants, P,P'-di(2-ethylhexyl) methanediphosphonic acid (H2DEH[MDP]) and P.P'-dioctyl methanediphosphonic acid (H2DO[MDP]) have been synthesized at high purity and yield. H₂DEH[MDP] was selected for metal extraction studies because of its better physical properties. An investigation of the extraction of alkaline earth cations, Fe(III) and representative tri-, tetra- and hexavalent actinide ions from nitric acid solutions into o-xylene solutions of H₂DEH[MDP] at different concentrations was performed. With a few exceptions, the acid dependencies of the extraction of the above metal species strongly resembles those measured in the uptake of the same metals by the chelating ion exchange resin Diphonix®, which contains gem-diphosphonic acid groups chemically attached to a polymeric matrix. H₂DEH[MDP] exhibits practically no selectivity among the alkaline earth cations. The almost lack of acid dependency observed with Fe(lll) and tetra- and hexavalent actinides indicates that these ions are chelated by H₂DEH[MDP] mostly through the P=0 groups of the extractant. With Fe(lll) and the actinides, variable slopes of the extractant dependencies were measured, their values being strongly dependent on the acidity of the aqueous phase. Typically, the slope of the extractant dependency has a value of about two if the metal is extracted from high acidity solutions. This value becomes progressively lower as the aqueous acidity is reduced, tending to almost zero for acidities around 0.1 M. This phenomenon has been attributed to the formation of metal complexes having different stoichiometrics, ligand protonation and solubility in the aqueous phase.

H₂DEH[MDP] possesses an extraordinary affinity for actinides and Fe(III). In analogy with the Diphonix resin, this property can be exploited for actinide preconcentration and separation from complex matrices of analytical interest and from mixed waste solutions.     

AGGREGATION OF P,P' -DI( 2-ETHYLHEXYL) METHANEDIPHOSPHONIC ACID AND ITS Fe(III) COMPLEXES ∗

ABSTRACT

The aggregation of P,P' -di( 2-ethylhexyl) methanediphosphonic acid, H2DEH[ MDP] dissolved in deuterated toluene has been investigated by small angle neutron scattering ( SANS) The title compound was shown to exist in solution as a dimer under all conditions. Dimer formation is independent of the acidity of the aqueous solution with which the organic solution is pre-equilibrated. Solutions of H₂ DEH[ MDP] containing increasing amounts of Fe( lll) extracted from aqueous solutions in the acidity range from 0.1 to 5 M were also investigated. The SANS results confirm the tendency of H2DEH[ MDP] -Fe( III) species in aromatic diluents to form rod-like aggregates characteristic by a constant cross section and a length which increases with increasing amounts of metal in the organic phase. Particle growth is independent of the acidity of the aqueous solutions from which the metal is extracted. These results are important for understanding the chemistry underlying the solvent extraction behavior H₂DEH[ MDP] and its practical application in separation procedures.     

Metal Extraction by Sulfur‐Containing Symmetrically‐Substituted Bisphosphonic Acids. Part I. P,P′‐di(2‐ethylhexyl) Methylenebisthio‐Phosphonic Acid

Abstract

P,P′‐dialkyl methylenebisphosphonic acids are powerful metal extraction reagents exhibiting strong affinity for a variety of metal ions, especially lanthanides and actinides. While the affinity of gem‐bisphosphonic acids is generally high for most metal ions because of their relative high acidity and ability to form six‐member chelate rings, the selectivity often is low. Thus, a strategy of incorporating soft‐donor atoms such as sulfur into gem‐bisphosphonic acids has been adopted to obtain enhanced metal selectivity while retaining high extraction efficiency. To this end a new class of sulfur‐containing gem‐bisphosphonic acid solvent extraction reagents was designed, synthesized, and evaluated for heavy element separations. Specifically, the novel sulfur‐containing P,P′‐di(2‐ethylhexyl) methylenebisthiophosphonic acid, H₂DEH[MBTP], was synthesized, characterized and its aggregation, metal extraction and acid‐base behavior assessed. Vapor phase osmometry measurements indicate that H₂DEH[MBTP] is less aggregated than its P,P′‐di(2‐ethylhexyl) methylenebisphosphonic acid analogue, H₂DEH[MBP], existing in toluene primarily as an equilibrium mixture of monomer and dimer in the concentration range studied. The acid dependency data for the extraction of Am³⁺ and Eu³⁺ from aqueous perchlorate solutions by H₂DEH[MBTP] in o‐xylene exhibit slopes close to ?3 at low acidity, consistent with extraction of a trivalent metal ion. The extractant dependency data exhibit pH dependent slopes, suggesting different stoichiometry of metal extraction under different acidities.     

Direct Selective Extraction of Trivalent Americium from PUREX Raffinate Using a Combination of CyMe4BTPhen and TEDGA—A Feasibility Study

The direct and selective extraction of Am(III) from simulated PUREX raffinate is demonstrated using a novel combination of the lipophilic extractant CyMe₄BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[e]-[1,2,4]triazin-3-yl)-1,10-phenanthroline) and the hydrophilic complexant TEDGA (N,N,N’,N’-tetraethyl-diglycolamide) to enhance selectivity toward Am(III) extraction. Separation factors (SF) of up to SF_Am/Cm = 4.9 were observed in tracer experiments using this combination of CyMe₄BTPhen and TEDGA. Distribution ratios of stable isotopes of fission and activation products contained in a simulated PUREX raffinate solution are reported for the first time with CyMe₄BTPhen, and some co-extracted metal ions are identified. The metal ions partly co-extracted from the simulated PUREX raffinate solution were Cu, Pd, Cd, Ag, Ni, and to a lesser extent Sn and Mo. The co-extraction of Pd and Ag was successfully suppressed using Bimet ((2S,2’S)-4,4’-(ethane-1,2-diylbis(sulfanediyl))bis(2-aminobutanoic acid)). The extraction was also studied as a function of the TEDGA concentration. The distribution ratios of Am and Cm can be adjusted by variation of the TEDGA concentration to yield D_Am values >1 and D_Cm values <1. Separation factors for Am(III) over Cm(III) of up to SF_Am/Cm = 2.4 were observed in these experiments. For Ln(III) + Y(III), distribution ratios below 1 were observed, thus enabling a direct extraction of Am(III) from simulated PUREX raffinate with a sufficient selectivity against trivalent lanthanides and Cm(III).     

THE EXTRACTION OF Am(III) FROM NITRIC ACID BY OCTYL(PHENYL)-N,N-DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE - TRI-n-BUTYL PHOSPHATE MIXTURES

Abstract

The extraction behavior of Am(III) from nitric acid by octy1(phenyl)-N,N-diisobutylcarbamoyl methyphosphine oxides, OØD[IB]CMPO, in the presence of tributylphosphate, TBP, has been studied using diethylbenzene, decalin, and normal aliphatic hydrocarbon diluents. Relative to ØD[IB]CMPO alone, mixtures of TBP and OØD[IB]CMPO show a slight enhancement in the extraction of Am(III) from nitric acid solution above 2 M and a moderate decrease in extraction for lower acid concentrations. The net effect of TBP addition to OØD[IB]CMPO (as well as other selected carbamoyl methylphosphoryl extractants) is a relative insensitivity of the distribution ratio of Am(III) to HNO₃ concentration in the range of 0.5 M to 6 M and facilitated stripping of Am(III) with dilute acid. Since a continuous variation study of Am(III) extraction using mixtures of ØOD[IB]CMPO and TBP at a fixed total concentration revealed no evidence of a mixed complex, the TBP appears to be behaving primarily as a phase modifier

The most significant benefit gained from addition of TBP to ØD[IB]CMPO is the increased metal ion loading capacity and extractant compatibility with alicyclic and aliphatic diluents. The use of TBP to overcome phase compatibility with other bifunctional extractants of the carbamoylmethylphosphoryl type and the use of other phase modifiers with ØD[IB]CMPO have also been investigated.     

Development of a Selective Americium Separation Process Using H4TPAEN as Water-Soluble Stripping Agent

ABSTRACT

Recycling americium from spent nuclear fuel is considered as an important option for a future sustainable nuclear fuel cycle. The PUREX solvent extraction process allows to separate uranium and plutonium from a solution of spent fuel dissolved in nitric acid. In a second step, it would be desirable to separate americium from fission products, and especially lanthanides, but also from curium in order to further transmute americium in future fast neutron reactors. For this purpose, we report the investigation of a new solvent extraction process based on the use of TODGA as an extractant in the organic phase and H₄TPAEN as a selective Am(III) stripping agent in the aqueous phase. With this promising system it is possible to co-extract Am, Cm and lanthanides at high acidity and then selectively strip americium from the loaded organic phase at pH around 1 with H₄TPAEN. Batch extraction data were acquired to evaluate best conditions to develop a liquid-liquid extraction flow sheet. The influence of several parameters like concentration of ligand, cations and temperature on Am(III)/Cm(III) and Am/lanthanides separation was evaluated. Especially, the ability of H₄TPAEN complexing agent to strip macro-concentrations of Am was demonstrated.     

Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides

The sterically constrained, macrocyclic, aqueous soluble ligand N,N′-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H₂BP18C6) was investigated for separating americium from curium and all the lanthanides by solvent extraction. Pairing H₂BP18C6, which favors complexation of larger f-element cations, with acidic organophosphorus extractants that favor extraction of smaller f-element cations, such as bis-(2-ethylhexyl)phosphoric acid (HDEHP) or (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]), created solvent extraction systems with good Cm/Am selectivity, excellent trans-lanthanide selectivity (K_ex,Lu/K_ex,La = 10⁸), but poor selectivity for Am against the lightest lanthanides. However, using an organic phase containing both a neutral extractant, N,N,N’,N’-tetra(2-ethylhexyl)diglycolamide (TEHDGA), and HEH[EHP] enabled rejection of the lightest lanthanides during loading of the organic phase from aqueous nitric acid, eliminating their interference in the americium stripping stages. In addition, although it is a macrocyclic ligand, H₂BP18C6 does not significantly impede the mass transfer kinetics of the HDEHP solvent extraction system.     

Solvent extraction of zirconium(IV) from acidic chloride solutions using the thiosubstituted organophosphorus acids Cyanex 301 and 302

Solvent extraction of zirconium(IV) from acidic chloride solutions has been carried out with the thiosubstituted organophosphorus acids Cyanex 301 and Cyanex 302. The extraction follows an ion exchange mechanism: MO²⁺_(aq) + 2 HA_(org) ? MOA_2(org) + 2 H⁺_(aq), where, M = Zr(IV); HA = Cyanex 301 or Cyanex 302. The plots of log D (distribution ratio) vs log [HA], are linear with slopes of 2, indicating the association of two moles of extractant with the extracted metal species. The plots of log D vs log [H⁺] gave straight lines with a negative slope of 1.7 for Cyanex 301 and 1.8 for Cyanex 302, indicating the exchange of two moles of hydrogen ions for every mole of Zr(IV). Addition of sodium salts enhanced the extraction of metal. The stripping behavior of metal from the loaded organic (LO) with HCl and H₂SO₄ was studied. Increase of temperature during the extraction and the stripping stage increases the metal transfer, showing the process is exothermic. Mixed extractants, the extraction behavior of associated elements such as Hf(IV), Ti(IV), Al(III), Fe(III) and the IR spectra of the metal complexes were studied. Copyright © 2004 Society of Chemical Industry     

Equilibrium,thermodynamics and kinetics study on Au(III) extraction by gemini surfactant with different spacer length

The effect of spacer lengths of imidazolium gemini surfactant [C₁₄-n-C₁₄im]Br₂ (n = 2, 4, 6) on the equilibrium, thermodynamics and kinetics of Au(III) extraction from hydrochloric acid medium were investigated in this article. The thermodynamic parameters, including the changes in enthalpy (ΔH*), entropy (ΔS*) and Gibbs free energy (ΔG*) were determined. The values of ΔH* demonstrated that the extraction of Au(III) by [C₁₄-n-C₁₄im]Br₂ was endothermic at first and exothermic at last. The kinetics study found that extraction rate became faster when the spacer lengths were increased. Moreover, kinetics results demonstrated that the diffusion is the controlling step, and the mass transfer coefficients of Au(III) in the investigated systems indicated that the resistance of mass transfer was smaller when the spacer lengths was longer. The studies of interfacial tension further confirmed the better extractability of [C₁₄-n-C₁₄im]Br₂ with longer spacer lengths. Our results reveal efficient and sustainable gold separation.     

Selected Alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine Oxides as Extractants for Am(III) from Nitric Acid Media

Abstract

A new series of neutral bifunctional extractants, alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides, has been prepared and studied as extractants for Am(III) from nitric acid media. Two types of alkyl(phenyl)-N,N-dialkyl CMPO compounds were prepared, one containing N,N-diethyl groups and the other containing N,N-diisobutyl groups. The N,N-diethyl series contained hexyl(phenyl) and 6-methylheptyl(phenyl) derivatives, abbreviated HφDECMPO, and 6-MHφDECMPO, respectively. The N,N-diisobutyl series contained the n-octyl(phenyl), 6-methylheptyl(phenyl), and the 2-ethylhexyl(phenyl) derivatives, abbreviated OφD[IB]CMPO, 6-MHφD[IB]CMPO, and 2-EHφD[IB]CMPO, respectively. Third power extractant dependencies for the extraction of Am(III) from 0.5 and 3 M HNO₃ were obtained at low (<0.25 M) concentrations of extractant, but higher power dependencies were obtained above 0.25 M extractant from 3 M HNO₃. The HφDECMPO, 6-MHφDECMPO, 6-MHφD[IB]CMPO, and OφD[IB]CMPO [all 0.5 M in diethylbenzene (DEB)] are significantly better extractants than DHDECMPO for Am(III) from 1 to 6 M HNO₃. These same extractants have lower D _Am values than DHDECMPO at low acidities. HφDECMPO and OφD[IB]CMPO also have better selectivity for Am(III) over Fe(III) than DHDECMPO. HφDECMPO in DEB has a strong tendency toward the formation of a second liquid organic phase on extracting macroconcentrations of Nd(III) and U(VI) from 3 M HNO₃; however, this behavior is substantially diminished with the OφD[IB]CMPO and 6-MHφD[IB]CMPO compounds.     

Synthesis and Evaluation of N,N′-dimethyl-N,N′-dicyclohexyl-Malonamide (DMDCMA) as an Extractant for Actinides

A malonamide based extractant, i.e., N,N′-dimethyl-N,N′-dicyclohexyl-malonamide (DMDCMA) was synthesized in a single step and tested for the extraction of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV), Pu(VI), etc., from nitric acid medium. The extractant was soluble in phenyltrifluoromethylsulphone (PTMS or FS-13) unless stated otherwise. The effect of various experimental parameters, such as the aqueous phase acidity (0.01–3 M HNO₃), nature of the acid, oxidation states of the metal ions, ligand concentration, nature of the diluent and temperature on the extraction behavior of metal ions was studied. The extracted Am(III) species was determined from slope analysis method as [Am(NO₃)₃(DMDCMA)₂]. The extraction of the metal ions was found to increase with the aqueous phase acidity. The temperature variation studies allowed the calculation of the heat of the two-phase extraction reaction as well as the corresponding extraction constants. These studies revealed that DMDCMA showed good extraction for all the actinide metal ions investigated, and have the advantage of single stage synthesis and easier purification protocol.     

Extraction of Trivalent Europium and Americium from Nitric Acid Solution with Bisdiglycolamides

Two bisdiglycolamides (BisDGAs) of N,N,N′′′,N′′′-tetrabutyl-N?,N′′-ethidene bisdiglycolamide (TBE-BisDGA) and N,N,N′′′,N′′′-tetrabutyl-N?,N′′-m-xylylene bisdiglycolamide (TBX-BisDGA) were synthesized. Their extraction behaviors of Eu(III) and Am(III), as well as nitric acid were investigated from nitric acid medium by using n-octanol as diluent. Nitric acid is extracted as the form of HNO₃·(BisDGAs)_0.6 by BisDGAs and the conditional acid uptake constants of TBE-BisDGA and TBX-BisDGA were 0.26 and 0.10, respectively. The distribution ratios of Eu(III) and Am(III) increased with the increase of nitric acid and extractant concentration, whilst decreased with temperature rise. TBX-BisDGA had a stronger extraction power for Eu(III) and Am(III) than TBE-BisDGA. Both of the extractants displayed a higher affinity toward Eu(III) than Am(III). In the examination of the acidity range from 0.5 to 5.0 M, a maximum separation factor SF_{Eu(III)/Am(III)} can reach 8.0 at 3.0 M HNO₃ for TBX-BisDGA; and 10 at 4.0 M HNO₃ for TBE-BisDGA, respectively. Slope analyses showed that Eu(III) and Am(III) are extracted as di-solvated species by TBX-BisDGA or TBE-BisDGA. The extraction mechanism was described and the apparent extraction equilibrium constant as well as Gibbs free energy change, enthalpy change and entropy change were presented. In addition, their Eu(III) complexes were analyzed by using infrared spectra.     

Distribution Studies of Actinides Using a Tetradentate Extractant, 4,4′-Nonanedioyl-Bis(2,4-Dihydro-5-Methyl-2-Phenyl-3H-Pyrazol-3-One)

Abstract

The extraction of Th(IV), UO₂(II), Am(III), and Eu(III) from aqueous acid by a tetradentate extractant, 4,4′-nonanedioyl-bis(2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one), H₂NDBP, has been studied and compared with two bidentate model compounds, 4-hexanoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HHMPP, and 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one, HBMPP. The distribution coefficients of UO₂(II), Am(III), and Eu(III) were somewhat larger using H₂NDBP relative to the model compounds under the conditions studied. However, the Th(IV) extraction using H₂NDBP was greatly enhanced when compared to HBMPP or HHMPP. The distribution coefficient for Th(IV) from 0.5 M HNO₃ was 11.6 using 3.0 × 10^?3 M H₂NDBP compared with values of D < 0.01 using 3.0 × 10^?3 M HBMPP or HHMPP.     

THE EFFECT OF TEMPERATURE ON THE SYNERGISTIC EXTRACTION OF THORIUM( IV) AND URANIUM( VI) BY 2-ETHYLHEXYL PHENYLPHOSPHONIC ACID AND MICELLES OF DINONYL NAPHTHALENE SULPHONIC ACID

ABSTRACT

The influence of temperature in the range 15 to 75° C on the extraction of thorium( IV) and uranium( VI) from nitric acid solutions into ligroine solutions of 2-ethylhexyl phenylphosphonic acid ( HEHφ P) micellar dinonyl naphthalene sulphonic acid ( HDNNS) extractants and mixture of the two extractants is reported. From the variation of the distribution ratio with temperature, the enthalpy changes associated with the extraction were determined, and an attempt was made to estimate the free energy and entropy changes associated with the extraction process. The results indicate that the extraction of thorium is favored by both entropy change and enthalpy change when the solvent is HEHφ P and the mixture of HEHOP and HDNNS, but entropy controlled when HDNNS is the extractant. On the other hand, the extraction of uranium by HEHφ P is enthalpy controlled but favored by entropy change when the solvent is HDNNS or a mixture of the two ligands. Temperature did not affect the extraction stoichiometry.