Extraction of certain actinide and lanthanide elements from different acidic media by polyurethane foams loaded with di-(2-ethylhexyl)phosphoric acid (HDEHP)

The extraction of cerium(III) from weakly acidic chloride solutions by HDEHP-nitrobenzene-loaded polyurethane foams could be analyzed quantitatively in terms of the equation: log(9.056 D_c)=log K_c+2.14 log (C_d?6C_c)+3 pH+log f_c where D_c is the distribution ratio of cerium(III) between the foam and aqueous phases, C_d and C_c are the total HDEHP and Ce(III) concentrations on the foam, respectively, log f_c=[Ce³⁺]_(sq)/[ΣCe(III)]_(aq), and K_c is the equilibrium constant of the equation: Ce _(aq) ³⁺ +2.14(HX)_2.8(o) ? ? CeX₆·H_3(o)+3H _(aq) ⁺ . Values of K_c under the different extraction conditions tested are given.     

Extraction of certain actinide and lanthanide elements from different acid media by polyurethane foams loaded with di(2-ethylhexyl)phosphoric acid (HDEHP)

Except for conditions of low acidity and low ratios of di(2-ethylhexyl)phosphoric acid (HDEHP) to U(VI) the data obtained for the distribution of U(VI) between sulfuric acid solutions and polyurethane foams loaded with solutions of HDEHP in nitrobenzene could be analyzed by the equation: log (4.36 D_u)=log K+1.43 log (C_d–4C_u)/(C_H)^1.4+log f_u where the polymerization number of HDEHP is about 2.8, D_u is the distribution ratio, and f_u=[UO ₂ ²⁺ ]_(aq)/[UO₂]_(aq) indicating that the extraction proceeds via the formation of a 14 UO₂:HDEHP complex. At both low acidity and HDEHP/U(VI) ratio a UO₂-HDEHP polymer is formed.     

Extraction of certain actinide and lanthanide elements from different acid media by polyurethane foams loaded with di(2-ethylhexyl)phosphoric acid (HDEHP)

The extraction of uranium(VI) from an aqueous HNO₃ phase into an organic phase consisting of a polyurethane foam immobilizing a solution of di(2-ethylhexyl)phosphoric acid (HDEHP) in o-dichlorobenzene has been investigated at varying concentrations of nitric acid and HDEHP. The mechanism of the extraction is discussed on the basis of the results obtained. The aggregation number of HDEHP immobilized on the foam was obtained from the analysis of data obtained for the extraction of cerium(III) from acidic perchlorate solutions of constant ionic strength.     

Extraction of certain actinide and lathanide elements from different acidic media by polyurethane foams loaded with di-(2-ethylhexyl)phosphoric acid (HDEHP)

The partition of cerium(III) between aqueous acid perchlorate solutions and polyurethane foams loaded with solutions of di-(2-ethylhexyl)phosphoric acid (HDEHP) in nitrobenzene has been investigated and the apparent polymerization number of HDEHP on the foam has been determined. The mechanism of extraction is discussed in the light of the results. It has been found that Ce(III) is generally extracted on the foam by a cation exchange mechanism.     

Extraction mechanism of Tc(IV) by Di-(2-ethylhexyl)phosphoric acid (HDEHP)

Journal of Radioanalytical and Nuclear Chemistry - Di-(2-ethylhexyl)phosphoric acid, HDEHP, is a well-known extractant used for metal ion extraction in an industrial scale and for research work....     

Extraction recovery of vanadium(IV) from acid sulfate solutions with di-(2-ethylhexyl)phosphoric acid

Extraction of vanadium(IV) with di-(2-ethylhexyl)phosphoric acid from acid sulfate solutions in the presence of sodium sulfate was studied. The composition of the complex being extracted was found, and the equation of the extraction reaction was determined. The equilibrium constant of the reaction by which vanadium(IV) is extracted with di-(2-ethylhexyl)phosphoric acid was found by taking into account the complexation of vanadium(IV) in acid sulfate solutions.     

Distribution of lanthanide and actinide elements between bis-(2-ethylhexyl)phosphoric acid and buffered lactate solutions containing selected complexants

With the renewed interest in the closure of the nuclear fuel cycle, the TALSPEAK process is being considered for the separation of Am and Cm from the lanthanide fission products in a next generation reprocessing plant. However, an efficient separation requires tight control of the pH which likely will be difficult to achieve on a large scale. To address this issue, we measured the distribution of lanthanide and actinide elements between aqueous and organic phases in the presence of complexants which were potentially less sensitive to pH control than the diethylenetriaminepentaacetic (DTPA) used in the process. To perform the extractions, a rapid and accurate method was developed for measuring distribution coefficients based on the preparation of lanthanide tracers in the Savannah River National Laboratory neutron activation analysis facility. The complexants tested included aceto-, benzo-, and salicylhydroxamic acids, N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), and ammonium thiocyanate (NH₄SCN). The hydroxamic acids were the least effective of the complexants tested. The separation factors for TPEN and NH₄SCN were higher, especially for the heaviest lanthanides in the series; however, no conditions were identified which resulted in separations factors which consistently approached those measured for the use of DTPA.     

Solvent extraction of Fe(III) by di-(2-ethylhexyl)phosphoric acid from phosphoric acid solutions

The extraction of iron(III) from aqueous phosphoric acid was studied using di-(2-ethylhexyl)phosphoric acid and trioctylphosphine oxide in nonaromatic hydrocarbon diluent. Distribution ratios have been investigated as a function of concentration of iron(III), phosphoric acid concentration, extractant concentration and extraction temperature. The apparent enthalpy change for the extraction reaction has been calculated from the temperature dependence data. It was found that the extractant dependency for iron(III) is first power indicating hydrolysis of iron(III) in the aqueous phase.     

Metal nanoparticle formation in oil media using di(2-ethylhexyl) phosphoric acid (HDEHP)

The metal ion extractant (HDEHP) that is commonly employed in liquid membrane extraction has been shown to stabilise Ag and Cu nanoparticles in oil media of size 5 and 10 nm, respectively. The particle are formed by reduction of the metal salts of HDEHP that are oil soluble and shown by SANS to form small reversed micelles of radius approximately 1 nm. The extractant is also effective at stabilising particles of similar size in an oil phase when the metal ion (e.g., AgNO3) is reduced in a coexisting aqueous phase.     

Extraction of Am(III) from different acid media by di-2-ethyl hexyl phosphoric acid containing phosphorous pentoxide

The extraction of Am(III) from nitric, hydrochloric, oxalic, phosphoric and hydrofluoric acids was studied using 0.4F di-2-ethyl hexyl phosphoric acid (HDEHP) containing 0.1M phosphorous pentoxide (P₂O₅) in dodecane/xylene. The extraction with pure 0.4F HDEHP was found to be negligible from all the media studied. However, the presence of a small amount of P₂O₅ in it increased the extraction substantially. The distribution ratios of Am(III) obtained for HDEHP - P₂O₅ mixture 3M nitric acid containing different concentrations of oxalic acid/phosphoric acid/hydrofluoric acid are in the order of 200-250. The same for 3M hydrochloric acid is very high (800). These distribution ratios are sufficiently high for the quantitative extraction of Am(III) from all the acid media studied. Different reagents such as ammonium oxalate, sodium oxalate, oxalic acid, hydrofluoric acid, sodium carbonate and potassium sulphate were explored for the back extraction of Am(III) from 0.4F HDEHP + 0.1M P₂O₅ in dodecane/xylene. Of these, 0.35M ammonium oxalate and 1M sodium carbonate were found to be most suitable. The back extraction of Am(III) was also attempted with water and 1M H₂SO₄, HNO₃, HClO₄ and HCl solutions after allowing the extracted organics to degrade on its own. It was found that more than 90% of Am could be back extracted with these acids. Using this method more than 90% of Am(III) was recovered from nitric acid solutions containing calcium and fluoride ions.     

Studies on the solvent extraction behaviour of Pu(IV) from sulfuric acid medium into di-2-ethylhexyl phosphoric acid (HDEHP)

Extraction of plutonium(IV) from aqueous sulfuric and sulfuric-nitric acid into di-2-ethylhexyl phosphoric acid (HY) in the diluents n-dodecane, toluene or chloroform has been investigated. The composition of the Pu(IV) species extracted from H₂SO₄ was found to be PuH₂Y₆, which changed to Pu(NO₃)H₂Y₅ and Pu(NO₃)₂H₂Y₄ with increasing concentration of nitrate ion in the aqueous medium. These three species can be represented as PuY₂(HY₂)₂, Pu(NO₃)Y(HY₂)₂ and Pu(NO₃)₂(HY₂)₂, respectively, where Y represents the anion of monomeric HY, and HY₂ the anion of dimeric H₂Y₂. Synergism in the extraction of Pu(IV) by the addition of thenoyltrifluoroacetone (HTTA) to HY was also investigated and attributed to extraction of the additional species, Pu(TTA)Y(HY₂)₂ and Pu(TTA)₂(HY₂)₂. The addition of the neutral extractant tri-n-octylphosphine oxide (TOPO) to HY did not result in synergism in the extraction of Pu(IV) from aqueous sulfuric acid. With aqueous nitric acid under similar conditions, however, synergism was observed. The possible equilibria in these systems were identified and the corresponding equilibrium constants were determined.     

Extraction of rare-earth elements with solutions of di-(2-ethylhexyl)phosphoric acid in flow-through system under local vibrational treatment

Results obtained in a study of the influence exerted by the vibrational treatment in the dynamic interfacial layer on the extraction of rare-earth elements with solutions of di-(2-ethylhexyl)phosphoric acid in a diluent in a flow-through system are presented. It was shown that the coefficient of extraction acceleration under a local vibrational treatment of the dynamic interfacial layer is smaller than that in the static system and is determined by the nature of an element being extracted and a solvent, frequency and amplitude of oscillations of the vibration element, and fluid flow rate. The degree of extraction of rare-earth elements in a certain time is noticeably higher and can reach a double excess if there is a local vibrational treatment of the dynamic interfacial layer. In this case, the accumulation of a lanthanide in the dynamic interfacial layer is substantially lower, and it does not exceed 10% of the total amount of rare-earth elements in the system.     

Influence of rare earth elements on extraction of actinium with di-(2-ethylhexyl)phosphoric acid from inorganic acid solutions

The extraction of actinium by HDEHP solutions in n-heptane as a function of mineral acids and some lanthanides (Ln) in the aqueous phase has been studied. It was found that the actinium extraction coefficient in the absence of Ln decreased linearly with acid concentration with the slope of –3 in the whole investigated range of its concentration. In the presence of Ln the extraction coefficient decreased with a smaller slope than in the absence of Ln. This slope decreased with the Ln salt concentration. The extraction coefficient of Ac decreased with a slope of –3 at acid concentrations above 0.1N, regardless of the Ln concentration in the extraction system.     

Extraction of lanthanoids and some associated elements by mono-(2-ethylhexyl)phosphoric acid and their separations

Mono-(2-ethylhexyl)phosphoric acid (H₂MEHP) has been used to study the extraction of some lanthanoids and other associated elements from nitric acid medium. Effect of various variables like kind of diluent, concentration of metal ion, nitric acid and extractant has been investigated. Based on distribution data, it was possible to achieve some separations of lighter lanthanoids from metals like titanium, zirconium, thorium and uranium with high separation factors.     

Atomic absorption determination of indium after extraction with di-(2-ethylhexyl)phosphoric acid

The equilibrium data show that indium can be quickly extracted from acidic aqueous solutions by di-(2-ethylhexyl)phosphoric acid in methyl isobutyl ketone. In this polar solvent the species ML₃·HL is extracted. The overall extraction constant is higher than that for other tervalent metals. The extraction process can be combined with AAS determination of the indium. The method is fast because stripping is not necessary, and the organic phase can be analysed directly by AAS. Use of a 51 v/v aqueous: organic phase ratio increases the sensitivity. In the pH-range used the method has good selectivity.     

Solvent extraction of neodymium,europium and thulium by di-(2-ethylhexyl)phosphoric acid

The extraction of Na³⁺, Eu³⁺ and Tm³⁺ by di-(2-ethylhexyl)phosphoric acid, HDEHP has been studied from various aqueous acidic solutions. The extraction of these elements is inversely proportional to the third power of the hydrogen ion concentration. Antagonistic effects were observed when the extraction was studied by mixtures of HDEHP and tributyl phosphate, TBP, or trioctylphosphine oxide, TOPO. The presence of water-miscible alcohols and acetone generally increases the extraction of these three elements from HCl solutions. Reaction mechanisms have been suggested and discussed in the light of the data obtained.     

Extraction of actinium with di (2-ethylhexyl) phosphoric acid from hydrochloric and nitric acid solutions

The extraction of actinium with HDEHP from Cl^– and NO ₃ ^– systems has been investigated. It was found that extraction of actinium from HCl solutions is much better than from HNO₃ solutions. Stability constants of the actinium complexes Ac(X^–)²⁺, X^–=Cl^– or NO ₃ ^– , were determined. Our results show that actinium formed less stable complexes with Cl^– than with NO ₃ ^– ligands.     

Extraction chromatographic separation of uranium and fission products in the system di-(2-ethylhexyl)phosphoric acid-hydrochloric acid

An elution scheme has been developed for obtaining separate fission product and uranium fractions using extraction chromatographic techniques with di-(2-ethylhexyl)phosphoric acid as a stationary phase and HCl of varying concentration as eluting agent. The investigations have been concentrated on the fission products cerium, europium, molybdenum and zirconium. The elution of zirconium by oxalic acid is characterized by a peak broadening and has been explained by considering extraction kinetics. Experiments on column performance with different support materials have proved Ftoroplast-4 and Celite Hyflo Super Cel to be capable of giving column fillings with equal separation ability.     

Mass spectrometric study of the radiolysis of di-(2-ethylhexyl)phosphoric acid

A mass spectrometric study on DEHPA was carried out and compared with radiolysis data on DEHPA for γ-irradiation in the liquid phase. The mass spectra of DEHPA show an extremely low intensity of parent ion and the presence of double rearrangement ions of (RO)P(OH) ₃ ⁺ and P(OH) ₄ ⁺ , where R is the 2-ethylhexyl group. The appearance potentials of the principal ions in the mass spectrum were determined and the dissociation processes of DEHPA in the phase discussed. The fragment ions show good agreement with the results in the liquid phase where the mono-ester, orthophosphoric acid, octane and heptane were formed by the dealkylation, however, the peak intensities of some fragment ions in the mass spectrum differ from the radiolytic yields of the corresponding products. These differences imply the significant role of neutralization and recombination reactions in the liquid phase radiolysis.