Solvent Extraction and Spectrophotometric Studies on Synergistic Extraction of Plutonium(IV) by Mixtures of Thenoyltrifluoroacetone (HTTA) and Tri-n-butylphosphate (TBP) in Benzene

Abstract

The synergistic extraction of Pu(IV) from perchloric acid solutions into mixtures of thenoyltrifluoroacetone (HTTA) and tri-n-butylphosphate (TBP) in benzene was investigated by solvent extraction methods. The adduct responsible for synergism was found to be Pu(TTA)₄·TBP. The adduct formation between Pu(TTA)₄ and TBP in the benzene phase was also investigated by spectrophotometry. The equilibrium constants for the equilibria involved were obtained both by solvent extraction and by spectrophotometric methods.     

Extraction of Ternary Beta‐Diketonates of Uranyl Ion Using Some Substituted Monoamides

Abstract

The extraction behavior of uranyl ion from dilute nitric acid medium employing 1‐phenyl‐3‐methyl‐4‐benzoyl‐5‐pyrazolone (HPMBP)/2‐thenoyl‐ trifluoroacetone (HTTA) in toluene and their mixture with several structurally modified monoamides viz. di‐2‐ethylhexyl acetamide (D2EHAA), di‐2‐ethylhexyl propanamide (D2EHPrA), di‐2‐ethylhexyl isobutyramide (D2EHiBA), and di‐2‐ethylhexyl pivalamide (D2EHPvA) was investigated. The species of the type UO₂(A)₂ and UO₂(A)₂·B were extracted for the binary and ternary extraction systems respectively where A = PMBP/TTA and B = D2EHAA, D2EHPrA, D2EHiBA, or D2EHPvA. The extraction constants (log K _ex) for the binary species UO₂(A)₂ were determined to be ?2.32 ± 0.03 for HTTA and 0.21 ± 0.02 for HPMBP, which was an inverse function of their pK _a value. The overall extraction constants (log K) for the ternary species UO₂(A)₂·B were determined as 4.70, 4.22, 4.00, 3.61, 2.65, 2.39, 2.32, and 1.76 for UO₂(PMBP)₂·D2EHAA, UO₂(PMBP)₂·D2EHPrA, UO₂(PMBP)₂·D2EHiBA, UO₂(PMBP)₂·D2EHPvA, UO₂(TTA)₂·D2EHAA, UO₂ (TTA)₂·D2EHPrA, UO₂(TTA)₂·D2EHiBA, and UO₂(TTA)₂·D2EHPvA, respectively. A linear correlation was observed between the basicity of the amide and the corresponding adduct's formation constants.     

Extraction equilibria of chromium(VI) from sulfuric acid solutions with tri-n-octylphosphine oxide

The extraction equilibria of chromium(VI) from sulfuric acid solutions with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene at 25°C have been studied. The possible complexes of chromium(VI) with TOPO in organic phase and extraction constants were determined by best fitting the distribution coefficient expression of Cr(VI) with experimental data using the Rosenbrock method. The extraction reactions, including the equilibria among seven species in aqueous phase (H₂CrO₄, HCrO₄⁻, HCr₂O₇⁻, Cr₂O₇²⁻, CrSO₇²⁻, HSO₄⁻ and SO₄²⁻) and five possible complexes in organic phase (H₂CrO₄·(TOPO), H₂Cr₂O₇·(TOPO)₃, H₂CrSO₇·(TOPO)₃, H₂SO₄·(TOPO)₂ and (H₂SO₄)₂·(TOPO)₂) were proposed. The influence of initial sulfuric acid concentration on the fraction of extracted complexes and on the distribution coefficients of Cr(VI) is discussed. This result was helpful for the clarification of the extraction reactions of Cr(VI). © 1998 Society of Chemical Industry     

Synergistic Extraction of Trivalent Actinides by Mixtures of Thenoyltrifluoroacetone and Neutral Oxo Donors

Abstract

The synergistic extraction of trivalent actinides Am, Cm, Bk, and Cf has been studied by mixtures of HTTA and TOPO as well as DOSO in xylene at 30°C. HTTA-S (TOPO, DOSO) interaction corrections have been applied to calculate the “free” S concentrations in the organic phase. In the extraction of trivalent actinides, the third-power dependence on [HTTA]_org at a fixed [S]_org has been observed only after applying this correction. The synergistic species M(TTA)₃.S and M(TTA)₃.2S were found to be extracted into the organic phase whose stability constants (β₁, β₂, and K ₂) have been evaluated. Extraction by HTTA + S(S = TOPO, DOSO, TBP, TBTP) shows the order of extraction to be Tm > Cf > Bk > Eu > Pm > Am > Cm for the trivalent ions. The Am/Cm separation factor with the synergistic mixtures is ～3 whereas with HTTA alone it is ～6 when they are extracted from the chloroacetate buffer.     

Extraction of Uranium(VI) and Thorium(IV) from Nitric Acid Solution by N,N,N′,N′ – Tetraoctylglutaricamide

Synthesis and characterization of N,N,N′,N′-tetraoctylglutaricamide (TOGA) was carried out and used for extraction of U(VI) and Th(IV) from nitric acid solutions. The processes of extraction were determined by the slope analysis and by analyzing a function that allows the simultaneous treatment of all the experimental points obtained in different conditions. The different factors affecting the extraction distribution ratio(D) of U(VI) and Th(IV) (extraction concentration, concentrations of nitric acid, salting-out agent NaNO₃ concentration, equilibration time, temperature, and types of diluents) were investigated. The results obtained indicated that the extraction species of U(VI) and Th(IV) are mainly extracted as UO₂(NO₃)₂·1.0TOGA and Th(NO₃)₄·1.5TOGA. The apparent equilibrium constant of U(VI) and Th(IV) extraction determined are 3.35 ± 0.03 L³/mol³ and 1.87 ± 0.01 L⁵/mol⁵ at 298 ± 1 K. Thermodynamic parameters such as the free energy(ΔG), enthalpy(ΔH), and entropy(ΔS) changes associated with the extraction processes could be evaluated. Back-extraction of U(VI) and Th(IV) from organic phases was also studied.     

Synergistic Extraction of Trivalent Actinides by Mixtures of 1-Phenyl-3-methyl-4-benzoyl-pyrazolone-5 and Neutral Oxo Donors

Abstract

The synergistic extraction of trivalent actinides Am, Cm, Bk, and Cf with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and TBP or TOPO has been investigated in xylene at 30°C. With HPMBP alone, all four trivalent actinides form M(PMBP)₃· HPMBP-type self-adducts. Bk(III) shows an abnormally high extraction with HPMBP alone. With TBP or TOPO(S) as neutral donor, except in the Bk/HPMBP/TBP system where Bk(PMBP)₃· HPMBP·TBP was extracted, all metal ions were extracted as M(PMBP)₃·S and M(PMBP)₃·(S)₂ into the organic phase. The equilibrium constants (β₁, β₂, and K ₂ for the organic phase synergistic reactions have been calculated. The β₁, β₂ values for Bk(III)/HPMBP/TOPO system are much lower as compared to the corresponding values for other trivalent actinides. The reasons for this extraordinary behavior of Bk(III) have been discussed. The extraction behavior of the M(III)/HPMBP/S and the M(III)/HTTA/S systems has also been compared.     

Solvent Extraction of Plutonium(IV), Uranium(VI), and Some Fission Products with Di-n-octylsulfoxide

Abstract

Extraction behavior of plutonium(IV), uranium(VI), and some fission products from aqueous nitric acid media with di-n-octylsulfoxide (DOSO) has been studied over a wide range of conditions. Both the actinides are extracted essentially completely, whereas fission product contaminants like Zr, Ru, Ce, Eu, and Sr show negligible extraction. The absorption spectra of sulfoxide extracts containing either Pu⁴⁺ or UO₂ ²⁺ indicate the species extracted from nitric acid into the organic phase to be Pu(NO₃)₄. 2DOSO and UO₂(NO₃)₂. 2DOSO, respectively. Extraction of these actinides decreases with increasing temperature, indicating the extraction to be exothermic. DOSO extracts plutonium and uranium better than di-n-hexylsulfoxide (DHSO) under all condition and is also more soluble in aromatic diluents than the latter. The effect of gamma radiation on the extraction properties of DOSO is found to be similar to that of DHSO.     

Extraction of some Hexavalent Actinide Ions from Nitric Acid Medium using Several Substituted Diglycolamides

Several substituted diglycolamides, namely TPDGA, THDGA, TODGA, and TDDGA, were evaluated in a comparative study on the extraction of hexavalent actinide ions such as UO₂²⁺, NpO₂²⁺, and PuO₂²⁺ from nitric acid medium. The acid extraction constants (K_H) for the diglycolamides were determined to be 3.8 ± 0.6, 1.6 ± 0.1, 4.1 ± 0.4, and 1.4 ± 0.2 for TPDGA, THDGA, TODGA, and TDDGA, respectively. Though metal ion extraction generally increased with increasing the feed acid concentration, the nature of the extracted species changed with aqueous-phase acidity. While complexes of the type MO₂(NO₃)₂·nL (where L is the diglycolamide extractant and n is 1 and 2) were found to be extracted at 1 M HNO₃, the average number of ligand molecules associated with the complex decreased to ?1 when the nitric acid concentration increased to 3 M. These results have great significance from the actinide separation point of view, as the actinides ions can be made virtually inextractable by adjusting their oxidation state. The thermodynamic parameters were also calculated, which indicated spontaneous reactions with large exothermicities.     

SYNERGISTIC EXTRACTION OF EUROPIUM(III) WITH BENZOIC ACID AND THENOYLTRIFLUOROACETONE

ABSTRACT

The solvent extraction of europium(III) into solutions of thenoyltrifluoroacetone and benzoic acid in cyclohexane, carbon tetrachloride, benzene, chloroform, pentachloroethane, and tetrachloroethane has been measured at 25°C. It has been found that the extracted species involve two types of adducts, EuA₃· HB and EuA₃· 2HB where A denotes the TTA anion and HB the benzoic acid monomer. The magnitude of the adduct formation constants in different solvents has been correlated with the dimerization constants of benzoic acid in the solvents.     

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.     

SOLVENT EXTRACTION EQUILIBRIA OF LEAD(II) WITH ACIDIC ORGANOPHOSPHATE AND PHOSPHONATE

Distribution equilibria of lead(II) in the extraction with di(2-ethylhexyl)phosphoric acid and 2-ethylhexyl 2-ethylhexylphosphonic acid in toluene from aqueous ammonium nitrate solutions were measured at 303 K to elucidate the concentration dependencies of the reactant species on the distribution ratio. It was found that lead(II) is extracted as the mononuclear complex, PbR₂2HR, with the former extrac-tant while it is extracted not only as the complex, PbR₂2HR, but also as the complex, Pb(NO₃)R;HR, accompanied by simultaneous transfer of nitrate anion with the latter ex-tractant. The extraction equilibrium constants of these complexes were evaluated as well as the stability constants of lead(II) -nitrato complexes, Pb(NO₃)⁺, Pb(NO₃)₂and Pb(NO₃)^? ₃.     

Thermodynamic Modeling of Solvent Extraction Systems: Successes and Problems

Abstract

Recent approaches to thermodynamic modeling of solvent extraction systems are applied to nitric acid and Am(III) extraction by dihexyl-N,N-diethylcarbamoylmethyl phosphonate in CCl₄, 1:1 and 2:1 complexes were found to form in the organic phase for nitric acid extraction with K₁ = 0.125 ± 0.00154 and K₂ = 1.41 × 10^?5 ± (2.60 × 10^?7). Extraction of nitric acid was also followed by IR spectrophotometry which verified the results obtained. Modeling of Am(III) extraction up to an initial aqueous nitric acid concentration of 4 M yielded good results. Extraction constants for species forming in the organic phase were found to be K _ex0 = 38.6 ± 30.4 for [Am(NO₃)₃-E₃]₀, K _ex1 = 7.43 ± 0.572 for [Am(NO₃)₃-E₂-(E-HNO₃)₂)]₀ and K _ex2 = 1.04 ± 0.0281 for [Am(NO₃)₃,-E-(E-HNO₃)₂)]₀. Problems encountered are highlighted and discussed, improvements to modeling approaches are suggested, and results obtained are critically discussed and compared to the literature.     

A CHEMICAL MODEL OF THE SOLVENT EXTRACTION SYSTEM: NITRIC ACID- URANYL NITRATE- WATER - TRI-n-BUTYL PHOSPHATE (TBP) - DILUENT

ABSTRACT

A mathematical model founded on the equilibrium constants expressions has been developed for the simultaneous extraction of nitric acid and uranyl nitrate with TBP in alkane diluents. The model uses chemical activities of nitric acid and uranyl nitrate in the aqueous phase and the stoichiometric concentrations of their TBP solvates in the organic phase. The apparent formation constants of the species (TBP)₂, (TBP)₂HNo₃, TBPHNO₃, and UO₂(NO)₃ 2TBP, present in the organic phase, have been established. The model fits well the distribution results over the whole concentration range of the extraction isotherms, and extractant concentrations 5–10% TBP. The starting data are the chemical activities of nitric acid and uranyl nitrate in the aqueous phase and their stoichiometric concentrations in the organic phase.     

THERMODYNAMIC EQUILIBRIA OF THE EXTRACTION OF CHROMIUM(VI) WITH TRI-N-OCTYLPHOSPHINE OXIDE FROM AQUEOUS SOLUTIONS

ABSTRACT

The distribution of chromium( VI ) between aqueous solutions and the kerosene solutions of tri-n-octyl-phosphine oxide (TOPO) have been studied at 25 °C and pH 2-4, in which range the predominant forms of Cr(VI) are HCrO₄ and Cr₂O₇ ^2?. The extraction equilibrium is influenced by the total chromium(VI) concentration, aqueous pH value, and total extractant concentration. The thermodynamic equilibria among all species in the aqueous phase were used for the analysis of distribution data, and the activity coefficients of ionic species were estimated according to Debye-Hiickel or Bromley equation. By numerical method, the complexes of Cr(VI ) with TOPO formed in the organic phase were found to be H₂CrO₄ (TOPO) and H₂Cr₂O₇ (TOPO) ₃. The corresponding extraction constants were 2019 and 3.69× 10⁸, respectively.     

Extraction of some mineral acids by tri-n-octyl phosphine oxide

The distribution equilibria of hydrochloric, nitric, perchloric, sulphuric and phosphoric acids between aqueous solutions and a solution of tri-n-octyl phosphine oxide (TOPO) in organic solvents have been investigated. The organic phases were studied by infrared and nuclear magnetic resonance spectroscopy. As a result, it is found that the extraction of these acids is governed by the formation of HCl·TOPO, HNO₃·TOPO and HClO₄·TOPO, of H₂SO₄·2 TOPO and H₂SO₄·TOPO, and of H₃PO₄·3 TOPO, H₃PO₄·2 TOPO and H₃PO₄·TOPO, respectively.     

SOLVENT EXTRACTION OF COPPER(II) WITH THE ACTIVE COMPONENT OF LIX 54. SYNERGIC EFFECT IN THE PRESENCE OF TRI-n-OCTYLPHOSPHINE OXIDE.

The extraction of Cu(II) from nitrate medium of ionic strength 1.0 mol.dm^-3 by l-phenyl-l,3-decanedione (HR) and by the mixture 1-phenyl-l,3-decanedione and tri-n-octylphosphine oxide (TOPO), dissolved in toluene, has been studied by distribution methods. The experimental data treated both graphical and numerically can be explained assuming the formation in the organic phase of the species CuR₂ and Cu(NO₃)R. The synergic effect found in the presence of TOPO has been explained by the formation of the complex CuR₂(TOPO). Equilibrium extraction constants for the species are given.     

EXTRACTION OF U(VI), Pu(IV) AND Th(IV) BY SOME TRIALKYL PHOSPHATES

ABSTRACT

This paper reports the data on the extraction of U(VI), Pu(IV) and Th(IV) from nitric acid by tri-isobutyl phosphate, tri-n-amyl phosphate, tri-isoamyl phosphate and tri-n-hexyl phosphate and provides a comparison of their extract ion behaviour with that of tri-n-butyl phosphate. Data on the third phase formation in the system Th(NO₃) ₄ ^?HNO₃ ^?1.1 M trialkyl phosphate/n-dodecane are also presented.     

Extraction of Nitric Acid into Alcohol: Kerosene Mixtures

Abstract

Nitric acid extraction from 0.1 mol/L – 5 mol/L nitric acid into varied volume fractions (5%–100%) of long-chain aliphatic alcohols (1-hexanol, 1-octanol, 2-ethylhexanol, 1-decanol) in alkanes (different kerosenes, n-dodecane, isooctane) was measured. At equal molar alcohol concentration, 1-hexanol, 1-octanol, and 1-decanol extract equal amounts of nitric acid. The amount of nitric acid extracted into 2-ethylhexanol is approxmately half compared to 1-octanol. The alkane does not influence nitric acid extraction. Extraction can accurately be calculated taking into account the formation of a species (HNO₃)(ROH)₂. Due to the change in diluent properties with alcohol volume fraction, conditional equilibrium constants must be used.     

Optical Spectroscopic Investigation of Hexavalent Actinide Ions in n-Dodecane Solutions of Tri-butyl Phosphate

ABSTRACT

The extraction of hexavalent actinides An(VI) by tri-butyl phosphate (TBP) was investigated by electronic absorption and vibrational spectroscopies. Through a series of spectral subtractions, vibrational spectra associated with TBP, TBP–HNO₃ adducts, and An(VI)–TBP complexes could be isolated. Investigation of U(VI) extracts indicated spectral features consistent with the formation of the expected [UO₂(NO₃)₂(TBP)₂] complex, but spectral features of other species were clearly evident. Likewise, multiple species were evident in the electronic absorption and vibrational spectra of TBP phases generated by extraction of Pu(VI). Although definitive characterization of the additional species formed could not be achieved in this work, it is hypothesized that they contain 3:1 TBP-to-An(VI) stoichiometry.