Study on the ternary synergistic extraction of uranium/VI/ by chelating-chelating-neutral extractant

The synergic extraction of uranyl nitrate from chloroform media with 1-phenyl-3-methyl-4-benzoyl-pyrazonole-5 /PMBP/, tributylphosphate /TBP/ and thenoyltrifluorylacetone /TTA/ was studied. It was found that synergic effect occurs during the extraction of uranyl nitrate with the chloroform solution of PMBP-TTA-TBP. The formation of the ternary extracted complex UO₂AA'B was confirmed by the usual slope method. A method was proposed for the calculation of the ternary equilibrium constant which was evaluated to be 1gK₁₁₁=2.65. Also the binary synergic extractions of uranyl nitrate with PMBP-TBP and TTA-TBP were studied. The binary equilibrium constants were found to be 1gK₂₀₁=3.07 and 1gK₀₂₁=1.39, respectively. An attempt has been made to interpret the data mainly on the basis of statistical factor.     

Liquid-liquid extraction of copper (II) with dialkyl sulphoxides

The extraction behaviour of Cu(II) from hydrochloric acid and lithium chloride solutions with di-n-pentyl sulphoxide (DPSO) and di-n-octyl sulphoxide (DOSO) has been investigated over a wide range of conditions. At a given strength of the extradant, the extraction increases with increase in HCl and LiCl concentrations. The extraction of the metal also increases with increase in extractant concentration at constant [HCl] or [LiCl]. The species extracted would appear to be CuCl₂·2DPSO/2DOSO and CuCl ₄ ²⁻ ·2DPSO. The extraction of the metal decreases with increase in initial aqueous metal concentration and also with increase in temperature. The extraction also depends on the nature of the diluent employed.     

N,N,N',N'-Tetrabutyladipicamide as a new extractant in toluene of nitric acid and uranium (VI)

N,N,N',N'-Tetrabutyladipicamide (TBAA) was used for the extraction of nitric acid and uranyl(II) ion from nitric acid media into toluene. The effects of nitric acid, uranyl(II) ion, and extractant concentration, temperature and back extraction on the distribution coefficient of uranyl(II) ion have been studied. The main adduct of TBAA and HNO₃ is TBAA·HNO₃ in 1.0 mol/l nitric acid solution. The 1:2:2 complex of uranyl(II) ion, nitrate ion and TBAA as extracted species is further confirmed by IR spectra of the extraction of uranyl(II) ion with TBAA. The values of the thermodynamic parameters have also been calculated.     

Thermophysical studies on uranyl nitrate hexahydrate–Iron (III) nitrate nonahydrate system

Individual nitrates, UO₂(NO₃)₂·6H₂O and Fe(NO₃)₃·9H₂O as well as their binary mixtures in various mol ratios have been studied using simultaneous thermal techniques and X-ray powder diffraction measurements. Nature and stoichiometry of hydroxynitrates of iron and uranium were altered by changing the heating rates for the equal mass of binary nitrate mixtures under identical gas flow conditions. Evolved gas analysis and thermogravimetric measurements indicated the absence of direct interaction between two nitrates in the binary nitrate mixtures. Both the nitrates decomposed independently in the mixtures to their respective oxides. These results have been supported by X-ray powder diffraction measurements. Phase diagram of UO₂(NO₃)₂·6H₂O–Fe(NO₃)₃·9H₂O system containing 0–100 mol% of UO₂(NO₃)₂·6H₂O was constructed using differential thermal analysis technique. The formation of the eutectic at 33 °C for 50 mol% uranyl nitrate hexahydrate–50 mol% iron (III) nitrate nonahydrate mixture has been observed for the first time.     

Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and some long chain aliphatic sulfoxides

Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoyl pyrazolone-5 (HPMBP) and aliphatic sulfoxides of varying basicities, viz di-isoamyl (DIASO), di-n-hexyl (DHSO), di-n-septyl (DSSO), di-n-octyl (DOSO), di-n-nonyl (DNSO), di-n-decyl (DDSO) or di-n-undecyl (DuDSO) sulfoxide has been studied at 30±0.1°C. Extraction with some of these sulfoxides has been studied at various fixed temperatures also. The organic phase equilibrium constant (log Ks) has been found to increase with the basicity of the sulfoxide up to DOSO beyond which there is a gradual decreasing trend which has been attributed to the effect of possible steric hindrance (spatial) involved in the bonding of the higher sulfoxides (greater than 8 carbon atoms) with UO₂ (PMBP)₂ chelate. This has been supported by thermodynamic data involved in these systems. The entropy values for sulfoxides with eight or more carbon atoms are much more negative as compared to the lower sulfoxides and are also in contrast to HTTA and BTFA systems with these sulfoxides studied earlier.     

N-dodecanoylpyrrolidine as a new extractant for uranyl(II) and nitric acid in toluene

N-dodecanoylpyrrolidine (DOPOD) was synthesized and used for the extraction of nitric acid and uranyl(VI) ions from nitric media in toluene. The effects of nitric acid concentration, extractant concentration, temperature, salting-out agent (LiNO₃) have been studied. The main adduct of DOPOD and HNO₃ is HNO₃·DOPOD. The complex formation of uranyl(VI) ion, nitrate ion and DOPOD (UO₂(NO₃)₂·2DOPOD) as extracted species are further confirmed by IR spectra and the values of thermodynamic parameters have also been calculated.     

Solvent extraction of zirconium from hydrochloric acid solutions by sulphoxides and their mixtures

The solvent extraction of zirconium from HCl solutions by dipentyl sulphoxide (DPSO), dioctyl sulphoxide (DOSO), tributyl phosphate (TBP), and their mixtures in various solvents has been studied. At a given H⁺ strength, the extraction coefficient η of the metal increases with an increase in Cl⁻ activity whereas it is almost independent of H⁺ at constant Cl⁻. Under otherwise identical conditions, η increases with an increase in the extractant concentration but is virtually independent of the metal ion concentration over a wide range. The species extracted are ZrCl₄·DPSO, ZrCl₄·DOSO, and ZrCl₄·2TBP. In the case of mixtures, the slope of the log η−log M extractant plot for one component decreases with an increase in the concentration of the second component, the lines crossing at a common point. Extraction is favoured by solvents of low dielectric constant. It is possible to separate zirconium from thorium and uranium by solvent extraction with sulphoxides.     

Solvent extraction of Cobalt/II/ from thiocyanate solutions by sulphoxides

The extraction of cobalt/II/ from ammonium thiocyanate solutions by di-n-pentyl sulphoxide /DPSO/, di-n-octyl sulphoxide /DOSO/ and their mixtures in carbon tetrachloride has been studied. The species extracted were found to be Co/SCN/₂. 4S /where S=DOSO or DOSO/. Synergic effects have been observed which are ascribed to the formation of mixed ligand metal complexes. The influence of the metal concentration, temperature and the diluent on the extraction of cobalt/II/has been investigated.     

Solvent extractions of zirconium and niobium from HCl solutions by Aliquat 336/Alamine 336 and DOSO mixtures

Liquid-liquid extractions of zirconium(IV) from aqueous HCl solutions by mixtures of Aliquat 336 or Alamine 336 and diocytl sulfoxide (DOSO) in the diluent benzene has been found to be always higher than that by any single extractant. While the cationic extractants extract Zr(IV) above 6M HCl, DOSO extracts from 4M onwards. Synergism has been observed in all cases. With any of these extractants extraction becomes almost quantitative at and above 10M HCl, but with mixtures of the cationic and neutral extractants, extraction is quantitative in the range 8–9M HCl. Although the extracted species with DOSO alone seems to be ZrCl₄·DOSO, with the mixture of extractants, however, the extracted species appear to be Q₂ZrCl₆·DOSO where Q is R₃ ⁺NH (for Alamine 336) and R₃ ⁺N(CH₃) (for Aliquat 336). Studies on separation of⁹⁵Zr–⁹⁵Nb pair from aqueous HCl media by Alamine 336 or DOSO and their mixtures in benzene exhibit preferential extraction of⁹⁵Nb leaving behind⁹⁵Zr in the aqueous phase, and extractions have been found to depend both upon the extractant and HCl concentrations.     

BEAMGAA with photons — the axial gradient

The extraction of uranyl nitrate by the novel extractant N,N’-dimethyl-N,N’-dioctylsuccinylamide (DMDOSA) from aqueous nitric/nitrate solutions was investigated. The effects of concentration of HNO₃ and DMDOSA on the U(VI) extraction distribution was studied. The extraction mechanism was established and the stoichiometry of the main extracted species was confirmed to be UO₂(NO₃)₂·2DMDOSA. The value of ΔH of the extraction is −23.9±1.7 kJ·mol⁻¹. A IR spectral study of the U(VI) extracted species was also made.     

Structure and composition of the polymeric products of UO2SO4 extraction by benzene solutions of uranyl bis(2-ethylhexyl) phosphate

UO₂SO₄ extracts obtained from neutral aqueous solutions of this compound and benzene solutions of uranyl bis(2-ethylhexyl) phosphate have been studied by³¹P NMR and IR spectroscopy. It has been found that in the presence of donor-active additions L=TBP or DOSO the recurrent unit of the polymer (UO₂X₂)_p adds one or two UO₂SO₄ molecules to form {UO₂X₂·UO₂SO₄·2L} and {UO₂X₂·2UO₂SO₄·6L} units. The structure of these units has been established. It has been shown that the distribution of UO₂SO₄ molecules along the polymer chain is random. Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhumal Struktumoi Khimii, Vol. 36, No. 4, pp. 682–689, July–August, 1995. Translated by L. Smolina     

Synergistic extraction of tetravalent actinides by mixtures of a β-diketone and a sulfoxide

Synergistic extraction of tetravalent actinides, using mixtures of a β-diketone and several neutral organophosphorous extractants, was recently demonstrated. In this work the extraction of the ions Th(IV), Np(IV) and Pu(IV), from perchloric acid medium, by benzene solutions of a β-diketone, thenoyltrifluoroacetone (HTTA), in combination with a neutral organosulfoxide donor, di-n-octyl sulfoxide (DOSO), has been investigated. Two methods viz. the slope analysis method and JOB's method have been employed for the study. The species mainly responsible for the observed synergism, with the M(IV) ions studied, was found to be M(TTA)₄·DOSO. The extraction and adduct formation equilibrium constants are given.     

Extraction of U(VI) with N,N′-dimethyl-N,N′-dioctylmalonamide from nitrate media

The extraction of uranyl nitrate with the novel extractant N,N′-dimethyl-N,N′-dioctylmalonamide (DMDOMA) from aqueous sodium nitrate (and nitric acid) was investigated. The extraction mechanism was established and the stoichiometry of the main extracted species confirms to UO₂(NO₃)₂ · DMDOMA. The IR spectral study was also made of the extracted species. Methyl substituent improves the extraction ability of malonamide for U(VI) compared with that of N,N,N′,N′-tertrabutylmalonamide (TBMA).     

Mechanochemistry of the 5f-element compounds

The effect of the mechanical treatment of UO₂(NO₃)₂·6H₂O in a planetary ball mill in air and as a suspension in toluene has been studied. The X-ray diffractometry results strongly suggest that part of the mechanoactivated material is transformed in nitrosyl uranyl nitrate.     

Composition and structure of complexes formed in the reaction of uranyl di(2-ethylhexyl)phosphate and tributyl phosphate or di-N-octyl sulfoxide in benzene solutions

This paper reprots of³¹P NMR and IR studies of the interaction of tributyl phosphate (TBP) and di-n-octyl sulfoxide (DOSO) with polymer molecules of uranyl di-2-ethylhexyl phosphate (UO₂X₂)_p (I) in C₆H₆ sulutions. Detailed interpretations of the³¹P NMR spectra and the v_as(POO) IR bands and determination of the fraction of nonequivalent phosphorus atoms of X⁻ anions and uranium (VI) atoms as well as the concentration of U(VI)-bonded TBP in I have shown that only a single TBP or DOSO molecule is coordinated to the uranium atoms of polymer I at C_TBP=0.1–2 M or C_DOSO=0.1–0.5 M. In the case of 100% TBP, two TBP molecules are coordinated to some U(VI) atoms. Distribution of TBP (DOSO) molecules along the polymer chain agrees with the mean statistical value. The portion of terminal chalate POO-groups of X⁻ anions is determined. The dependence of the degree of (UO₂X₂)_p·nL (L=TBP, DOSO) polymerization on C_L is obtained. Saturation of solutions with water only slightly affects the terminal POO-groups and has no effects on the distribution of L along the polymer chain of I. Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 6, pp. 66–73, November–December, 1994. Translated by K. Shaposhnikova     

Extraction of pertechnetate anion as a ligand in metal complexes with tributylphosphate

The extraction of the pertechnetate anion has been investigated in the systems tributylphosphate (TBP)—solvent (carbon tetrachloride, n-heptane, chloroform)—metal salt (uranyl nitrate and chloride, thorium nitrate)—ammonium salt. In the absence of a metal, the solvates HTeO₄. iTBP (i=4) are extracted, while in the presence of uranium and thorium, the distribution of technetium corresponds to the formation of the mixed complexes: UO₂(NO₃)(TeO₄)·2TBP, UO₂Cl(TcO₄)·2TBP and Th(NO₃)₃ (TcO₁)·2TBP. The effective constants of the reactions H⁺+TcO ₄ ⁻ +i(TBP)_org←(HTcO₁·iTBP)_org, and (ML_n·2TBP)_org+TcO ₄ ⁻ ←(ML_n−1TcO₄·2TBP)_org+L were established in the above systems. The extraction of pertechnetate ion is more effective when it is coordinated to a cation solvated by TBP than the extraction in the form of pertechnetate acid solvated by TBP.     

Nitrate ion transport across TBP-kerosene oil supported liquid membranes coupled with uranyl ions

The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO₃ and NaNO₃ has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO₃ · TBP, in addition to as UO₂(NO₃)₂ · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10^–3 mol · m^–2 · s^–1 compared to that of uranium ions (4.56 · 10^–6 mol · m^–2 · s^–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10^–10 m^–2 · s^–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction.     

The unusual extraction behavior of americium(III) and dioxouranium(VI) from picric acid medium using neutral oxodonors II. A thermodynamic study

The role of temperature on the distribution of Am³⁺ and UO₂ ²⁺ was investigated in the extraction systems involving TBP and DOSO as the neutral oxodonors and picrate as the organophilic counter anion. The inner-sphere water molecules and their substitution by the oxodonor molecules appeared to influence the extraction constants of these metal ions. The conditional extraction constants for Am³⁺ were found to be larger (about 3 order of magnitude) than those for UO₂ ²⁺. From the thermodynamics data it appeared that both TBP as well as DOSO bind Am³⁺ ion through outer-sphere coordination. In presence of 1M NaCl, though the interaction with TBP remains unaltered DOSO tend to form an inner-sphere complex. On the other hand, UO₂ ²⁺ forms inner-sphere complexes with DOSO and outer-sphere complex with TBP in the absence of salt. In the presence of 1M NaCl, both TBP and DOSO form inner-sphere complexes. The effect of ionic strength on metal ion extraction was also investigated. For Part I see Ref. 9.     

Solvent extraction of neptunium(IV) from nitric acid solutions by sulphoxides and their mixtures

Studies have been performed on the liquid-liquid extraction of neptunium from nitric acid solutions by di-n-hexylsulphoxide (DHSO) di-no-octylsulphoxide (DOSO) and di-iso-amylsulphoxide (DISO) and their mixtures over a wide range of conditions. At a given strength of the extractant, extraction of Np(IV) increases initially rapidly with increase in the acid concentration; at high acidities, above 8M HNO₃, the extraction decreases. Under otherwise identical conditions, extraction increases with an increase in the extractant concentration. The species extracted would appear to be Np(NO₃)₄·2(R₂SO). A mixture of two extractants extracts more than the sum of the extractions due to the individual components at concentrations corresponding to those of the mixture. After loading the organic phase with uranium(VI), extractability of Np(IV) becomes considerably lower. The diminution in extraction with increase in temperature is small. A comparison of the extraction behaviour of Np(IV) with those of Pu(IV), U(VI) and some associated fission products has been made.     

Development of Mathematical Model of H2O-HNO3-UO2(NO3)2-TBP-diluent System

The mathematical model of H₂O-HNO₃-UO₂(NO₃)₂-TBP-dodecane system has been elaborated. Mole fractions and volume ones and rational activity coefficients have been used in order to create the system of equations on the base of mass action law. Method for calculating activity coefficients was provided. The formation constants of uranyl nitrate di-solvate and mono-solvate and di-solvate of acid have been determined. Interaction between uranyl nitrate di-solvate and dodecane and between TBP and dodecane was taken into account. Activity coefficients of nitric acid and uranyl nitrate in mixed solutions were considered. Errors of adequacy have been determined for the systems containing 30% and 12% TBP concentrations.