Synergistic solvent extraction of lutetium(III). Computer aided analysis

Synergism in the extraction of Lu(III) from thiocyanate solutions has been investigated using mixtures of bis-2-ethylhexyl sulfoxide (B2EHSO) and 2-thenoyltrifluoroacetone (HTTA) or di-n-octyl sulfoxide (DOSO) or tri-n-octylphosphine oxide (TOPO) in benzene. For comparison, the synergistic extraction of Lu(III) from perchlorate solutions has also been investigated with a mixture of B2EHSO and HTTA. These extraction data have been analyzed theoretically with the aid of a computer by taking into account complexation of the metal in the aqueous phase by inorganic ligands and plausible complexation in the organic phase. The equilibrium constants of the various product species have been deduced by non-linear regression analysis.     

Solvent extraction of Er(III) and Lu(III) with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester in presence of some reagents

The extraction of Er(III) and Lu(III) from thiocyanate media with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHEHPA) and also with mixtures of EHEHPA and thenoltrifluoroacetone (HTTA) or tri-n-octylphosphine oxide (TOPO) or bis 2-ethylhexyl sulfoxide (B2EHSO) in benzene has been studied systematically. Synergistic effects have been observed with mixtures of EHEHPA+HTTA or TOPO. On the other hand, antagonistic effects have been observed with mixtures of EHEHPA+B2EHSO. These extraction data have been analyzed theoretically with the aid of a computer by taking into account complexation of the metal in the aqueous phase by SCN^– and plausible complexation in the organic phase. The extraction constants of the various product species have been deduced by non-linear regression analysis. The stability constants for the thiocyanate complexes of the metal ions have also been determined.     

Extraction equilibrium of ytterbium(III) with sulfoxides and their mixtures

The extraction equilibria of¹⁷⁵Yb from thiocyanate solutions with di-n-pentyl sulfoxide (DPSO), di-n-octyl sulfoxide (DOSO), tri-n-octylphosphine oxide (TOPO) and their mixtures in carbon tetrachloride has been investigated. A relatively small synergistic enhancement has been observed with mixtures of dialkyl sulfoxides (DPSO+DOSO) and also with mixtures of DPSO+TOPO. These extraction data have been analyzed with the aid of a computer by taking into account complexation of the metal in the aqueous phase by inorganic ligands and assuming a set of product species in the organic phase and adjusting their formation constants through an iterative non-linear least-squares procedure to obtain the best fit to the data. The extraction of the metal is inversely and linearly dependent upon the dielectric constant of the solvent and temperature of the system.     

The separation of zinc(II) and cadmium(II) by liquid-liquid extraction

The extraction of Zn(II) and Cd(II) from thiocyanate solutions with bis-2-ethylhexyl sulphoxide (B₂EHSO) in benzene as an extractant has been studied by tracer techniques. For comparison, extraction has also been carried out with tributylphosphate (TBP). The extraction data have been analysed by both graphical and theoretical methods by taking into account complexation of the metal in the aqueous phase by inorganic ligands and plausible complexes extracted into the organic phase. The results demonstrate that Zn(II) is extracted as Zn(SCN)₂·2B2EHSO and Zn(SCN)₂·2TBP. In the case of Cd(II), the extracted species are Cd(SCN)₂·4B2EHSO/4TBP. The synergistic extraction of Zn(II) and Cd(II) with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and B2EHSO or TBP or trioctylphosphine oxide (TOPO) from acetate buffer solutions has also been investigated. Zn(II) is extracted as Zn(PMBP)₂·B2EHSO/TBP/TOPO. On the other hand, Cd(II) is found to be not extracted with these mixed-ligand systems under the experimental conditions. These results also demonstrate the mutual separation of Zn(II) and Cd(II) using the synergistic extraction with HPMBP in the presence of various neutral oxodonors.     

Studies of radioactivity and heavy metals in phosphate fertilizer

The extraction of mercury(II) from chloride and thiocyanate solutions has been studied by tracer techniques using bis(2-ethylhexyl) sulphoxide (B2EHSO) in benzene as an extractant. These extraction data have been analyzed theoretically by taking into account complexation of the metal in the aqueous phase by inorganic ligands and plausible complexation in the organic phase. The results demonstrate that Hg(II) is extracted as HgX₂ and HgX₂·nB2EHSO (where X=Cl^– or SCN^– andn=1 or 2). The effect of the foreign ions on the extraction of Hg(II) has also been investigated.     

Mixed-ligand chelate extraction of neodymium(III) with thenoyltrifluoroacetone and various sulphoxides

Mixed-ligand chelate extraction of Nd(III) into benzene with mixtures of thenoyltrifluoroacetone (HTTA) and bis-2-ethylhexyl sulphoxide (B2EHSO) or di-n-octyl sulphoxide (DOSO) or diphenyl sulphoxide (DPhSO) or trioctylphosphine oxide (TOPO) from thiocyanate solutions has been studied. A very high synergistic enhancement of the order 10(3) has been observed in these systems. Thus this mixed-ligand chelate system may be useful in the extraction and separation of Nd(III) from other metal ions. The mechanism of extraction can be explained by a simple chemically based model presented in this paper.     

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.     

Synergistic extraction of uranium(VI) with 1-phenyl-3methyl-4-(2′-chlorobenzoyl)pyrazolone-5 and neutral extractants

The synergistic extractions of uranium(VI) from hydrochloric acid solution and sulfuric acid solution with 1-phenyl-3-methyl-4-(2-chlorobenzoyl)-pyrazolone-5 (PMCBP) together with the neutral extractants: tributyl phosphate(TBP), di-octyl sulfoxide(DOSO) and trioctylphosphine oxide(TOPO) in chloroform have been investigated. A high synergistic extraction effect was found. The formulas of the extracted species have been shown to be UO₂A₂B (where A=PMCBP, B=neutral extractant). The synergistic extraction power increases as follows: PMCBP-TOPO>PMCBP-DOSO>PMCBP-TBP. The equilibrium constants have been calculated. Models for the extraction mechanism are also discussed.     

Synergistic extraction of uranium(VI) from nitric acid solution by mixture of DMHMP and DOSO in benzene

Solvent extraction of uranyl nitrate in nitric acid medium with the binary system of DMHMP and DOSO has been investigated. It was found that synergistic effect occurs during the extraction of uranyl nitrate with benzene solution of DMHMP and DOSO, the binary species extracted UO₂ (NO₃)₂·DMHMP·DOSO has been confirmed. From the data the equilibrium constants have been determined.     

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.     

Synergistic extraction of uranium(VI) with 1-phenyl-3-methyl-4-acylpyrazolone-5 and neutral extractants

The synergistic extraction of uranium(VI) from hydrochloric acid solution with five chelating agents: 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (PMBP), 1-phenyl-3-methyl-4-acetylpyrazolone-5 (PMAP), 1-phenyl-3-methyl-4-(2-chlorobenzoyl)pyrazolone-5 (PMCBP), 1-phenyl-3-methyl-4-(p-nitrobenzoyl)pyrazolone-5 (PMNBP) and 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5 (PMTFP) plus the neutral extractants tributylphosphate (TBP), dioctyl sulfoxide (DOSO) and trioctylphosphine oxide (TOPO) in chloroform has been investigated. The extraction coefficients have been found to be greater for such mixtures than the individual component. The formulas of the extracted species have been determined to be UO₂A₂B (where HA = chelating agent, B = neutral extractant). Extraction power of these chelating agents increases as follows: PMCBP>PMNBP>PMTFP=PMBP>PMAP. Synergistic extraction power of the neutral extractants increases as follows: TOPO>DOSO>TBP. The extraction equilibrium constants have been calculated. The mechanism of the synergistic extraction and possible structure of the extracted species are discussed.     

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.     

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.     

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.     

Synergistic effect of HBMPPT with PSO, DOSO and TBP on the extraction of U(VI) and on the separation of U(VI) and Th(IV)

Some popular neutral extractants (PSO-petroleum sulfoxide, DOSO-di-n-octyl sulfoxide, TBP-tributylphosphate etc.) were chosen as synergist to study the synergistic effect on the extraction reaction with HBMPPT (4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione) for U(VI), and the synergistic separation ability of HBMPPT for U(VI) and Th(IV). The synergistic extraction ability shown by the studied systems for U(VI) is as follows: PSO>DOSO>TBP, and the same sequence was also verified for the separation coefficient of U(VI) and Th(IV). The synergistic complexes may be presented as: UO₂NO₃·BMPPT·S and UO₂(BMPPT)₂·S for U(VI) (S is PSO, DOSO or TBP).     

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.     

Some ternary sulfoxide and amide adducts of plutonyl pyrazolonates

Solid complexes of plutonylion with benzoyl (PMBP), acetyl (PMAP) and trifluoroacetyl (PMTFP) derivatives of 1-phenyl-3-methylpyrazol-5-one and various oxo donors such as dihexyl sulfoxide (DHSO), dioctyl sulfoxide (DOSO), dibutyl hexanamide (DBHA), dibutyl octanamide (DBOA) and dibutyl decanamide (DBDA) have been synthesized and characterized. Analytical data establish that sulfoxides form 11 adducts and have the stoichiometry PuO₂·X₂·Y (X=PMBP, PMAP and PMTFP) and Y=DHSO and DOSO while amides form 12 adducts of the type PuO₂X₂·2A where A=DBHA, DBOA and DBDA. The I. R. spectra of sulfoxide and amide complexes indicate that the ligands are O-bonded. Spectrophotometric investigations of the benzene solution of these complexes indicate a bathochromic shift of the 831 nm peak to 848–853 nm region, which confirms the retention of PuO ₂ ²⁺ moiety in these synergistic adducts.     

Radiochemical extraction of mercury(II) from acidic chloride solutions using dialkylsulphides

The liquid-liquid extraction behavior of Hg(II) from aqueous acidic chloride solutions has been investigated by tracer techniques using dialkylsulphides (R₂S) namely, dibutylsulphide (DBS) and dioctylsulphide (DOS) as extractants. These extraction data have been analyzed by both graphical and theoretical methods by taking into account complexation of the metal ion in the aqueous phase with inorganic ligands and all plausible complexes extracted into the organic phase. The results clearly indicate that Hg(II) is extracted into xylene as HgCl₂ ^. nDBS/nDOS (where n = 2 and 3). The equilibrium constants of the extracted complexes have been deduced by non-linear regression analysis. The separation possibilities of Hg(II) from other metal ions viz. Ca(II), Mg(II), Ba(II) and Fe((III), which are present in the industrial wastes of the chlor-alkali industry has also been discussed.     

Characterization of strong complexing agents in natural waters by liquid-liquid extraction

The solvent extraction method for characterization of strong complexing agents in natural waters has been developed. The titration curve the relationship between the concentration of a metal added in a sample solution and that of the metal in the organic phase after extraction, has been modelled on the basis of Ringbom's theory. The concentration of the metal in the organic phase is easily calibrated by the activities of the radioisotopic spike. The conditional stability products for complexation of natural ligands with cobalt (⁵⁷Co), manganese (⁵⁴Mn) and zinc (⁶⁵Zn) were calculated from the titration curves.     

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.