Solvent extraction of europium from aqueous-organic solutions by solvating extractants

The partition of Eu(III) between benzene containing solvating extractants (TBP, TOPO, dioctylsulfoxide) and aqueous nitrate, perchlorate and thiocyanate solutions containing various organic solvents miscible with water (alcohols, acetone, acetonitrile, ethylene glycol, dimethyl sulfoxide and dimethylformamide) was investigated. Depending on the specific extraction system, the presence of organic solvents in the mixed phase showed various effects on the distribution ratio of Eu(III). These were discussed in terms of solute-solvent interactions. The results in the systems containing dimethylformamide and dimethyl sulfoxide indicated complexation of Eu(III) with these solvents in the polar phase.     

Solvent extraction of alkali metal ion-pairs into nitrobenzene from aqueous-organic solutions

Solvent extraction of¹³⁷Cs,⁸⁶Rb and⁴²K by dipicrylaminate and tetraphenyl borate into nitrobenzene was studied from solutions containing various solvents miscible with water. In all cases the distribution ratios of alkali metals were lower in mixed solutions than in water. In discussing the results, water structure, ion-association, solubility of Cs(I) ionpairs, ionic strength, and organic phase effects were taken into account. Part III in the series Solvent Extraction of Ion-pairs. Part II. Ref.⁸     

Solvent extraction of tetrachloronitridotechnetate(VI) ion with tetraphenylarsonium chloride

Radiochemical and spectrophotometric studies on the solvent extraction of tetrachloronitridotechnetate(VI) ion with tetraphenylarsonium chloride into chloroform have been reported. Analysis of the dependence of the distribution ratio for technetium species on the concentration of hydrogen ion (0.1–1.0M) revealed that an equilibrium between tetrachloronitridotechnetate(VI) ion and [(H₂OCl₃NTc–O–TcNCl₃(H₂O)]^2– is established in the aqueous phase. However, formation of di(-O) dimer was suggested, when the concentration of hydrochloric acid is less than 0.2M. The extraction constant for technetium and formation constant for -oxo technetium nitrido complex were evaluated.     

Solvent extraction of uranium(VI) into toluene by dicyclohexano-18-crown-6 from mixed aqueous-organic solutions

Extraction behaviour of uranium(VI) from mixed organo-aqueous solutions containing water-miscible protic aliphatic alcohols and several aprotic solvents was investigated by using dicyclohexano-18-crown-6(DC18C6) as an extractant. The organic phase was a binary solution of DC18C6 and toluene while the polar phase was a three component solution of uranyl nitrate, polar additive and aqueous nitric acid. Methanol, ethanol, isobutanol, dioxane, acetone, propylene carbonate and acetonitrile were used as the organic components of the mixed (polar) phase. Propylene carbonate, acetone, acetonitrile and dioxane increased the extractability of U(VI), whereas alcoholic additives showed only an antagonistic effect. The relative increase in extraction was found to be more at lower nitric acid concentrations. Possible reasons for such behaviour are briefly discussed. Recovery of U(VI) from loaded organic phase was easily accomplished using dilute perchloric acid and sulphuric acid. A sample method was standardized for the separation of plutonium(IV) from uranium(VI) based on its reductive stripping.     

Solvent extraction mechanism of pertechnetate with tetraphenylarsonium chloride

A systematic study of extraction of pertechnetate with tetraphenylarsonium chloride (TPAC) in chloroform from aqueous chloride solutions has been carried out at 25°C at ionic strength of 1.0. Fundamental parameters governing the distribution equilibrium of TPAC were determined. Extraction behavior of pertechnetate was established on the basis of the distribution mechanism of TPAC.     

Solvent extraction of some metals from aqueous solutions

The results for the extractions of divalent (manganese, cobalt, zinc and cadmium) and trivalent (gallium and indium) metals and hexavalent uranium from aqueous solutions by various extractants such as organophosphorus compounds (tributyl phosphate, trioctylphosphine oxide, di-(2-ethylhexyl)phosphoric acid and 2-ethylhexyl 2-ethylhexylphosphonic acid), sulfur-containing compound (dihexyl sulfoxide), high-molecular weight amines (trioctylamine and trioctylmethylammonium chloride) and 7-alkylated hydroxyquinoline (7-(5,5,7,7-tetramethyl-1-octen-3-yl)-8-hydroxyquinoline are discussed in the viewpoint of separation chemistry.     

Solvent extraction of reduced technetium from mineral acid solutions

The extraction of reduced^99mTc with 5,7-dichloroxine, tributyl phosphate (TBP) and 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (PMBP) from HCl−LiCl mixtures has been studied. A mechanism of extraction is proposed and the stability of the chlorocomplexes of technetium (V) in a hydrochloric and—lithium chlorid—perchloric acid mixture has been established using extraction data of^99mTc and spectrophotometric measurements with⁹⁹Tc.     

Studies on the extraction behaviour of plutonium(IV) from mixed aqueous-organic media with sulphoxides

Extraction behaviour of plutonium (IV) from nitric acid media by two long-chain aliphatic sulphoxides, namely, di-n-hexylsulphoxide and di-n-octylsulphoxide has been investigated in the presence of several water-miscible organic solvents to study their possible synergistic effect on metal ion extraction. Methanol, ethanol, n-and iso-propanol, dioxane, acetone as well as as acetonitrile were used as the organic component of the mixed (polar) phase. These additives affected the extraction to varying degrees. Thus, extractability of Pu increases 2–3 fold with increasing concentration (upto 20%) of acetonitrile, acetone, methanol and ethanol while it decreases with increasing concentration of n-and isopropanol. At high concentration of the former, synergism changes into antagonism. Possible reasons for such behaviour are briefly discussed. Among these organic additives, maximum enhancement in the extraction of Pu(IV) was observed in the presence of acetonitrile. The relative increase in extraction was found to be more at lower sulphoxide concentrations.     

Solvent extraction of Hf(IV) from mixed electrolyte solutions into di-2-ethylhexylphosphoric acid (HDEHP)

Extraction of hafnium(IV) from aqueous sulfuric and sulfuric-nitric acid solutions into di-2-ethylhexylphosphoric acid (HDEHP) in xylene has been investigated. The Hf(IV) species extracted from 5M sulfuric acid was found to be HfY₂(HY₂)₂ where Y and HY₂ represent the anions of monomeric HY and dimeric H₂Y₂ forms of HDEHP, respectively. In the presence of nitrate ion the species extracted are found to be Hf(NO₃)Y(HY₂)₂ and Hf(NO₃)₂)(HY₂)₂. But when the aqueous phase is 3.0M HNO₃+2.5M H₂SO₄ only one species, Hf(NO₃)₂(HY₂)₂ was extrated. No synergism was observed from 5M H₂SO₄ by HDEHP with the addition of thenoyltrifluoracetone (HTTA).     

Solvent extraction behaviour of iodine and bromine in aqueous-organic systems,analogy with radioactive decay

The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl₄, C₆H₆ and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H₂O(I₂)−CCl₄ and H₂O(I₂)−C₆H₆ systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H₂O(I₂)−CCl₄ system, 650±50 cal·mol⁻¹ is lower than that of H₂O(I₂)−C₆H₆, 3600±300 cal·mol⁻¹. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half number of extraction for each system is determined. The complex curves obtained in the H₂O(I₂)−CCl₄ and H₂O(I₂) −Br₂)−CCl₄ systems are resolved into two components.     

Solvent extraction of thorium(IV) ion with N,N,N,N-tetrabutylsuccinylamide from nitric acid solutions

It was found that N,N,N,N-tetrabutylsuccinylamide (TBSA) in a diluent composed of 50% 1,2,3-trimethylbenzene (TMB) and 50% kerosene (OK) can extract thorium(IV) ion from a nitric acid solution. The results of the extraction study suggested the formation of a 141 thorium(IV) ion, nitrate ion and N,N,N,N-tetrabutylsuccinylamide complex as extracted species. The related thermodynamic functions were also calculated.     

Solvent extraction of ionic solutes in aqueous solutions

Extraction of ionic solutes in aqueous solutions into various organic solvents is reviewed by showing several examples. The extraction of strong acids into polar organic solvents and nonpolar solvents containing hydrogen-bonding extractants is described as the first example and the extraction of simple metal salts into strongly dielectric or solvating polarsolvents and nonpolar solvents containing solvating extractants is then reported. Finally, the solvent extraction of anionic metal complexes with bulky cations into nonpolar solvents as ion-paris is described and the statistical method for such extraction equilibria is considered.     

Solvent extraction of Co/III/ by benzoylacetone from acetate solutions

The extraction of Co/III/ by benzoylacetone solutions has been carried out from acetateacetic acid solutions. The effect of different parameters affecting the distribution coefficient of Co/III/ have been determined. Lg D for Co was found to be a third order dependent on extractant concentration and a negative first order with respect to [H⁺]. From the thermodynamic parameters and the data of distribution ratios, the extraction mechanism has been suggested. Addition of some electron donor compounds shows no possibility for the increase of coordination number.     

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 extraction of yttrium(III) by TBP from acidic organic-aqueous solutions

Extraction by benzene solutions of TBP of carrier-free⁹⁰Y(III) from mixed aqueous-organic nitrate and perchlorate solutions was studied with special respect to the S-shaped D_Y versus acid concentration plots observed in aqueous systems. The presence of organic solvents in the aqueous phase enhanced the extraction of Y(III) and also influenced the shape of the D_Y vs. acid concentration plots in that the minimum was shifted towards lower acid concentration, became less pronounced, and eventually vanished completely.     

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.     

Transient ion pairs from OH-radical reactions: Pulse radiolysis of aqueous alkyl iodide solutions

Pulse radiolysis studies of aqueous alkyl iodide solutions reveal the existence of the transient ion pair (HOI^?.R⁺)_aq. This species is formed by OH-radical reaction with the alkyl iodide followed by a rapid solvent-assisted rearrangement from the outer to the inner charge-transfer complex.     

Solvent extraction of lanthanum(III) from sulphuric acid solutions by Primene JMT

The distribution of lanthanum(III) between aqueous H₂SO₄ solutions and Primene JMT in the organic phase is described. The dependence of the extraction on acidity, extractant concentration and type of diluent was investigated. Aggregation numbers are calculated and a mechanism for the extraction is suggested. The separation of thorium(IV) from lanthanum(III), cerium(III) and cerium(IV) is outlined.     

Possible mechanism of metal ion extraction from aqueous solutions by fibrous polypropylene

Peculiarities of the extraction of metal ions from aqueous solutions by fibrous polypropylene have been investigated. It has been found that metal ion adsorption proceeds owing to the existence of a gas-liquid-hydrophobic polymer boundary line. The process mechanism has been discussed.     

Solvent extraction of thorium from mixed organic — aqueous nitric acid media by try-n-octylphosphine oxide

The extraction equilibria of Th in tri-n-octylphosphine oxide (TOPO)–HNO₃–H₂O systems have been investigated in the absence and presence of water-miscible alcohols and acetone. The influence of TOPO concentration in an inert diluent (toluene) and the concentration of nitric acid and the water-miscible additives have been systematically examined. The slopes of the log-log plots of D_Th vs. the TOPO concentration (up to 0.02M) are found to be close to 3 over a wide range of polar phase compositions leading to a coordination number of 11 for Th. The D_Th values were determined as a function of the concentration of uranyl nitrate in the aqueous phase, while the effect of additives was also examined in the absence and presence of uranyl nitrate in the polar phase. The results show that at TOPO concentrations above about 2.5 · 10^–3 M (about 1%) in toluene, polymerization of the solvent occurs.