The extraction of thorium from nitric acid solutions by long-chain aliphatic amines

The partition of thorium between nitric acid solutions and solutions of long-chain aliphatic amines in benzene is described. The organic phase was examined by infrared spectroscopy. Tertiary amines are more efficient extractants for thorium than are secondary amines; the efficiency is enhanced when the alkyl chain is branched and is strongly influenced by the organic solvent used as diluent.     

Co-extraction and separation of zirconium and hafnium by long-chain amines from sulphate media

The extraction of Zr and Hf from sulphuric acid systems by solutions of Primene JMT (a long-chain primary amine) in kerosene, is described. The effect of contact time, free acidity, solvent concentration and temperature, has been thoroughly examined. A rapid improved method for HfZr separation is suggested.     

Studies on extraction of thorium(IV) from sulfate media with mixtures of long-chain primary amines and tributyl phosphate

The partition of Th(IV) from H₂SO₄ solutions with extractant mixtures of long-chain primary amine (Primene JMT, PrJT) and tributyl phosphate (TBP) is described. Exraction was optimized at PrJT/TBP molar ratio of about 3. The dependence of extraction on acidity, salting agent, extractant concentration, diluent type and temperature, was investigated. From the results obtained, the extracted species are suggested and enthalpy data determined.     

Palladium extraction by amines from nitrate medium in the presence of chloride ions

The extraction of palladium has been studied in amine-solvent-HNO₃–HCl systems. It has been found that palladium is extracted in the forms Am₂PdCl₄ and Am₂Pd₂Cl₆ simultaneously /Am=ammonium cation/.     

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.     

Studies on extraction of indium(III) chloride complexes by long-chain amines

The distribution of In(III) between aqueous HCl solutions and organic phases of tricaprylamine in kerosene has been described. The dependence of extraction on acidity, salting agent, metal and extractant concentration, was investigated. Extraction mechanism was proposed on the basis of results obtained. The effect of temperature and organic additives on extraction has also been examined.     

Micellar extraction of the lanthanide ions from acidic media

A procedure of micellar extraction of the lanthanide ions (La, Gd, and Lu) from nitric acid media based on the use of novel phosphine oxide derivatives is developed. In the micellar extraction, complexes of the lanthanide ions with the extractant in the ratio of 1 : 2 (metal : extractant) form. The dependence of the selectivity of extraction on the length of hydrophobic radicals attached to the P=O group was shown. The conditions of the selective micellar extraction in the series La > Gd > Lu with the use of an extractant containing octyl substituents at the P=O group were found.     

Solvent extraction of zinc by 2-hexylpyridine in benzene from aqueous mineral acid — Thiocyanate media

Solvent extraction of Zn(II) by 2-hexylpyridine (HPy) in benzene has been studied from aqueous mineral acid—thiocyanate media. The extraction, though dependent on the acidity of the aqueous phase, is poor from mineral acids (HCl, HNO₃ or H₂SO₄). Addition of 0.02M KSCN to the aqueous phase enhances the distribution ratio by a factor of almost one thousand. The stoichiometry of the extracted complex established by the usual slope analysis method indicates that an ionic type complex, e.g. Zn(SCN)₄·(HPyH)₂, is responsible for extraction. Complexing anions like acetate, oxalate or citrate at 1 M concentration mask the extraction of Zn(II) almost completely. Separation factors determined at optimal conditions (0.1M HPy in benzene −0.05M H₂SO₄+0.2M SCN⁻) indicate that Zn(II), along with Hg(II), can be separated in a single extraction from a number of metals, e.g. Cs(I), Sr(II), Ln(III), Y(III), Cr(III) and (VI). Other metals of interest like Cu(II), Co(II), Fe(III), Mo(VI), U(VI) and Tc(VII) are coextracted but the separation factors are large enough to allow separation in a multistage extraction process.     

Photometric cyclic-injection determination of phosphate ions in aqueous media using extraction preconcentration

A procedure for the automated extraction photometric determination of phosphate ions in aqueous media was proposed based on the formation of colored phosphomolybdic heteropoly acid followed by its extraction from the aqueous phase to 1-butanol in the units of a hydraulic facility for cyclic-injection analysis. The procedure ensures a lower limit of the analytical range at a level of 80 μg/L at a sample volume of 10 mL.     

Vapor-phase extraction of organic substances from aqueous media

A method for the vapor-phase extraction of dissolved organic substances from an aqueous medium into an organic solvent was developed. This method allowed us to introduce hydrophilic extractants into extraction. The experimental results were discussed in terms of the kinetic model proposed for the mechanism of vapor-phase extraction. The analytical capabilities of this method were demonstrated using the study of sulfide mineral waters as an example.     

Sructural parameters of the nearest surrounding of tri- and tetravalent actinide ions in aqueous solutions of actinide salts

Published data are generalized on different research methods for structural characterization of the nearest surrounding of trivalent and tetravalent actinide ions in aqueous solutions of their salts under standard conditions. The structural parameters such as coordination numbers, interparticle distances, the parameters of the second coordination sphere, and the types of ionic association are discussed. The quantitative characteristics of hydrated complexes of poorly known trivalent actinide ions are determined on the basis of comparative analysis with lanthanide ions.     

Studies on the extraction of americium(III) from aqueous nitrate media by sulfoxides

Solvent extraction behaviour of Am(III) from dilute nitric acid media with sulfoxides (R₂SO) in Solvesso-100 has been investigated over a wide range of conditions. Very poor extractability of Am necessitated the use of salting-out agents, viz., nitrates of Al, Mg, Ca, Li and NH ₄ ⁺ . Effects of certain variables such as acidity, extractant concentration, saltingout agent, temperature etc., on metal extraction by sulfoxides have been examined systematically. For a fixed sulfoxide concentration, extraction attains a maximum value up to around 0.2–0.4M HNO₃ and decreasing above 1M HNO₃. In contrast, increasing the concentration of sulfoxide (0.8M DISO, 1.3M DBuSO) gives almost quantitative Am extraction up to 1M HNO₃. For satisfactory extraction, di-n-octyl as well as di-n-hexyl sulfoxide are the most suitable extracting agents. Extractability of Am increases with increasing amounts of all the salting-out agents studied and their effect follows the sequence: Al³⁺>Mg²⁺>Ca²⁺>Li⁺>NH ₄ ⁺ ; this is also the relative dehydrating effect of the cations. The species extracted would appear to be Am(NO₃)₃.3R₂SO. Americium is easily stripped with 1–3M HNO₃ solutions from the loaded organic phase. Extraction decreases with increasing temperature, indicating the extraction to be exothermic. Extraction from partially non-aqueous solutions was also investigated.     

Interaction between primary aliphatic amines and carboxylic acid esters in aqueous micellar solutions of cationic surfactants

The effects of cetylpyridinium bromide (CPB) on the acid-base equilibria of primary aliphatic amines and on the kinetics of reactions of the amines withp-nitrophenyl acetate (PNPA) andp-nitrophenyl caprylate (PNPC) were studied by potentiometric titration and UV spectroscopy. The values of apparent pK _a of the amines in the micellar phase, binding constants of their neutral forms, and the surface potentials of micelles were determined. Cetylpyridinium bromide accelerates the aminolysis of PNPA by factors of 3 to 8 by forming mixed micellar aggregates with the amines. The shift of pK _a values of the amines in micellar solutions is not the only factor that enhances their reactivity. The substrate specificity was found: in contrast to the reaction with PNPA, CPB accelerates (by factors of 15 to 65) or retards (by factors of 4 to 6) the aminolysis of PNPA depending on the hydrophobicity of the nucleophilic reagent. The binding constants of substrates, the rate constants in the micellar phase, and the critical concentrations of micellization were determined from the data obtained. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1333–1338, July, 1998.     

Rules governing vapor-phase extraction of carboxylic acids and phenols from aqueous solutions

The influence of the molecular structure of the components to be extracted and the type of the extractant used on the effectiveness of vapor-phase extraction from water was studied for the example of low-molecular-weight carboxylic acids C₂-C₆ and phenols. Extraction parameters were found to depend on the length of the analyte molecule and its polarity. The experimental data and correlations observed substantiated the validity of the suggested mechanism of vapor-phase extraction. Changes in the Gibbs energy of extraction equilibrium as the length of the analyte molecule (in the homologous series of organic acids C₂-C₆) and molecule polarity (for the example of cresol isomers) increased were evaluated.     

Studies on the extraction behaviour of zirconium from mixed aqueous media with TBP

A systematic study is presented on the extraction of Zr(IV) by tri-n-butylphosphate from H₂SO₄, HNO₃, HCl and HBr solutions as well from binary mixtures of H₂SO₄ and halogen acids. It has been found that Zr(IV) extraction is appreciably increased by addition of halogen acid to sulphuric acid solutions. On the other hand, the presence of water-miscible alcohols and acetone was found to enhance Zr(IV) extraction from HCl and HNO₃ solutions. An investigation of extracted Zr complexes from pure acids and mixed aqueous media enabled an explanation of the observed enhancements. In the light of the obtained results, an extraction mechanism is suggested.     

The cavity elongation effect. Calorimetric studies of the complexes of long-chain carboxylic acids with methyl-α-cyclodextrin in aqueous solutions

The formation of complexes between methyl-α-cyclodextrin (MαCD) and monocarboxylic acids from C₅ to C₁₂ or cycloalkanols has been studied calorimetrically at 298 K in aqueous phosphate buffer, pH 11.3. The forces involved in the association process are discussed according to the signs and values of the thermodynamic parameters obtained: association enthalpy, constant, Gibbs energy and entropy. Methyl-α-cyclodextrin forms 1:1 inclusion complexes with monocarboxylic acids, characterized by a monotonous increase in the values of enthalpies and association constants at increasing alkyl chain length. Association is characterized by negative enthalpies and by positive entropies: that determines large association constants. That behaviour is compared to the unusual trend in the values of the association constants shown by the parent α-cyclodextrin interacting␣with the same monocarboxylic acids. The model proposed to rationalize the present data provides a cavity elongation effect. Namely, because of the presence of the methyl groups on the outside, the cavity behaves as it were deeper than that of the parent cyclodextrin. The association with cycloalkanols—cyclohexanol, cycloheptanol, cyclooctanol and 1-cylohexyl-ethanol—is characterized by lower entropies, as determined by the␣enhanced negative contribution originating from the␣tighter fit of the guest into the cavity.     

Mechanistic studies on oxidation of L-ascorbic acid by an oxo-bridged diiron complex in aqueous acidic media

[Fe2(micro-O)(phen)4(H2O)2]4+ (1) (Fig. 1, phen = 1,10-phenanthroline) equilibrates with [Fe2(micro-O)(phen)4(H2O)(OH)]3+ (2) and [Fe2(micro-O)(phen)4(OH)2]2+ (3) in aqueous solution in the presence of excess phen, where no phen-releasing equilibria from 1, 2 and 3 exist. 1 quantitatively oxidizes ascorbic acid (H2A) to dehydroascorbic acid (A) in the pH range 3.00-5.50 in the presence of excess phen, which buffers the reaction within 0.05 pH units and ensures complete formation of end iron product ferroin, [Fe(phen)3]2+. The reactive species are 1, 2 and HA- and the reaction proceeds through an initial 1 : 1 inner-sphere adduct formation between 1 and 2 with HA-, followed by a rate limiting outer-sphere one electron one proton (electroprotic) transfer from a second HA- to the ascorbate-unbound iron(III).     

Development of prototype titanate ion-exchange loaded-membranes for strontium, cesium and actinide decontamination from aqueous media

We have successfully incorporated high surface area particles of titanate ion-exchange materials (monosodium titanate and crystalline silicotitanate) into porous and inert support membrane fibrils. The resulting membrane sheets were used to evaluate the removal of surrogate radioactive materials for cesium-137 and strontium-90 from high caustic nuclear waste simulants. The membrane supports met the nominal requirement for non-chemical interaction with the embedded ion-exchange materials and were porous enough to allow sufficient liquid flow. Most of the stamped out 47-mm size titanium impregnated ion-exchange membrane discs removed more than 96% of dissolved cesium-133 and strontium-88 from caustic nuclear waste salt simulants.