V. I. Zhilov

Lithium isotope effects in extraction of lithium chloride by benzo-15-crown-5 in the 1,1,7-trihydrododecafluoroheptanol–water system

The extraction characteristics of the 1,1,7-trihydrododecafluoroheptanol water system have been studied for lithium chloride as the salt to be extracted and benzo-15-crown-5 as the extracting agent, as well as blank extraction of lithium chloride in this system. Single-stage lithium isotope separation factors (a) have been measured at various lithium chloride concentrations in water, and the isotope effect has been multiplied by extraction chromatography. The value of a for the Li6–Li7 pair was 1.024. The light lithium isotope is concentrated in the organic phase.

Lithium and boron isotope effects in extraction systems

Extraction characteristics of chloroform-water system were studied using lithium chloride and tetrafluoroborate as extracted salts and benzo-15-crown-5 as an extractant. Single-stage isotope separation factors (α) for lithium isotopes at different concentrations of lithium chloride in water were measured and multiplication of isotope effect was made by extraction chromatography. The magnitude of α for Li6-Li7 pair was 1.036 for chloride and 1.030 for tetrafluoroborate. Light lithium isotope is concentrated in organic phase. Extraction chromatography experiments were conducted in 1,1,7-trihydrododecafluoroheptanol-water extraction system for boron isotope separation using boric acid as extracted compound and trioctylamine as an extractant as well as in chloroform-water system with lithium tetrafluoroborate as extracted compound and benzo-15-crown-5 as an extractant. The upper assessment of α values for B10-B11 boron isotopes was found to be not larger than 1.005 for both systems.

Extraction of rare earth elements with 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene with the use of 1,1,7-trihydrododecafluoroheptanol as a solvent

Extraction of rare earth elements from nitric acid solutions in a 1,1,7-trihydrododecafluoroheptanol-water system with the use of phosphoryl-containing podand 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene (L) was studied. The content of metals in organic phase was shown to be negligible at nitric acid concentration lower 1 mol/L. Distribution ratio sharply increases with nitric acid concentration from 1 mol/L and reaches 5.5 for the yttrium subgroup elements at HNO3 concentration of 6 mol/L. The rare earth elements of the yttrium subgroup were found to be extracted much better than the rare earth elements of the cerium subgroup under the same conditions, the distribution ratios in both subgroups smoothly rise with atomic number of element. It was shown using the shift of extraction equilibrium that the M: L ratio in extracted complexes is 1: 2 irrespective of the nature of rare earth element. The structure of complex {Yb[η2-(O,O′)-L]2(η2-O2NO)2}(O2NOHNO3), whose single crystals were isolated from extraction solution, was established by X-ray diffraction study. The system can be used for the isolation and separation of rare earth elements.

Extraction of rare-earth elements by alkylated dibenzo-18-crown-6 and dicyclohexano-18-crown-6 from acid solutions

The extraction of rare-earth elements (REE) by alkylated crown ethers (dibenzo-and dicyclohexano-18-crown 6; DB18C6 and DCH18C6) from acid solutions in the chloroform-water system is studied. The extraction of the REE with DCH18C6 and its alkylated derivatives in the presence of trichloroacetic acid (TCA) is far more efficient than the extraction with DB18C6 and its alkylated derivatives or when nitric or acetic acid is used instead of TCA. The distribution coefficients for the cerium metals are far higher than for the yttrium metals. The metal: crown ether ratio in the extracted complex in all cases is 1:1.

Americium(III) sorption from multicomponent solutions by macrocyclic polyester-based sorbents

Americium sorption by crown-ether-impregnated polymeric sorbents from nitric acid solutions and multicomponent nitrate solutions that model process solutions was studied. Sorption of ballast elements by the unimpregnated Porolas-T support was studied. The sorption coefficients Kd of these elements on Porolas-T do not exceed 0.01. Sorption of the same elements by crown-ether-impregnated sorbents was also studied. Dicyclohexano-18-crown-6 (DCH18C6) and its alkyl derivatives were used. Sorption coefficients were determined for all ballast elements. At the final stage of the study, 241Am sorption coefficients of from multi-component solutions were determined. The data obtained signify the utility of crown-ether-impregnated sorbents for recovering 241Am from multicomponent technological solutions.

Exhaustive removal of thorium and uranium traces from neodymium by liquid extraction

The Th content in commercially available Nd2O3 samples with the main substance content of 99.0–99.998% was found to be 2–8, and that of U, 3–230 ppb. Therefore, to obtain Nd meeting the requirements of the experiment on studying neutrinoless double β-decay, it should be purified to reduce the content of Th and U impurities by a factor of 103–104. To this end, the extraction of Nd, Th, and U from hydrochloric acid media with solutions of trioctylphosphine oxide (TOPO) in toluene was studied. The distribution ratios of Th increase with a decrease in the HCl concentration in the initial aqueous solution. With an increase in the Cl− concentration in the aqueous phase, the U distribution ratios decrease, probably because of a decrease in the concentration of the free extractant due to the extraction of Nd and HCl. On the contrary, the distribution ratios of Th increase with an increase in the Cl− concentration in the aqueous phase, with the slope of the straight line in the coordinates logDTh-log[Cl−]aq close to 7, which may be due to coextraction of Th with Nd in the form of the complex ThNdCl7. The enthalpies of formation of the extractable complexes of Th and U were determined from the temperature dependence of the extraction of Nd, Th, and U chlorides with a 0.1 M solution of TOPO in toluene. The optimal extraction system was chosen for Nd purification to remove traces of Th and U: organic phase, 0.1 M solution of TOPO in toluene; aqueous phase, 2.4 M NdCl3 + 0.1 M HCl. From the initial aqueous solution contaning 574 ppt Th and 2837 ppt U, by single extraction with an equal volume of 0.1 M TOPO in toluene, an aqueous solution containing <10 ppt Th and 31 ppt U (detection limit 10 ppt) was obtained. By semicountercurrent extraction, from the initial aqueous NdCl3 solution containing 200 ppb Th, the raffinate containing <10 ppt Th was obtained in one extraction step. The results obtained confirm the possibility of exhaustive removal of Th and U impurities (to the level of ≤1 ppt) from Nd by extraction with TOPO solutions from chloride solutions.

Control of the Extractive Power of Crown Ethers by Alkyl Substitution

Aiming to find extractants suitable for recovery of cesium from nitric acid solutions with a high sodium content, two types of alkylated derivatives of 18-crown-6 were studied. Derivatives of the first type (five compounds) were prepared by introducing alkyl substituents into the macroring. Derivatives of the second type were prepared by introducing alkyl substituents into phenyl or cyclohexyl fragments of dibenzo-18-crown-6 (DB18C6) and dicyclohexyl-18-crown-6 (DCH18C6) (16 compounds). The alkylated crown ethers exhibit different reactivity depending on the substitution mode. Introduction of two alkyl substituents into the phenyl rings of dibenzo-18-crown-6 allowed preparation of compounds ensuring the Cs/Na separation factor as high as 100 and more.

Study of isotope effect upon lithium iodide complexation with benzo-15-crown-5 in water–chloroform extraction system

Extraction characteristics of chloroform–water system in lithium iodide extraction with benzo-15-crown-5 (B15C5) were studied. The complexation of the crown ether with LiI in organic phase was shown by IR spectroscopy. Isotope effect multiplication was performed by extraction chromatography technique. The magnitude of isotope separation factor (α) for 6Li-7Li pair was 1.017. The light lithium isotope is concentrated in organic phase.

Tetra-15-Crown-5-Phthalocyaninatocobalt as a Reagent for the Spectrophotometric Determination of Potassium and Sodium in Chloroform–Ethanol–Water Solutions

It is shown that potassium and sodium simultaneously present in aqueous solutions can be determined by photometry with the use of tetra-15-crown-5-phthalocyaninatocobalt.

Study of lithium complexes with benzo-15-crown-5 ether by X-ray diffraction and IR spectroscopy

The complex formation of lithium with benzo-15-crown-5 (B15C5) was investigated. The complexes LiB15C5H2OX, where X = Cl− (1), I− (2), (3), (5), and LiBF4B15C5 (4) were synthesized and studied by IR spectroscopy. Complexes 1–4 were examined by X-ray diffraction. According to IR spectroscopy data, the crown ether conformation changes upon dissolution. The interaction of the extracted complex with the solvent was identified.