NDLI: Selective binding of ions of uranium and of transuranium and rare-earth metals with functionally substituted crown ethers

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Selective binding of ions of uranium and of transuranium and rare-earth metals with functionally substituted crown ethers

Content Provider	Springer Nature Link
Author	Tsivadze, A. Yu. Tananaev, I. G. Myasoedov, B. F. Yakshin, V. V. Pribylova, G. A. Atamas’, L. I. Vilkova, O. M.
Copyright Year	2006
Abstract	The extraction of uranium and of transuranium and rare-earth elements from nitric acid solutions with solutions of 4,4′(5′)-bis(dialkylphosphoryl)-,-bis(diphenylphosphoryl)-, and-bis[(O-alkyl)phosphoryl]-benzo-n-crown-m ethers (n = 18, m = 6; n = 21, m = 7; n = 24, m = 8) in 1,2-dichloroethane and chloroform was studied. The distribution ratios of U(VI), Pu(IV), Am(III), and Eu(III) in the extraction depend both on the experimental conditions and on the structural features of the ligands. In the range [HNO$_{3}$] = 0.02–1.0 M, the metal distribution ratios D $_{M}$ depend on the mutual steric orientation of the phosphoryl groups. With the cis (4,4′) isomers, D $_{M}$ is higher than with the trans (4,5′) isomers and with the isomer mixtures. With the compound containing the (n-BuO)$_{2}$P(O) groups in the cis position as example, it was found that the highest distribution ratios D $_{U}$ = 0.98 were observed in 3 M HNO$_{3}$; D $_{Pu}$ = 5.1, in 0.5 M HNO$_{3}$; and D $_{Am}$ = 0.007, at pH 2. For the trans conformer under the same conditions, D $_{M}$ of U(VI), Pu(IV), and Am(III) is 0.091, 1.8, and 0.003, respectively. The macroring size (number of carbon atoms n), under other conditions equal, also significantly affect the extraction activity of the reagent. With the extraction of Am(III) from 0.01–3 M HNO$_{3}$ as example, it was shown that the crown ethers with n = 21 are the most efficient with all the substituents. The maximum of D $_{Am}$ shifts toward higher HNO$_{3}$ concentrations with increasing n. The coordinating power of phosphoryl-containing ligands based on functionally substituted benzo-21-crown-7 ether in the extraction of Am(III) from 0.01–3 M HNO$_{3}$ decreases in the order (n-BuO)(OH)P(O)-≫ (n-BuO)$_{2}$P(O)-> Ph$_{2}$P(O)-, under other conditions equal. The extraction ability of di(n-BuO)(OH)P(O)-dibenzo-21-crown-7 (D $_{Am}$ = 814 in extraction from 0.1 M HNO$_{3}$) exceeds that of the other compounds studied by more than two orders of magnitude. Conditions were found for the selective extractive separation of Am(III) and Eu(III) using bis[(O-alkyl)(OH)phosphoryl]dibenzo-21-crown-7, with a separation factor of >90 at [HNO$_{3}$] = 0.01 M.
Ending Page	476
Page Count	5
Starting Page	472
File Format	PDF
ISSN	10663622
e-ISSN	16083288
Journal	Radiochemistry
Issue Number	5
Volume Number	48
Language	English
Publisher	Nauka/Interperiodica
Publisher Date	2006-01-01
Publisher Place	Moscow
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Chemistry/Food Science Nuclear Chemistry
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry

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