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Title: Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction

Authors:
; ; ; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1398617
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Inorganic Chemistry Communications
Additional Journal Information:
Journal Volume: 71; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-07 04:50:21; Journal ID: ISSN 1387-7003
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Kou, Fei, Yang, Suliang, Zhang, Lihua, Teat, Simon J., and Tian, Guoxin. Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction. Netherlands: N. p., 2016. Web. doi:10.1016/j.inoche.2016.06.035.
Kou, Fei, Yang, Suliang, Zhang, Lihua, Teat, Simon J., & Tian, Guoxin. Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction. Netherlands. doi:10.1016/j.inoche.2016.06.035.
Kou, Fei, Yang, Suliang, Zhang, Lihua, Teat, Simon J., and Tian, Guoxin. 2016. "Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction". Netherlands. doi:10.1016/j.inoche.2016.06.035.
@article{osti_1398617,
title = {Complexation of Ho(III) with tetraalkyl-diglycolamide in aqueous solutions and a solid state compared in organic solutions of solvent extraction},
author = {Kou, Fei and Yang, Suliang and Zhang, Lihua and Teat, Simon J. and Tian, Guoxin},
abstractNote = {},
doi = {10.1016/j.inoche.2016.06.035},
journal = {Inorganic Chemistry Communications},
number = C,
volume = 71,
place = {Netherlands},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.inoche.2016.06.035

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  • Apparent stability constants of the nitrato thorium complexes, Th(NO/sub 3/)/sup 3 +/, Th(NO/sub 3/)/sub 2//sup 2 +/, Th(NO/sub 3/)/sub 3//sup +/ and Th(NO/sub 3/)/sub 4/, in aqueous solutions having ionic strengths in the range 0.5 to 3.0 mol/L have been determined using a liquid-liquid extraction method. The data have been used to calculate free nitrate ion concentrations in aqueous solutions with compositions typical of those in the THOREX extraction process. A model based on extraction chemistry has been developed to predict thorium distribution coefficients under a variety of conditions. 34 references, 5 figures, 2 tables.
  • The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu3+ that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O[double bond, length as m-dash]Ca–Cb–O–Cb–Ca[double bond, length as m-dash]O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether Omore » atom bond to Eu3+. Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3]3+ with six 5-membered chelate rings, the six Eu–Ca and six Eu–Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4]- anions are beyond the cationic [Eu(TODGA)3]3+ cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu3+ coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln3+) complexes with tetraalkyldiglycolamide ligands (of the same 1 : 3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln3+ ions in terms of the local structure of Eu3+ in a solid state coordination complex with TODGA.« less
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