Universität zu Köln

Cao, Xiaoyan ORCID: 0000-0002-3438-575X, Zhang, Jun, Weissmann, Daniel, Dolg, Michael ORCID: 0000-0002-0538-0837 and Chen, Xuebo (2015). Accurate quantum chemical modelling of the separation of Eu3+ from Am3+/Cm3+ by liquid-liquid extraction with Cyanex272. Phys. Chem. Chem. Phys., 17 (32). S. 20605 - 20617. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1463-9084

Full text not available from this repository.

Abstract

The experimentally observed extraction complexes of trivalent lanthanide Eu3+ and actinide Am3+/Cm3+ cations with Cyanex272 [bis(2,4,4-trimethylpentyl) phosphinic acid, denoted as HC272] and Cyanex301 [bis(2,4,4-trimethylpentyl) dithiophosphinic acid, denoted as HC301] have been studied by using relativistic energy-consistent 4f- and 5f-in-core pseudopotentials for trivalent f elements, combined with density functional theory and a continuum solvation model. It has been found that, as a result of hydrogen bonding, HC272 exists primarily as a self-associated species, whereas HC301 is preferably a monomer. The calculations show that in case of all three M3+ (M = Eu, Am, Cm) ions for HC272 the extraction complexes M[H(C272)(2)](3) are formed prior to M(C272)(3), whereas for HC301 the extraction complexes M(C301)(3) have priority over M[H(C301)(2)](3). The calculated M-O and M-S bond lengths and the M-P distances of these preferred extraction complexes agree very well with the available experimental data. The obtained changes of the Gibbs free energies in the liquid-liquid extraction reactions (1): Maqu3+ + 3(HC272)(2,org) -> M[H(C272)(2)](3, org) + 3H(aqu) + and (2): M-aqu(3+) + 3HC301(org) -> M(C301)(3,org) + 3(Haqu)(+) agree with the experimentally observed thermodynamical priorities of HC272 and HC301, i.e., HC272 prefers Eu3+ over Am3+/Cm3+ and HC301 prefers Am3+/Cm3+ over Eu3+. The obtained changes of the Gibbs free energies in reaction (2) (Eu, 68.1 kJ mol(-1); Am, 46.5 kJ mol(-1)) agree quite well with the experimental findings (Eu, 63.3 kJ mol(-1); Am, 44.1 kJ mol(-1)).

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED Zhang, Jun UNSPECIFIED UNSPECIFIED UNSPECIFIED Weissmann, Daniel UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED Chen, Xuebo UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-419659
DOI:	10.1039/c5cp03100a
Journal or Publication Title:	Phys. Chem. Chem. Phys.
Volume:	17
Number:	32
Page Range:	S. 20605 - 20617
Date:	2015
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1463-9084
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Theoretical Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language CONSISTENT 5F-IN-CORE PSEUDOPOTENTIALS; ENERGY-ADJUSTED PSEUDOPOTENTIALS; RARE-EARTH-ELEMENTS; GAUSSIAN-BASIS SETS; TRIVALENT ACTINIDES; BIS(2,4,4-TRIMETHYLPENTYL)DITHIOPHOSPHINIC ACID; SOLVENT-EXTRACTION; AQUO IONS; LANTHANIDES; HYDRATION Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/41965