Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex

Picayo, Gabriela A.; Etz, Brian D.; Vyas, Shubham; Jensen, Mark P.

doi:10.1021/acsomega.0c00209

Title: Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex

Journal Article · Mon Mar 30 00:00:00 EDT 2020 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.0c00209· OSTI ID:1614814

^[1]; Etz, Brian D. ^[1];

^[1];

^[2]

Colorado School of Mines, Golden, CO (United States). Dept. of Chemistry
Colorado School of Mines, Golden, CO (United States). Dept. of Chemistry and Nuclear Science and Engineering Program

We have determined the identity of the complexes extracted into the ALSEP process solvent from solutions of nitric acid. The ALSEP process is a new solvent extraction separation designed to separate americium and curium from trivalent lanthanides in irradiated nuclear fuel. ALSEP employs a mixture of two extractants, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) and N,N,N',N'-tetra(2-ethylhexyl)diglycolamide (TEHDGA) in n-dodecane, which makes it difficult to ascertain the nature of the extracted metal complexes. It is often asserted that the weak acid extractant HEH[EHP] does not participate in the extracted complex under ALSEP extraction conditions (2–4 M HNO₃). However, the analysis of the Am extraction equilibria, Nd absorption spectra, and Eu fluorescence emission spectra of metal-loaded organic phases argues for the participation of HEH[EHP] in the extracted complex despite the high acidity of the aqueous phases. The extracted complex was determined to contain fully protonated molecules of HEH[EHP] with an overall stoichiometry of M(TEHDGA)₂(HEH[EHP])₂·3NO₃. Computations also demonstrate that replacing one TEHDGA molecule with one (HEH[EHP])₂ dimer is likely energetically favorable compared to Eu(TEHDGA)₃·3NO₃, whether the HEH[EHP] dimer is monodentate or bidentate.

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Research Organization:: Colorado School of Mines, Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: NE0008554

OSTI ID:: 1614814

Journal Information:: ACS Omega, Vol. 5, Issue 14; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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Title: Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex

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