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

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

doi:10.1021/acsomega.0c00209

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

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

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24 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	8076-8089
Number of pages	14
Journal	ACS Omega
Volume	5
Issue number	14
DOIs	https://doi.org/10.1021/acsomega.0c00209
State	Published - Apr 14 2020
Externally published	Yes

Funding

This work was supported by the Department of Energy, Office of Nuclear Energy, Nuclear Energy University Program (USDOE Office of Nuclear Energy) under Grant DE-NE0008554.

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title = "Characterization of the ALSEP Process at Equilibrium: Speciation and Stoichiometry of the Extracted Complex",

abstract = "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.",

author = "Picayo, \{Gabriela A.\} and Etz, \{Brian D.\} and Shubham Vyas and Jensen, \{Mark P.\}",

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AU - Picayo, Gabriela A.

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AU - Vyas, Shubham

AU - Jensen, Mark P.

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N2 - 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.

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

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