Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]- Ionic Liquid
Abstract
A new methodology for gas-phase uranium ion formation is described in which UO2 is dissolved in neat N-ethyl,N'-methylimidazolium fluorohydrogenate ionic liquid [EMIm+][F(HF)2.3-], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF6- (a U(V) species) was observed at m/z = 352, and other than cluster ions derived from the ionic liquid, nothing else was observed. When the sample was analyzed using infusion desorption chemical ionization, UF6- was the base peak, and it was accompanied by a less intense UF5- that most likely was formed by elimination of a fluorine radical from UF6-. Formation of UF6- required dissolution of UO2 followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Further, dissolution of UO3 produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF6- provides a vehicle for accurate measurement of uranium isotopic abundances free from interference from minor isotopes of other elements and a convenient ion synthesis route that is needed gas-phase structure and reactivity studies like infrared multiphoton dissociation and ion-molecule dissociation and condensation reactions.more »
- Authors:
-
[1];
[1];
[1];
[1];
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Osaka Univ. (Japan)
- Kyoto Univ. (Japan)
- Publication Date:
- Research Org.:
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 2282741
- Report Number(s):
- INL/JOU-18-44601-Rev000
Journal ID: ISSN 1044-0305
- Grant/Contract Number:
- AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Society for Mass Spectrometry
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 10; Journal ID: ISSN 1044-0305
- Publisher:
- American Society for Mass Spectrometry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; fluorohydrogenate; ionic liquid; uranium; mass spectrometry; uranium oxide; fluoroanion
Citation Formats
Zarzana, Christopher A., Groenewold, Gary S., Benson, Michael T., Delmore, James E., Tsuda, Tetsuya, and Hagiwara, Rika. Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]- Ionic Liquid. United States: N. p., 2018.
Web. doi:10.1007/s13361-018-2006-y.
Zarzana, Christopher A., Groenewold, Gary S., Benson, Michael T., Delmore, James E., Tsuda, Tetsuya, & Hagiwara, Rika. Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]- Ionic Liquid. United States. https://doi.org/10.1007/s13361-018-2006-y
Zarzana, Christopher A., Groenewold, Gary S., Benson, Michael T., Delmore, James E., Tsuda, Tetsuya, and Hagiwara, Rika. Thu .
"Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]- Ionic Liquid". United States. https://doi.org/10.1007/s13361-018-2006-y. https://www.osti.gov/servlets/purl/2282741.
@article{osti_2282741,
title = {Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]+[F(HF)2.3]- Ionic Liquid},
author = {Zarzana, Christopher A. and Groenewold, Gary S. and Benson, Michael T. and Delmore, James E. and Tsuda, Tetsuya and Hagiwara, Rika},
abstractNote = {A new methodology for gas-phase uranium ion formation is described in which UO2 is dissolved in neat N-ethyl,N'-methylimidazolium fluorohydrogenate ionic liquid [EMIm+][F(HF)2.3-], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF6- (a U(V) species) was observed at m/z = 352, and other than cluster ions derived from the ionic liquid, nothing else was observed. When the sample was analyzed using infusion desorption chemical ionization, UF6- was the base peak, and it was accompanied by a less intense UF5- that most likely was formed by elimination of a fluorine radical from UF6-. Formation of UF6- required dissolution of UO2 followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Further, dissolution of UO3 produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF6- provides a vehicle for accurate measurement of uranium isotopic abundances free from interference from minor isotopes of other elements and a convenient ion synthesis route that is needed gas-phase structure and reactivity studies like infrared multiphoton dissociation and ion-molecule dissociation and condensation reactions. The reactive fluorohydrogenate ionic liquid may also enable conversion of uranium in oxidic matrices into uranium fluorides that slowly oxidize to uranyl fluoride under ambient conditions, liberating the metal for facile measurement of isotope ratios without extensive chemical separations.},
doi = {10.1007/s13361-018-2006-y},
journal = {Journal of the American Society for Mass Spectrometry},
number = 10,
volume = 29,
place = {United States},
year = {Thu Jun 28 00:00:00 EDT 2018},
month = {Thu Jun 28 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 6 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides
journal, November 2008
- Nockemann, Peter; Thijs, Ben; Parac-Vogt, Tatjana N.
- Inorganic Chemistry, Vol. 47, Issue 21
Syntheses and Physicochemical Properties of New Ionic Liquids Based on the Hexafluorouranate Anion
journal, June 2009
- Kanatani, Takatsugu; Matsumoto, Kazuhiko; Hagiwara, Rika
- Chemistry Letters, Vol. 38, Issue 7
Soft material with intense photoluminescence obtained by dissolving Eu2O3 and organic ligand into a task-specific ionic liquid
journal, January 2008
- Li, Huanrong; Shao, Huifang; Wang, Yige
- Chemical Communications, Issue 41
Electrospray mass spectrometry of undiluted ionic liquidsThis manuscript has been authored by a contractor of the U.S. Government under contract No. DE-AC05-00OR22725. Accordingly, the U.S. Government retains paid-up, nonexclusive, irrevocable, worldwide license to publish or reproduce the published form of this contribution, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, or allow others to do so, for U.S. Government purposes.
journal, January 2004
- Jackson, Glen P.; Duckworth, Douglas C.
- Chemical Communications, Issue 5
Molecular Dynamics Simulation of Hydrogen Fluoride Mixtures with 1-Ethyl-3-methylimidazolium Fluoride: A Simple Model for the Study of Structural Features
journal, November 2005
- Salanne, M.; Simon, C.; Turq, P.
- The Journal of Physical Chemistry B, Vol. 110, Issue 8
The direct dissolution of Ce2(CO3)3 and electrochemical deposition of Ce species using ionic liquid trimethyl-n-butylammonium bis(trifluoromethanesulfonyl)imide containing bis(trifluoromethanesulfonyl)imide
journal, February 2013
- Hatchett, David W.; Droessler, Janelle; Kinyanjui, John M.
- Electrochimica Acta, Vol. 89
Structural characteristics of alkylimidazolium-based salts containing fluoroanions
journal, April 2007
- Matsumoto, Kazuhiko; Hagiwara, Rika
- Journal of Fluorine Chemistry, Vol. 128, Issue 4
Electrochemically-Induced Reactions of Hexafluorophosphate Anions with Water in Negative Ion Electrospray Mass Spectrometry of Undiluted Ionic Liquids
journal, July 2006
- Lu, Yuchen; King, Fred L.; Duckworth, Douglas C.
- Journal of the American Society for Mass Spectrometry, Vol. 17, Issue 7
Recycling of rare earths from NdFeB magnets using a combined leaching/extraction system based on the acidity and thermomorphism of the ionic liquid [Hbet][Tf 2 N]
journal, January 2015
- Dupont, David; Binnemans, Koen
- Green Chemistry, Vol. 17, Issue 4
Acidic 1-ethyl-3-methylimidazolium fluoride: a new room temperature ionic liquid
journal, October 1999
- Hagiwara, Rika; Hirashige, Takayuki; Tsuda, Tetsuya
- Journal of Fluorine Chemistry, Vol. 99, Issue 1
Task-Specific Ionic Liquid for Solubilizing Metal Oxides
journal, October 2006
- Nockemann, Peter; Thijs, Ben; Pittois, Stijn
- The Journal of Physical Chemistry B, Vol. 110, Issue 42
Iron Fluoroanions and Their Clusters by Electrospray Ionization of a Fluorinating Ionic Liquid
journal, May 2015
- Zarzana, Christopher A.; Groenewold, Gary S.; Benson, Michael T.
- Journal of the American Society for Mass Spectrometry, Vol. 26, Issue 9
Rare-earth recycling using a functionalized ionic liquid for the selective dissolution and revalorization of Y 2 O 3 :Eu 3+ from lamp phosphor waste
journal, January 2015
- Dupont, David; Binnemans, Koen
- Green Chemistry, Vol. 17, Issue 2
A new room temperature ionic liquid of oxyfluorometallate anion: 1-Ethyl-3-methylimidazolium oxypentafluorotungstate (EMImWOF5)
journal, July 2005
- Matsumoto, Kazuhiko; Hagiwara, Rika
- Journal of Fluorine Chemistry, Vol. 126, Issue 7
Preliminary studies of Pu measurement by AMS using PuF 4 -
journal, January 2013
- Zhao, X. -L.; Kieser, W. E.; Dai, X.
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 294
Studies of anions from sputtering I: Survey of
journal, April 2010
- Zhao, X. -L.; Litherland, A. E.; Eliades, J.
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 7-8
Uranyl Complexes of Carboxyl-Functionalized Ionic Liquids
journal, April 2010
- Nockemann, Peter; Van Deun, Rik; Thijs, Ben
- Inorganic Chemistry, Vol. 49, Issue 7
Electrochemistry of soluble UO22+ from the direct dissolution of UO2CO3 in acidic ionic liquid containing water
journal, March 2013
- Pemberton, Wendy J.; Droessler, Janelle E.; Kinyanjui, John M.
- Electrochimica Acta, Vol. 93, p. 264-271
The mechanism of HF/H[sub 2]O chemical etching of SiO[sub 2]
journal, January 2002
- Kang, Jeung Ku; Musgrave, Charles B.
- The Journal of Chemical Physics, Vol. 116, Issue 1
Electrodeposition of metallic uranium at near ambient conditions from room temperature ionic liquid
journal, January 2011
- Jagadeeswara Rao, Ch.; Venkatesan, K. A.; Nagarajan, K.
- Journal of Nuclear Materials, Vol. 408, Issue 1
Room temperature ionic liquids of alkylimidazolium cations and fluoroanions
journal, September 2000
- Hagiwara, Rika; Ito, Yasuhiko
- Journal of Fluorine Chemistry, Vol. 105, Issue 2
Ion-pair evaporation from ionic liquid clusters
journal, August 2010
- Hogan, Christopher J.; Fernandez de la Mora, Juan
- Journal of the American Society for Mass Spectrometry, Vol. 21, Issue 8
Direct analysis of catalysts immobilised in ionic liquids using electrospray ionisation ion trap mass spectrometry
journal, January 2003
- Dyson, Paul J.; McIndoe, J. Scott; Zhao, Dongbin
- Chemical Communications, Issue 4
Dissolution of metal oxides in an acid-saturated ionic liquid solution and investigation of the back-extraction behaviour to the aqueous phase
journal, April 2014
- Wellens, Sil; Vander Hoogerstraete, Tom; Möller, Claudia
- Hydrometallurgy, Vol. 144-145
Generation of gas‐phase zirconium fluoroanions by electrospray of an ionic liquid
journal, April 2014
- Groenewold, Gary S.; Delmore, James E.; Benson, Michael T.
- Rapid Communications in Mass Spectrometry, Vol. 28, Issue 11
Syntheses, structures and properties of 1-ethyl-3-methylimidazolium salts of fluorocomplex anions
journal, January 2004
- Matsumoto, Kazuhiko; Hagiwara, Rika; Yoshida, Ryuhei
- Dalton Trans., Issue 1
Sulfonic acid functionalized ionic liquids for dissolution of metal oxides and solvent extraction of metal ions
journal, January 2015
- Dupont, David; Raiguel, Stijn; Binnemans, Koen
- Chemical Communications, Vol. 51, Issue 43
Fluorohydrogenate Cluster Ions in the Gas Phase: Electrospray Ionization Mass Spectrometry of the [1-Ethyl-3-methylimidazolium+][F(HF)2.3–] Ionic Liquid
journal, December 2013
- Groenewold, Gary S.; Delmore, James E.; Benson, Michael T.
- The Journal of Physical Chemistry A, Vol. 117, Issue 51
Room temperature molten fluorometallates: 1-ethyl-3-methylimidazolium hexafluoroniobate(V) and hexafluorotantalate(V)
journal, June 2002
- Matsumoto, Kazuhiko; Hagiwara, Rika; Ito, Yasuhiko
- Journal of Fluorine Chemistry, Vol. 115, Issue 2