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Title: Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid

Abstract

A new methodology for gas-phase uranium ion formation is described in which UO{sub 2} is dissolved in neat N-ethyl,N′-methylimidazolium fluorohydrogenate ionic liquid [EMIm{sup +}][F(HF){sub 2.3}{sup −}], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF{sub 6}{sup −} (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, UF{sub 6}{sup −} was the base peak, and it was accompanied by a less intense UF{sub 5}{sup −} that most likely was formed by elimination of a fluorine radical from UF{sub 6}{sup −}. Formation of UF{sub 6}{sup −} required dissolution of UO{sub 2} followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Dissolution of UO{sub 3} produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF{sub 6}{sup −} 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 structuremore » 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. .« less

Authors:
; ;  [1];  [2];  [3]
  1. Idaho National Laboratory (United States)
  2. Osaka University, Graduate School of Engineering, Department of Applied Chemistry (Japan)
  3. Kyoto University, Graduate School of Energy Science, Department of Fundamental Energy Science (Japan)
Publication Date:
OSTI Identifier:
22776838
Resource Type:
Journal Article
Journal Name:
Journal of the American Society for Mass Spectrometry
Additional Journal Information:
Journal Volume: 29; Journal Issue: 10; Other Information: Copyright (c) 2018 American Society for Mass Spectrometry; http://www.springer-ny.com; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 1044-0305
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DESORPTION; DISSOCIATION; IONIZATION; ISOTOPE RATIO; MASS SPECTROSCOPY; MOLECULES; URANIUM DIOXIDE; URANIUM FLUORIDES; URANIUM IONS; URANIUM TRIOXIDE; URANYL FLUORIDES

Citation Formats

Zarzana, Christopher A., E-mail: christopher.zarzana@inl.gov, 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]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid. United States: N. p., 2018. Web. doi:10.1007/S13361-018-2006-Y.
Zarzana, Christopher A., E-mail: christopher.zarzana@inl.gov, 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]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid. United States. doi:10.1007/S13361-018-2006-Y.
Zarzana, Christopher A., E-mail: christopher.zarzana@inl.gov, Groenewold, Gary S., Benson, Michael T., Delmore, James E., Tsuda, Tetsuya, and Hagiwara, Rika. Mon . "Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid". United States. doi:10.1007/S13361-018-2006-Y.
@article{osti_22776838,
title = {Production of Gas-Phase Uranium Fluoroanions Via Solubilization of Uranium Oxides in the [1-Ethyl-3-Methylimidazolium]{sup +}[F(HF){sub 2.3}]{sup −} Ionic Liquid},
author = {Zarzana, Christopher A., E-mail: christopher.zarzana@inl.gov 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 UO{sub 2} is dissolved in neat N-ethyl,N′-methylimidazolium fluorohydrogenate ionic liquid [EMIm{sup +}][F(HF){sub 2.3}{sup −}], yielding a blue-green solution. The solution was diluted with acetonitrile and then analyzed by electrospray ionization mass spectrometry. UF{sub 6}{sup −} (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, UF{sub 6}{sup −} was the base peak, and it was accompanied by a less intense UF{sub 5}{sup −} that most likely was formed by elimination of a fluorine radical from UF{sub 6}{sup −}. Formation of UF{sub 6}{sup −} required dissolution of UO{sub 2} followed by or concurrent with oxidation of uranium from the + 4 to the + 5 state and finally formation of the fluorouranate. Dissolution of UO{sub 3} produced a bright yellow solution indicative of a U(VI) species; however, electrospray ionization did not produce abundant U-containing ions. The abundant UF{sub 6}{sup −} 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},
issn = {1044-0305},
number = 10,
volume = 29,
place = {United States},
year = {2018},
month = {10}
}