Xenon nitrate: Difference between revisions
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'''Xenon nitrate''' is a transient compound made by reacting [[xenon difluoride]] with [[anhydrous]] nitric acid. Although xenon dinitrate (Xe(NO<sub>3</sub>)<sub>2</sub>) has not been isolated and characterised a related mononitrate, known as |
'''Xenon nitrate''' is a transient compound made by reacting [[xenon difluoride]] with [[anhydrous]] nitric acid. Although xenon dinitrate (Xe(NO<sub>3</sub>)<sub>2</sub>) has not been isolated and characterised, a related mononitrate, known as [[xenon fluoride nitrate]], has also been made and is more well-studied. |
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==Production== |
==Production== |
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:Xe(NO<sub>3</sub>)<sub>2</sub> → Xe + O<sub>2</sub>NOONO<sub>2</sub> (an unstable nitrogen [[main group peroxides|peroxide]]) |
:Xe(NO<sub>3</sub>)<sub>2</sub> → Xe + O<sub>2</sub>NOONO<sub>2</sub> (an unstable nitrogen [[main group peroxides|peroxide]]) |
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Although xenon nitrate is not well-characterized, the mixed nitrate [[Xenon fluoride nitrate|FXeONO<sub>2</sub>]] definitely exists.<ref name="MoranM2007"/> |
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Although xenon nitrate is not well-characterized, the mixed nitrate FXeONO<sub>2</sub> definitely exists,<ref name="MoranM2007"/> referred to as fluoroxenonium nitrate<ref name="Atta-ur-Rahman2006">{{cite book|last=Atta-ur-Rahman|first=|title=Advances in Organic Synthesis: Modern Organofluorine Chemistry-Synthetic Aspects|url=https://books.google.com/books?id=vkcLOFEo9xIC&pg=PA78|accessdate=5 October 2014|date=2006-01-01|publisher=Bentham Science Publishers|isbn=9781608051984|page=78}}</ref> or xenon fluoride nitrate.<ref name="Moran2010">{{cite journal|last=Moran|first=Matthew D.|author2=David S. Brock |author3=Hélène P. A. Mercier |author4=Gary J. Schrobilgen |year=2010|title=Xe3OF3+, a Precursor to a Noble-Gas Nitrate; Syntheses and Structural Characterizations of FXeONO2, XeF2·HNO3, and XeF2·N2O4|journal=Journal of the American Chemical Society|volume=132|issue=39|pages=13823–13839|issn=0002-7863|doi=10.1021/ja105618w|pmid=20843046}}</ref> This compound is formed via the reaction:<ref name="MoranM2007"/> |
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:[FXeOXeFXeF][AsF<sub>6</sub>] + 2NO<sub>2</sub>F → FXeONO<sub>2</sub> + NO<sub>2</sub>AsF<sub>6</sub>. |
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Purification of FXeONO<sub>2</sub> can take place by dissolving in SO<sub>2</sub>ClF, which leaves the nitronium arsenic hexafluoride behind as a solid.<ref name="MoranM2007"/> |
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An alternate low yield method to make FXeONO<sub>2</sub> is to dissolve [[xenon difluoride]] in liquid [[dinitrogen tetroxide]] at 0 °C.<ref name="MoranM2007"/> |
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:XeF<sub>2</sub> + NO<sup>+</sup> + NO<sub>3</sub><sup>−</sup> → FXeONO<sub>2</sub> + NOF |
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This method is inefficient as not much nitrate ion exists in the liquid and the xenon nitrate decomposes.<ref name="MoranM2007"/> |
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Another method claimed to make this substance is:<ref name="MoranM2007"/> |
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:XeF<sub>2</sub> + HNO<sub>3</sub> → FXeNO<sub>3</sub> + HF |
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==Properties== |
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FXeONO<sub>2</sub> is a white crystalline material.<ref name="MoranM2007"/> The [[space group]] of the crystals is P2<sub>1</sub>/c, which is [[monoclinic]]. The unit cell contains four molecules with a total volume of 386.6 Å<sup>3</sup>. The unit cell dimensions are a = 4.6663 Å, b = 8.799 Å c = 9.415 Å, with non-perpendicular angle β = 90.325°.<ref name="MoranM2007"/> With a molecular weight of 212.3, the crystal has density 3.648. (These measurements at -173 °C.)<ref name="MoranM2007"/> |
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[[File:FXeNO3 bond length.jpg|thumb|Bond length of FXeNO<sub>3</sub>]] |
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[[File:FXeNO3 bond angle.jpg|thumb| Bond angle of FXeNO<sub>3</sub>]] |
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The bond lengths in the molecule are 1.992 Å for Xe–O, 126 Å, 1.36 Å for O–NO<sub>2</sub>, 1.199 for N–O<sub>cis</sub> and 1.224 Å for N–O<sub>trans</sub>.<ref name="MoranM2007"/> The bond angles are 177.6° for F–Xe–O, 114.7° for Xe-O-N, 114.5° for (Xe)O–N–O<sub>cis</sub>, 118.4° for (Xe)O–N–O<sub>trans</sub> and 127.1° for O<sub>cis</sub>–N–O<sub>trans</sub>.<ref name="MoranM2007"/> The bond lengths and angles on the xenon atom are similar to that in FXeOSO<sub>2</sub>F and FXeOTeF<sub>5</sub>, indicating a polar oxygen bond. The Xe–O–N angle is larger than those in halogen nitrates, which indicates a lower bond density for the Xe–O bond.The N–O<sub>cis</sub> bond length is longer than the N–O<sub>trans</sub> bond length, opposite to other halogen nitrates.<ref name="MoranM2007"/> |
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FXeONO<sub>2</sub> is not particularly stable and slowly breaks down at -78 °C, yielding XeF<sub>2</sub>·N<sub>2</sub>O<sub>4</sub>. This happens on a timescale of several days.<ref name="MoranM2007"/> At 0 °C, FXeONO<sub>2</sub> has a half life of seven hours, decomposing to XeF<sub>2</sub>.<ref name="MoranM2007"/> |
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==References== |
==References== |
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Revision as of 11:09, 3 August 2020
Xenon nitrate is a transient compound made by reacting xenon difluoride with anhydrous nitric acid. Although xenon dinitrate (Xe(NO3)2) has not been isolated and characterised, a related mononitrate, known as xenon fluoride nitrate, has also been made and is more well-studied.
Production
Attempted production has used the reaction:[1][2][3]
- XeF2 + 2 HNO3 → Xe(NO3)2 + 2 HF
This reaction makes a red-brown solid. However, it decomposes spontaneously at 23 °C, turning blue temporarily while doing so:[2]
- Xe(NO3)2 → Xe + O2NOONO2 (an unstable nitrogen peroxide)
Although xenon nitrate is not well-characterized, the mixed nitrate FXeONO2 definitely exists.[1]
References
- ^ a b Moran, Matthew D. (2007). Synthesis and Structural Characterization of new Xenon(II) Compounds and the Use of a Xenon(II) Cation as an Oxidant for the Preparation of Halogenated Hydrocarbons (PDF). McMaster University. pp. 42, 99–145. Retrieved 4 Oct 2014.
- ^ a b Eisenberg, Max; Darryl D. DesMarteau (1970). "The reaction of xenon difluoride with some strong oxy-acids". Inorganic and Nuclear Chemistry Letters. 6 (1): 29–34. doi:10.1016/0020-1650(70)80279-3. ISSN 0020-1650.
- ^ Zefirov, N. S; Gakh, A. A.; Zhdankin, V. V.; Stang, P. J. (1991). "Interaction of Fluoroxenonium Triflate, Fluorosulfate, and Νitrate with Alkenes. Stereochemical Evidence for the Electrophilic Noble Gas Cation Addition to the Carbon-Carbon Double Bond". J. Org. Chem. 56: 1416–1418. doi:10.1021/jo00004a015.