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Xenon hexafluoride

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Xenon hexafluoride
Structural formula
Structural formula
Space-filling model
Space-filling model
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/F6Xe/c1-7(2,3,4,5)6Key: ARUUTJKURHLAMI-UHFFFAOYSA-N
  • InChI=1/F6Xe/c1-7(2,3,4,5)6Key: ARUUTJKURHLAMI-UHFFFAOYAF
SMILES
  • F(F)(F)(F)(F)F
Properties
Chemical formula XeF6
Molar mass 245.28 g mol
Density 3.56 g cm
Melting point 49.25 °C (120.65 °F; 322.40 K)
Boiling point 75.6 °C (168.1 °F; 348.8 K)
Solubility in water reacts
Thermochemistry
Std enthalpy of
formation
fH298)
−294 kJ·mol
Related compounds
Related compounds Krypton hexafluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒verify (what is  ?) Infobox references
Chemical compound

Xenon hexafluoride is a noble gas compound with the formula XeF6. It is one of the three binary fluorides of xenon that have been studied experimentally, the other two being XeF2 and XeF4. All known are exergonic and stable at normal temperatures. XeF6 is the strongest fluorinating agent of the series. It is a colorless solid that readily sublimes into intensely yellow vapors.

Preparation

Xenon hexafluoride can be prepared by heating of XeF2 at about 300 °C under 6 MPa (60 atmospheres) of fluorine. With NiF
2
as catalyst, however, this reaction can proceed at 120 °C even in xenon-fluorine molar ratios as low as 1:5.

Structure

The structure of XeF6 required several years to establish in contrast to the cases of XeF
2 and XeF
4. In the gas phase the compound is monomeric. VSEPR theory predicts that due to the presence of six fluoride ligands and one lone pair of electrons the structure lacks perfect octahedral symmetry, and indeed electron diffraction combined with high-level calculations indicate that the compound's point group is C3v. It is a fluxional molecule. Oh is only insignificantly higher, indicating that the minimum on the energy surface is very shallow.

Xe and F NMR spectroscopy indicates that in solution the compound assumes a tetrameric structure: four equivalent xenon atoms are arranged in a tetrahedron surrounded by a fluctuating array of 24 fluorine atoms that interchange positions in a "cogwheel mechanism".

Six polymorphs of XeF
6 are known. including one that contains XeF
5 ions with bridging F
ions.

Reactions

Hydrolysis

Xenon hexafluoride hydrolyzes, ultimately affording xenon trioxide:

XeF6 + H2O → XeOF4 + 2 HF
XeOF4 + H2O → XeO2F2 + 2 HF
XeO2F2 + H2O → XeO3 + 2 HF
XeF6 + 3 H2O → XeO3 + 6 HF

XeF6 is a Lewis acid, binding one and two fluoride anions:

XeF6 + F → XeF
7
XeF
7 + F → XeF
8

Octafluoroxenates

Salts of the octafluoroxenate(VI) anion (XeF
8) are very stable, decomposing only above 400 °C. This anion has been shown to have square antiprismatic geometry, based on single-crystal X-ray counter analysis of its nitrosonium salt, (NO)
2XeF
8
. The sodium and potassium salts are formed directly from sodium fluoride and potassium fluoride:

2 NaF + XeF
6 → Na
2XeF
8
2 KF + XeF
6 → K
2XeF
8

These are thermally less stable than the caesium and rubidium salts, which are synthesized by first forming the heptafluoroxenate salts:

CsF + XeF
6CsXeF
7
RbF + XeF
6 → RbXeF
7

which are then pyrolysed at 50 °C and 20 °C, respectively, to form the yellow octafluoroxenate salts:

2 CsXeF
7 → Cs
2XeF
8 + XeF
6
2 RbXeF
7 → Rb
2XeF
8 + XeF
6

These salts are hydrolysed by water, yielding various products containing xenon and oxygen.

The two other binary fluorides of xenon do not form such stable adducts with fluoride.

With fluoride acceptors

XeF
6 reacts with strong fluoride acceptors such as RuF
5 and BrF
3·AuF
3 to form the XeF
5 cation:

XeF
6 + RuF
5 → XeF
5RuF
6
XeF
6 + BrF
3·AuF
3 → XeF
5AuF
4 + BrF
3

References

  1. Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A23. ISBN 978-0-618-94690-7.
  2. Melita Tramšek; Boris Žemva (December 5, 2006). "Synthesis, Properties and Chemistry of Xenon(II) Fluoride" (PDF). Acta Chim. Slov. 53 (2): 105–116. doi:10.1002/chin.200721209. Archived from the original (PDF) on May 12, 2013. Retrieved July 10, 2009.
  3. Chernic, C. L.; Malm, J. G. (2007). "Xenon Hexafluoride". Inorganic Syntheses. Vol. VIII. pp. 258–260. doi:10.1002/9780470132395.ch68. ISBN 9780470132395.
  4. Seppelt, Konrad (June 1979). "Recent Developments in the Chemistry of Some Electronegative Elements". Accounts of Chemical Research. 12 (6): 211–216. doi:10.1021/ar50138a004.
  5. Hoyer, S.; Emmler, K.; Seppelt, T. (October 2006). "The structure of xenon hexafluoride in the solid state". Journal of Fluorine Chemistry. 127 (10): 1415–1422. Bibcode:2006JFluC.127.1415H. doi:10.1016/j.jfluchem.2006.04.014. ISSN 0022-1139.
  6. ^ James E. House (2008). Inorganic Chemistry. Academic Press. p. 569. ISBN 978-0-12-356786-4.
  7. Appelman, E. H.; J. G. Malm (June 1964). "Hydrolysis of Xenon Hexafluoride and the Aqueous Solution Chemistry of Xenon". Journal of the American Chemical Society. 86 (11): 2141–2148. doi:10.1021/ja01065a009.
  8. ^ Holleman, A. F.; Wiberg, E. (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN 0-12-352651-5.
  9. ^ Riedel, Erwin; Janiak, Christoph (2007). Anorganische Chemie (7th ed.). Walter de Gruyter. p. 393. ISBN 978-3-11-018903-2.
  10. ^ Chandra, Sulekh (2004). Comprehensive Inorganic Chemistry. New Age International. p. 308. ISBN 81-224-1512-1.
  11. Peterson, W.; Holloway, H.; Coyle, A.; Williams, M. (September 1971). "Antiprismatic Coordination about Xenon: the Structure of Nitrosonium Octafluoroxenate(VI)". Science. 173 (4003): 1238–1239. Bibcode:1971Sci...173.1238P. doi:10.1126/science.173.4003.1238. ISSN 0036-8075. PMID 17775218. S2CID 22384146.
  12. "Xenon". Encyclopædia Britannica. Encyclopædia Britannica Inc. 1995.
  13. Cotton (2007). Advanced Inorganic Chemistry (6th ed.). Wiley-India. p. 591. ISBN 978-81-265-1338-3.

External links

Binary hexafluorides
Known binary hexafluorides
Chalcogen binary hexafluorides
Noble gas binary hexafluorides
Transition metal binary hexafluorides
Actinide binary hexafluorides
Predicted binary hexafluorides
Noble gas binary hexafluorides
Transition metal binary hexafluorides
Actinide binary hexafluorides
Xenon compounds
Xenon(0)
Xenon(I)
Xenon(II)
Organoxenon(II) compounds
  • XeC6F5F
  • XeC6F5C2F3
  • XeC6F5CF3
  • Xe(C6F5)2
  • XeC6F5C6H2F3
  • XeC6F5CN
  • Xe(CF3)2
  • Xenon(IV)
    Organoxenon(IV) compounds
  • XeF2C6F5BF4
  • Xenon(VI)
    Xenon(VIII)
    Category:Xenon compounds
    Noble gas compounds
    Helium compounds
    Neon compounds
    Argon compounds
    Krypton compounds
    Xenon compounds
    Xe(0)
    Xe(I)
    Xe(II)
    Xe(IV)
    Xe(VI)
    Xe(VIII)
    Radon compounds
    Rn(II)
    Rn(IV)
    Rn(VI)
    Oganesson compounds
    (predicted)
    Og(0)
    • Og2
    • OgH
    Og(II)
    • OgF2
    • OgCl2
    • OgO
    Og(IV)
    • OgF4
    • OgO2
    • OgTs4
    Og(VI)
    • OgF6
    Hypothetical compound
    Fluorine compounds
    Salts and covalent derivatives of the fluoride ion
    HF ?HeF2
    LiF BeF2 BF
    BF3
    B2F4
    +BO3
    CF4
    CxFy
    +CO3
    NF3
    FN3
    N2F2
    NF
    N2F4
    NF2
    ?NF5
    OF2
    O2F2
    OF
    O3F2
    O4F2
    ?OF4
    F2 Ne
    NaF MgF2 AlF
    AlF3
    SiF4 P2F4
    PF3
    PF5
    S2F2
    SF2
    S2F4
    SF3
    SF4
    S2F10
    SF6
    +SO4
    ClF
    ClF3
    ClF5
    ?ArF2
    ?ArF4
    KF CaF
    CaF2
    ScF3 TiF2
    TiF3
    TiF4
    VF2
    VF3
    VF4
    VF5
    CrF2
    CrF3
    CrF4
    CrF5
    ?CrF6
    MnF2
    MnF3
    MnF4
    ?MnF5
    FeF2
    FeF3
    FeF4
    CoF2
    CoF3
    CoF4
    NiF2
    NiF3
    NiF4
    CuF
    CuF2
    ?CuF3
    ZnF2 GaF2
    GaF3
    GeF2
    GeF4
    AsF3
    AsF5
    Se2F2
    SeF4
    SeF6
    +SeO3
    BrF
    BrF3
    BrF5
    KrF2
    ?KrF4
    ?KrF6
    RbF SrF
    SrF2
    YF3 ZrF2
    ZrF3
    ZrF4
    NbF4
    NbF5
    MoF4
    MoF5
    MoF6
    TcF4
    TcF
    5

    TcF6
    RuF3
    RuF
    4

    RuF5
    RuF6
    RhF3
    RhF4
    RhF5
    RhF6
    PdF2
    Pd
    PdF4
    ?PdF6
    Ag2F
    AgF
    AgF2
    AgF3
    CdF2 InF
    InF3
    SnF2
    SnF4
    SbF3
    SbF5
    TeF4
    ?Te2F10
    TeF6
    +TeO3
    IF
    IF3
    IF5
    IF7
    +IO3
    XeF2
    XeF4
    XeF6
    ?XeF8
    CsF BaF2   LuF3 HfF4 TaF5 WF4
    WF5
    WF6
    ReF4
    ReF5
    ReF6
    ReF7
    OsF4
    OsF5
    OsF6
    ?OsF
    7

    ?OsF
    8
    IrF2
    IrF3
    IrF4
    IrF5
    IrF6
    PtF2
    Pt
    PtF4
    PtF5
    PtF6
    AuF
    AuF3
    Au2F10
    ?AuF6
    AuF5•F2
    Hg2F2
    HgF2
    ?HgF4
    TlF
    TlF3
    PbF2
    PbF4
    BiF3
    BiF5
    ?PoF2
    PoF4
    PoF6
    AtF
    ?AtF3
    ?AtF5
    RnF2
    ?RnF
    4

    ?RnF
    6
    FrF RaF2   LrF3 Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
    LaF3 CeF3
    CeF4
    PrF3
    PrF4
    NdF2
    NdF3
    NdF4
    PmF3 SmF
    SmF2
    SmF3
    EuF2
    EuF3
    GdF3 TbF3
    TbF4
    DyF2
    DyF3
    DyF4
    HoF3 ErF3 TmF2
    TmF3
    YbF2
    YbF3
    AcF3 ThF3
    ThF4
    PaF4
    PaF5
    UF3
    UF4
    UF5
    UF6
    NpF3
    NpF4
    NpF5
    NpF6
    PuF3
    PuF4
    PuF5
    PuF6
    AmF2
    AmF3
    AmF4
    ?AmF6
    CmF3
    CmF4
     ?CmF6
    BkF3
    BkF
    4
    CfF3
    CfF4
    EsF3
    EsF4
    ?EsF6
    Fm Md No
    PF−6, AsF−6, SbF−6 compounds
    AlF2−5, AlF3−6 compounds
    chlorides, bromides, iodides
    and pseudohalogenides
    SiF2−6, GeF2−6 compounds
    Oxyfluorides
    Organofluorides
    with transition metal,
    lanthanide, actinide, ammonium
    nitric acids
    bifluorides
    thionyl, phosphoryl,
    and iodosyl
    Chemical formulas
    Categories: