Xenon tetrafluoride

{{chembox

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 470633478

| Name = Xenon tetrafluoride

| ImageFile = Xenon tetrafluoride.png

| ImageName = {{chem|XeF|4}} crystals. 1962.

| ImageFileL1 = Xenon-tetrafluoride-3D-balls.png

| ImageFileR1 = Xenon-tetrafluoride-3D-vdW.png

| IUPACName = Xenon tetrafluoride

| OtherNames =

|Section1={{Chembox Identifiers

| SMILES = F[Xe](F)(F)F

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| ChemSpiderID = 109927

| InChI = 1/F4Xe/c1-5(2,3)4

| InChIKey = RPSSQXXJRBEGEE-UHFFFAOYAW

| StdInChI_Ref = {{stdinchicite|correct|chemspider}}

| StdInChI = 1S/F4Xe/c1-5(2,3)4

| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

| StdInChIKey = RPSSQXXJRBEGEE-UHFFFAOYSA-N

| CASNo_Ref = {{cascite|correct|CAS}}

| CASNo = 13709-61-0

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = O825AI8P4W

| RTECS =

| PubChem = 123324

}}

|Section2={{Chembox Properties

| Formula = {{chem|XeF|4}}

| MolarMass = 207.2836 g mol⁻¹

| Appearance = White solid

| Density = 4.040 g cm⁻³, solid

| Solubility = Reacts

| MeltingPtC = 117

| MeltingPt_notes = sublimes{{cite book | title = Inorganic Chemistry | first1 = Arnold F. | last1 = Holleman | first2 = Egon | last2 = Wiberg | editor-first = Nils | editor-last = Wiberg | translator-first = Mary | translator-last = Eagleson | translator2-first = William | translator2-last = Brewer | publisher = Academic Press | year = 2001 | isbn = 0-12-352651-5 | page = 394 }}

| BoilingPt =

| pKa =

| pKb =

| Viscosity =

}}

|Section3={{Chembox Structure

| MolShape = square planar

| CrystalStruct =

| Coordination = D_4h

| Dipole = 0 D

}}

|Section4={{Chembox Thermochemistry

| DeltaHf = −251 kJ·mol⁻¹{{cite book| author = Zumdahl, Steven S.|title =Chemical Principles|edition =6th| publisher = Houghton Mifflin Company| year = 2009| isbn = 978-0-618-94690-7|page=A23}}

| Entropy = 146 J·mol⁻¹·K⁻¹

}}

|Section7={{Chembox Hazards

| ExternalMSDS =

| MainHazards =

| FlashPt =

| HPhrases =

| PPhrases =

| GHS_ref =

}}

|Section8={{Chembox Related

| OtherAnions =

| OtherCations =

| OtherFunction =

| OtherFunction_label =

| OtherCompounds =

}}

Xenon tetrafluoride is a chemical compound with chemical formula {{chem|XeF|4}}. It was the first discovered binary compound of a noble gas.{{cite book|last=Zumdahl|title=Chemistry|isbn=978-0-618-52844-8|page=243|year=2007|publisher=Houghton Mifflin|location=Boston}} It is produced by the chemical reaction of xenon with fluorine:{{cite journal

| journal = J. Am. Chem. Soc.

| volume = 84

| issue = 18

| pages = 3593

| year = 1962

| doi = 10.1021/ja00877a042 }}{{cite journal |journal= Science

| year = 1962

| volume = 138

| issue = 3537

| pages = 136–138

| doi = 10.1126/science.138.3537.136

| title = Fluorine Compounds of Xenon and Radon

| first1= C. L. |last1=Chernick| first2 = H. H. |last2=Claassen

| first3 = P. R. |last3=Fields| first4 = H. H. |last4=Hyman

| first5 = J. G. |last5=Malm| first6 = W. M. |last6=Manning

| first7 = M. S. |last7=Matheson| first8 = L. A. |last8=Quarterman

| first9 = F. |last9=Schreiner| first10 = H. H. |last10=Selig

| first11 = I. |last11=Sheft| first12 = S. |last12=Siegel

| first13 = E. N. |last13=Sloth| first14 = L. |last14=Stein

| first15 = M. H. |last15=Studier| first16 = J. L. |last16=Weeks

| first17 = M. H. |last17=Zirin

| pmid = 17818399|bibcode = 1962Sci...138..136C | s2cid = 10330125

}}

: Xe + 2 {{chem|F|2}} → {{chem|XeF|4}}

This reaction is exothermic, releasing an energy of 251 kJ/mol.

Xenon tetrafluoride is a colorless crystalline solid that sublimes at 117 °C. Its structure was determined by both NMR spectroscopy and X-ray crystallography in 1963.{{cite journal

| journal = Science

| year = 1963

| volume = 140

| issue = 3563

| pages = 178

| doi = 10.1126/science.140.3563.178

| title = Xenon Tetrafluoride: Fluorine-19 High-Resolution Magnetic Resonance Spectrum

}}{{cite journal

| journal = Science

| year = 1963

| volume = 139

| issue = 3550

| pages = 106–107

| doi = 10.1126/science.139.3550.106

| title = Xenon Tetrafluoride: Crystal Structure

|first1=James A. |last1=Ibers |first2=Walter C. |last2=Hamilton

| pmid = 17798707|bibcode = 1963Sci...139..106I | s2cid = 42119788

}} The structure is square planar, as has been confirmed by neutron diffraction studies.{{cite journal

| journal = Science

| volume = 139

| issue = 3560

| pages = 1208–1209

| title = Xenon Tetrafluoride Molecule and Its Thermal Motion: A Neutron Diffraction Study

| last1 = Burns |first1=John H.

| last2 = Agron |first2=P. A.

| last3 = Levy |first3=Henri A

| doi = 10.1126/science.139.3560.1208

| pmid = 17757912

| year = 1963

| bibcode = 1963Sci...139.1208B | s2cid = 35858682

}} According to VSEPR theory, in addition to four fluoride ligands, the xenon center has two lone pairs of electrons. These lone pairs are mutually trans.

Synthesis

The original synthesis of xenon tetrafluoride occurred through direct 1:5-molar-ratio combination of the elements in a nickel (Monel) vessel at 400 °C. The nickel does not catalyze the reaction,{{cn|date=January 2025}} but rather protects the container surfaces against fluoride corrosion. Controlling the process against impurities is difficult, as xenon difluoride ({{chem|XeF|2}}), tetrafluoride, and hexafluoride ({{chem|XeF|6}}) are all in chemical equilibrium, the difluoride favored at low temperatures and little fluorine and the hexafluoride favored at high temperatures and excess fluorine.{{cite journal | last1=Haner | first1=Jamie | last2=Schrobilgen | first2=Gary J. | title=The Chemistry of Xenon(IV) | journal=Chem. Rev. | volume=115 | issue=2 | date=2015 | pages=1255–1295 | issn=0009-2665 | doi=10.1021/cr500427p

| pmid=25559700 }}{{cite book

| title = Standard Potentials in Aqueous Solution

| first1 = Allen J. |last1=Bard

| first2 = Roger |last2=Parsons

| first3 = Joseph |last3=Jordan

| author4= International Union of Pure and Applied Chemistry

| publisher = CRC Press

| year = 1985

| isbn = 0-8247-7291-1

| pages = [https://archive.org/details/standardpotentia0000unse/page/767 767–768]

| url = https://archive.org/details/standardpotentia0000unse/page/767

}} Fractional sublimation (xenon tetrafluoride is particularly involatile) or other equilibria generally allow purification of the product mixture.

The elements combine more selectively when γ- or UV-irradiated in a nickel container or dissolved in anhydrous hydrogen fluoride with catalytic oxygen. That reaction is believed selective because dioxygen difluoride at standard conditions is too weak an oxidant to generate xenon(VI) species.

Alternatively, fluoroxenonium perfluorometallate salts pyrolyze to XeF₄.

Reactions

Xenon tetrafluoride hydrolyzes at low temperatures to form elemental xenon, oxygen, hydrofluoric acid, and aqueous xenon trioxide:{{Cite journal| author1 = Williamson | first2 = C. W.| title = Xenon Tetrafluoride: Reaction with Aqueous Solutions | journal = Science | volume = 139 | issue = 3559 | pages = 1046–1047 | date=Mar 1963 | issn = 0036-8075 | pmid = 17812981| last2 = Koch | doi = 10.1126/science.139.3559.1046|bibcode = 1963Sci...139.1046W | s2cid = 33320384}}

: $\rm \ 6XeF_4 + 12H_2O \rightarrow 2XeO_3 + 4Xe\uparrow + 3O_2\uparrow + 24HF$

It is used as a precursor for synthesis of all tetravalent Xe compounds. Reaction with tetramethylammonium fluoride gives tetramethylammonium pentafluoroxenate, which contains the pentagonal {{chem|XeF|5|-}} anion. The {{chem|XeF|5|-}} anion is also formed by reaction with cesium fluoride:{{cite book | title = Elements of the p Block |volume=9 |series=Molecular World | first1= Charlie |last1=Harding | first2= David Arthur |last2=Johnson | first3= Rob |last3=Janes | publisher = Royal Society of Chemistry | year = 2002 | isbn = 0-85404-690-9 | page = 93}}

:CsF + {{chem|XeF|4}} → {{chem|CsXeF|5}}

Reaction with bismuth pentafluoride ({{chem|BiF|5}}) forms the {{chem|XeF|3|+}} cation:{{cite book

| title = Organobismuth chemistry

| first1= Hitomi |last1=Suzuki

| first2= Yoshihiro |last2=Matano

| publisher = Elsevier

| year = 2001

| isbn = 0-444-20528-4

| page = 8

}}

: {{chem|BiF|5}} + {{chem|XeF|4}} → XeF₃BiF₆

The {{chem|XeF|3|+}} cation in the salt XeF₃Sb₂F₁₁ has been characterized by NMR spectroscopy.{{Cite journal| first1 = R. J.| first2= B. |last2=Landa| first3 = G. J. |last3=Schrobilgen | title = Trifluoroxenon(IV) µ-fluoro-bispentafluoroantimonate(V): the {{chem|XeF|3|+}} cation| journal = Journal of the Chemical Society D: Chemical Communications| issue = 23| last1 = Gillespie | pages = 1543–1544 | year = 1971 | doi = 10.1039/C29710001543}}

At 400 °C, {{chem|XeF|4}} reacts with xenon to form {{chem|link=Xenon difluoride|XeF|2}}:

:XeF₄ + Xe → 2 XeF₂

The reaction of xenon tetrafluoride with platinum yields platinum tetrafluoride and xenon:

:XeF₄ + Pt → PtF₄ + Xe

Applications

Xenon tetrafluoride has few applications. It has been shown to degrade silicone rubber for analyzing trace metal impurities in the rubber. {{chem|XeF|4}} reacts with the silicone to form simple gaseous products, leaving a residue of metal impurities.{{Cite journal| last1 = Rigin | first1 = V. | first2 = N. K. | last2 = Skvortsov | first3 = V. V. | last3 = Rigin | title = Xenon tetrafluoride as a decomposition agent for silicone rubber for isolation and atomic emission spectrometric determination of trace metals| journal = Analytica Chimica Acta | volume = 340| issue = 1–3| pages = 1–3 | date=March 1997 | doi = 10.1016/S0003-2670(96)00563-6| bibcode = 1997AcAC..340....1R }}

References

External links

[http://webbook.nist.gov/cgi/cbook.cgi?ID=C13709610 WebBook page for XeF₄]

Category:Fluorides

Category:Nonmetal halides

Category:Xenon(IV) compounds