perchloryl fluoride
{{distinguish|fluorine perchlorate}}
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 476997852
| Name = Perchloryl fluoride
| ImageFile =
| ImageFileL1 = Perchloryl-fluoride-2D.png
| ImageSizeL1 =
| ImageNameL1 = Perchloryl fluoride
| ImageFileR1 = Perchloryl-fluoride-3D-vdW.png
| ImageSizeR1 =
| ImageName1 = Perchloryl fluoride
| IUPACName = Perchloryl fluoride
| OtherNames = {{ubl|Chlorine oxyfluoride|Perchlorofluoride|Chlorine fluorine oxide|Trioxychlorofluoride|Perchloric acid fluoride}}
| SystematicName =
| Section1 = {{Chembox Identifiers
| SMILES = FCl(=O)(=O)=O
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 22680
| InChI = 1/ClFO3/c2-1(3,4)5
| InChIKey = XHFXMNZYIKFCPN-UHFFFAOYAO
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/ClFO3/c2-1(3,4)5
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = XHFXMNZYIKFCPN-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 7616-94-6
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 73NC8XM516
| PubChem = 24258
| RTECS = SD1925000
| EINECS = 231-526-0
}}
| Section2 = {{Chembox Properties
| Formula = {{chem2|ClO3F}}
| MolarMass = 102.4496 g/mol
| Appearance = Colorless gas
| Odor = sweet odor
| Density = 1.434 g/cm3
| Solubility = 0.06 g/(100 ml) (20 °C), slow hydrolysis
| MeltingPtC = −147.8
| BoilingPtC = −46.7
| CriticalTP = {{convert|95.2|°C|°F K|1}}, {{convert|53|atm|kPa psi}}{{cite encyclopedia|title=7297. Perchloryl Fluoride|page=1231|encyclopedia=The Merck Index — Encyclopedia of Chemicals, Drugs and Biologicals|year=1989|editor-last=Budavari|editor-first=Susan|publisher=Merck|location=Rahway, New Jersey|id=IA147021}}
| Viscosity = 3.91 x 10−3 Pa·s (@ melting point)
| VaporPressure = 10.5 atm (20 °C)
}}
| Section3 = {{Chembox Structure
| MolShape = Tetrahedral{{rp|373}}
| Dipole =
}}
| Section4 = {{Chembox Thermochemistry
| DeltaHf = −21.42 kJ/mol {{cite book |url= https://webbook.nist.gov/cgi/cbook.cgi?ID=C7616946&Units=SI&Mask=1#Thermo-Gas|title=NIST Chemistry WebBook, SRD 69 |article=Perchloryl fluoride|date=2018|pages=1–1951 |last1=Chase |first1=M. W.}}{{rp|380}}
| DeltaHc =
| Entropy = 278.97 J/(mol·K)
| HeatCapacity =
}}
| Section5 =
| Section6 =
| Section7 = {{Chembox Hazards
| ExternalSDS =
| MainHazards = oxidizing, toxic. Non-corrosive.
| FlashPt =
| HPhrases =
| PPhrases =
| GHS_ref =
| NFPA-H = 3
| NFPA-F = 0
| NFPA-R = 3
| NFPA-S = OX
| TLV = 3 ppm
| PEL = TWA 3 ppm (13.5 mg/m3){{PGCH|0490}}
| LC50 = 385 ppm (rat, 4 hr)
451 ppm (dog, 4 hr){{IDLH|7616946|Perchloryl fluoride}}
| REL = TWA 3 ppm (14 mg/m3) ST 6 ppm (28 mg/m3)
| LCLo = 2000 ppm (rat, 40 min)
451 ppm (dog, 4 hr)
}}
| Section8 = {{Chembox Related
| OtherAnions =
| OtherCations =
| OtherCompounds =
}}
}}
Perchloryl fluoride{{cite web | url = http://webbook.nist.gov/cgi/cbook.cgi?ID=C7616946 | title = Perchloryl fluoride | author = Chemical Science and Technology Laboratory | publisher = National Institute of Standards and Technology | access-date = 2009-11-28}} is a reactive gas with the chemical formula {{chem2|ClO3F|auto=1}}. It has a characteristic sweet odor that resembles gasoline and kerosene. It is toxic and is a powerful oxidizing and fluorinating agent. It is the acid fluoride of perchloric acid.
In spite of its small enthalpy of formation (ΔfH° = {{convert|−5.2| kcal/mol|abbr=on}}), it is kinetically stable, decomposing only at 400 °C.{{rp|380}} It is quite reactive towards reducing agents and anions, however, with the chlorine atom acting as an electrophile.{{rp|382}} It reacts explosively with reducing agents such as metal amides, metals, hydrides, etc.{{cite book | title = The Preparatory Manual of Explosives | author = Jared Ledgard | edition = 3rd | publisher = Lulu.com | year = 2007 | isbn = 978-0-615-14290-6 | page = 77}} Its hydrolysis in water occurs very slowly, unlike that of chloryl fluoride.
Synthesis and chemistry
Perchloryl fluoride is produced primarily by the fluorination of perchlorates. The initial syntheses in the early 1950s used fluorine gas or fluorides and anodic oxidation as the fluorinating agents, but these give explosive gaseous mixtures.{{sfn|Clark|2018|p=80}} A common fluorinator in modern syntheses is antimony pentafluoride:{{rp|372–373}}
:{{chem2|ClO4- + 3 HF + 2 SbF5 → ClO3F + [H3O]+ + 2 [SbF6]-}}
Alternatively, potassium perchlorate reacts with excess fluorosulfuric acid to give potassium bisulfate and perchloryl fluoride:{{sfn|Clark|2018|p=80}}
:{{chem2|KClO4 + HSO3F → KHSO4 + FClO3}}
{{chem2|ClO3F}} reacts with alcohols to produce alkyl perchlorates, which are extremely shock-sensitive explosives. In the presence of a Lewis acid, it can be used for introducing the {{chem2|\sClO3}} group into aromatic rings via electrophilic aromatic substitution.{{cite book | title = Electrophilic halogenation: reaction pathways involving attack by electrophilic halogens on unsaturated compounds | author = Peter Bernard David De la Mare | publisher = CUP Archive | year = 1976 | isbn = 0-521-29014-7 | page = 63}}
Applications
Perchloryl fluoride is used in organic chemistry as a mild fluorinating agent.{{rp|383}} It was the first industrially relevant electrophilic fluorinating agent, used since the 1960s for producing fluorinated steroids.{{cite book | title = Modern fluoroorganic chemistry: synthesis, reactivity, applications | author = Peer Kirsch | publisher = Wiley-VCH | year = 2004 | isbn = 3-527-30691-9 | page = 74}} In the presence of aluminum trichloride, it has also been used as an electrophilic perchlorylation reagent for aromatic compounds.{{Cite journal|last1=Inman|first1=C. E.|last2=Oesterling|first2=R. E.|last3=Tyczkowski|first3=E. A.|date=1958-10-01|title=Reactions of Perchloryl Fluoride with Organic Compounds. I. Perchlorylation of Aromatic Compounds1|journal=Journal of the American Chemical Society|volume=80|issue=19|pages=5286–5288|doi=10.1021/ja01552a069|issn=0002-7863}}
Perchloryl fluoride was investigated as a high performance liquid rocket fuel oxidizer.{{cite book | title = Clinical environmental health and toxic exposures | author1 = John Burke Sullivan | author2 = Gary R. Krieger | edition = 2nd | publisher = Lippincott Williams & Wilkins | year = 2001 | isbn = 0-683-08027-X | page = 969}} In comparison with chlorine pentafluoride and bromine pentafluoride, it has significantly lower specific impulse, but does not tend to corrode tanks. It does not require cryogenic storage. Rocket fuel chemist John Drury Clark reported in his book Ignition! that perchloryl fluoride is completely miscible with all-halogen oxidizers such as chlorine trifluoride and chlorine pentafluoride, and such a mixture provides the needed oxygen to properly burn carbon-containing fuels.{{cite book |isbn = 978-0-8135-9918-2 |title = Ignition!: An Informal History of Liquid Rocket Propellants |last1 = Clark |first1 = John Drury |author-link=John Drury Clark |date = 23 May 2018 |publisher = Rutgers University Press |url=https://books.google.com/books?id=BdU4DwAAQBAJ&q=perchloryl%20fluoride |pages=302 |oclc=281664}} It can also be used in flame photometry as an excitation source.{{Cite journal | doi = 10.1366/000370258774615483 | title = The Use of Perchloryl Fluoride in Flame Photometry | year = 1958 | last1 = Schmauch | first1 = G. E. | last2 = Serfass | first2 = E. J. | journal = Applied Spectroscopy | volume = 12 | issue = 3| pages = 98–102|bibcode = 1958ApSpe..12...98S | s2cid = 95615583}}
Safety
Perchloryl fluoride is toxic, with a TLV of 3 ppm.{{cite web | url = https://www.cdc.gov/niosh/npg/npgd0490.html | title = NIOSH Pocket Guide to Chemical Hazards | author = National Institute for Occupational Safety and Health | publisher = Centers for Disease Control and Prevention | access-date = 2013-10-31}} It is a strong lung- and eye-irritant capable of producing burns on exposed skin. Its IDLH level is 100 ppm.{{cite web | url = https://www.cdc.gov/niosh/idlh/7616946.html | title = Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs) | author = National Institute for Occupational Safety and Health | publisher = Centers for Disease Control and Prevention | access-date = 2013-10-31}} Symptoms of exposure include dizziness, headaches, syncope, and cyanosis. Exposure to toxic levels causes severe respiratory tract inflammation and pulmonary edema.
See also
References
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{{Chemical agents}}
{{Chlorine compounds}}
{{DEFAULTSORT:Perchloryl Fluoride}}