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Perchloryl fluoride

December 08, 2023

Not to be confused with fluorine perchlorate.

Perchloryl fluoride[6] is a reactive gas with the chemical formula ClO
3F. It has a characteristic sweet odor[7] that resembles gasoline and kerosene. It is toxic and is a powerful oxidizing and fluorinating agent. It is the acid fluoride of perchloric acid.

Perchloryl fluoride
Perchloryl fluoride
Names
IUPAC name
Perchloryl fluoride
Other names
Chlorine oxyfluoride, Perchlorofluoride, Chlorine fluorine oxide, Trioxychlorofluoride, Perchloric acid fluoride
Identifiers
  • 7616-94-6 Y
3D model (JSmol)
  • Interactive image
ChemSpider
  • 22680 Y
ECHA InfoCard 100.028.660
EC Number
  • 231-526-0
  • 24258
RTECS number
  • SD1925000
UNII
  • 73NC8XM516 Y
  • DTXSID60894169
  • InChI=1S/ClFO3/c2-1(3,4)5 Y
    Key: XHFXMNZYIKFCPN-UHFFFAOYSA-N Y
  • InChI=1/ClFO3/c2-1(3,4)5
    Key: XHFXMNZYIKFCPN-UHFFFAOYAO
  • FCl(=O)(=O)=O
Properties
ClO3F
Molar mass 102.4496 g/mol
Appearance Colorless gas
Odor sweet odor
Density 1.434 g/cm3
Melting point −147.8 °C (−234.0 °F; 125.3 K)
Boiling point −46.7 °C (−52.1 °F; 226.5 K)
Critical point (T, P) 95.2 °C (203.4 °F; 368.3 K), 53 standard atmospheres (5,400 kPa; 780 psi)[1]
0.06 g/100 ml (20 °C), slow hydrolysis
Vapor pressure 10.5 atm (20°C)[2]
Viscosity 3.91 x 10−3 Pa.s (@ melting point)
Structure
Tetrahedral[3]: 373 
Thermochemistry
278.97 J/(mol*K)
-21.42 kJ/mol [4]: 380 
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 oxidizing, toxic. Non-corrosive.
NFPA 704 (fire diamond)
Health 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
3
0
3
OX
3 ppm
Lethal dose or concentration (LD, LC):
385 ppm (rat, 4 hr)
451 ppm (dog, 4 hr)[5]
2000 ppm (rat, 40 min)
451 ppm (dog, 4 hr)[5]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 3 ppm (13.5 mg/m3)[2]
REL (Recommended)
 TWA 3 ppm (14 mg/m3) ST 6 ppm (28 mg/m3)[2]
IDLH (Immediate danger)
 100 ppm[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)

In spite of its small enthalpy of formation (ΔHf° = −5.2 kcal/mol), it is kinetically stable, decomposing only at 400 °C.[3]: 380  It is quite reactive towards reducing agents and anions, however, with the chlorine atom acting as an electrophile.[3]: 382  It reacts explosively with reducing agents such as metal amides, metals, hydrides, etc.[7] Its hydrolysis in water occurs very slowly, unlike that of chloryl fluoride.

Synthesis and chemistry edit

Perchloryl fluoride is produced primarily by the fluorination of perchlorates. Antimony pentafluoride is a commonly used fluorinating agent:[3]: 372–373 

ClO−
4 + 3 HF + 2 SbF
5 → ClO
3F + H
3O+
 + 2 SbF−
6

ClO
3F reacts with alcohols to produce alkyl perchlorates, which are extremely shock-sensitive explosives.[8] In the presence of a Lewis acid, it can be used for introducing the –ClO
3 group into aromatic rings via electrophilic aromatic substitution.[9]

Applications edit

Perchloryl fluoride is used in organic chemistry as a mild fluorinating agent.[3]: 383  It was the first industrially relevant electrophilic fluorinating agent, used since the 1960s for producing fluorinated steroids.[8] In the presence of aluminum trichloride, it has also been used as an electrophilic perchlorylation reagent for aromatic compounds.[10]

Perchloryl fluoride was investigated as a high performance liquid rocket fuel oxidizer.[11] 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.[12]

It can also be used in flame photometry as an excitation source.[13]

Safety edit

Perchloryl fluoride is toxic, with a TLV of 3 ppm.[14] It is a strong lung- and eye-irritant capable of producing burns on exposed skin. Its IDLH level is 100 ppm.[15] Symptoms of exposure include dizziness, headaches, syncope, and cyanosis. Exposure to toxic levels causes severe respiratory tract inflammation and pulmonary edema.[11]

See also edit

References edit

  1. ^ Budavari, Susan, ed. (1989). "7297. Perchloryl Fluoride". The Merck Index — Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, New Jersey: Merck. p. 1231. IA147021.
  2. ^ a b c d NIOSH Pocket Guide to Chemical Hazards. "#0490". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ a b c d e Harry Julius Emeléus; A. G. Sharpe (1976). Advances in inorganic chemistry and radiochemistry, Volume 18. Academic Press. ISBN 0-12-023618-4.
  4. ^ "Perchloryl fluoride". NIST Chemistry WebBook, SRD 69. 2018.
  5. ^ a b "Perchloryl fluoride". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  6. ^ Chemical Science and Technology Laboratory. "Perchloryl fluoride". National Institute of Standards and Technology. Retrieved 2009-11-28.
  7. ^ a b Jared Ledgard (2007). The Preparatory Manual of Explosives (3rd ed.). Lulu.com. p. 77. ISBN 978-0-615-14290-6.
  8. ^ a b Peer Kirsch (2004). Modern fluoroorganic chemistry: synthesis, reactivity, applications. Wiley-VCH. p. 74. ISBN 3-527-30691-9.
  9. ^ Peter Bernard David De la Mare (1976). Electrophilic halogenation: reaction pathways involving attack by electrophilic halogens on unsaturated compounds. CUP Archive. p. 63. ISBN 0-521-29014-7.
  10. ^ Inman, C. E.; Oesterling, R. E.; Tyczkowski, E. A. (1958-10-01). "Reactions of Perchloryl Fluoride with Organic Compounds. I. Perchlorylation of Aromatic Compounds1". Journal of the American Chemical Society. 80 (19): 5286–5288. doi:10.1021/ja01552a069. ISSN 0002-7863.
  11. ^ a b John Burke Sullivan; Gary R. Krieger (2001). Clinical environmental health and toxic exposures (2nd ed.). Lippincott Williams & Wilkins. p. 969. ISBN 0-683-08027-X.
  12. ^ Clark, John D. (1972). Ignition! An informal history of liquid rocket propellants (PDF). Rutgers University Press. ISBN 0-8135-0725-1. OCLC 281664.[page needed]
  13. ^ Schmauch, G. E.; Serfass, E. J. (1958). "The Use of Perchloryl Fluoride in Flame Photometry". Applied Spectroscopy. 12 (3): 98–102. Bibcode:1958ApSpe..12...98S. doi:10.1366/000370258774615483. S2CID 95615583.
  14. ^ National Institute for Occupational Safety and Health. "NIOSH Pocket Guide to Chemical Hazards". Centers for Disease Control and Prevention. Retrieved 2013-10-31.
  15. ^ National Institute for Occupational Safety and Health. "Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs)". Centers for Disease Control and Prevention. Retrieved 2013-10-31.

December 08, 2023
perchloryl, fluoride, confused, with, fluorine, perchlorate, reactive, with, chemical, formula, clo3, characteristic, sweet, odor, that, resembles, gasoline, kerosene, toxic, powerful, oxidizing, fluorinating, agent, acid, fluoride, perchloric, acid, namesiupa. Not to be confused with fluorine perchlorate Perchloryl fluoride 6 is a reactive gas with the chemical formula ClO3 F It has a characteristic sweet odor 7 that resembles gasoline and kerosene It is toxic and is a powerful oxidizing and fluorinating agent It is the acid fluoride of perchloric acid Perchloryl fluoride Perchloryl fluorideNamesIUPAC name Perchloryl fluorideOther names Chlorine oxyfluoride Perchlorofluoride Chlorine fluorine oxide Trioxychlorofluoride Perchloric acid fluorideIdentifiersCAS Number 7616 94 6 Y3D model JSmol Interactive imageChemSpider 22680 YECHA InfoCard 100 028 660EC Number 231 526 0PubChem CID 24258RTECS number SD1925000UNII 73NC8XM516 YCompTox Dashboard EPA DTXSID60894169InChI InChI 1S ClFO3 c2 1 3 4 5 YKey XHFXMNZYIKFCPN UHFFFAOYSA N YInChI 1 ClFO3 c2 1 3 4 5Key XHFXMNZYIKFCPN UHFFFAOYAOSMILES FCl O O OPropertiesChemical formula ClO3FMolar mass 102 4496 g molAppearance Colorless gasOdor sweet odorDensity 1 434 g cm3Melting point 147 8 C 234 0 F 125 3 K Boiling point 46 7 C 52 1 F 226 5 K Critical point T P 95 2 C 203 4 F 368 3 K 53 standard atmospheres 5 400 kPa 780 psi 1 Solubility in water 0 06 g 100 ml 20 C slow hydrolysisVapor pressure 10 5 atm 20 C 2 Viscosity 3 91 x 10 3 Pa s melting point StructureMolecular shape Tetrahedral 3 373 ThermochemistryStd molarentropy S 298 278 97 J mol K Std enthalpy offormation DfH 298 21 42 kJ mol 4 380 HazardsOccupational safety and health OHS OSH Main hazards oxidizing toxic Non corrosive NFPA 704 fire diamond 303OXThreshold limit value TLV 3 ppmLethal dose or concentration LD LC LC50 median concentration 385 ppm rat 4 hr 451 ppm dog 4 hr 5 LCLo lowest published 2000 ppm rat 40 min 451 ppm dog 4 hr 5 NIOSH US health exposure limits PEL Permissible TWA 3 ppm 13 5 mg m3 2 REL Recommended TWA 3 ppm 14 mg m3 ST 6 ppm 28 mg m3 2 IDLH Immediate danger 100 ppm 2 Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references In spite of its small enthalpy of formation DHf 5 2 kcal mol it is kinetically stable decomposing only at 400 C 3 380 It is quite reactive towards reducing agents and anions however with the chlorine atom acting as an electrophile 3 382 It reacts explosively with reducing agents such as metal amides metals hydrides etc 7 Its hydrolysis in water occurs very slowly unlike that of chloryl fluoride Contents 1 Synthesis and chemistry 2 Applications 3 Safety 4 See also 5 ReferencesSynthesis and chemistry editPerchloryl fluoride is produced primarily by the fluorination of perchlorates Antimony pentafluoride is a commonly used fluorinating agent 3 372 373 ClO 4 3 HF 2 SbF5 ClO3 F H3 O 2 SbF 6ClO3 F reacts with alcohols to produce alkyl perchlorates which are extremely shock sensitive explosives 8 In the presence of a Lewis acid it can be used for introducing the ClO3 group into aromatic rings via electrophilic aromatic substitution 9 Applications editPerchloryl fluoride is used in organic chemistry as a mild fluorinating agent 3 383 It was the first industrially relevant electrophilic fluorinating agent used since the 1960s for producing fluorinated steroids 8 In the presence of aluminum trichloride it has also been used as an electrophilic perchlorylation reagent for aromatic compounds 10 Perchloryl fluoride was investigated as a high performance liquid rocket fuel oxidizer 11 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 12 It can also be used in flame photometry as an excitation source 13 Safety editPerchloryl fluoride is toxic with a TLV of 3 ppm 14 It is a strong lung and eye irritant capable of producing burns on exposed skin Its IDLH level is 100 ppm 15 Symptoms of exposure include dizziness headaches syncope and cyanosis Exposure to toxic levels causes severe respiratory tract inflammation and pulmonary edema 11 See also editPeriodyl fluoride Perbromyl fluorideReferences edit Budavari Susan ed 1989 7297 Perchloryl Fluoride The Merck Index Encyclopedia of Chemicals Drugs and Biologicals Rahway New Jersey Merck p 1231 IA147021 a b c d NIOSH Pocket Guide to Chemical Hazards 0490 National Institute for Occupational Safety and Health NIOSH a b c d e Harry Julius Emeleus A G Sharpe 1976 Advances in inorganic chemistry and radiochemistry Volume 18 Academic Press ISBN 0 12 023618 4 Perchloryl fluoride NIST Chemistry WebBook SRD 69 2018 a b Perchloryl fluoride Immediately Dangerous to Life or Health Concentrations IDLH National Institute for Occupational Safety and Health NIOSH Chemical Science and Technology Laboratory Perchloryl fluoride National Institute of Standards and Technology Retrieved 2009 11 28 a b Jared Ledgard 2007 The Preparatory Manual of Explosives 3rd ed Lulu com p 77 ISBN 978 0 615 14290 6 a b Peer Kirsch 2004 Modern fluoroorganic chemistry synthesis reactivity applications Wiley VCH p 74 ISBN 3 527 30691 9 Peter Bernard David De la Mare 1976 Electrophilic halogenation reaction pathways involving attack by electrophilic halogens on unsaturated compounds CUP Archive p 63 ISBN 0 521 29014 7 Inman C E Oesterling R E Tyczkowski E A 1958 10 01 Reactions of Perchloryl Fluoride with Organic Compounds I Perchlorylation of Aromatic Compounds1 Journal of the American Chemical Society 80 19 5286 5288 doi 10 1021 ja01552a069 ISSN 0002 7863 a b John Burke Sullivan Gary R Krieger 2001 Clinical environmental health and toxic exposures 2nd ed Lippincott Williams amp Wilkins p 969 ISBN 0 683 08027 X Clark John D 1972 Ignition An informal history of liquid rocket propellants PDF Rutgers University Press ISBN 0 8135 0725 1 OCLC 281664 page needed Schmauch G E Serfass E J 1958 The Use of Perchloryl Fluoride in Flame Photometry Applied Spectroscopy 12 3 98 102 Bibcode 1958ApSpe 12 98S doi 10 1366 000370258774615483 S2CID 95615583 National Institute for Occupational Safety and Health NIOSH Pocket Guide to Chemical Hazards Centers for Disease Control and Prevention Retrieved 2013 10 31 National Institute for Occupational Safety and Health Documentation for Immediately Dangerous To Life or Health Concentrations IDLHs Centers for Disease Control and Prevention Retrieved 2013 10 31 Retrieved from https en wikipedia org w index php title Perchloryl fluoride amp oldid 1178529358, wikipedia, wiki, book, books, library,

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