Names | |||
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IUPAC name Perchloryl fluoride | |||
Other names Chlorine oxyfluoride, Perchlorofluoride, Chlorine fluorine oxide, Trioxychlorofluoride, Perchloric acid fluoride | |||
Identifiers | |||
3D model (JSmol) | |||
ChemSpider | |||
ECHA InfoCard | 100.028.660 | ||
EC Number |
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PubChem CID | |||
RTECS number |
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UNII | |||
CompTox Dashboard (EPA) | |||
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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 | |||
Std molar entropy (S⦵298) | 278.97 J/(mol*K) | ||
Std enthalpy of formation (ΔfH⦵298) | -21.42 kJ/mol [4] : 380 | ||
Hazards | |||
Occupational safety and health (OHS/OSH): | |||
Main hazards | oxidizing, toxic. Non-corrosive. | ||
NFPA 704 (fire diamond) | |||
Threshold limit value (TLV) | 3 ppm | ||
Lethal 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). |
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.
In spite of its small enthalpy of formation (ΔfH° = −5.2 kcal/mol (−22 kJ/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.
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. [8] A common fluorinator in modern syntheses is antimony pentafluoride: [3] : 372–373
Alternatively, potassium perchlorate reacts with excess fluorosulfuric acid to give potassium bisulfate and perchloryl fluoride: [8]
ClO
3F reacts with alcohols to produce alkyl perchlorates, which are extremely shock-sensitive explosives. [9] In the presence of a Lewis acid, it can be used for introducing the –ClO
3 group into aromatic rings via electrophilic aromatic substitution. [10]
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. [9] In the presence of aluminum trichloride, it has also been used as an electrophilic perchlorylation reagent for aromatic compounds. [11]
Perchloryl fluoride was investigated as a high performance liquid rocket fuel oxidizer. [12] 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. [13] It can also be used in flame photometry as an excitation source. [14]
Perchloryl fluoride is toxic, with a TLV of 3 ppm. [15] It is a strong lung- and eye-irritant capable of producing burns on exposed skin. Its IDLH level is 100 ppm. [16] Symptoms of exposure include dizziness, headaches, syncope, and cyanosis. Exposure to toxic levels causes severe respiratory tract inflammation and pulmonary edema. [12]
Bromine is a chemical element; it has symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell.
Chlorine is a chemical element; it has symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.
The halogens are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of gallium. In the modern IUPAC nomenclature, this group is known as group 17.
In chemistry, halogenation is a chemical reaction which introduces of one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.
In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.
Chlorine trifluoride is an interhalogen compound with the formula ClF3. It is a colorless, poisonous, corrosive, and extremely reactive gas that condenses to a pale-greenish yellow liquid, the form in which it is most often sold. It is famous for its extreme oxidation properties. The compound is primarily of interest in plasmaless cleaning and etching operations in the semiconductor industry, in nuclear reactor fuel processing, historically as a component in rocket fuels, and various other industrial operations owing to its corrosive nature.
Oxygen difluoride is a chemical compound with the formula OF2. As predicted by VSEPR theory, the molecule adopts a bent molecular geometry. It is a strong oxidizer and has attracted attention in rocketry for this reason. With a boiling point of −144.75 °C, OF2 is the most volatile (isolable) triatomic compound. The compound is one of many known oxygen fluorides.
Trichlorofluoromethane, also called freon-11, CFC-11, or R-11, is a chlorofluorocarbon (CFC). It is a colorless, faintly ethereal, and sweetish-smelling liquid that boils around room temperature. CFC-11 is a Class 1 ozone-depleting substance which damages Earth's protective stratospheric ozone layer. Also r11 is not flammable at ambient temperature and pressure but it can become very combustible if heated and ignited by a strong ignition source
Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentoxide:
Chlorobenzene (abbreviated PhCl) is an aryl chloride and the simplest of the chlorobenzenes, consisting of a benzene ring substituted with one chlorine atom. Its chemical formula is C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals.
Chlorine pentafluoride is an interhalogen compound with formula ClF5. This colourless gas is a strong oxidant that was once a candidate oxidizer for rockets. The molecule adopts a square pyramidal structure with C4v symmetry, as confirmed by its high-resolution 19F NMR spectrum. It was first synthesized in 1963.
Bromine pentafluoride, BrF5, is an interhalogen compound and a fluoride of bromine. It is a strong fluorinating agent.
Nitrogen trifluoride is the inorganic compound with the formula. It is a colorless, non-flammable, toxic gas with a slightly musty odor. In contrast with ammonia, it is nonbasic. It finds increasing use within the manufacturing of flat-panel displays, photovoltaics, LEDs and other microelectronics. NF
3 is a greenhouse gas, with a global warming potential (GWP) 17,200 times greater than that of CO
2 when compared over a 100-year period.
Antimony pentafluoride is the inorganic compound with the formula SbF5. This colourless, viscous liquid is a strong Lewis acid and a component of the superacid fluoroantimonic acid, formed upon mixing liquid HF with liquid SbF5 in 1:1 ratio. It is notable for its strong Lewis acidity and the ability to react with almost all known compounds.
Disulfur decafluoride is a chemical compound with the formula S2F10. It was discovered in 1934 by Denbigh and Whytlaw-Gray. Each sulfur atom of the S2F10 molecule is octahedral, and surrounded by five fluorine atoms and one sulfur atom. The two sulfur atoms are connected by a single bond. In the S2F10 molecule, the oxidation state of each sulfur atoms is +5, but their valency is 6. S2F10 is highly toxic, with toxicity four times that of phosgene.
Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X− couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.
1,2-Dichlorobenzene, or orthodichlorobenzene (ODCB), is an aryl chloride and isomer of dichlorobenzene with the formula C6H4Cl2. This colourless liquid is poorly soluble in water but miscible with most organic solvents. It is a derivative of benzene, consisting of two adjacent chlorine atoms.
Antimony trifluoride is the inorganic compound with the formula SbF3. Sometimes called Swarts' reagent, it is one of two principal fluorides of antimony, the other being SbF5. It appears as a white solid. As well as some industrial applications, it is used as a reagent in inorganic and organofluorine chemistry.
The tetrafluoroammonium cation is a positively charged polyatomic ion with chemical formula NF+
4. It is equivalent to the ammonium ion where the hydrogen atoms surrounding the central nitrogen atom have been replaced by fluorine. Tetrafluoroammonium ion is isoelectronic with tetrafluoromethane CF
4, trifluoramine oxide ONF
3 and the tetrafluoroborate BF−
4 anion.
Vanadium(V) fluoride is the inorganic compound with the chemical formula VF5. It is a colorless volatile liquid that freezes near room temperature. It is a highly reactive compound, as indicated by its ability to fluorinate organic substances.