Chlorine trifluoride reaction with

Chlorine monofluoride oxide, 18 328-330 force field of, 18 329, 330 infrared spectrum of, 18 328, 329 stretching force constants for, 18 330 synthesis of, 18 328 Chlorine nitrate fluorination of, 18 332 preparation of, 5 54 Chlorine oxides, 46 109-110, 158 fluorination of, 18 348 Chlorine oxyfluorides, 18 319-389, see also specific compounds adduct formation, 18 327, 328 amphoteric nature of, 18 327, 328 bond lengths, 18 326 bond strengths, 18 323-327 geometry of, 18 320-323 ligand distribution, 18 323 reactivity of, 18 327, 328 stretching force constants, 18 324-327 Chlorine pentafluoride oxide, 18 345, 346 Chlorine trifluoride, reaction with difluoramine, 33 157... 

Chlorine Trifluoride. Reaction with acetic acid is very violent and sometimes explosive.7... 

Violent exothermic reaction can occur when concentrated sulfuric acid is mixed with acrylonitrile, picrates, bromine penta-fiuoride (Mellor 1956), and chlorine trifluoride. Reactions with caustic alkalies, amines, alcohols, aldehydes, epoxides, vinyl and ally compounds, cellulose, and sugar are vigorously exothermic. 

Chlorine trifluoride is produced by a continuous gas-phase reaction of fluorine with chlorine. The manufacturing of chlorine trifluoride is somewhat complicated due to the formation of chlorine monofluoride. To eliminate the formation of chlorine monofluoride in chlorine trifluoride, reaction temperature is kept at 290°C and the ratio of fluorine to chlorine is maintained slightly more than 3 1 to promote a conversion of C1F to C1F3. Excess Cl2 will produce C1F while excess F2 will convert C1F to CIF3, as shown below ... 

Boron trifluoride forms addition compounds that incorporate an sp hybridized boron into a tetravalent structure. Salts of BF4 are readily formed with BF3 and a suitable fluoride donor. Halogen fluorides such as chlorine trifluoride react with BF3 to generate interhalogen cations such as [C1F2]+[BF4]. Some further examples are shown in equations (43) and (44). In an organic application, the Schiemann reaction provides an entry into fluorinated aromatics by thermal decomposition of a diazonimn tetrafluoroborate (equation 45). 

SAFETY PROFILE Poison by intravenous route. Moderately toxic by ingestion and intraperitoneal routes. Human teratogenic effects by ingestion developmental abnormalities of the endocrine system. Experimental teratogenic and reproductive effects. Mutation data reported. Explosive reaction with charcoal + ozone, trifluoroacetyl hypofluorite, fluorine perchlorate. Violent reaction or ignition on contact with diazonium salts, diisopropyl peroxydicarbonate, bromine pentafluoride, chlorine trifluoride. Incompatible with oxidants, BrFs, FCIO, metallic salts, calomel. When heated to decomposition it emits very toxic fumes of K20 and I . See also IODIDES. 

HYDROXYNITROBENZENE (88-75-5) Combustible solid (flash point 215°F/102°C). Dust or powders form explosive mixture with air. A strong oxidizer. Thermally unstable burns even in absence of air, causing fast rise in pressure closed containers may explode. Violent reaction with reducing agents. Reacts with combustible, organic, and other easily ox-idizable materials. Forms shock-sensitive explosive mixtures with chlorine trifluoride. Incompatible with strong acids, caustics, aliphatic amines, amides, diethyl amine, potassium hydroxide. 

The halogen fluorides are binary compounds of bromine, chlorine, and iodine with fluorine. Of the eight known compounds, only bromine trifluoride, chlorine trifluoride, and iodine pentafluoride have been of commercial importance. Properties and appHcations have been reviewed (1 7) as have the reactions with organic compounds (8). Reviews covering the methods of preparation, properties, and analytical chemistry of the halogen fluorides are also available (9). 

The halogen fluorides are best prepared by the reaction of fluorine with the corresponding halogen. These compounds are powerful oxidising agents chlorine trifluoride approaches the reactivity of fluorine. In descending order of reactivity the halogen fluorides are chlorine pentafluoride [13637-63-3] 1 5 chlorine trifluoride [7790-91-2] 3 bromine pentafluoride [7789-30-2], BrF iodine heptafluoride [16921 -96-3], chlorine... 

The use of CIF and BrF as ionizing solvents has been studied (102,103). At 100°C and elevated pressures, significant yields of KCIF [19195-69-8] CsClF [15321-04-7], RbClF [15321-10-5], I-CBrF [32312-224], RbBrF [32312-224], and CsBrF [26222-924]obtained. Chlorine trifluoride showed no reaction with lithium fluoride or sodium fluoride. 

Treatment of coal with chlorine or bromine results in addition and substitution reactions. At temperatures up to 600°C chlorinolysis produces carbon tetrachloride, phosgene, and thionyl chloride (73). Treatment with fluorine or chlorine trifluoride at atmospheric pressure and 300°C can produce large yields of Hquid products. 

This last reaction is typical of many in which F3CIO can act as a Lewis base by fluoride ion donation to acceptors such as MF5 (M = P, As, Sb, Bi, V, Nb, Ta, Pt, U), M0F4O, Sip4, BF3, etc. These products are all white, stable, crystalline solids (except the canary yellow PtFe ) and contain the [F2CIO] cation (see Fig. 17.26h) which is isostructural with the isoelectronic F2SO. Chlorine trifluoride oxide can also act as a Lewis acid (fluoride ion acceptor) and is therefore to be considered as amphoteric (p. 225). For example KF, RbF and CsF yield M [F4C10] as white solids whose stabilities increase with increasing size of M+. Vibration spectroscopy establishes the C4 structure of the anion (Fig. 17.29g). 

Chlorine trifluoride will dissolve in carbon tetrachloride at low temperatures without reaction. Such solutions are dangerous, being capable of detonation. If it is used as a solvent for fluorination with the trifluoride, it is therefore important to prevent build-up of high concentrations of the latter. 

Interaction is violent and may be explosive, even with ice, oxygen being evolved [1]. Part of the water dropped into a flask of the gas was expelled by the violent reaction ensuing [2], An analytical procedure, involving absorption of chlorine trifluoride into 10% sodium hydroxide solution from the open capillary neck of a quartz ampoule to avoid explosion, was described [3], Inadvertent collection of chlorine trifluoride and ice in a cryogenic trap led to a small but violent explosion when the trap began to warm up overnight [4],... 

When the metallic additive to the intermediate 374 was zinc dihalide (or another Lewis acid, such as aluminum trichloride, iron trichloride or boron trifluoride), a conjugate addition to electrophilic olefins affords 381 . In the case of the lithium-zinc transmetallation, a palladium-catalyzed Negishi cross-coupling reaction with aryl bromides or iodides allowed the preparation of arylated componnds 384 ° in 26-77% yield. In addition, a Sn2 allylation of the mentioned zinc intermediates with reagents of type R CH=CHCH(R )X (X = chlorine, bromine) gave the corresponding compounds 385 in 52-68% yield. ... 

Reaction with iodine forms iodine monochloride, ICl which combines with excess SbCls to form adducts, SbCR 2IC1 and SbCls 31 Cl similarly reaction with chlorine trifluoride, CIF3 gives antimony dichlorotrifluoride, SbCbFs. 

Heating with chlorine, or passing the gas into the molten trichloride yields antimony pentachloride, SbCls. Reaction with HF produces trifluoride, SbF3. 

When heated in air at 800°C AS4S4 vapors begin to dissociate to AS2S2 which then ignites to form arsenic oxides. Ignition in chlorine produces arsenic chloride. Reaction with fluorine forms arsenic trifluoride. It is stable in water and also in the air at ambient temperatures. It does not react with hot concentrated HCl but is decomposed by nitric acid. It forms thioarsenite ion, AsS3 and elemental arsenic when warmed with caustic soda solution. Similar reaction occurs with sodium sulfide. 

Reactions with fluorine and chlorine give arsenic trifluoride AsFs and arsenic trichloride AsCls, respectively. 

Fluorine also reacts with other halogens, forming interhalogen compounds. While with bromine and iodine it reacts vigorously at ordinary temperatures, with chlorine the reaction occurs at 200°C. Such interhalogen products with these halogens include iodine heptafluoride, bromine trifluoride, bromine pentafluoride, and chlorine trifluoride. Metalloid elements, such as arsenic, silicon, selenium, and boron also inflame in a stream of fluorine, forming fluorides. 

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