Chlorine trifluoride

Chlorine trifluoride, CIF3. M.p. — 76°C, b.p. 12°C, T-shaped, a powerful fluorinating agent. 

Lead Ammonium nitrate, chlorine trifluoride, hydrogen peroxide, sodium azide and carbide, zirconium, oxidants... 

Molybdenum trioxide Chlorine trifluoride, interhalogens, metals... 

Fluorine was first produced commercially ca 50 years after its discovery. In the intervening period, fluorine chemistry was restricted to the development of various types of electrolytic cells on a laboratory scale. In World War 11, the demand for uranium hexafluoride [7783-81-5] UF, in the United States and United Kingdom, and chlorine trifluoride [7790-91 -2J, CIF, in Germany, led to the development of commercial fluorine-generating cells. The main use of fluorine in the 1990s is in the production of UF for the nuclear power industry (see Nuclearreactors). However, its use in the preparation of some specialty products and in the surface treatment of polymers is growing. 

Fluorine reacts with the halogens and antimony to produce several compounds of commercial importance antimony pentafluoride [7783-70-2J, bromine trifluoride [7787-71 chlorine trifluoride [7790-91 -2J, and iodine pentafluoride [7783-66-6J. Chlorine trifluoride is used in the processing of UF (see Uraniumand uranium compounds). Bromine trifluoride is used in chemical cutting by the oil well industry (see Petroleum). Antimony and iodine pentafluorides are used as selective fluorinating agents to produce fluorochemical intermediates (see Fluorine compounds, inorganic). 

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... 

An equiHbrium exists between chlorine trifluoride, chlorine monofluoride, and fluorine gas (38). The equiHbrium constant may be expressed as... 

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. 

Chlorine Trifluoride. Chlorine trifluoride is produced commercially by the continuous gas-phase reaction of fluorine and chlorine ia a nickel reactor at ca 290°C. The ratio of fluorine to chlorine is maintained slightly in excess of 3 1 to promote conversion of the chlorine monofluoride to chlorine trifluoride. Sufficient time ia the reactor must be provided to maintain high conversions to chlorine trifluoride. Temperature control is also critical because the equiHbrium shift of chlorine trifluoride to chlorine monofluoride and fluorine is significant at elevated temperatures. 

U.S. chlorine trifluoride production is several metric tons per year. Most of the product is used in nuclear fuel processing. A large production plant for chlorine trifluoride was operated in Germany during World War II with a reported capacity of 5 t/d (106,107). As of 1993, Air Products and Chemicals, Inc. was the only U.S. producer. The 1992 price was ca 100/kg. 

Chlorine Trifluoride HandlingManual, AD266,121, U.S. Department of Commerce, OTS, Washiagton, D.C., 1961. 

R. L. Earrar, Safe Handling of Chlorine Trifluoride, report K-1416, U.C.C. Nuclear Company, Oak Ridge, Term., 1960. 

K [14881-07-3], Rb [72151 -96-3], and Cs [72138-72-8]), are prepared by reaction of elemental fluorine, chlorine trifluoride, or xenon difluoride and a mixture of nickel fluoride and alkaH metal fluorides or other metal haHdes (16,17). If the fluorination is carried out using mixed fluorides, a lower temperature can be used, yields are quantitative, and the final products are of high purity. Bis(tetrafluoroammonium) hexafluoronickelate [6310540-8], (NE 2N iF6> prepared from Cs2NiF3 and NE SbE by a metathesis in anhydrous HE, is also known (18). 

Safety. Magnesium oxide (fume) has a permissible exposure limit (PEL) (134) (8 hours, TWA), of 10 mg/m total dust and 5 mg/m respirable fraction. Tumorigenic data (intravenous in hamsters) show a TD q of 480 mg/kg after 30 weeks of intermittent dosing (135), and toxicity effects data show a TC q of 400 mg/m for inhalation in humans (136). Magnesium oxide is compatible with most chemicals exceptions are strong acids, bromine pentafluoride, chlorine trifluoride, interhalogens, strong oxidizers, and phosphorous pentachloride. 

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. 

Interest has continued with these materials because of their non-inflammable nature (they will not bum, even in pure oxygen), their excellent chemical resistance, including that of nitrogen tetroxide and chlorine trifluoride, a low Tg of -51°C and an extremely low solubility parameter of 10.6MPa. ... 

Bromine trifluoride and pentafluoride Chlorine trifluoride Iodine monochloride... 

Chlorinated camphene Chlorinated diphenyl oxide Chlorine Chlorine dioxide Chlorine trifluoride Chloroacetaldehyde... 

Chlorine Chemistry Comicil (CCC), 270 Chlorine dioxide, 38 Chlorine trifluoride, 38 Chlomiephos, 38 Chlomiequat chloride, 38 Chloroacetaldhyde, 38 Chloroacetic acid, 38 2-Chloroacetophenone, 38 Chloroacetyl chloride, 38 Chloroanihnes, 39 Chlorobenzene, 39... 

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