Chlorine fluoride oxide radicals

Very little is known about chlorine fluoride oxide radicals. Although the formation of the FClOs" radical anion in the reaction of FCIO3 with nucleophilic agents has been postulated (286), it has not been isolated and characterized. 

Chlorine fluoride, 21 235, 236, 238, 240, 242, 244, 246, 247, 249 geometry of, 18 320-322 oxygenation of, 18 349 oxygen-containing, 21 245 Chlorine fluoride oxide radicals, 18 385, 386 Chlorine hydroxide, 5 219 Chlorine isotope, half-life determination, 2 ... 

Detailed studies of the chlorine-atom-sensitized oxidation of chloromethane, dichloromethane, 1,1,2-trichloroethane, CH2CC12, and C2C14148 have been reported. Reports on the photolysis of Freons of interest to upper-atmosphere chemistry are discussed in the last section of this Report, and laser enhancement of some halogen-containing molecular reactions is discussed in Section 11. A paper concerned with the mechanism of photodissociation of alkyl and aryl halides was discussed earlier.38 The photochemical chlorination of 1,2-dichloroethane149 and fluorination of carbonyl fluoride,150 reactions of 2 radicals,151 and the photochemical decomposition of FaO at elevated temperatures152 have been reported. 

Methane forms explosive mixtures with air the LEL and UEL values are 5.5% and 14% by volume of air, respectively. The explosion is loudest at 10% volume concentration. The combustion of methane in air forming CO2 involves chain reactions, propagated by free radicals, CH3-, HO-, H-, and O- (Meyer 1989). Being a saturated molecule, the reactivity of methane toward most substances is very low. However, under catalytic conditions, violent reactions have been reported with halogens and certain fluorides of nonmetals. This includes reactions with chlorine at room temperature over yellow mercuric oxide, bromine pentafluoride, oxygen difluoride in the presence of a spark (MeUor 1946, Suppl. 1956), and nitrogen trifluoride (Lawless and Smith 1968). 

The electronic absorption spectra of molecular O2F2 and of the radical O2F have been measured in liquid Ar and in other solvents in the region 190—600 nm/° An analysis of the data concerning the nature of the unstable violet and blue compounds that were first reported in 1962 by Streng and Grosse suggests that the colours are due to oxygen fluoride radicals, such as O2F, and not to chlorine oxide fluorides. Thus, it has now been shown that intensely coloured species are formed by O2 salts in liquid HF these species show the same characteristics as the violet and blue compounds . 

---