INORGANIC HALOGEN OXIDIZERS
Abstract
Ultraviolet activated fluorinations of chlorine oxyfluorides at low temperatures to produce Florox were continued. The involvement of elemental Cl2 and O2 in the Florox forming process was deduced and was verified experimentally by the preparation of Florox from Cl2, F2, and O2. The chlorofluoro chloronium (III) cation, Cl2F(+), a new oxidizing species, has been prepared in the form of its AsF6(-) and BF4(-) salts. The white crystalline Cl2F AsF6 complex is stable at -78 C and is completely dissociated in the gas phase at 25 C. Low- temperature infrared measurements on both salts prove the ionic nature of the solids and indicate that Cl2F(+) has a bent structure with chlorine as the central atom. The Cl2F(+) cation is the first example of a catenated polyhalogen cation. The utility of ClF as a chlorofluorinating agent was demonstrated in the preparation of some new covalent hypochlorites, R(f)OCl. These syntheses are catalyzed by alkali metal fluorides but may also be affected by reaction of preformed complexes. High-purity bromine nitrate has been prepared by the reaction of Br2, Cl2, and ClNO3 at -30 to 0 C. Solid BrNO3 is pale yellow and melts to a golden colored liquid at -31 C. The vapor pressure- temperature equation for -25 to 10 C is log p(mm) = 9.6905 - 2254.5/T. Fluorination of BrNO3 has shown that FNO2 and BrF5 are the principal products (95+ percent yield).
Document Details
- Document Type
- Technical Report
- Publication Date
- Dec 30, 1967
- Accession Number
- AD0386352
Entities
People
- C. J. Schack
- D. Pilipovich
- K. O. Christe
- R. D. Wilson