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Publisher Summary The nitrogen fluorides were completely unknown until 1928, when the trifluoride was prepared by electrolysis of molten acid ammonium fluoride, NH4F.HF. Since then three other binary compounds of these two elements have been isolated—namely, difluorodiazene (N2F2), tetrafluorohydrazine (N2F4), and fluorine azide (N3F). This chapter describes the chemistry of these four binary fluorides, together with that of the related compounds—difluoroamine (HNF2), chloro- and bromodifluoroamine (CINF2, BrNF2), and trifluoroamine oxide (NF3O). The chapter discusses the original preparation of the trifluoride. The interest in nitrogen fluoride has increased significantly over the past several years because of its potential applications as a high-energy oxidizer for HF–DF chemical lasers, where it can replace elemental fluorine in the reaction with hydrogen. Two independent groups were responsible for the original discovery of tetrafluoroammonium salts, both basing the synthesis on the reaction of NF3 with fluorine in the presence of a strong Lewis acid, which acts as a fluoride ion acceptor. Metathetical reactions have been used to prepare several new tetrafluoroammonium salts from the hexafluoroantimonate NF4SbF6 that is readily produced in the thermal reaction between NF3, F2, and SbF5 at an elevated temperature. |
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