Oxides fluorides

The oxide fluoride SOFj (SOCI2 plus NaF) and (NSF)4 are known. 

Te2Fio, and oxide fluorides, e.g. TeFjOTeFs, are also formed during the fluor-ination of tellurium oxides, tellurium, organic derivatives Tellurium forms organic derivatives in the +2 and +4 slates. The +2 compounds are similar to divalent sulphur derivatives although less stable. Tellurium(IV) derivatives are comparatively unstable. 

Hexafluorozirconic acid [12021 -95-3]], H2ZrP, is formed by dissolving freshly prepared oxide, fluoride, or carbonate of zirconium in aqueous HP. This acid is produced commercially in a concentration range of 10 to 47%. The acid can be stored at ambient temperatures in polyethylene or Teflon containers... 

A. Glassner, The Thermochemical Properties of the Oxides, Fluorides, and Chlorides to 2500 K, Argonne National Laboratory Report ANL-5750, U.S. Government Printing Office, Washington, D.C., 1957. 

Antimony(Ill) fluoride may be prepared by treating antimony trioxide or trichloride with hydrofluoric acid. Pure SbF is then obtained by carefully evaporating all of the water from the cmde product, which is subsequently sublimed. SbF does not hydrolyze as readily as do the other antimony ttihahdes. When heated in open air at 100°C, a crystalline soHd quickly forms of composition Sb302(0H)2F3, which, upon further heating, is transformed into antimony oxide fluoride [11083-22-0] SbOF. This compound may also be prepared by heating 1 1 mixtures of Sb203 and SbF. There are three known crystalline modifications. 

Perhaps the most reactive compound of the group is BiFs- It reacts extremely vigorously with H2O to form O3, OF2 and a voluminous brown precipitate which is probably a hydrated bismuth(V) oxide fluoride. At room temperature BiFs reacts vigorously with iodine or sulfur above 50° it converts paraffin oil to fluorocarbons at 150° it fluorinates UF4 to UF and at 180° it converts Brs to BrFs and BrFs, and CI2 to CIF. 

Of the 6 possible oxide fluorides of Cl, 5 have been characterized they range in stability from the thermally unstable FCl "0 to the chemically rather inert perchloryl fluoride FCl "03. The others are FC1 02, F3C1 0 and F3C1 "02-... 

The structures of the chlorine oxide fluorides are summarized in Fig. 17.26, together with those of related cationic and anionic species formed from the neutral molecules by gain or loss or F . The first conclusive evidence for free FCIO in the gas phase came in 1972 during a study of the hydrolysis of CIF3 with substoichiometric amounts of H2O in a flow reactor ... 

Figure 17.26 Structures of chlorine oxide fluorides and related cations and anions.

The other Cl oxide fluoride FCIO2 (1942) can be made by the low-temperature fluorination of CIO2 but is best prepared by the reaction ... 

Despite several attempts at synthesis, there is little or no evidence for the existence of FBrO, p3Br02 or FsBrO. The bromine oxide fluorides are somewhat less thermally stable than their chlorine analogues and somewhat more reactive chemically. The structures are as already described for the chlorine oxide fluorides (Fig. 17.26). 

Of the oxide fluorides FIO3 has been prepared by the action of F2/liquid HF on HIO4. It is a white, crystalline solid, stable in glass but decomposing with loss of oxygen on being heated ... 

As opposed to the oxides, fluoride compounds are characterized by the formation of mostly ionic bonds. This peculiarity is related to fluorine s high electronegativity. 

On the other hand, fluorine s high electronegativity and its ability to form mostly ionic chemical bonds, provide materials with several useful properties. First, compared to oxides, fluoride compounds have a wide forbidden zone and as a result, have low electroconductivity. In addition, fluorides are characterized by a high transparency in a wide optical range that allows for their application in the manufacturing of electro-optical devices that operate in the UV region [42,43]. 

Preparations and reactions of inorganic main-group oxide fluorides. J. H. Holloway and D. Lay-cock, Adv. Inorg. Chem. Radiochem., 1983,27,157-195 (342). 

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