Hydrogen fluoride temperature

Properties. Antimony pentafluoride [7783-70-2], SbF, is a colorless, hygroscopic, very viscous liquid that fumes ia air. Its viscosity at 20°C is 460 mPa-s(=cP) which is very close to the value for glycerol. The polymerization of high purity SbF at ambient temperature can be prevented by addition of 1% anhydrous hydrogen fluoride, which can be removed by distillation prior to the use of SbF. The pure product melts at 7°C (11), boils at 142.7°C,... 

Barium fluoride [7782-32-8] Bap2, is a white crystal or powder. Under the microscope crystals may be clear and colorless. Reported melting points vary from 1290 (1) to 1355°C (2), including values of 1301 (3) and 1353°C (4). Differences may result from impurities, reaction with containers, or inaccurate temperature measurements. The heat of fusion is 28 kj/mol (6.8 kcal/mol) (5), the boiling point 2260°C (6), and the density 4.9 g/cm. The solubiUty in water is about 1.6 g/L at 25°C and 5.6 g/100 g (7) in anhydrous hydrogen fluoride. Several preparations for barium fluoride have been reported (8—10). 

Aqueous hydrogen fluoride of greater than 60% maybe handled in steel up to 38°C, provided velocities are kept low (<0.3 m/s) and iron pickup in the process stream is acceptable. Otherwise, mbber or polytetrafluoroethylene (PTFE) linings are used. For all appHcations, PTFE or PTEE-lined materials are suitable up to the maximum use temperature of 200°C. PTEE is also the material of choice for gasketing. AHoy 20 or Monel is typically used for valve and pump appHcations. Materials unacceptable for use in HE include cast iron, type 400 stainless steel, hardened steels, titanium, glass, and siHcate ceramics. 

Properties. Lithium fluoride [7789-24-4] LiF, is a white nonhygroscopic crystaUine material that does not form a hydrate. The properties of lithium fluoride are similar to the aLkaline-earth fluorides. The solubility in water is quite low and chemical reactivity is low, similar to that of calcium fluoride and magnesium fluoride. Several chemical and physical properties of lithium fluoride are listed in Table 1. At high temperatures, lithium fluoride hydroly2es to hydrogen fluoride when heated in the presence of moisture. A bifluoride [12159-92-17, LiF HF, which forms on reaction of LiF with hydrofluoric acid, is unstable to loss of HF in the solid form. 

Titanium trifluoride is prepared by dissolving titanium metal in hydrofluoric acid (1,2) or by passing anhydrous hydrogen fluoride over titanium trihydrate at 700°C or over heated titanium powder (3). Reaction of titanium trichloride and anhydrous hydrogen fluoride at room temperature yields a cmde product that can be purified by sublimation under high vacuum at 930—950°C. 

The stmcture of the ketones produced from unsymmetrical internal perfluoroepoxides has been reported (5). The epoxide ring may also be opened by strong protic acids such as fluorosulfonic acid or hydrogen fluoride at elevated temperatures (23—25). The ring opening of HFPO by sulfur trioxide at 150°C has been interpreted as an example of an electrophilic reaction (26) (eq. 3). 

Fluoroaromatics are produced on an industrial scale by diazotization of substituted anilines with sodium nitrite or other nitrosating agents in anhydrous hydrogen fluoride, followed by in situ decomposition (fluorodediazoniation) of the aryldiazonium fluoride (21). The decomposition temperature depends on the stabiHty of the diazonium fluoride (22,23). A significant development was the addition of pyridine (24), tertiary amines (25), and ammonium fluoride (or bifluoride) (26,27) to permit higher decomposition temperatures (>50° C) under atmospheric pressure with minimum hydrogen fluoride loss. 

Because PTFE resins decompose slowly, they may be heated to a high temperature. The toxicity of the pyrolysis products warrants care where exposure of personnel is likely to occur (120). Above 230°C decomposition rates become measurable (0.0001% per hour). Small amounts of toxic perfiuoroisobutylene have been isolated at 400°C and above free fluorine has never been found. Above 690°C the decomposition products bum but do not support combustion if the heat is removed. Combustion products consist primarily of carbon dioxide, carbon tetrafluoride, and small quantities of toxic and corrosive hydrogen fluoride. The PTFE resins are nonflammable and do not propagate flame. 

The self-ignition temperature of PVF film is 390°C. The limiting oxygen iadex (LOI) for PVF is 22.6% (98), which can be raised to 30% ia antimony oxide-modified film (99). Hydrogen fluoride and a mixture of aromatic and aUphatic hydrocarbons (100) are generated from the thermal degradation of PVF. Toxicity studies, ie, survival and time to iacapacitation, of polymers, ceUulosics (101,102), and airplane iaterior materials (103) expose... 

PVDE is not hazardous under typical processing conditions. If the polymer is accidentaky exposed to temperatures exceeding 350°C, thermal decomposition occurs with evolution of toxic hydrogen fluoride (HE). 

Sulfonation of aromatic hydrocarbons with sulfuric acid is cataly2ed by hydrogen fluoride or, at lower temperatures, by boron trifluoride (144). The products obtained are more uniform and considerably less sulfuric acid is needed, probably because BF forms complexes with the water formed ia the reaction, and thus prevents dilution of the sulfuric acid. 

Olefins are carbonylated in concentrated sulfuric acid at moderate temperatures (0—40°C) and low pressures with formic acid, which serves as the source of carbon monoxide (Koch-Haaf reaction) (187). Liquid hydrogen fluoride, preferably in the presence of boron trifluoride, is an equally good catalyst and solvent system (see Carboxylic acids). 

Propylene, butylenes, or amylenes are combiaed with isobutane ia the presence of an acid catalyst, eg, sulfuric acid or hydrofluoric acid, at low temperatures (1—40°C) and pressures, 102—1035 kPa (1—10 atm). Sulfuric acid or hydrogen fluoride are the catalysts used commercially ia refineries. The acid is pumped through the reactor and forms an emulsion with reactants, and the emulsion is maintained at 50% acid. The rate of deactivation varies with the feed and isobutane charge rate. Butene feeds cause less acid consumption than the propylene feeds. 

Fused basic salts and basic oxides react with vitreous siUca at elevated temperatures. Reaction with alkaline-earth oxides takes place at approximately 900°C. Hahdes tend to dissolve vitreous siUca at high temperatures fluorides are the most reactive (95). Dry halogen gases do not react with vitreous siUca below 300°C. Hydrogen fluoride, however, readily attacks vitreous siUca. 

Titanium Tetrafluoride. Titanium tetrafluoride [7783-63-3] is a white hygroscopic soHd, density 2798 kg/m, that sublimes at 284°C. The properties suggest that it is a fluorine-bridged polymer in which the titanium is six-coordinate. The preferred method of preparation is by direct fluorination of titanium sponge at 200°C in a flow system. At this temperature, the product is sufficiently volatile that it does not protect the unreacted sponge and the reaction proceeds to completion. The reaction of titanium tetrachloride with cooled, anhydrous, Hquid hydrogen fluoride may be used if pure hydrogen fluoride is available. 

Tungsten tetrafluofide [13766-47-7] WF, is a nonvolatile, hygroscopic, reddish-brown soHd. It has been prepared in low yields by the reduction of the hexafluoride with phosphoms trifluofide in the presence of Hquid anhydrous hydrogen fluoride at room temperature (6). 

When treated with aluminum bromide at 100°C, carbon tetrachloride is converted to carbon tetrabromide [558-13-4], reaction with calcium iodide, Cal2, at 75°C gives carbon tetraiodide [507-25-5]. With concentrated hydroiodic acid at 130°C, iodoform [75-47-8], CHI, is produced. Carbon tetrachloride is unaffected by gaseous fluorine at ordinary temperatures. Replacement of its chlorine by fluorine is brought about by reaction with hydrogen fluoride at a... 

---