Hydrogen fluoride, boiling

Hydrogen fluoride is at present stored in bulk and used at only the Shellhaven refinery, bat future use is envisioned. Hydrogen fluoride boils point 19° C but stored and handled as a hq lie tied gas. Its vapor is highly irritating and toxic. A cold cloud will be denser than air in the early stages when released but wall become neutral or buoyant as it warms with dispersion. This r-sessment assumes negative buoyancy... 

Hydrogen fluoride boils at 19.5°C while hydrogen chloride boils at -84°C. Which one of the following statements accounts for this difference ... 

Hydrated Cobaltous Fluoride, CoF2.2H20, is easily prepared as rose-red crystals by evaporation of a solution of the oxide or carbonate in aqueous hydrogen fluoride. Boiling water decomposes the salt., yielding an insoluble oxy-fluoride of light red colour. 

Clearly, ammonia, water, and hydrogen fluoride boil at significantly higher temperatures than methane. The N—H, O—H, and F—H bonds are far more polar than the C—H bond, owing to the high electronegativity of N, O, and F. 

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). 

Zirconium is readily attacked by acidic solutions containing fluorides. As Httle as 3 ppm flouride ion in 50% boiling sulfuric acid corrodes zirconium at 1.25 mm/yr. Solutions of ammonium hydrogen fluoride or potassium hydrogen fluoride have been used for pickling and electropolishing zirconium. Commercial pickling is conducted with nitric—hydrofluoric acid mixtures (see Metal surface treatments). 

At 225—275°C, bromination of the vapor yields bromochloromethanes CCl Br, CCl2Br2, and CClBr. Chloroform reacts with aluminum bromide to form bromoform, CHBr. Chloroform cannot be direcdy fluorinated with elementary flourine fluoroform, CHF, is produced from chloroform by reaction with hydrogen fluoride in the presence of a metallic fluoride catalyst (8). It is also a coproduct of monochlorodifluoromethane from the HF—CHCl reaction over antimony chlorofluoride. Iodine gives a characteristic purple solution in chloroform but does not react even at the boiling point. Iodoform, CHI, may be produced from chloroform by reaction with ethyl iodide in the presence of aluminum chloride however, this is not the route normally used for its preparation. 

Hydrogen bonding aeeounts for the abnormally high boiling points of, e.g., water, hydrogen fluoride, ammonia, and many organie eompounds (see later) sueh as aleohols. 

Consider first the boiling points of HI, HBr, HQ, and HF. The last, hydrogen fluoride, is far out of line, boiling at 19.9°C instead of below —95°C as would be predicted by extrapolation from the other three. There is an even larger discordancy between the boiling point of HjO and the value we would predict from the trend suggested by HjTe, HjSe, and H2S. 

FIGURE 5.8 The boiling points of most of the molecular hydrides of the p-block elements show a smooth increase with molar mass in each group. However, three compounds—ammonia, water, and hydrogen fluoride are strikingly out of line. 

A solvent that resembles water in many ways is liquid hydrogen fluoride. The molecule is polar, there is some autoionization, and it is a fairly good solvent for numerous ionic solids. Although the boiling point of liquid HF is rather low (19.5 °C), it has a liquid range that is comparable to that of water, partially as a result of extensive hydrogen bonding. One of the problems associated with the use of liquid... 

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