Hydrogen anhydrous

An acid was once defined simply as a substance which produces hydrogen ions, or protons. However, the simple proton, H , is never found under ordinary conditions, and this definition required amendment. Bronsted and, independently, Lowry, therefore redefined an acid as a susbstance able to donate protons to other molecules or ions, and a base as a substance capable of accepting such protons. If we consider hydrogen chloride, HCl, as an example, the HCl molecule is essentially covalent, and hydrogen chloride (gas or liquid) contains no protons. But anhydrous hydrogen chloride in benzene will react with anhydrous ammonia ... 

This reaction can be reversed by heating and is a convenient method of obtaining anhydrous hydrogen fluoride from an aqueous solution. 

Anhydrous hydrogen fluoride (as distinct from an aqueous solution of hydrofluoric acid) does not attack silica or glass. It reacts with metals to give fluorides, for example with heated iron the anhydrous iron(II) fluoride is formed the same product is obtained by displacement of chlorine from iron(II) chloride ... 

Anhydrous hydrogen chloride is not particularly reactive, either as a gas at ordinary temperatures, or a liquid (b.p. 188 K) and does not react with metals such as iron or zinc, nor with dry oxides. A few reactive metals such as sodium, will bum in the gas to give the chloride and hydrogen ... 

Perchloric acid (HCIO4 Ho —13.0), fluorosulfuric acid (HSO3F Ho — 15.1), and trifluoromethanesulfonic acid (CF3SO3H Ho —14.1) are considered to be superacids, as is truly anhydrous hydrogen fluoride. Complexing with Lewis acidic metal fluorides of higher valence, such as antimony, tantalum, or niobium pentafluoride, greatly enhances the acidity of all these acids. 

Ammonia, anhydrous Mercury, halogens, hypochlorites, chlorites, chlorine(I) oxide, hydrofluoric acid (anhydrous), hydrogen peroxide, chromium(VI) oxide, nitrogen dioxide, chromyl(VI) chloride, sulflnyl chloride, magnesium perchlorate, peroxodisul-fates, phosphorus pentoxide, acetaldehyde, ethylene oxide, acrolein, gold(III) chloride... 

Frequendy unique and synthetically usehil are a series of ring-opening reactions. Butyrolactone and anhydrous hydrogen haUdes give high yields of 4-halobutyric acids (164). In the presence of alcohols, esters are formed. 

Because hydrogen fluoride is extremely reactive, special materials are necessary for its handling and storage. Glass reacts with HF to produce SiF which leads to pressure buildup and potential mptures. Anhydrous hydrogen fluoride is produced and stored ia mild steel equipment. Teflon or polyethylene are frequently used for aqueous solutions. 

Manufacture. Anhydrous ammonium bifluoride containing 0.1% H2O and 93% NH4HF2 can be made by dehydrating ammonium fluoride solutions and by thermally decomposing the dry crystals (7). Commercial ammonium bifluoride, which usually contains 1% NH F, is made by gas-phase reaction of one mole of anhydrous ammonia and two moles of anhydrous hydrogen fluoride (8) the melt that forms is flaked on a cooled dmm. The cost of the material in 1992 was 1.48/kg. 

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). 

Physical Properties. Physical properties of anhydrous hydrogen fluoride are summarized in Table 1. Figure 1 shows the vapor pressure and latent heat of vaporization. The specific gravity of the Hquid decreases almost linearly from 1.1 at —40°C to 0.84 at 80°C (4). The specific heat of anhydrous HF is shown in Figure 2 and the heat of solution in Figure 3. 

Fig. 1. (---) Latent heat of vaporization (1,7) and (-) vapor pressure (1,4,7,15) of anhydrous hydrogen fluoride. To convert kPa to psi, multiply by...

Fig. 2. Specific heat of Hquid anhydrous hydrogen fluoride (5,16). To convert to cal, divide by 4.184.

Fig. 3. Heat of solution per gram of anhydrous hydrogen fluoride in water when mixed to the final concentration shown in wt % of HF (16—18).

The strong catalytic activity of anhydrous hydrogen fluoride results from the abiUty to donate a proton, as in the dimerization of isobutylene (see Butylenes) ... 

Anhydrous hydrogen fluoride is an excellent solvent for ionic fluorides (Table 3). The soluble fluorides act as simple bases, becoming fully ionized and increasing the concentration of HF 2- Foi example,... 

Table 3. Solubility of Metal Fluorides in Anhydrous Hydrogen Flnoride ...

For anhydrous hydrogen fluoride, the Hammett acidity function Hq approaches —11. The high negative value of Hq shows anhydrous hydrogen fluoride to be in the class of superacids. Addition of antimony pentafluoride to make a 3 Af solution in anhydrous hydrogen fluoride raises the Hammett function to —15.2, nearly the strongest of all acids (34). 

Anhydrous hydrogen fluoride is also available in cylinders, and aqueous hydrogen fluoride, either 50% or 70%, is also shipped in polyethylene bottles and carboys. Typical product specifications and analysis methods are given in Table 4. 

Preparation. Silver fluoride can be prepared by dissolving Ag20 or Ag2C02 iu anhydrous hydrogen fluoride or aqueous hydrofluoric acid, evaporating to dryness, and then treating with methanol or ether. 

Silver difluoride [7783-95-1], AgF2, is a black crystalline powder. It has been classified as a hard fluorinating agent (3) which Hberates iodine from KI solutions and o2one from dilute aqueous acid solutions on heating. It spontaneously oxidizes xenon gas to Xe(II) in anhydrous hydrogen fluoride solutions (20). 

Stannous fluoride [7783-47-3] Snp2, is a white crystalline salt that has mp 215°C (1), bp 850°C, and is readily soluble in water and hydrogen fluoride. At 20°C stannous fluoride dissolves in water to a concentration of 30—39% in anhydrous hydrogen fluoride to 72—82% (2—4). 

Stannous fluoride probably was first prepared by Scheele in 1771 and was described by Gay-Lussac and Thenard in 1809. Commercial production of stannous fluoride is by the reaction of stannous oxide and aqueous hydrofluoric acid, or metallic tin and anhydrous hydrogen fluoride (5,6). Snp2 is also produced by the reaction of tin metal, HP, and a halogen in the presence of a nitrile (7). 

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. 

Fluorocarbons are made commercially also by the electrolysis of hydrocarbons in anhydrous hydrogen fluoride (Simons process) (14). Nickel anodes and nickel or steel cathodes are used. Special porous anodes improve the yields. This method is limited to starting materials that are appreciably soluble in hydrogen fluoride, and is most useflil for manufacturing perfluoroalkyl carboxyflc and sulfonic acids, and tertiary amines. For volatile materials with tittle solubility in hydrofluoric acid, a complementary method that uses porous carbon anodes and HF 2KF electrolyte (Phillips process) is useflil (14). 

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