Hydrogen fluoride

Hydrogen fluoride does not boil until 20 °C in contrast to the heavier hydrogen halides, which boil between −85 °C (−120 °F) and −35 °C (−30 °F).[6][7][8] This hydrogen bonding between HF molecules gives rise to high viscosity in the liquid phase and lower than expected pressure in the gas phase.

HF is miscible with water (dissolves in any proportion). In contrast, the other hydrogen halides exhibit limiting solubilities in water. Hydrogen fluoride forms a monohydrate HF^.H₂O with m.p.−40 °C (−40 °F), which is 44 °C (79 °F) above the melting point of pure HF.[9]

HF and H2O similarities
Boiling points of the hydrogen halides (blue) and hydrogen chalcogenides (red): HF and H2O break trends.	Freezing point of HF/ H2O mixtures: arrows indicate compounds in the solid state.

Aqueous solutions of HF are called hydrofluoric acid. When dilute, hydrofluoric acid behaves like a weak acid, unlike the other hydrohalic acids, due to the formation of hydrogen-bonded ion pairs [H
3O+
·F⁻]. However concentrated solutions are strong acids, because bifluoride anions are predominant, instead of ion pairs. In liquid anhydrous HF, self-ionization occurs:[10][11]

3 HF ⇌ H₂F⁺ + HF⁻
₂

which forms an extremely acidic liquid (1=H₀ = −11).

HF reacts with Lewis acids to give superacids. A Hammett acidity function (H₀) of −21 is obtained with antimony pentafluoride (SbF₅), forming fluoroantimonic acid.[12][13]

HF reacts with chlorocarbons to give fluorocarbons. An important application of this reaction is the production of tetrafluoroethylene (TFE), precursor to Teflon. Chloroform is fluorinated by HF to produce chlorodifluoromethane (R-22):[14]

CHCl₃ + 2 HF → CHClF₂ + 2 HCl

Pyrolysis of chlorodifluoromethane (at 550-750 °C) yields TFE.

HF is a reactive solvent in the electrochemical fluorination of organic compounds. In this approach, HF is oxidized in the presence of a hydrocarbon and the fluorine replaces C–H bonds with C–F bonds. Perfluorinated carboxylic acids and sulfonic acids are produced in this way.[15]

1,1-Difluoroethane is produced by adding HF to acetylene using mercury as a catalyst.[15]

HC≡CH + 2 HF → CH₃CHF₂

The intermediate in this process is vinyl fluoride or fluoroethylene, the monomeric precursor to polyvinyl fluoride.

The electrowinning of aluminium relies on the electrolysis of aluminium fluoride in molten cryolite. Several kilograms of HF are consumed per ton of Al produced. Other metal fluorides are produced using HF, including uranium hexafluoride.[14]

HF is the precursor to elemental fluorine, F₂, by electrolysis of a solution of HF and potassium bifluoride. The potassium bifluoride is needed because anhydrous HF does not conduct electricity. Several thousand tons of F₂ are produced annually.[16]

HF serves as a catalyst in alkylation processes in refineries. It is used in the majority of the installed linear alkyl benzene production facilities in the world. The process involves dehydrogenation of n-paraffins to olefins, and subsequent reaction with benzene using HF as catalyst. For example, in oil refineries "alkylate", a component of high-octane petrol (gasoline), is generated in alkylation units, which combine C₃ and C₄ olefins and iso-butane.[14]

Hydrogen fluoride is an excellent solvent. Reflecting the ability of HF to participate in hydrogen bonding, even proteins and carbohydrates dissolve in HF and can be recovered from it. In contrast, most non-fluoride inorganic chemicals react with HF rather than dissolving.[17]