Hydrogen fluoride is a chemical compound with the chemical formula HF. This colorless gas or liquid is the principal industrial source of fluorine, often as an aqueous solution called hydrofluoric acid. It is an important feedstock in the preparation of many important compounds including pharmaceuticals and polymers (e.g. Teflon). HF is widely used in the petrochemical industry as a component of superacids. Hydrogen fluoride boils near room temperature, much higher than other hydrogen halides.
3D model (JSmol)
CompTox Dashboard (EPA)
|Molar mass||20.006 g·mol−1|
|Appearance||colourless gas or colourless liquid (below 19.5 °C)|
|Density||1.15 g/L, gas (25 °C)|
0.99 g/mL, liquid (19.5 °C)
1.663 g/mL, solid (–125 °C)
|Melting point||−83.6 °C (−118.5 °F; 189.6 K)|
|Boiling point||19.5 °C (67.1 °F; 292.6 K)|
|completely miscible (liquid)|
|Vapor pressure||783 mmHg (20 °C)|
Refractive index (nD)
|8.687 J/g K (gas)|
Std enthalpy of
|−13.66 kJ/g (gas) |
−14.99 kJ/g (liquid)
|GHS Signal word||Danger|
|H300, H310, H314, H330|
|P260, P262, P264, P270, P271, P280, P284, P301+310, P301+330+331, P302+350, P303+361+353, P304+340, P305+351+338, P310, P320, P321, P322, P330, P361, P363, P403+233, P405, P501|
|NFPA 704 (fire diamond)|
|Lethal dose or concentration (LD, LC):|
LC50 (median concentration)
|1276 ppm (rat, 1 hr)|
1774 ppm (monkey, 1 hr)
4327 ppm (guinea pig, 15 min)
LCLo (lowest published)
|313 ppm (rabbit, 7 hr)|
|NIOSH (US health exposure limits):|
|TWA 3 ppm|
|TWA 3 ppm (2.5 mg/m3) C 6 ppm (5 mg/m3) [15-minute]|
IDLH (Immediate danger)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Hydrogen fluoride is a highly dangerous gas, forming corrosive and penetrating hydrofluoric acid upon contact with moisture. The gas can also cause blindness by rapid destruction of the corneas.
In 1771 Carl Wilhelm Scheele prepared the aqueous solution, hydrofluoric acid in large quantities, although hydrofluoric acid had been known in the glass industry before then. French chemist Edmond Frémy (1814–1894) is credited with discovering anhydrous hydrogen fluoride (HF) while trying to isolate fluorine.
Structure and reactions
Although a diatomic molecule, HF forms relatively strong intermolecular hydrogen bonds. Solid HF consists of zig-zag chains of HF molecules. The HF molecules, with a short H–F bond of 95 pm, are linked to neighboring molecules by intermolecular H–F distances of 155 pm. Liquid HF also consists of chains of HF molecules, but the chains are shorter, consisting on average of only five or six molecules.
Comparison with other hydrogen halides
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). 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 form a monohydrate HF.H2O (−40 °C (−40 °F), which is 44 °C (79 °F) above the melting point of pure HF.
|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 is a weak acid, unlike the other hydrohalic acids. However concentrated solutions are strong acids due to the formation of hydrogen-bonded ion pairs [H
·F−]. In liquid anhydrous HF, self-ionization occurs:
- 3 HF ⇌ H2F+ + HF−
which forms an extremely acidic solution (H0 = −11).
- CaF2 + H2SO4 → 2 HF + CaSO4
About 20% of manufactured HF is a byproduct of fertilizer production, which generates hexafluorosilicic acid. This acid can be degraded to release HF thermally and by hydrolysis:
- H2SiF6 → 2 HF + SiF4
- SiF4 + 2 H2O → 4 HF + SiO2
In general, the anhydrous compound hydrogen fluoride is more common industrially than its aqueous solution, hydrofluoric acid. Its main uses, on a tonnage basis, are as a precursor to organofluorine compounds and a precursor to cryolite for the electrolysis of aluminium.
Precursor to organofluorine compounds
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):
- 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.
- HC≡CH + 2 HF → CH3CHF2
Precursor to metal fluorides and fluorine
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.
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 million kilograms of F2 are produced annually.
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.
Upon contact with moisture, including tissue, hydrogen fluoride immediately converts to hydrofluoric acid, which is highly corrosive and toxic. Exposure requires immediate medical attention. It can cause blindness by rapid destruction of the corneas. Breathing in hydrogen fluoride at high levels or in combination with skin contact can cause death from an irregular heartbeat or from fluid buildup in the lungs.
- NIOSH Pocket Guide to Chemical Hazards. "#0334". National Institute for Occupational Safety and Health (NIOSH).
- "pKa's of Inorganic and Oxo-Acids" (PDF). Harvard. Retrieved 9 September 2013.
- Bruckenstein, S.; Kolthoff, I.M., in Kolthoff, I.M.; Elving, P.J. Treatise on Analytical Chemistry, Vol. 1, pt. 1; Wiley, NY, 1959, pp. 432-433.
- "Hydrogen fluoride". Immediately Dangerous to Life and Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
- Johnson, M. W.; Sándor, E.; Arzi, E. (1975). "The Crystal Structure of Deuterium Fluoride". Acta Crystallographica. B31 (8): 1998–2003. doi:10.1107/S0567740875006711.
- McLain, Sylvia E.; Benmore, C. J.; Siewenie, J. E.; Urquidi, J.; Turner, J. F. (2004). "On the Structure of Liquid Hydrogen Fluoride". Angewandte Chemie International Edition. 43 (15): 1952–55. doi:10.1002/anie.200353289. PMID 15065271.
- Pauling, Linus A. (1960). The Nature of the Chemical Bond and the Structure of Molecules and Crystals: An Introduction to Modern Structural Chemistry. Cornell University Press. pp. 454–464. ISBN 978-0-8014-0333-0.
- Atkins, Peter; Jones, Loretta (2008). Chemical principles: The quest for insight. W. H. Freeman & Co. pp. 184–185. ISBN 978-1-4292-0965-6.
- Emsley, John (1981). "The hidden strength of hydrogen". New Scientist. 91 (1264): 291–292. Retrieved 25 December 2012.
- Greenwood, N. N.; Earnshaw, A. (1998). Chemistry of the Elements (2nd ed.). Oxford: Butterworth Heinemann. pp. 812–816. ISBN 0-7506-3365-4.
- C. E. Housecroft and A. G. Sharpe Inorganic Chemistry, p. 221.
- F. A. Cotton and G. Wilkinson Advanced Inorganic Chemistry, p. 111.
- W. L. Jolly "Modern Inorganic Chemistry" (McGraw-Hill 1984), p. 203. ISBN 0-07-032768-8.
- F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry (5th ed.) John Wiley and Sons: New York, 1988. ISBN 0-471-84997-9. p. 109.
- J. Aigueperse, P. Mollard, D. Devilliers, M. Chemla, R. Faron, R. Romano, J. P. Cuer (2000). "Fluorine Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_307.CS1 maint: multiple names: authors list (link)
- G. Siegemund, W. Schwertfeger, A. Feiring, B. Smart, F. Behr, H. Vogel, B. McKusick (2005). "Fluorine Compounds, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_349.CS1 maint: multiple names: authors list (link)
- M. Jaccaud, R. Faron, D. Devilliers, R. Romano (2005). "Fluorine". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_293.CS1 maint: multiple names: authors list (link).
- Greenwood and Earnshaw, "Chemistry of the Elements", pp. 816–819.
- Facts About Hydrogen Fluoride (Hydrofluoric Acid)
|Wikimedia Commons has media related to Hydrogen fluoride.|
- "ATSDR – Fluorides, Hydrogen Fluoride, and Fluorine". Retrieved September 30, 2019
- CDC - NIOSH Pocket Guide to Chemical Hazards
- Toxics Use Reduction Institute - Hydrogen Fluoride Fact Sheet