Ammonium bifluoride
Space fill model of the ammonium cation
Space fill model of the ammonium cation
Space fill model of the bifluoride anion
Space fill model of the bifluoride anion
Sample of Ammonium bifluoride
IUPAC name
Ammonium bifluoride
Other names
  • Ammonium acid fluoride
  • Ammonium hydrofluoride
  • Ammonium difluoride
  • Ammonium hydrogendifluoride
  • Ammonium hydrogen difluoride
3D model (JSmol)
ECHA InfoCard 100.014.252 Edit this at Wikidata
EC Number
  • 215-676-4
UN number 1727
  • InChI=1S/F2H.H3N/c1-3-2;/h;1H3/q-1;/p+1 ☒N
  • InChI=1/2FH.H3N/h2*1H;1H3
  • [NH4+].F[H-]F
  • [F-].F.[NH4+]
Molar mass 57.044 g·mol−1
Appearance Colourless crystals
Density 1.50 g cm−3
Melting point 126 °C (259 °F; 399 K)
Boiling point 240 °C (464 °F; 513 K)(decomposes)
63g/(100 ml) (20 °C)
Solubility in alcohol slightly soluble
Cubic, related to the CsCl structure
[NH4]+ cation: tetrahedral
[HF2] anion: linear
GHS labelling:
GHS05: CorrosiveGHS06: Toxic[1]
H301, H314[1]
P280, P301+P310, P305+P351+P338, P310[1]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
Related compounds
Other cations
potassium bifluoride
Related compounds
ammonium fluoride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Ammonium bifluoride is the inorganic compound with the formula [NH4][HF2] or [NH4]F·HF. It is produced from ammonia and hydrogen fluoride. This colourless salt is a glass-etchant and an intermediate in a once-contemplated route to hydrofluoric acid.


Ammonium bifluoride, as its name indicates, contains an ammonium cation ([NH4]+), and a bifluoride or hydrogen(difluoride) anion ([HF2]). The centrosymmetric triatomic bifluoride anion features the strongest known hydrogen bond, with a FH length of 114 pm.[2] and a bond energy greater than 155 kJ/mol.[3]

In solid [NH4][HF2], each ammonium cation is surrounded by four fluoride centers in a tetrahedron, with hydrogen-fluorine hydrogen bonds present between the hydrogen atoms of the ammonium ion and the fluorine atoms.[4][5] Solutions contain tetrahedral [NH4]+ cations and linear [HF2] anions.

Production and applications

Ammonium bifluoride is a component of some etchants. It attacks silica component of glass:

SiO2 + 4 [NH4][HF2] → SiF4 + 4 [NH4]F + 2 H2O

Potassium bifluoride is a related more commonly used etchant.

Ammonium bifluoride has been considered as an intermediate in the production of hydrofluoric acid from hexafluorosilicic acid. Thus, hexafluorosilicic acid is hydrolyzed to give ammonium fluoride, which thermally decomposes to give the bifluoride:

H2[SiF6] + 6 NH3 + 2 H2O → SiO2 + 6 [NH4]F
2 [NH4]F → NH3 + [NH4][HF2]

The resulting ammonium bifluoride is converted to sodium bifluoride, which thermally decomposes to release HF.[6]

Ammonium bifluoride is also used as an additive in tin-nickel plating processes as the fluoride ion acts as a complexing agent with the tin, allowing for greater control over the resulting composition and finish.


Ammonium bifluoride is toxic to consume and a skin corrosion agent. Upon exposure to skin, rinsing with water followed by a treatment of calcium gluconate is required.[1] In water, ammonium bifluoride exists in chemical equilibrium with hydrofluoric acid and heating releases hydrogen fluoride gas.[7] Consequently, there is an equivalent toxicological risk as is present with hydrofluoric acid, and the same safety precautions apply.[8][7]

Ammonium bifluoride is used in some automotive wheel cleaning products. Many injuries have resulted in users not being aware of the risks posed by the products.[9] Ammonium bifluoride based products are often considered a safer alternative to hydrofluoric acid, yet still pose clear risks to the handler.[8] Ammonium bifluoride, ammonium fluoride, and hydrofluoric acid have been described as "too dangerous for any use in a car wash environment" by Professional Car Washing and Detailing magazine,[10] advice that accords with a 2015 report from the U.S. Centers for Disease Control and Prevention.[11]


  1. ^ a b c d Sigma-Aldrich Co., Ammonium bifluoride. Retrieved on 2013-07-20.
  2. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  3. ^ Emsley, J. (1980) Very Strong Hydrogen Bonds, Chemical Society Reviews, 9, 91–124. doi:10.1039/CS9800900091
  4. ^ McDonald, T. R. R. (1960). "The electron-density distribution in ammonium bifluoride". Acta Crystallogr. 13 (2): 113–124. Bibcode:1960AcCry..13..113M. doi:10.1107/S0365110X60000261.
  5. ^ "ICSD Entry: 14140". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre. Retrieved 2022-06-25.
  6. ^ Aigueperse, Jean; Mollard, Paul; Devilliers, Didier; Chemla, Marius; Faron, Robert; Romano, René; Cuer, Jean Pierre (2000). "Fluorine Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_307. ISBN 978-3527306732.
  7. ^ a b National Industrial Chemicals Notification and Assessment Scheme (April 17, 2020). "Bifluorides: Human health tier II assessment" (PDF). Department of Health (Australia). Retrieved February 8, 2023.
  8. ^ a b Genuino, Homer C.; Opembe, Naftali N.; Njagi, Eric C.; McClain, Skye; Suib, Steven L. (2012). "A review of hydrofluoric acid and its use in the car wash industry". Journal of Industrial and Engineering Chemistry. 18 (5): 1529–1539. doi:10.1016/j.jiec.2012.03.001. ISSN 1226-086X.
  9. ^ Gormley, James (May 29, 2001). "The truth about ammonium bifluoride". Professional Car Washing and Detailing. Archived from the original on 2001-05-29.
  10. ^ Cook, Ryan (October 9, 2013). "The Five Factors of Clean: Chemistry, Part 1". Professional Car Washing and Detailing. Retrieved February 8, 2023.
  11. ^ Woodie, Maria (December 1, 2015). "OSHA gives employees the right to know". Professional Car Washing and Detailing. Retrieved February 8, 2023.