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Bifluoride

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The bifluoride anion

The bifluoride, or hydrogen(difluoride), ion is the species HF2. This centrosymmetric triatomic anion features the strongest known hydrogen bond, with an FH length of 114 pm[1] and a bond strength of >155 kJ mol−1.[2] A molecular orbital diagram reveals the atoms to be held together by a 3-center 4-electron bond.[3] Hydrogen(difluoride) is written as one word because it is an anion. Hydrogen difluoride would imply an electrically neutral compound, HF2, which does not exist.

[edit] Salts

Some HF2 salts are common, examples include potassium hydrogen fluoride, KHF2, and [NH4][HF2]. Many salts claimed to be anhydrous sources of fluoride (e.g. tetra-n-butylammonium fluoride) can decompose yielding bifluoride.

[edit] Autodissociation of pure HF

The bifluoride ion also contributes to the unusually high auto-protolysis constant of liquid anhydrous hydrofluoric acid, which autodissociates in a manner similar to the self-ionization of water. This equilibrium can be denoted as

HF \rightleftharpoons H+ + F

However, both the H+ and F ions are solvated by HF, so a better descriptive equation is

3HF \rightleftharpoons H2F+(HF) + HF2(HF)

[edit] References

  1. ^ Greenwood, Norman N.; Earnshaw, A. (1997), Chemistry of the Elements (2nd ed.), Oxford: Butterworth-Heinemann, ISBN 0-7506-3365-4 
  2. ^ Emsley, J., "Very Strong Hydrogen Bonds", Chemical Society Reviews, 1980, 9, 91-124.
  3. ^ Pimentel, G. C. The Bonding of Trihalide and Bifluoride Ions by the Molecular Orbital Method. J. Chem. Phys. 1951, 19, 446-448. doi:10.1063/1.1748245

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