Fluoroantimonic Acid

Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions (the simplest being and ). This mixture is a superacid stronger than pure sulfuric acid, by many orders of magnitude, according to its Hammett acidity function. It even protonates some hydrocarbons to afford pentacoordinate carbocations ( carbonium ions). Like its precursor hydrogen fluoride, it attacks glass, but can be stored in containers lined with PTFE (Teflon) or PFA.

Chemical composition

Fluoroantimonic acid is formed by combining hydrogen fluoride and antimony pentafluoride:
:SbF₅ + 2 HF + H₂F⁺

The speciation (i.e., the inventory of components) of fluoroantimonic acid is complex. Spectroscopic measurements show that fluoroantimonic acid consists of a mixture of HF-solvated protons, (such as ), and SbF₅-adducts of fluoride, [(SbF₅)''_n''Fsup>– (such as ). Thus, the formula "" is a convenient but oversimplified approximation of the true composition. Nevertheless, the extreme acidity of this mixture is evident from the inferior proton-accepting ability of the species present in the solution. Hydrogen fluoride, a weak acid in aqueous solution that is normally not thought to have any appreciable Brønsted base">Brønsted basicity at all, is in fact the strongest Brønsted base in the mixture, protonating to H₂F⁺ in the same way water protonates to H₃O⁺ in aqueous acid. It is the fluoronium ion that accounts for fluoroantimonic acid's extreme acidity. The protons easily migrate through the solution, moving from H₂F⁺ to HF, when present, by the Grotthuss mechanism.

Two related products have been crystallized from HF-SbF₅ mixtures, and both have been analyzed by single crystal X-ray crystallography. These salts have the formulas and . In both salts, the anion is . As mentioned above, is weakly basic; the larger anion is expected to be a still weaker base.

Acidity

Fluoroantimonic acid is the strongest superacid based on the measured value of its Hammett acidity function (''H''₀), which has been determined for various ratios of HF:SbF₅. The ''H''₀ of HF is −15.1±0.1（Instead of around -11 as previously determined） Gillespie et al. accurately measured the Hammett acidity of a series of pentafluorides in anhydrous hydrogen fluoride in 1988, demonstrating that the anhydrous hydrogen fluoride solution of pentafluoride (i.e. "fluoroantimonic acid") has stronger acidity than the fluorosulfonic acid solution. A solution of HF containing 1 mol % of SbF₅ is −20. The ''H''₀ is −21 for 10 mol%. For > 50 mol % SbF₅, the ''H''₀ is between −21 and −23. The lowest attained H₀ is about −28 (although some sources have reported to reach below −31.) The following ''H''₀ values show that fluoroantimonic acid is stronger than other superacids. Increased acidity is indicated by lower (in this case, more negative) values of ''H''₀.
* Fluoroantimonic acid (−23 > ''H''₀ > −28)
* Magic acid (''H''₀ = −23)
* Carborane acid (''H''₀ < −18)
* Fluorosulfuric acid (''H''₀ = −15)
* Triflic acid (''H''₀ = −15)
* Perchloric acid (''H''₀ = −13)

Of the above, only the carborane acids, whose ''H''₀ could not be directly determined due to their high melting points, may be stronger acids than fluoroantimonic acid.

The ''H''₀ value measures the protonating ability of the bulk, liquid acid, and this value has been directly determined or estimated for various compositions of the mixture. The p''K''_a on the other hand, measures the equilibrium of proton dissociation of a discrete chemical species when dissolved in a particular solvent. Since fluoroantimonic acid is not a single chemical species, its p''K''_a value is not well-defined.

The gas-phase acidity (GPA) of individual species present in the mixture have been calculated using density functional theory methods. (Solution-phase p''K''_as of these species can, in principle, be estimated by taking into account solvation energies, but do not appear to be reported in the literature as of 2019.) For example, the ion-pair ₂Fsup>+· was estimated to have a GPA of 254 kcal/mol. For comparison, the commonly encountered superacid triflic acid, TfOH, is a substantially weaker acid by this measure, with a GPA of 299 kcal/mol. However, certain carborane superacids have GPAs lower than that of ₂Fsup>+·. For example, H(CHB₁₁Cl₁₁) has an experimentally determined GPA of 241 kcal/mol.

Reactions

Fluoroantimonic acid solution is so reactive that it is challenging to identify media with which it is unreactive. Materials compatible with fluoroantimonic acid as a solvent include SO₂ClF, and sulfur dioxide; some chlorofluorocarbons have also been used. Containers for HF/SbF₅ are made of PTFE.

Fluoroantimonic acid solutions decompose when heated, generating free hydrogen fluoride gas and liquid antimony pentafluoride at a temperature of 40 °C.

As a superacid, fluoroantimonic acid solutions protonate nearly all organic compounds, often causing dehydrogenation, or dehydration. In 1967, Bickel and Hogeveen showed that 2HF·SbF₅ reacts with isobutane and neopentane to form carbenium ions:
:(CH₃)₃CH + H⁺ → (CH₃)₃C⁺ + H₂
:(CH₃)₄C + H⁺ → (CH₃)₃C⁺ + CH₄
It is also used in the synthesis of tetraxenonogold complexes.

Safety

HF/SbF₅ is a highly corrosive substance that reacts violently with water. Heating it is dangerous as well, as it decomposes into toxic hydrogen fluoride. With superacids that are fuming and toxic, proper personal protective equipment should be used. In addition to the obligatory gloves and goggles, the use of a face shield and respirator are also required. Regular lab gloves are not recommended, as this acid can react with the gloves. Safety gear must be worn at all times when handling or going anywhere near the substance, as fluoroantimonic acid can protonate every compound in the human body.

See also

* Fluoroboric acid
* Fluorosulfuric acid
* Hexafluorophosphoric acid

References

{{Fluorine compounds

Antimony(V) compounds
Fluoro complexes
Inorganic compounds
Superacids
Mineral acids
Ionic liquids