Fluorosulfuric acid (

IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...

name: sulfurofluoridic acid) is the

inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...

with the

chemical formula In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbols, ...

HSO₃F. It is one of the strongest acids commercially available. It is a tetrahedral molecule and is closely related to

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...

, H₂SO₄, substituting a fluorine atom for one of the hydroxyl groups. It is a colourless liquid, although commercial samples are often yellow.Erhardt Tabel, Eberhard Zirngiebl, Joachim Maas "Fluorosulfuric Acid" in "Ullmann's Encyclopedia of Industrial Chemistry" 2005, Wiley-VCH, Weinheim.

Chemical properties

Fluorosulfuric acid is a free-flowing colorless liquid. It is soluble in polar organic solvents (e.g.

nitrobenzene Nitrobenzene is an organic compound with the chemical formula C6H5 NO2. It is a water-insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It is produced on a large scale from benzene as a precursor t ...

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

, and

ethyl acetate Ethyl acetate ( systematically ethyl ethanoate, commonly abbreviated EtOAc, ETAC or EA) is the organic compound with the formula , simplified to . This colorless liquid has a characteristic sweet smell (similar to pear drops) and is used in glues ...

), but poorly soluble in nonpolar solvents such as alkanes. Reflecting its strong acidity, it dissolves almost all organic compounds that are even weak proton acceptors. HSO₃F

hydrolyze Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysis ...

s slowly to

hydrogen fluoride Hydrogen fluoride (fluorane) is an inorganic compound with the chemical formula . 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 i ...

(HF) and

. The related

triflic acid Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for este ...

() retains the high acidity of HSO₃F but is more hydrolytically stable. The self-ionization of fluorosulfonic acid also occurs: : ''K'' = 4.0 × 10⁻⁸ (at 298 K)

Production

Fluorosulfuric acid is prepared by the reaction of HF and

sulfur trioxide Sulfur trioxide (alternative spelling sulphur trioxide, also known as ''nisso sulfan'') is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an ind ...

: :SO₃ + HF → HSO₃F Alternatively, KHF₂ or CaF₂ can be treated with

oleum Oleum (Latin ''oleum'', meaning oil), or fuming sulfuric acid, is a term referring to solutions of various compositions of sulfur trioxide in sulfuric acid, or sometimes more specifically to disulfuric acid (also known as pyrosulfuric acid). Ole ...

at 250 °C. Once freed from HF by sweeping with an inert gas, HSO₃F can be distilled in a glass apparatus.

Super-acids

HSO₃F is one of the strongest known simple Brønsted acids, although

carborane Carboranes are electron-delocalized (non-classically bonded) clusters composed of boron, carbon and hydrogen atoms.Grimes, R. N., ''Carboranes 3rd Ed.'', Elsevier, Amsterdam and New York (2016), . Like many of the related boron hydrides, these c ...

-based acids are still stronger. It has an ''H''₀ value of −15.1 compared to −12 for sulfuric acid. The combination of HSO₃F and the

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...

antimony pentafluoride Antimony pentafluoride is the inorganic compound with the formula Sb F5. This colourless, viscous liquid is a valuable Lewis acid and a component of the superacid fluoroantimonic acid, formed when mixing liquid HF with liquid SbF5 in a 2:1 ratio. ...

produces " Magic acid", which is a far stronger protonating agent. These acids all fall into the category of "

superacids In chemistry, a superacid (according to the classical definition) is an acid with an acidity greater than that of 100% pure sulfuric acid (), which has a Hammett acidity function (''H''0) of −12. According to the modern definition, a superacid ...

", acids stronger than 100% sulfuric acid.

Applications

HSO₃F is useful for regenerating mixtures of HF and H₂SO₄ for etching

lead glass Lead glass, commonly called crystal, is a variety of glass in which lead replaces the calcium content of a typical potash glass. Lead glass contains typically 18–40% (by weight) lead(II) oxide (PbO), while modern lead crystal, historically als ...

. HSO₃F isomerizes

alkanes In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in which ...

and the alkylation of hydrocarbons with alkenes, although it is unclear if such applications are of commercial importance. It can also be used as a laboratory fluorinating agent.

Safety

Fluorosulfuric acid is considered to be highly toxic and extremely corrosive. It hydrolyzes to release HF. Addition of water to HSO₃F can be violent, similar to the addition of water to sulfuric acid but much more violent.

References