Superacids
   HOME

TheInfoList



OR:

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 The Hammett acidity function (''H''0) is a measure of acidity that is used for very concentrated solutions of strong acids, including superacids. It was proposed by the physical organic chemist Louis Plack Hammett and is the best-known acidity ...
(''H''0) of −12. According to the modern definition, a superacid is a medium in which the
chemical potential In thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species ...
of the proton is higher than in pure sulfuric acid. Commercially available superacids include
trifluoromethanesulfonic 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 est ...
(), also known as triflic acid, and
fluorosulfuric acid Fluorosulfuric acid (IUPAC name: sulfurofluoridic acid) is the inorganic compound with the chemical formula HSO3F. It is one of the strongest acids commercially available. It is a tetrahedral molecule and is closely related to sulfuric acid, H2SO4 ...
(), both of which are about a thousand times stronger (i.e. have more negative ''H''0 values) than sulfuric acid. Most strong superacids are prepared by the combination of a strong
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 ...
and a strong Brønsted acid. A strong superacid of this kind is
fluoroantimonic acid Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions (the simplest being and ). This substance is a superacid that can be over a billion times stronger than 100% pure sulfuric ac ...
. Another group of superacids, the
carborane acid Carborane acids (X, Y, Z = H, Alk, F, Cl, Br, CF3) are a class of superacids, some of which are estimated to be at least one million times stronger than 100% pure sulfuric acid in terms of their Hammett acidity function values (''H''0 ≤ – ...
group, contains some of the strongest known acids. Finally, when treated with
anhydrous A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achi ...
acid,
zeolites Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ・y where is either a metal ion or H+. These ...
(microporous aluminosilicate minerals) will contain superacidic sites within their pores. These materials are used on massive scale by the petrochemical industry in the upgrading of hydrocarbons to make fuels.


History

The term ''superacid'' was originally coined by
James Bryant Conant James Bryant Conant (March 26, 1893 – February 11, 1978) was an American chemist, a transformative President of Harvard University, and the first U.S. Ambassador to West Germany. Conant obtained a Ph.D. in Chemistry from Harvard in 1916 ...
in 1927 to describe acids that were stronger than conventional
mineral acid A mineral acid (or inorganic acid) is an acid derived from one or more inorganic compounds, as opposed to organic acids which are acidic, organic compounds. All mineral acids form hydrogen ions and the conjugate base when dissolved in water. Ch ...
s. This definition was refined by
Ronald Gillespie Ronald James Gillespie, (August 21, 1924 – February 26, 2021) was a British chemist specializing in the field of molecular geometry, who arrived in Canada after accepting an offer that included his own laboratory with new equipment, which post ...
in 1971, as any acid with an ''H''0 value lower than that of 100% sulfuric acid (−11.93). George A. Olah prepared the so-called " magic acid", so named for its ability to attack
hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...
, by mixing antimony pentafluoride (SbF5) and
fluorosulfonic acid Fluorosulfuric acid (IUPAC name: sulfurofluoridic acid) is the inorganic compound with the chemical formula HSO3F. It is one of the strongest acids commercially available. It is a tetrahedral molecule and is closely related to sulfuric acid, H2SO ...
(FSO3H). The name was coined after a candle was placed in a sample of magic acid after a Christmas party. The candle dissolved, showing the ability of the acid to protonate
alkane In organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms tha ...
s, which under normal acidic conditions do not protonate to any extent. At 140°C (284°F), FSO3H–SbF5 protonates
methane Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Ear ...
to give the tertiary-butyl
carbocation A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encoun ...
, a reaction that begins with the
protonation In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), (H+) to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid ...
of methane: :CH4 + H+ → : → + H2 : + 3 CH4 → (CH3)3C+ + 3H2 Common uses of superacids include providing an environment to create, maintain, and characterize carbocations. Carbocations are intermediates in numerous useful reactions such as those forming plastics and in the production of high-octane
gasoline Gasoline (; ) or petrol (; ) (see ) is a transparent, petroleum-derived flammable liquid that is used primarily as a fuel in most spark-ignited internal combustion engines (also known as petrol engines). It consists mostly of organic ...
.


Origin of extreme acid strength

Traditionally, superacids are made from mixing a Brønsted acid with a Lewis acid. The function of the Lewis acid is to bind to and stabilize the anion that is formed upon dissociation of the Brønsted acid, thereby removing a proton acceptor from the solution and strengthening the proton donating ability of the solution. For example,
fluoroantimonic acid Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions (the simplest being and ). This substance is a superacid that can be over a billion times stronger than 100% pure sulfuric ac ...
, nominally (), can produce solutions with a ''H''0 lower than –21, giving it a protonating ability over a billion times greater than 100% sulfuric acid. Fluoroantimonic acid is made by dissolving antimony pentafluoride (SbF5) in anhydrous hydrogen fluoride (HF). In this mixture, HF releases its proton (H+) concomitant with the binding of F by the antimony pentafluoride. The resulting
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
() delocalizes charge effectively and holds onto its electron pairs tightly, making it an extremely poor
nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they a ...
and base. The mixture owes its extraordinary acidity to the weakness of proton acceptors (and electron pair donors) (Brønsted or Lewis bases) in solution. Because of this, the
protons A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron m ...
in fluoroantimonic acid and other superacids are popularly described as "naked", being readily donated to substances not normally regarded as proton acceptors, like the C–H bonds of hydrocarbons. However, even for superacidic solutions, protons in the condensed phase are far from being unbound. For instance, in fluoroantimonic acid, they are bound to one or more molecules of hydrogen fluoride. Though hydrogen fluoride is normally regarded as an exceptionally weak proton acceptor (though a somewhat better one than the SbF6 anion), dissociation of its protonated form, the fluoronium ion H2F+ to HF and the truly naked H+ is still a highly endothermic process (Δ''G''° = +113 kcal/mol), and imagining the proton in the condensed phase as being "naked" or "unbound", like charged particles in a plasma, is highly inaccurate and misleading. More recently, carborane acids have been prepared as single component superacids that owe their strength to the extraordinary stability of the carboranate anion, a family of anions stabilized by three-dimensional aromaticity, as well as by electron-withdrawing group typically attached thereto. In superacids, the proton is shuttled rapidly from proton acceptor to proton acceptor by tunneling through a hydrogen bond via the Grotthuss mechanism, just as in other hydrogen-bonded networks, like water or ammonia.


Applications

In
petrochemistry Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewabl ...
, superacidic media are used as catalysts, especially for
alkylation Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effectin ...
s. Typical catalysts are sulfated oxides of
titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
and
zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
or specially treated alumina or
zeolite Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula ・y where is either a metal ion or H+. These ...
s. The
solid acid Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural r ...
s are used for alkylating benzene with
ethene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene is ...
and
propene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula CH3CH=CH2. It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petrole ...
as well as difficult
acylation In chemistry, acylation (or alkanoylation) is the chemical reaction in which an acyl group () is added to a compound. The compound providing the acyl group is called the acylating agent. Because they form a strong electrophile when treated wit ...
s, e.g. of
chlorobenzene Chlorobenzene is an aromatic organic compound with the chemical formula C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals. Uses Historical The major use of chloro ...
.


Examples

The following values show the
Hammett acidity function The Hammett acidity function (''H''0) is a measure of acidity that is used for very concentrated solutions of strong acids, including superacids. It was proposed by the physical organic chemist Louis Plack Hammett and is the best-known acidity ...
for several superacids, the strongest being
fluoroantimonic acid Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions (the simplest being and ). This substance is a superacid that can be over a billion times stronger than 100% pure sulfuric ac ...
. Increased acidity is indicated by smaller (in this case, more negative) values of ''H''0. *
Fluoroantimonic acid Fluoroantimonic acid is a mixture of hydrogen fluoride and antimony pentafluoride, containing various cations and anions (the simplest being and ). This substance is a superacid that can be over a billion times stronger than 100% pure sulfuric ac ...
(HF:SbF5, ''H''0 between −21 and −23) * Magic acid (HSO3F:SbF5, ''H''0 = −19.2) * Triflidic acid (CH(CF3SO2)3, ''H''0 = −18.6) * Carborane acids (H(HCB11X11), ''H''0 ≤ −18, indirectly determined and depends on substituents) *
Fluoroboric acid Fluoroboric acid or tetrafluoroboric acid (archaically, fluoboric acid) is an inorganic compound with the chemical formula +BF4−], where H+ represents the solvated proton. The solvent can be any suitably Lewis-basic entity. For instance, in w ...
(HF:BF3, ''H''0 = −16.6) *
Fluorosulfuric acid Fluorosulfuric acid (IUPAC name: sulfurofluoridic acid) is the inorganic compound with the chemical formula HSO3F. It is one of the strongest acids commercially available. It is a tetrahedral molecule and is closely related to sulfuric acid, H2SO4 ...
(FSO3H, ''H''0 = −15.1) * Hydrogen fluoride (HF, ''H''0 = −15.1) *
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 est ...
(HOSO2CF3, ''H''0 = −14.9) *
Perchloric acid Perchloric acid is a mineral acid with the formula H Cl O4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous s ...
(HClO4, ''H''0 = −13) * Sulfuric acid (H2SO4, ''H''0 = −11.9)


See also

*
Superbase A superbase is a compound that has a particularly high affinity for protons. Superbases are of theoretical interest and potentially valuable in organic synthesis. Superbases have been described and used since the 1850s.''Superbases for Organic ...
*
Acid dissociation constant In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction : ...


References

{{Reflist, 30em