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Sulfanyl (•), also known as the mercapto radical, hydrosulfide radical, or hydridosulfur, is a simple radical molecule consisting of one hydrogen and one sulfur atom. The S-H distance in the radical is 0.134 nm. The radical is also proposed to be formed by the action of
ultraviolet radiation Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of t ...
on hydrogen sulfide. A
wavelength In physics and mathematics, wavelength or spatial period of a wave or periodic function is the distance over which the wave's shape repeats. In other words, it is the distance between consecutive corresponding points of the same ''phase (waves ...
of 190 nm gives maximum absorption.


Gaseous sulfanyl

Sulfanyl is one of the top three sulfur-containing gasses in
gas giant A gas giant is a giant planet composed mainly of hydrogen and helium. Jupiter and Saturn are the gas giants of the Solar System. The term "gas giant" was originally synonymous with "giant planet". However, in the 1990s, it became known that Uranu ...
s such as
Jupiter Jupiter is the fifth planet from the Sun and the List of Solar System objects by size, largest in the Solar System. It is a gas giant with a Jupiter mass, mass more than 2.5 times that of all the other planets in the Solar System combined a ...
and is very likely to be found in
brown dwarf Brown dwarfs are substellar objects that have more mass than the biggest gas giant planets, but less than the least massive main sequence, main-sequence stars. Their mass is approximately 13 to 80 Jupiter mass, times that of Jupiter ()not big en ...
s and cool stars. It was originally discovered by Margaret N. Lewis and John U. White at the
University of California The University of California (UC) is a public university, public Land-grant university, land-grant research university, research university system in the U.S. state of California. Headquartered in Oakland, California, Oakland, the system is co ...
in 1939. They observed molecular absorption bands around 325 nm belonging to the system designated by 2Σ+ ← 2Πi. They generated the radical by means of a radio frequency discharge in
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is toxic, corrosive, and flammable. Trace amounts in ambient atmosphere have a characteristic foul odor of rotten eggs. Swedish chemist ...
. HS• is formed during the degradation of hydrogen sulfide in the atmosphere of the Earth. This may be a deliberate action to destroy odours or a natural phenomenon. Absorption lines of sulfanyl in space were first detected in the
infrared Infrared (IR; sometimes called infrared light) is electromagnetic radiation (EMR) with wavelengths longer than that of visible light but shorter than microwaves. The infrared spectral band begins with the waves that are just longer than those ...
by Yamamura (2000) in a star R And. In the sun •SH was detected at several
ultraviolet Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of ...
wavelength In physics and mathematics, wavelength or spatial period of a wave or periodic function is the distance over which the wave's shape repeats. In other words, it is the distance between consecutive corresponding points of the same ''phase (waves ...
s: 326.0459, 327.5468, 328.9749, 330.0892 and 330.1112 nm. Sulfanyl has been detected in interstellar gas, and it is possibly present in comets. Various theoretical studies have examined HS• in atmospheres. In Earth's atmosphere HS• reacts with NO2 to make two products HSNO2 and HSONO. HSONO decomposes to HSO and NO. HS• also reacts with O2 and N2O. HS• can also react with Cl2 producing HSCl and a Cl• atom. HS• destroys
ozone Ozone () (or trioxygen) is an Inorganic compound, inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , break ...
producing HSO• and oxygen. HS• is formed in the Earth's atmosphere by the reaction of HO•, the
hydroxyl radical The hydroxyl radical, •HO, is the neutral form of the hydroxide ion (HO–). Hydroxyl radicals are highly reactive and consequently short-lived; however, they form an important part of radical chemistry. Most notably hydroxyl radicals are pr ...
, on carbon disulfide, carbon oxysulfide and
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is toxic, corrosive, and flammable. Trace amounts in ambient atmosphere have a characteristic foul odor of rotten eggs. Swedish chemist ...
with side products of
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
and water. Photodissociation of hydrogen sulfide also produces the radical in air. In a planetary atmosphere that contains H2S, HS• will be formed if the temperature and pressure are high enough. The ratio of H2S and HS• is given by: :log(''X''/''X'') = −3.37 + 8785/''T'' + 0.5 log ''PT'' + 0.5 log ''X''H2 For a hydrogen dominated atmosphere in a gas giant or star: H2S has the same level as HS• at :\log P_T = 6.82 - 17570/T. At higher temperatures HS• breaks up into sulfur vapour and H2. The line of equal S and HS concentration follows the line :gas giant A gas giant is a giant planet composed mainly of hydrogen and helium. Jupiter and Saturn are the gas giants of the Solar System. The term "gas giant" was originally synonymous with "giant planet". However, in the 1990s, it became known that Uranu ...
s or
brown dwarf Brown dwarfs are substellar objects that have more mass than the biggest gas giant planets, but less than the least massive main sequence, main-sequence stars. Their mass is approximately 13 to 80 Jupiter mass, times that of Jupiter ()not big en ...
s.


Organic thiyl

The organic analogue of sulfanyl is thiyl radical with the formula , where R is some organic group (e.g.,
alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl group is derived from a cy ...
or
aryl In organic chemistry, an aryl is any functional group or substituent derived from an aromatic ring, usually an aromatic hydrocarbon, such as phenyl and naphthyl. "Aryl" is used for the sake of abbreviation or generalization, and "Ar" is used ...
). Thermal decomposition of mercaptans, such as ethyl mercaptan has been proposed to involve •.


HS. in biology

In humans superoxide dismutase u-Znis proposed to convert the hydrosulfide ion (HS−) to •. In the proposed mechanism Cu2+ is convert to Cu+. Sulfide dehydrogenase as found in sulfur bacteria catalyses the oxidation of HS−. It has been proposed that this reaction proceeds via •, by removing a single electron. When some sulfur minerals are leached with ferric ions, HS• is proposed to proceed as follows: :MS + Fe3+ + 2H+ → M2+ + Fe2+ + H2S•+ with the H2S•+ radical then passing a proton to water to make the HS• radical. M is a metal such as zinc or copper. This has potential for
bioleaching Bioleaching is the extraction or liberation of metals from their ores through the use of living organisms. Bioleaching is one of several applications within biohydrometallurgy and several methods are used to treat ores or concentrates containing ...
in metallic ore extraction. The hydrosulfide ion HS− can be oxidized with cerium (IV) sulfate. The process again has been proposed to involve HS•.


Reactions

In water HS is proposed to react with O2 producing SO2− and H+. This SO2− is further proposed to react with O2 to give SO2 and
superoxide In chemistry, a superoxide is a compound that contains the superoxide ion, which has the chemical formula . The systematic name of the anion is dioxide(1−). The reactive oxygen ion superoxide is particularly important as the product of t ...
O2−. HS• has an equilibrium with S− • and H+. The hydroxyl radical •OH has also been proposed to combine with H2S to form HS• and water. Other reactions investigated are: :HS• + ethylene :HS• + O2 → HO• + SO :2 HS• → H2S2 :2 HS• → H2 and S :H2S2 + HS• -> HS–S• + H2S The hydrogen disulfide is well known.


Properties

The ionization energy of HS is 10.4219 eV. The reduction potential to go to HS− is 0.92 eV. HS• in water can ionize to S•− and H+. The S•− can catalyze a cis-trans conversion in
lipid Lipids are a broad group of organic compounds which include fats, waxes, sterols, fat-soluble vitamins (such as vitamins A, D, E and K), monoglycerides, diglycerides, phospholipids, and others. The functions of lipids include storing ...
s. HS• reacts with
carboxylic acids In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...
to make
carbonyl sulfide Carbonyl sulfide is the chemical compound with the linear formula . It is a colorless flammable gas with an unpleasant odor. It is a linear molecule consisting of a carbonyl double bonded to a sulfur atom. Carbonyl sulfide can be considered to ...
(COS) and probably is the main source of this substance in the atmosphere of Earth.


Related molecules

HS—S• is called disufanyl with lengthening chains as trisulfanyl, tetrasulfanyl and pentasulfanyl HSSSSS•. S−* is termed sulfanidyl. HS+ is known as sulfanylium, and the common hydrosulfide ion HS− is also known as sulfanido for a ligand or sulfanide as an anion. Further down the periodic table, HSe• is known as selanyl, and HTe• is termed tellanyl.


References


External links


Mercapto radical
from NIST * * * Sulfur deuteride radical SD• microwave spectrum {{Hydrides by group Hydrides Sulfur compounds