Sulfur

Sulfur (also spelled sulphur in British English) is a

chemical element; it has symbol S and atomic number 16.
Sulfur, 16S
It is abundant, multivalent and nonmetallic. Under normal
conditions, sulfur atoms form cyclic octatomic molecules
with the chemical formula S8 . Elemental sulfur is a bright
yellow, crystalline solid at room temperature.

Sulfur is the tenth most abundant element by mass in the

universe and the fifth most abundant on Earth. Though
sometimes found in pure, native form, sulfur on Earth
usually occurs as sulfide and sulfate minerals. Being
abundant in native form, sulfur was known in ancient
times, being mentioned for its uses in ancient India, ancient Sulfur
Greece, China, and ancient Egypt. Historically and in Alternative name Sulphur (British spelling)
literature sulfur is also called brimstone,[5] which means
Allotropes see Allotropes of sulfur
"burning stone".[6] Today, almost all elemental sulfur is
produced as a byproduct of removing sulfur-containing Appearance Lemon yellow sintered
contaminants from natural gas and petroleum.[7][8] The microcrystals
greatest commercial use of the element is the production of
Standard atomic weight Ar°(S)
sulfuric acid for sulfate and phosphate fertilizers, and other
chemical processes. Sulfur is used in matches, insecticides, [32.059, 32.076]
and fungicides. Many sulfur compounds are odoriferous, 32.06 ± 0.02 (abridged)[1]
and the smells of odorized natural gas, skunk scent, bad
breath, grapefruit, and garlic are due to organosulfur Sulfur in the periodic table
compounds. Hydrogen sulfide gives the characteristic odor O
to rotting eggs and other biological processes. ↑
S
↓
Sulfur is an essential element for all life, almost always in Se
the form of organosulfur compounds or metal sulfides. phosphorus ← sulfur → chlorine
Amino acids (two proteinogenic: cysteine and methionine,
Atomic number (Z) 16
and many other non-coded: cystine, taurine, etc.) and two
vitamins (biotin and thiamine) are organosulfur compounds Group group 16 (chalcogens)
crucial for life. Many cofactors also contain sulfur, Period period 3
including glutathione, and iron–sulfur proteins. Disulfides,
S–S bonds, confer mechanical strength and insolubility of Block p-block
the (among others) protein keratin, found in outer skin, Electron [Ne] 3s2 3p4
configuration
Electrons per 2, 8, 6
shell
Physical properties
Phase at STP solid
Melting point 388.36 K ​(115.21 °C, ​
239.38 °F)
hair, and feathers. Sulfur is one of the core chemical Boiling point 717.8 K ​(444.6 °C, ​
elements needed for biochemical functioning and is an 832.3 °F)
elemental macronutrient for all living organisms.
Density (near r.t.) alpha: 2.07 g/cm3
beta: 1.96 g/cm3
Characteristics gamma: 1.92 g/cm3
when liquid 1.819 g/cm3
Physical properties (at m.p.)
Critical point 1314 K, 20.7 MPa
Sulfur forms several Heat of fusion mono: 1.727 kJ/mol
polyatomic molecules. The
best-known allotrope is Heat of mono: 45 kJ/mol
octasulfur, cyclo-S8 . The vaporization
point group of cyclo-S8 is Molar heat 22.75 J/(mol·K)
D4d and its dipole moment capacity
is 0 D.[9] Octasulfur is a Vapor pressure
soft, bright-yellow solid
P (Pa) 1 10 100 1k 10 k 100 k
that is odorless, but impure
samples have an odor at T (K) 375 408 449 508 591 717
As a solid, sulfur is a similar to that of
characteristic lemon yellow; matches.[10] It melts at Atomic properties
when burned, sulfur melts 115.21 °C (239.38 °F), Oxidation states −2, −1, 0, +1, +2, +3,
into a blood-red liquid and boils at 444.6 °C
[5] +4, +5, +6 (a strongly
emits a blue flame. (832.3 °F) and sublimes
acidic oxide)
more or less between
20 °C (68 °F) and 50 °C Electronegativity Pauling scale: 2.58
(122 °F). [11] At 95.2 °C (203.4 °F), below its melting Ionization 1st: 999.6 kJ/mol
temperature, cyclo-octasulfur changes from α-octasulfur to energies 2nd: 2252 kJ/mol
the β-polymorph.[12] The structure of the S8 ring is
3rd: 3357 kJ/mol
virtually unchanged by this phase change, which affects
the intermolecular interactions. Between its melting and (more)
boiling temperatures, octasulfur changes its allotrope again, Covalent radius 105±3 pm
turning from β-octasulfur to γ-sulfur, again accompanied
by a lower density but increased viscosity due to the Van der Waals 180 pm
formation of polymers.[12] At higher temperatures, the radius
viscosity decreases as depolymerization occurs. Molten
sulfur assumes a dark red color above 200 °C (392 °F).
The density of sulfur is about 2 g/cm3 , depending on the Spectral lines of sulfur
allotrope; all of the stable allotropes are excellent electrical
Other properties
insulators.
Natural primordial
Sulfur is insoluble in water but soluble in carbon disulfide occurrence
and, to a lesser extent, in other nonpolar organic solvents,
Crystal structure ​orthorhombic
such as benzene and toluene.

Chemical properties Thermal 0.205 W/(m⋅K)

conductivity (amorphous)
Under normal conditions, sulfur hydrolyzes very slowly to
mainly form hydrogen sulfide and sulfuric acid: Electrical 2×1015 Ω⋅m (at 20 °C)
resistivity (amorphous)
1⁄
2 S8 + 4 H 2 O → 3 H 2 S + H 2 SO 4
The reaction involves adsorption of protons onto S8 Magnetic ordering diamagnetic[2]
clusters, followed by disproportionation into the reaction Molar magnetic (α) −15.5 × 10−6 cm3/mol
products.[13] susceptibility (298 K)[3]
The second, fourth and sixth ionization energies of sulfur Bulk modulus 7.7 GPa
are 2252 kJ/mol, 4556 kJ/mol and 8495.8 kJ/mol, Mohs hardness 2.0
respectively. A composition of products of sulfur's
reactions with oxidants (and its oxidation state) depends on CAS Number 7704-34-9
that whether releasing out of a reaction energy overcomes History
these thresholds. Applying catalysts and / or supply of Discovery before 2000 BCE[4]
outer energy may vary sulfur's oxidation state and a
composition of reaction products. While reaction between Recognized as an Antoine Lavoisier (1777)
sulfur and oxygen at normal conditions gives sulfur element by
dioxide (oxidation state +4), formation of sulfur trioxide Isotopes of sulfur
(oxidation state +6) requires temperature 400–600 °C
(750–1,100 °F) and presence of a catalyst. Main isotopes Decay

In reactions with elements of lesser electronegativity, it abun­dance half-life (t1/2) mode pro­duct
reacts as an oxidant and forms sulfides, where it has 32
S 94.8% stable
oxidation state –2.
33
S 0.760% stable
Sulfur reacts with nearly all other elements with the
34
exception of the noble gases, even with the notoriously S 4.37% stable
unreactive metal iridium (yielding iridium disulfide).[14] 35
S trace 87.37 d β− 35
Cl
Some of those reactions need elevated temperatures.[15]
36
S 0.02% stable
34
Allotropes S abundances vary greatly (between 3.96
and 4.77 percent) in natural samples.

Sulfur forms over 30 solid allotropes, more than any other element.[16]
Besides S8 , several other rings are known.[17] Removing one atom
from the crown gives S7 , which is more of a deep yellow than the S8 .
HPLC analysis of "elemental sulfur" reveals an equilibrium mixture of
mainly S8 , but with S7 and small amounts of S6 .[18] Larger rings have
been prepared, including S12 and S18 .[19][20]

The structure of the cyclooctasulfur Amorphous or "plastic" sulfur is produced by rapid cooling of molten
molecule, S8 sulfur—for example, by pouring it into cold water. X-ray
crystallography studies show that the amorphous form may have a
helical structure with eight atoms per turn. The long coiled polymeric
molecules make the brownish substance elastic, and in bulk this form has the feel of crude rubber. This form is
metastable at room temperature and gradually reverts to crystalline molecular allotrope, which is no longer
elastic. This process happens within a matter of hours to days, but can be rapidly catalyzed.

Isotopes

Sulfur has 23 known isotopes, four of which are stable: 32 S (94.99% ± 0.26%), 33 S (0.75% ± 0.02%), 34 S
(4.25% ± 0.24%), and 36 S (0.01% ± 0.01%).[21][22] Other than 35 S, with a half-life of 87 days, the radioactive
isotopes of sulfur have half-lives less than 3 hours.
The preponderance of 32 S is explained by its production in the so-called alpha-process (one of the main classes
of nuclear fusion reactions) in exploding stars. Other stable sulfur isotopes are produced in the bypass
processes related with 34 Ar, and their composition depends on a type of a stellar explosion. For example, there
is more 33 S come from novae, than from supernovae.[23]

On the planet Earth the sulfur isotopic composition was determined by the Sun. Though it is assumed that the
distribution of different sulfur isotopes should be more or less equal, it has been found that proportions of two
most abundant sulfur isotopes 32 S and 34 S varies in different samples. Assaying of these isotopes ratio (δ34 S)
in the samples allows to make suggestions about their chemical history, and with support of other methods, it
allows to age-date the samples, estimate temperature of equilibrium between ore and water, determine pH and
oxygen fugacity, identify the activity of sulfate-reducing bacteria in the time of formation of the sample, or
suggest the main sources of sulfur in ecosystems.[24] However, discussions about what is the real reason of the
δ34 S shifts, biological activity or postdeposital alteration, go on.[25]

For example, when sulfide minerals are precipitated, isotopic equilibration among solids and liquid may cause
small differences in the δ34 S values of co-genetic minerals. The differences between minerals can be used to
estimate the temperature of equilibration. The δ13 C and δ34 S of coexisting carbonate minerals and sulfides can
be used to determine the pH and oxygen fugacity of the ore-bearing fluid during ore formation.

Scientists measure the sulfur isotopes of minerals in rocks and sediments to study the redox conditions in the
oceans in the past. Sulfate-reducing bacteria in marine sediment fractionate sulfur isotopes as they take in
sulfate and produce sulfide. Prior to 2010s, it was thought that sulfate reduction could fractionate sulfur
isotopes up to 46 permil[26] and fractionation larger than 46 permil recorded in sediments must be due to
disproportionation of sulfur compounds in the sediment. This view has changed since the 2010s as
experiments show that sulfate-reducing bacteria can fractionate to 66 permil.[27] As substrates for
disproportionation are limited by the product of sulfate reduction, the isotopic effect of disproportionation
should be less than 16 permil in most sedimentary settings.[28]

In most forest ecosystems, sulfate is derived mostly from the atmosphere; weathering of ore minerals and
evaporites contribute some sulfur. Sulfur with a distinctive isotopic composition has been used to identify
pollution sources, and enriched sulfur has been added as a tracer in hydrologic studies. Differences in the
natural abundances can be used in systems where there is sufficient variation in the 34 S of ecosystem
components. Rocky Mountain lakes thought to be dominated by atmospheric sources of sulfate have been
found to have characteristic 34 S values from lakes believed to be dominated by watershed sources of sulfate.

The radioactive 35 S is formed in cosmic ray spallation of the atmospheric 40 Ar. This fact may be used for
proving the presence of recent (not more than 1 year) atmospheric sediments in various things. This isotope
may be obtained artificially by different ways. In practice, the reaction 35 Cl + n → 35 S + p is used by
irradiating potassium chloride with neutrons.[29] The isotope 35 S is used in various sulfur-containing
compounds as a radioactive tracer for many biological studies, for example, the Hershey-Chase experiment.

Because of its weak beta activity, 35 S compounds are relatively safe as long as they are not ingested or
absorbed by the body.[30]

Natural occurrence
32 Sis created inside massive stars, at a depth where the temperature exceeds 2.5×109 K, by the fusion of one
nucleus of silicon plus one nucleus of helium.[31] As this nuclear reaction is part of the alpha process that
produces elements in abundance, sulfur is the 10th most common element in the universe.
Sulfur, usually as sulfide, is present in many types of meteorites.
Ordinary chondrites contain on average 2.1% sulfur, and carbonaceous
chondrites may contain as much as 6.6%. It is normally present as
troilite (FeS), but there are exceptions, with carbonaceous chondrites
containing free sulfur, sulfates and other sulfur compounds.[32] The
distinctive colors of Jupiter's volcanic moon Io are attributed to various
forms of molten, solid, and gaseous sulfur.[33]

It is the fifth most common element by mass in the Earth. Elemental

sulfur can be found near hot springs and volcanic regions in many Sulfur vat from which railroad cars
parts of the world, especially along the Pacific Ring of Fire; such are loaded, Freeport Sulphur Co.,
volcanic deposits are currently mined in Indonesia, Chile, and Japan. Hoskins Mound, Texas (1943)
These deposits are polycrystalline, with the largest documented single
crystal measuring 22×16×11 cm.[34] Historically, Sicily was a major
source of sulfur in the Industrial Revolution.[35] Lakes of molten sulfur
up to ~200 m in diameter have been found on the sea floor, associated
with submarine volcanoes, at depths where the boiling point of water
is higher than the melting point of sulfur.[36]

Native sulfur is synthesised by anaerobic bacteria acting on sulfate

minerals such as gypsum in salt domes.[37][38] Significant deposits in
salt domes occur along the coast of the Gulf of Mexico, and in
evaporites in eastern Europe and western Asia. Native sulfur may be
produced by geological processes alone. Fossil-based sulfur deposits
from salt domes were once the basis for commercial production in the
United States, Russia, Turkmenistan, and Ukraine.[39] Currently,
commercial production is still carried out in the Osiek mine in Poland. Most of the yellow and orange hues
Such sources are now of secondary commercial importance, and most of Io are due to elemental sulfur and
are no longer worked. sulfur compounds deposited by
active volcanoes.
Common naturally occurring sulfur compounds include the sulfide
minerals, such as pyrite (iron sulfide), cinnabar (mercury sulfide),
galena (lead sulfide), sphalerite (zinc sulfide), and stibnite (antimony
sulfide); and the sulfate minerals, such as gypsum (calcium sulfate),
alunite (potassium aluminium sulfate), and barite (barium sulfate). On
Earth, just as upon Jupiter's moon Io, elemental sulfur occurs naturally
in volcanic emissions, including emissions from hydrothermal vents.

The main industrial source of sulfur is now petroleum and natural

gas.[7]
Sulfur extraction, East Java

Compounds
Common oxidation states of sulfur range from −2 to +6. Sulfur forms stable compounds with all elements
except the noble gases.

Electron transfer reactions

Sulfur polycations, S8 2+, S4 2+ and S16 2+ are produced when sulfur is reacted with oxidising agents in a
strongly acidic solution.[40] The colored solutions produced by dissolving sulfur in oleum were first reported as
early as 1804 by C.F. Bucholz, but the cause of the color and the structure of the polycations involved was
only determined in the late 1960s. S8 2+ is deep blue, S4 2+ is yellow
and S16 2+ is red.[12]

Reduction of sulfur gives various polysulfides with the formula Sx2−,

many of which have been obtained in crystalline form. Illustrative is
the production of sodium tetrasulfide:

4 Na + S8 → 2 Na2 S4
A man carrying sulfur blocks from
Some of these dianions dissociate to give radical anions, such as S3 − Kawah Ijen, a volcano in East Java,
gives the blue color of the rock lapis lazuli. Indonesia, 2009

This reaction highlights a distinctive property of sulfur: its ability to

catenate (bind to itself by formation of chains). Protonation of these polysulfide
anions produces the polysulfanes, H2 Sx, where x = 2, 3, and 4.[42] Ultimately,
reduction of sulfur produces sulfide salts:

16 Na + S8 → 8 Na2 S

The interconversion of these species is exploited in the sodium–sulfur battery.

Hydrogenation

Treatment of sulfur with hydrogen gives hydrogen sulfide. When dissolved in

water, hydrogen sulfide is mildly acidic:[5]

H2 S ⇌ HS− + H+

Hydrogen sulfide gas and the hydrosulfide anion are extremely toxic to Lapis lazuli owes its blue
mammals, due to their inhibition of the oxygen-carrying capacity of color to a trisulfur radical
hemoglobin and certain cytochromes in a manner analogous to cyanide and anion (S−3)
azide (see below, under precautions).

Combustion

The two principal sulfur oxides are obtained by burning sulfur:

S + O2 → SO2 (sulfur dioxide)

2 SO2 + O2 → 2 SO3 (sulfur trioxide)

Many other sulfur oxides are observed including the sulfur-rich oxides
include sulfur monoxide, disulfur monoxide, disulfur dioxides, and
higher oxides containing peroxo groups.

Halogenation
Two parallel sulfur chains grown
Sulfur reacts with fluorine to give the highly reactive sulfur
inside a single-wall carbon nanotube
tetrafluoride and the highly inert sulfur hexafluoride.[43] Whereas
(CNT, a). Zig-zag (b) and straight (c)
fluorine gives S(IV) and S(VI) compounds, chlorine gives S(II) and
S chains inside double-wall CNTs[41]
S(I) derivatives. Thus, sulfur dichloride, disulfur dichloride, and higher
chlorosulfanes arise from the chlorination of sulfur. Sulfuryl chloride and chlorosulfuric acid are derivatives of
sulfuric acid; thionyl chloride (SOCl2 ) is a common reagent in organic synthesis.[44]

Pseudohalides

Sulfur oxidizes cyanide and sulfite to give thiocyanate and thiosulfate, respectively.

Metal sulfides

Sulfur reacts with many metals. Electropositive metals give polysulfide salts. Copper, zinc, and silver are
attacked by sulfur; see tarnishing. Although many metal sulfides are known, most are prepared by high
temperature reactions of the elements.[45] Geoscientists also study the isotopes of metal sulfides in rocks and
sediment to study environmental conditions in the Earth's past.[46]

Organic compounds
Illustrative organosulfur compounds

Allicin, a chemical (L)-cysteine, an Methionine, an Diphenyl disulfide, a

compound in garlic amino acid amino acid representative
containing a thiol containing a disulfide
group thioether

Perfluorooctanesulfo Dibenzothiophene, Penicillin, an

nic acid, a surfactant a component of antibiotic where "R"
crude oil is the variable group

Some of the main classes of sulfur-containing organic compounds include the following:[47]

Thiols or mercaptans (so called because they capture mercury as chelators) are the sulfur
analogs of alcohols; treatment of thiols with base gives thiolate ions.
Thioethers are the sulfur analogs of ethers.
 Sulfonium ions have three groups attached to a cationic sulfur center.
Dimethylsulfoniopropionate (DMSP) is one such compound, important in the marine organic
sulfur cycle.
Sulfoxides and sulfones are thioethers with one and two oxygen atoms attached to the sulfur
atom, respectively. The simplest sulfoxide, dimethyl sulfoxide, is a common solvent; a common
sulfone is sulfolane.
Sulfonic acids are used in many detergents.

Compounds with carbon–sulfur multiple bonds are uncommon, an exception being carbon disulfide, a volatile
colorless liquid that is structurally similar to carbon dioxide. It is used as a reagent to make the polymer rayon
and many organosulfur compounds. Unlike carbon monoxide, carbon monosulfide is stable only as an
extremely dilute gas, found between solar systems.[48]

Organosulfur compounds are responsible for some of the unpleasant odors of decaying organic matter. They
are widely known as the odorant in domestic natural gas, garlic odor, and skunk spray, as well as a component
of bad breath odor. Not all organic sulfur compounds smell unpleasant at all concentrations: the sulfur-
containing monoterpenoid grapefruit mercaptan in small concentrations is the characteristic scent of grapefruit,
but has a generic thiol odor at larger concentrations. Sulfur mustard, a potent vesicant, was used in World War
I as a disabling agent.[49]

Sulfur–sulfur bonds are a structural component used to stiffen rubber, similar to the disulfide bridges that
rigidify proteins (see biological below). In the most common type of industrial "curing" or hardening and
strengthening of natural rubber, elemental sulfur is heated with the rubber to the point that chemical reactions
form disulfide bridges between isoprene units of the polymer. This process, patented in 1843, made rubber a
major industrial product, especially in automobile tires. Because of the heat and sulfur, the process was named
vulcanization, after the Roman god of the forge and volcanism.

History

Antiquity

Being abundantly available in native form, sulfur was known in

ancient times and is referred to in the Torah (Genesis). English
translations of the Christian Bible commonly referred to burning sulfur
as "brimstone", giving rise to the term "fire-and-brimstone" sermons,
in which listeners are reminded of the fate of eternal damnation that
await the unbelieving and unrepentant. It is from this part of the
Bible[50] that Hell is implied to "smell of sulfur" (likely due to its
association with volcanic activity). According to the Ebers Papyrus, a
sulfur ointment was used in ancient Egypt to treat granular eyelids. Pharmaceutical container for sulfur
Sulfur was used for fumigation in preclassical Greece;[51] this is from the first half of the 20th century.
mentioned in the Odyssey.[52] Pliny the Elder discusses sulfur in book From the Museo del Objeto del
35 of his Natural History, saying that its best-known source is the Objeto collection
island of Melos. He mentions its use for fumigation, medicine, and
bleaching cloth.[53]

A natural form of sulfur known as shiliuhuang (

[54]
石硫黄 ) was known in China since the 6th century BC and
found in Hanzhong. By the 3rd century, the Chinese had discovered that sulfur could be extracted from
pyrite. [54] Chinese Daoists were interested in sulfur's flammability and its reactivity with certain metals, yet its
earliest practical uses were found in traditional Chinese medicine.[54] The Wujing Zongyao of 1044 AD
described various formulas for Chinese black powder, which is a mixture of potassium nitrate (KNO3 ),
charcoal, and sulfur.[55]

Sulfur Brimstone

Alchemical signs for sulfur, or the combustible elements, and brimstone, an older/archaic name for sulfur.[56]

Indian alchemists, practitioners of the "science of chemicals" (Sanskrit: रसशास्त्र, romanized: rasaśāstra), wrote
extensively about the use of sulfur in alchemical operations with mercury, from the eighth century AD
onwards.[57] In the rasaśāstra tradition, sulfur is called "the smelly" (गन्धक, gandhaka).

Early European alchemists gave sulfur a unique alchemical symbol, a triangle atop a cross (🜍). (This is
sometimes confused with the astronomical crossed-spear symbol ⚴ for 2 Pallas.) The variation known as
brimstone has a symbol combining a two-barred cross atop a lemniscate (🜏). In traditional skin treatment,
elemental sulfur was used (mainly in creams) to alleviate such conditions as scabies, ringworm, psoriasis,
eczema, and acne. The mechanism of action is unknown—though elemental sulfur does oxidize slowly to
sulfurous acid, which is (through the action of sulfite) a mild reducing and antibacterial agent.[58][59][60]

Modern times

Sulfur appears in a column of fixed (non-acidic) alkali in a chemical table of 1718.[62] Antoine Lavoisier used
sulfur in combustion experiments, writing of some of these in 1777.[63]

Sulfur deposits in Sicily were the dominant source for more than a century. By the late 18th century, about
2,000 tonnes per year of sulfur were imported into Marseille, France, for the production of sulfuric acid for use
in the Leblanc process. In industrializing Britain, with the repeal of tariffs on salt in 1824, demand for sulfur
from Sicily surged upward. The increasing British control and exploitation of the mining, refining, and
transportation of the sulfur, coupled with the failure of this lucrative export to transform Sicily's backward and
impoverished economy, led to the Sulfur Crisis of 1840, when King Ferdinand II gave a monopoly of the
sulfur industry to a French firm, violating an earlier 1816 trade agreement with Britain. A peaceful solution was
eventually negotiated by France.[64][65]

In 1867, elemental sulfur was discovered in underground deposits in Louisiana and Texas. The highly
successful Frasch process was developed to extract this resource.[66]

In the late 18th century, furniture makers used molten sulfur to produce decorative inlays.[67] Molten sulfur is
sometimes still used for setting steel bolts into drilled concrete holes where high shock resistance is desired for
floor-mounted equipment attachment points. Pure powdered sulfur was used as a medicinal tonic and
laxative.[39]

With the advent of the contact process, the majority of sulfur today is used to make sulfuric acid for a wide
range of uses, particularly fertilizer.[68]
In recent times, the main source of sulfur has become petroleum and natural
gas. This is due to the requirement to remove sulfur from fuels in order to
prevent acid rain, and has resulted in a surplus of sulfur.[7]

Spelling and etymology

Sulfur is derived from the Latin word sulpur, which was Hellenized to
sulphur in the erroneous belief that the Latin word came from Greek. This
spelling was later reinterpreted as representing an /f/ sound and resulted in the
spelling sulfur, which appears in Latin toward the end of the Classical period.
The true Ancient Greek word for sulfur, θεῖον, theîon (from earlier θέειον,
théeion), is the source of the international chemical prefix thio-. The Modern
Standard Greek word for sulfur is θείο, theío.

In 12th-century Anglo-French, it was sulfre. In the 14th century, the

erroneously Hellenized Latin -ph- was restored in Middle English sulphre.
By the 15th century, both full Latin spelling variants sulfur and sulphur
became common in English. The parallel f~ph spellings continued in Britain
until the 19th century, when the word was standardized as sulphur.[69] On
the other hand, sulfur was the form chosen in the United States, whereas
Canada uses both.

The IUPAC adopted the spelling sulfur in 1990 or 1971, depending on the
source cited,[70] as did the Nomenclature Committee of the Royal Society of Today sulfur is known to have
Chemistry in 1992, restoring the spelling sulfur to Britain.[71] Oxford antifungal, antibacterial, and
keratolytic activity; in the past
Dictionaries note that "in chemistry and other technical uses ... the -f- spelling
it was used against acne
is now the standard form for this and related words in British as well as US
vulgaris, rosacea, seborrheic
contexts, and is increasingly used in general contexts as well."[72]
dermatitis, dandruff, pityriasis
versicolor, scabies, and
Production warts.[61] This 1881
advertisement baselessly
Sulfur may be found by itself and claims efficacy against
historically was usually obtained in rheumatism, gout, baldness,
this form; pyrite has also been a and graying of hair.
source of sulfur.[73] In volcanic
regions in Sicily, in ancient times, it
was found on the surface of the Earth, and the "Sicilian process" was
used: sulfur deposits were piled and stacked in brick kilns built on
sloping hillsides, with airspaces between them. Then, some sulfur was
pulverized, spread over the stacked ore and ignited, causing the free
sulfur to melt down the hills. Eventually the surface-borne deposits
Sicilian kiln used to obtain sulfur
played out, and miners excavated veins that ultimately dotted the
from volcanic rock (diagram from a Sicilian landscape with labyrinthine mines. Mining was unmechanized
1906 chemistry book) and labor-intensive, with pickmen freeing the ore from the rock, and
mine-boys or carusi carrying baskets of ore to the surface, often
through a mile or more of tunnels. Once the ore was at the surface, it
was reduced and extracted in smelting ovens. The conditions in Sicilian sulfur mines were horrific, prompting
Booker T. Washington to write "I am not prepared just now to say to what extent I believe in a physical hell in
the next world, but a sulfur mine in Sicily is about the nearest thing to hell that I expect to see in this life."[74]
Sulfur is still mined from surface deposits in poorer nations with volcanoes, such as Indonesia, and worker
conditions have not improved much since Booker T. Washington's days.[75]
Elemental sulfur was extracted from salt domes (in which it sometimes occurs
in nearly pure form) until the late 20th century. Sulfur is now produced as a
side product of other industrial processes such as in oil refining, in which
sulfur is undesired. As a mineral, native sulfur under salt domes is thought to
be a fossil mineral resource, produced by the action of anaerobic bacteria on
sulfate deposits. It was removed from such salt-dome mines mainly by the
Frasch process.[39] In this method, superheated water was pumped into a
native sulfur deposit to melt the sulfur, and then compressed air returned the
99.5% pure melted product to the surface. Throughout the 20th century this
procedure produced elemental sulfur that required no further purification. Due
to a limited number of such sulfur deposits and the high cost of working them,
this process for mining sulfur has not been employed in a major way anywhere
in the world since 2002.[76][77]

Today, sulfur is produced from Traditional sulfur mining at

petroleum, natural gas, and related Ijen Volcano, East Java,
fossil resources, from which it is Indonesia. This image
obtained mainly as hydrogen sulfide.[7] shows the dangerous and
Organosulfur compounds, undesirable rugged conditions the
impurities in petroleum, may be miners face, including toxic
upgraded by subjecting them to smoke and high drops, as
Sulfur recovered from hydrocarbons hydrodesulfurization, which cleaves well as their lack of
in Alberta, stockpiled for shipment in the C–S bonds:[76][77] protective equipment. The
North Vancouver, British Columbia pipes over which they are
R-S-R + 2 H2 → 2 RH + H2 S standing are for condensing
sulfur vapors.
The resulting hydrogen sulfide from this process, and also as it occurs in
natural gas, is converted into elemental sulfur by the Claus process. This
process entails oxidation of some hydrogen sulfide to sulfur dioxide and then the comproportionation of the
two:[76][77]

3 O2 + 2 H2 S → 2 SO2 + 2 H2 O
SO2 + 2 H2 S → 3 S + 2 H2 O

Owing to the high sulfur content of the Athabasca Oil

Sands, stockpiles of elemental sulfur from this process
now exist throughout Alberta, Canada.[78] Another way
of storing sulfur is as a binder for concrete, the resulting
product having many desirable properties (see sulfur
concrete).[79]

The world production of sulfur in 2011 amounted to

69 million tonnes (Mt), with more than 15 countries Production and price (US market) of elemental
contributing more than 1 Mt each. Countries producing sulfur
more than 5 Mt are China (9.6), the United States (8.8),
Canada (7.1) and Russia (7.1).[80] Production has been
slowly increasing from 1900 to 2010; the price was unstable in the 1980s and around 2010.[81]

Applications

Sulfuric acid
Elemental sulfur is used mainly as a precursor to other chemicals. Approximately 85% (1989) is converted to
sulfuric acid (H2 SO4 ):
1⁄ S8 + 3 ⁄2 O2 + H2 O → H2 SO4
8

In 2010, the United States produced more sulfuric acid

than any other inorganic industrial chemical.[81] The
principal use for the acid is the extraction of phosphate
ores for the production of fertilizer manufacturing. Other
applications of sulfuric acid include oil refining,
wastewater processing, and mineral extraction.[39]
Sulfuric acid production in 2000
Other important sulfur chemistry

Sulfur reacts directly with methane to give carbon disulfide, which is used to manufacture cellophane and
rayon.[39] One of the uses of elemental sulfur is in vulcanization of rubber, where polysulfide chains crosslink
organic polymers. Large quantities of sulfites are used to bleach paper and to preserve dried fruit. Many
surfactants and detergents (e.g. sodium lauryl sulfate) are sulfate derivatives. Calcium sulfate, gypsum
(CaSO4 ·2H2 O) is mined on the scale of 100 million tonnes each year for use in Portland cement and fertilizers.

When silver-based photography was widespread, sodium and ammonium thiosulfate were widely used as
"fixing agents". Sulfur is a component of gunpowder ("black powder").

Fertilizer

Amino acids synthesized by living organisms such as methionine and cysteine contain organosulfur groups
(thioester and thiol respectively). The antioxidant glutathione protecting many living organisms against free
radicals and oxidative stress also contains organic sulfur. Some crops such as onion and garlic also produce
different organosulfur compounds such as syn-propanethial-S-oxide responsible of lacrymal irritation (onions),
or diallyl disulfide and allicin (garlic). Sulfates, commonly found in soils and groundwaters are often a
sufficient natural source of sulfur for plants and bacteria. Atmospheric deposition of sulfur dioxide (SO2 ) is
also a common artificial source (coal combustion) of sulfur for the soils. Under normal circumstances, in most
agricultural soils, sulfur is not a limiting nutrient for plants and microorganisms (see Liebig's barrel). However,
in some circumstances, soils can be depleted in sulfate, e.g. if this later is leached by meteoric water (rain) or if
the requirements in sulfur for some types of crops are high. This explains that sulfur is increasingly recognized
and used as a component of fertilizers. The most important form of sulfur for fertilizer is calcium sulfate,
commonly found in nature as the mineral gypsum (CaSO4 ·2H2 O). Elemental sulfur is hydrophobic (not
soluble in water) and cannot be used directly by plants. Elemental sulfur (ES) is sometimes mixed with
bentonite to amend depleted soils for crops with high requirement in organo-sulfur. Over time, oxidation
abiotic processes with atmospheric oxygen and soil bacteria can oxidize and convert elemental sulfur to soluble
derivatives, which can then be used by microorganisms and plants. Sulfur improves the efficiency of other
essential plant nutrients, particularly nitrogen and phosphorus.[82] Biologically produced sulfur particles are
naturally hydrophilic due to a biopolymer coating and are easier to disperse over the land in a spray of diluted
slurry, resulting in a faster uptake by plants.
The plants requirement for sulfur equals or exceeds the requirement for phosphorus. It is an essential nutrient
for plant growth, root nodule formation of legumes, and immunity and defense systems. Sulfur deficiency has
become widespread in many countries in Europe.[83][84][85] Because atmospheric inputs of sulfur continue to
decrease, the deficit in the sulfur input/output is likely to increase unless sulfur fertilizers are used. Atmospheric
inputs of sulfur decrease because of actions taken to limit acid rains.[86][82]

Fungicide and pesticide

Elemental sulfur is one of the oldest fungicides and pesticides. "Dusting

sulfur", elemental sulfur in powdered form, is a common fungicide for
grapes, strawberry, many vegetables and several other crops. It has a good
efficacy against a wide range of powdery mildew diseases as well as black
spot. In organic production, sulfur is the most important fungicide. It is the
only fungicide used in organically farmed apple production against the main
disease apple scab under colder conditions. Biosulfur (biologically produced
elemental sulfur with hydrophilic characteristics) can also be used for these
applications.

Standard-formulation dusting sulfur is applied to crops with a sulfur duster or

from a dusting plane. Wettable sulfur is the commercial name for dusting
Sulfur candle originally sold
sulfur formulated with additional ingredients to make it water
for home fumigation
miscible.[79][87] It has similar applications and is used as a fungicide against
mildew and other mold-related problems with plants and soil.

Elemental sulfur powder is used as an "organic" (i.e., "green") insecticide (actually an acaricide) against ticks
and mites. A common method of application is dusting the clothing or limbs with sulfur powder.

A diluted solution of lime sulfur (made by combining calcium hydroxide with elemental sulfur in water) is used
as a dip for pets to destroy ringworm (fungus), mange, and other dermatoses and parasites.

Sulfur candles of almost pure sulfur were burned to fumigate structures and wine barrels, but are now
considered too toxic for residences.

Pharmaceuticals

Sulfur (specifically octasulfur, S8 ) is used in pharmaceutical skin preparations for the treatment of acne and
other conditions. It acts as a keratolytic agent and also kills bacteria, fungi, scabies mites, and other
parasites.[88] Precipitated sulfur and colloidal sulfur are used, in form of lotions, creams, powders, soaps, and
bath additives, for the treatment of acne vulgaris, acne rosacea, and seborrhoeic dermatitis.[89]

Many drugs contain sulfur.[90] Early examples include antibacterial sulfonamides, known as sulfa drugs. A
more recent example is mucolytic acetylcysteine. Sulfur is a part of many bacterial defense molecules. Most β-
lactam antibiotics, including the penicillins, cephalosporins and monobactams contain sulfur.[47]

Batteries
Due to their high energy density and the availability of sulfur, there is ongoing research in creating
rechargeable lithium–sulfur batteries. Until now, carbonate electrolytes have caused failures in such batteries
after a single cycle. In February 2022, researchers at Drexel University have not only created a prototypical
battery that lasted 4000 recharge cycles, but also found the first monoclinic gamma sulfur that remained stable
below 95 degrees Celsius.[91]

Biological role
Sulfur is an essential component of all living cells. It is the eighth most abundant element in the human body
by weight,[92] about equal in abundance to potassium, and slightly greater than sodium and chlorine.[93] A
70 kg (150 lb) human body contains about 140 grams of sulfur.[94] The main dietary source of sulfur for
humans is sulfur-containing amino-acids,[95] which can be found in plant and animal proteins.[96]

Transferring sulfur between inorganic and biomolecules

In the 1880s, while studying Beggiatoa (a bacterium living in a sulfur rich environment), Sergei Winogradsky
found that it oxidized hydrogen sulfide (H2 S) as an energy source, forming intracellular sulfur droplets.
Winogradsky referred to this form of metabolism as inorgoxidation (oxidation of inorganic compounds).[97]
Another contributor, who continued to study it was Selman Waksman.[98] Primitive bacteria that live around
deep ocean volcanic vents oxidize hydrogen sulfide for their nutrition, as discovered by Robert Ballard.[8]

Sulfur oxidizers can use as energy sources reduced sulfur compounds, including hydrogen sulfide, elemental
sulfur, sulfite, thiosulfate, and various polythionates (e.g., tetrathionate).[99] They depend on enzymes such as
sulfur oxygenase and sulfite oxidase to oxidize sulfur to sulfate. Some lithotrophs can even use the energy
contained in sulfur compounds to produce sugars, a process known as chemosynthesis. Some bacteria and
archaea use hydrogen sulfide in place of water as the electron donor in chemosynthesis, a process similar to
photosynthesis that produces sugars and uses oxygen as the electron acceptor. Sulfur-based chemosynthesis
may be simplifiedly compared with photosynthesis:

H2 S + CO2 → sugars + S
H2 O + CO2 → sugars + O2

There are bacteria combining these two ways of nutrition: green sulfur bacteria and purple sulfur bacteria.[100]
Also sulfur-oxidizing bacteria can go into symbiosis with larger organisms, enabling the later to use hydrogen
sulfide as food to be oxidized. Example: the giant tube worm.[101]

There are sulfate-reducing bacteria, that, by contrast, "breathe sulfate" instead of oxygen. They use organic
compounds or molecular hydrogen as the energy source. They use sulfur as the electron acceptor, and reduce
various oxidized sulfur compounds back into sulfide, often into hydrogen sulfide. They can grow on other
partially oxidized sulfur compounds (e.g. thiosulfates, thionates, polysulfides, sulfites).

There are studies pointing that many deposits of native sulfur in places that were the bottom of the ancient
oceans have biological origin.[102][103][104] These studies indicate that this native sulfur have been obtained
through biological activity, but what is responsible for that (sulfur-oxidizing bacteria or sulfate-reducing
bacteria) is still unknown for sure.

Sulfur is absorbed by plants roots from soil as sulfate and transported as a phosphate ester. Sulfate is reduced to
sulfide via sulfite before it is incorporated into cysteine and other organosulfur compounds.[105]

SO4 2− → SO3 2− → H2 S → cysteine (thiol) → methionine (thioether)

While the plants' role in transferring sulfur to animals by food chains is more or less understood, the role of
sulfur bacteria is just getting investigated.[106][107]

Protein and organic metabolites

In all forms of life, most of the sulfur is contained in two proteinogenic amino acids (cysteine and methionine),
thus the element is present in all proteins that contain these amino acids, as well as in respective peptides.[108]
Some of the sulfur is comprised in certain metabolites — many of which are cofactors — and sulfated
polysaccharides of connective tissue (chondroitin sulfates, heparin).

Proteins, to execute their biological function, need to have specific

space geometry. Formation of this geometry is performed in a process
called protein folding, and is provided by intra- and inter-molecular
bonds. The process has several stages. While at premier stages a
polypeptide chain folds due to hydrogen bonds, at later stages folding
is provided (apart from hydrogen bonds) by covalent bonds between
two sulfur atoms of two cysteine residues (so called disulfide bridges)
at different places of a chain (tertiary protein structure) as well as
between two cysteine residues in two separated protein subunits
(quaternary protein structure). Both structures easily may be seen in
insulin. As the bond energy of a covalent disulfide bridge is higher
than the energy of a coordinate bond or hydrophobic interaction,
higher disulfide bridges content leads to higher energy needed for
protein denaturation. In general disulfide bonds are necessary in
proteins functioning outside cellular space, and they do not change
proteins' conformation (geometry), but serve as its stabilizers.[109]
Within cytoplasm cysteine residues of proteins are saved in reduced
state (i.e. in -SH form) by thioredoxins.[110]
Schematic representation of disulfide
bridges (in yellow) between two This property manifests in following examples. Lysozyme is stable
protein helices enough to be applied as a drug.[111] Feathers and hair have relative
strength, and consisting in them keratin is considered indigestible by
most organisms. However, there are fungi and bacteria containing
keratinase, and are able to destruct keratin.

Many important cellular enzymes use prosthetic groups ending with -SH moieties to handle reactions involving
acyl-containing biochemicals: two common examples from basic metabolism are coenzyme A and alpha-lipoic
acid.[112] Cysteine-related metabolites homocysteine and taurine are other sulfur-containing amino acids that
are similar in structure, but not coded by DNA, and are not part of the primary structure of proteins, take part
in various locations of mammalian physiology.[113][114] Two of the 13 classical vitamins, biotin and thiamine,
contain sulfur, and serve as cofactors to several enzymes.[115][116]

In intracellular chemistry, sulfur operates as a carrier of reducing hydrogen and its electrons for cellular repair
of oxidation. Reduced glutathione, a sulfur-containing tripeptide, is a reducing agent through its sulfhydryl (-
SH) moiety derived from cysteine.

Methanogenesis, the route to most of the world's methane, is a multistep biochemical transformation of carbon
dioxide. This conversion requires several organosulfur cofactors. These include coenzyme M,
CH3 SCH2 CH2 SO3 −, the immediate precursor to methane.[117]

Metalloproteins and inorganic cofactors

Metalloproteins — in which the active site is a transition metal ion (or metal-sulfide cluster) often coordinated
by sulfur atoms of cysteine residues[118] — are essential components of enzymes involved in electron transfer
processes. Examples include plastocyanin (Cu2+) and nitrous oxide reductase (Cu–S). The function of these
enzymes is dependent on the fact that the transition metal ion can undergo redox reactions. Other examples
include many zinc proteins,[119] as well as iron–sulfur clusters. Most pervasive are the ferrodoxins, which
serve as electron shuttles in cells. In bacteria, the important nitrogenase enzymes contain an Fe–Mo–S cluster
and is a catalyst that performs the important function of nitrogen fixation, converting atmospheric nitrogen to
ammonia that can be used by microorganisms and plants to make proteins, DNA, RNA, alkaloids, and the
other organic nitrogen compounds necessary for life.[120]

Easiness of electron flow in a cluster provides catalytic effect of a respective enzyme.

Deficiency

In humans methionine is an essential amino acid; cysteine is conditionally essential and may be synthesized
from non-essential serine (sulfur donor would be methionine in this case). Dietary deficiency rarely happens in
common conditions. Artificial methionine deficiency is attempted to apply in cancer treatment,[121] but the
method is still potentially dangerous.[122]

Isolated sulfite oxidase deficiency is a rare, fatal genetic disease preventing production of sulfite oxidase,
needed to metabolize sulfites to sulfates.[123]

Precautions
Though elemental sulfur is only minimally absorbed through the skin Sulfur
and is of low toxicity to humans, inhalation of sulfur dust or contact
Hazards
with eyes or skin may cause irritation. Excessive ingestion of sulfur
can cause a burning sensation or diarrhea,[126] and cases of life- GHS labelling:
threatening metabolic acidosis have been reported after patients Pictograms
deliberately consumed sulfur as a folk remedy.[127][128]

Signal word Warning

Toxicity of sulfur compounds Hazard H315[124]
statements
When sulfur burns in air, it produces sulfur dioxide. In water, this gas
NFPA 704 [125]
produces sulfurous acid and sulfites; sulfites are antioxidants that
inhibit growth of aerobic bacteria and a useful food additive in small (fire diamond)
amounts. At high concentrations these acids harm the lungs, eyes, or
1
2 0
other tissues.[129] In organisms without lungs such as insects or plants,
sulfite in high concentration prevents respiration.
Sulfur trioxide (made by catalysis from sulfur dioxide) and sulfuric
acid are similarly highly acidic and corrosive in the presence of water.
Concentrated sulfuric acid is a strong dehydrating agent that can strip
available water molecules and water components from sugar and
organic tissue.[130]

The burning of coal and/or petroleum by industry and power plants

generates sulfur dioxide (SO2 ) that reacts with atmospheric water and
oxygen to produce sulfuric acid (H2 SO4 ) and sulfurous acid
(H2 SO3 ).[131] These acids are components of acid rain, lowering the Effect of acid rain on a forest, Jizera
pH of soil and freshwater bodies, sometimes resulting in substantial Mountains, Czech Republic
damage to the environment and chemical weathering of statues and
structures. Fuel standards increasingly require that fuel producers
extract sulfur from fossil fuels to prevent acid rain formation. This extracted and refined sulfur represents a
large portion of sulfur production. In coal-fired power plants, flue gases are sometimes purified. More modern
power plants that use synthesis gas extract the sulfur before they burn the gas.

Hydrogen sulfide is about one-half as toxic as hydrogen cyanide, and intoxicates by the same mechanism
(inhibition of the respiratory enzyme cytochrome oxidase),[132] though hydrogen sulfide is less likely to cause
sudden poisonings from small inhaled amounts (near its permissible exposure limit (PEL) of 20 ppm) because
of its disagreeable odor.[133] However, its presence in ambient air at concentration over 100–150 ppm quickly
deadens the sense of smell,[134] and a victim may breathe increasing quantities without noticing until severe
symptoms cause death. Dissolved sulfide and hydrosulfide salts are toxic by the same mechanism.

See also
Chemistry portal

Blue lava
Stratospheric sulfur aerosols
Sulfur assimilation
Sulfur isotope biogeochemistry
Ultra-low sulfur diesel

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Further reading
Sigel, Astrid; Freisinger, Eva; Sigel, Roland K.O., eds. (2020). Transition Metals and Sulfur: A Strong
Relationship for Life. Guest Editors Martha E Sosa Torres and Peter M.H.Kroneck. Berlin/Boston: de Gruyter.
pp. xlv+455. ISBN 978-3-11-058889-7.

External links
Sulfur (http://www.periodicvideos.com/videos/016.htm) at The Periodic Table of Videos
(University of Nottingham)
Atomic Data for Sulfur (https://physics.nist.gov/PhysRefData/Handbook/Tables/sulfurtable1.ht
m), NIST Physical Measurement Laboratory
Sulfur phase diagram (https://library.tedankara.k12.tr/chemistry/vol2/allotropy/z129.htm)
Archived (https://web.archive.org/web/20100223201329/http://library.tedankara.k12.tr/chemistr
 y/vol2/allotropy/z129.htm) 23 February 2010 at the Wayback Machine, Introduction to Chemistry
for Ages 13–17
Crystalline, liquid and polymerization of sulfur on Vulcano Island, Italy (https://www.swisseduc.c
h/stromboli/perm/vulcano/sulphur-vulcano-en.html)
Sulfur and its use as a pesticide (http://extoxnet.orst.edu/pips/sulfur.htm)
The Sulphur Institute (https://www.sulphurinstitute.org/)
Nutrient Stewardship and The Sulphur Institute (https://web.archive.org/web/20140714221502/
http://www.nutrientstewardship.com/partners/products-and-services/sulfur-institute)

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