Sulfur (or
Sulphur; see spelling below) is the
chemical element in the
periodic table that has the symbol
S and
atomic number 16. It is an abundant, tasteless, odorless, multivalent non-metal. Sulfur, in its native form, is a yellow crystaline solid. In nature, it can be found as the pure element or as
sulfide and
sulfate minerals. It is an essential element for life and is found in several
amino acids. Its commercial uses are primarily in
fertilizers but it is also widely used in
gunpowder,
matches,
insecticides and
fungicides.
Notable characteristics
At room temperature, sulfur is a soft bright yellow solid. Although sulfur is infamous for its smell - frequently compared to rotten eggs - the odor is actually characteristic of
hydrogen sulfide (H
2S); elemental sulfur is odorless. It burns with a blue flame that emits
sulfur dioxide, notable for its peculiar suffocating odor. Sulfur is insoluble in water but soluble in
carbon disulfide and other nonpolar solvents. Common oxidation states of sulfur include −2, +2, +4 and +6. Sulfur forms stable compounds with all elements except the noble gases.
Sulfur in the solid state ordinarily exists as a cyclic crown-shaped S
8 molecules. Sulfur has many
allotropes besides S
8. Removing one atom from the crown gives S
7, which is responsible for sulfur's distinctive yellow color. Many other rings have been prepared, including S
12 and S
18. By contrast, its lighter neighbor
oxygen only exists in two states of chemical significance: O
2 and O
3.
Selenium, the heavier analogue of sulfur can form rings but is more often found as a polymer chain.
The
crystallography of sulfur is complex. Depending on the specific conditions, the sulfur allotropes form several distinct
crystal structures, with
rhombic and
monoclinic S
8 best known.
A noteworthy property is that the
viscosity of molten sulfur, unlike most other liquids, increases with temperature due to the formation of
polymer chains.
Amorphous or "plastic" sulfur can be produced through the rapid cooling of molten sulfur.
X-ray crystallography studies show that the amorphous form may have a
helical structure with eight atoms per turn. This form is metastable at room temperature and gradually reverts back to crystalline form. This process happens within a matter of hours to days but can be rapidly catalyzed by human
saliva.
Applications
Sulfur has many industrial uses. Through its major derivative,
sulfuric acid (
H2S
O4), sulfur ranks as one of the more important elements used as an industrial raw material. It is of prime importance to every sector of the
world's economies. Sulfuric acid production is the major end use for sulfur, and consumption of sulfuric acid has been regarded as one of the best indices of a nation's industrial development. More sulfuric acid is produced in the
United States every year than any other industrial chemical. Sulfur is also used in
batteries, detergents, the
vulcanization of
rubber,
fungicides, and in the manufacture of
phosphate fertilizers.
Sulfites are used to bleach
paper and as a preservative in
wine and dried
fruit. Because of its flammable nature, sulfur also finds use in
matches,
gunpowder, and
fireworks. Sodium or ammonium
thiosulfate are used as photographic fixing agents.
Magnesium sulfate, better known as Epsom salts can be used as a
laxative, a bath additive, an exfoliant, or a
magnesium supplement for plants.
Biological role
The
amino acids cysteine and
methionine contain sulfur, as do all polypeptides,
proteins, and
enzymes which contain these amino acids. This makes sulfur a necessary component of all living
cells.
Disulfide bonds between polypeptides are very important in protein assembly and structure.
Homocysteine and
taurine are also sulfur containing amino acids but are not coded for by
DNA nor are they part of the
primary structure of proteins. Some forms of
bacteria use
hydrogen sulfide (H
2S) in the place of water as the
electron donor in a primitive
photosynthesis-like process. Sulfur is absorbed by
plants from soil as the
sulfate ion. Inorganic sulfur forms a part of
iron-sulfur clusters, and sulfur is the bridging ligand in the
CuA site of
cytochrome c oxidase. Sulfur is an important component of coenzyme A
Environmental Impact
The burning of
coal and
petroleum by industry and power plants liberates huge amounts of
sulfur dioxide S
O2, which reacts with atmospheric water and oxygen to produce sulfuric acid. This causes
acid rain which lowers the
pH of
soil and freshwater bodies, resulting in substantial damage to the
natural environment and chemical weathering of statues and architecture. Fuel standards increasingly require sulfur to be extracted from
fossil fuels to prevent the formation of acid rain. This extracted sulfur is then refined and represents a large portion of sulfur production.
History
Sulfur crystal
Sulfur (Sanskrit,
sulvere;
Latin sulpur) was known in ancient times, and is referred to in the
Biblical story of Pentateuch (Genesis). English translations of this commonly refer to sulfur as "brimstone", giving rise to the name of
Fire and brimstone sermons, which are sermons where
hell and eternal damnation for sinners is stressed. It is from this part of the bible that
hell is thought to smell of sulfur.
The word itself is almost certainly from the Arabic "sufra" meaning yellow, from the bright color of the naturally-occurring form.
Homer mentioned "pest-averting sulfur" in the
9th century BC and in
424 BC, the tribe of
Boeotia destroyed the walls of a city by burning a mixture of coal, sulfur, and tar under them.
Sometime in the
12th century, the
Chinese invented gun powder which is a mixture of
potassium nitrate (
KNO3),
carbon, and sulfur. Early
alchemists gave sulfur its own alchemical symbol which was a triangle at the top of a cross. In the late
1770s,
Antoine Lavoisier helped convince the scientific community that sulfur was an element and not a compound.
In 1867 sulfur was discovered in underground deposits in
Louisiana and
Texas. The overlying layer of earth was
quicksand, prohibiting ordinary mining operations. Therefore the
Frasch process was utilized.
Occurrence
Sulfur
Sulfur crystalites at [[Wai-o-tapu
hot springs,
New Zealand]]
Elemental sulfur can be found near
hot springs and volcanic regions in many parts of the world, especially along the
Pacific Ring of Fire. These occurrences are the basis for the traditional name brimstone, since sulfur could be found near the brims of volcanic craters. Such volcanic deposits are currently exploited in
Indonesia,
Chile, and
Japan.
Significant desposits of elemental sulfur also exist in salt domes along the coast of the
Gulf of Mexico, and in
evaporites in eastern Europe and western Asia. The sulfur in these deposits is believed to come from the action of anaerobic bacteria on
sulfate minerals, especially
gypsum. Such deposits are the basis for commercial production in the
United States,
Poland,
Russia,
Turkmenistan, and
Ukraine.
Common naturally-occurring sulfur compounds include the metal
sulfides, such as
pyrite (iron sulfide),
cinnabar (mercury sulfide),
Galena (lead sulfide),
sphalerite (zinc sulfide) and
stibnite (antimony sulfide); and the metal sulfates, such as gypsum (calcium sulfate),
alunite (potassium aluminium sulfate), and
barite (barium sulfate).
Hydrogen sulfide is the gas responsible for the odor of rotten
eggs. It occurs naturally in volcanic emissions, such as from
hydrothermal vents, and from bacterial action on decaying sulfur-containing organic matter.
The distinctive colors of Jupiter's
volcanic moon
Io, are from various forms of molten, solid and gaseous sulfur. There is also a dark area near the
Lunar crater Aristarchus that may be a sulfur deposit. Sulfur is also present in many types of
meteorites.
Compounds
Hydrogen sulfide has the characteristic smell of rotten eggs. Dissolved in water, hydrogen sulfide is acidic and will react with metals to form a series of metal sulfides. Natural metal sulfides are common, especially those of iron. Iron sulfide is called
pyrite, the so called
fool's gold. Interestingly, pyrite can show semiconductor properties.
http://home.earthlink.net/~lenyr/iposc.htm Galena, a naturally occurring lead sulfide, was the first
semiconductor discovered, and found a use as a signal
rectifier in the "cat's whiskers" of early crystal radios.
Many of the unpleasant odors of organic matter are based on sulfur-containing compounds such as ethyl and methyl mercaptan used to scent natural gas so that leaks are easily detectable. The odor of
garlic and "
skunk stink" are also caused by sulfur containing organic compounds.
Polymeric sulfur nitride has metallic properties even though it does not contain any
metal atoms. This compound also has unusual electrical and optical properties.
Other important compounds of sulfur include:
- dimethylsulfoniopropionate (DMSP; (CH3 )2S+CH2CH2COO-) which is the central component of the marine organic sulfur cycle.
- sodium dithionite, Na2S2O4, a powerful reducing agent.
- sulfurous acid, H2SO3, created by dissolving SO2 in water. Sulfurous acid and the corresponding sulfites are fairly strong reducing agents. Other compounds derived from SO2 include the pyrosulfite ion (S2O52−).
- The thiosulfates (S2O32−). Thiosulfates are used in photographic fixing, are reducing agents, and ammonium thiosulfate is being investigated as a cyanide replacement in leaching gold.http://doccopper.tripod.com/gold/AltLixiv.html
- Compounds of dithionic acid (H2S2O6)
- The polythionic acids, (H2SnO6), where n can range from 3 to 80.
- The sulfates, the salts of sulfuric acid.
- Sulfides are simple compounds of sulfur with some other chemical element.
- Sulfuric acid reacts with SO3 in equimolar ratios to form pyrosulfuric acid.
- peroxymonosulfuric acid and peroxydisulfuric acids, made from the action of SO3 on concentrated H2O2, and H2SO4 on concentrated H2O2 respectively.
- tetrasulfur tetranitride S4N4.
- Thiocyanates are compounds containing the thiocyanate ion, SCN-
- thiocyanogen, (SCN)2.
- A thioether is a molecule with the form R-S-R', where R and R' are organic groups. These are the sulfur equivalents of ethers.
- A thiol (also known as a mercaptan) is a molecule with an -SH functional group. These are the sulfur equivalents of alcohols.
- A thiolate ion has an -S- functional group attached. These are the sulfur equivalent of alkoxide ions.
- A sulfone is a molecule with an R-S(=O)-R' functional group where R and R' are organic groups.
- A sulfoxide is a molecule with an R-S(=O)(=O)-R' functional group where R and R' are organic groups. A common example of a sulfoxide is DMSO.
Isotopes
Sulfur has 18
isotopes, of which four are stable:
32S (95.02%),
33S (0.75%),
34S (4.21%), and
36S (0.02%). Other than
35S, the radioactive isotopes of sulfur are all short lived. Sulfur-35 is formed from
cosmic ray spallation of
argon-40 in the
atmosphere. It has a
half-life of 87 days.
When sulfide
minerals are precipitated, isotopic equilibration among solids and liquid may cause small differences in the dS-34 values of co-genetic minerals. The differences between minerals can be used to estimate the temperature of equilibration. The d
C-13 and dS-34 of co-existing
carbonates and sulfides can be used to determine the
pH and
oxygen fugacity of the ore-bearing fluid during ore formation.
In most
forest ecosystems, sulfate is derived mostly from the atmosphere; weathering of ore minerals and evaporites also 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 also be used in systems where there is sufficient variation in the S-34 of ecosystem components. Rocky Mountain lakes thought to be dominated by atmospheric sources of sulfate have been found to have different dS-34 values from lakes believed to be dominated by watershed sources of sulfate.
Precautions
Carbon disulfide, hydrogen sulfide, and sulfur dioxide should all be handled with care.
Although
sulfur dioxide is sufficiently safe to be used as a
food additive in small amounts, at high concentrations it reacts with moisture to form
sulfurous acid which in sufficient quantities may harm the lungs, eyes or other
tissues. In creatures without lungs such as insects or plants, it otherwise prevents
respiration.
Hydrogen sulfide is quite toxic (more toxic than
cyanide). Although very smelly at first, it quickly deadens the sense of smell, so potential victims may be unaware of its presence until it is too late.
Spelling
The element has traditionally been spelled
sulphur in the
United Kingdom,
India, and
New Zealand, but
sulfur in the
United States, while both spellings are used in
Australia and
Canada. The IUPAC adopted the spelling "sulfur" in 1990, as did the
Royal Society of Chemistry Nomenclature Committee in 1992.
See also
References
External links
Category:Nonmetals
Category:Chalcogens
Category:Pyrotechnic chemicals
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