Carbon disulfide (also spelled as carbon disulphide) is a
neurotoxic, colorless,
volatile liquid with the
formula
In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...
and
structure
A structure is an arrangement and organization of interrelated elements in a material object or system, or the object or system so organized. Material structures include man-made objects such as buildings and machines and natural objects such a ...
. The
compound is used frequently as a building block in
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J ...
as well as an industrial and chemical non-polar
solvent
A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
. It has an "
ether
In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again ...
-like" odor, but commercial samples are typically contaminated with foul-smelling impurities.
[.] It is of comparable toxicity to
carbon monoxide
Carbon monoxide ( chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simpl ...
.
History
In 1796, the German chemist
Wilhelm August Lampadius (1772–1842) first prepared carbon disulfide by heating
pyrite
The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral.
Pyrite's metallic Luster (mineralogy), lust ...
with moist charcoal. He called it "liquid sulfur" (''flüssig Schwefel''). The composition of carbon disulfide was finally determined in 1813 by the team of the Swedish chemist
Jöns Jacob Berzelius
Baron Jöns Jacob Berzelius (; by himself and his contemporaries named only Jacob Berzelius, 20 August 1779 – 7 August 1848) was a Swedish chemist. Berzelius is considered, along with Robert Boyle, John Dalton, and Antoine Lavoisier, to be o ...
(1779–1848) and the Swiss-British chemist
Alexander Marcet (1770–1822). Their analysis was consistent with an
empirical formula of CS
2.
Occurrence, manufacture, properties
Small amounts of carbon disulfide are released by
volcanic
A volcano is a rupture in the crust of a planetary-mass object, such as Earth, that allows hot lava, volcanic ash, and gases to escape from a magma chamber below the surface.
On Earth, volcanoes are most often found where tectonic plat ...
eruptions and
marsh
A marsh is a wetland that is dominated by herbaceous rather than woody plant species.Keddy, P.A. 2010. Wetland Ecology: Principles and Conservation (2nd edition). Cambridge University Press, Cambridge, UK. 497 p Marshes can often be found ...
es. CS
2 once was manufactured by combining
carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...
(or
coke) and
sulfur
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...
at 800–1000 °C.
:C + 2S → CS
2
A lower-temperature reaction, requiring only 600 °C, utilizes
natural gas
Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbon d ...
as the carbon source in the presence of
silica gel or
alumina catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s:
:2 CH
4 + S
8 → 2 CS
2 + 4 H
2S
The reaction is analogous to the combustion of methane.
Global production/consumption of carbon disulfide is approximately one million tonnes, with China consuming 49%, followed by India at 13%, mostly for the production of rayon fiber. United States production in 2007 was 56,000 tonnes.
Solvent
Carbon disulfide is a solvent for
phosphorus
Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...
, sulfur,
selenium,
bromine
Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
,
iodine
Iodine is a chemical element with the Symbol (chemistry), symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , ...
,
fats,
resin
In polymer chemistry and materials science, resin is a solid or highly viscous substance of plant or synthetic origin that is typically convertible into polymers. Resins are usually mixtures of organic compounds. This article focuses on nat ...
s,
rubber
Rubber, also called India rubber, latex, Amazonian rubber, ''caucho'', or ''caoutchouc'', as initially produced, consists of polymers of the organic compound isoprene, with minor impurities of other organic compounds. Thailand, Malaysia, and ...
, and
asphalt
Asphalt, also known as bitumen (, ), is a sticky, black, highly viscous liquid or semi-solid form of petroleum. It may be found in natural deposits or may be a refined product, and is classed as a pitch. Before the 20th century, the term ...
. It has been used in the purification of single-walled carbon nanotubes.
Reactions
CS
2 is highly flammable. Its combustion affords
sulfur dioxide
Sulfur dioxide (IUPAC-recommended spelling) or sulphur dioxide (traditional Commonwealth English) is the chemical compound with the formula . It is a toxic gas responsible for the odor of burnt matches. It is released naturally by volcanic a ...
according to this ideal stoichiometry:
:CS
2 + 3O
2 → CO
2 + 2SO
2
With nucleophiles
Compared to the
isoelectronic
Isoelectronicity is a phenomenon observed when two or more molecules have the same structure (positions and connectivities among atoms) and the same electronic configurations, but differ by what specific elements are at certain locations in th ...
carbon dioxide
Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
, CS
2 is a weaker
electrophile. While, however, reactions of
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 ar ...
s with CO
2 are highly reversible and products are only isolated with very strong nucleophiles, the reactions with CS
2 are thermodynamically more favored allowing the formation of products with less reactive nucleophiles. For example, amines afford
dithiocarbamates:
:2R
2NH + CS
2 →
2NH2+">2NH2+R
2NCS
2−]
Xanthates form similarly from
alkoxide
In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as , where R is the organic substituent. Alkoxides are strong bases and, whe ...
s:
:RONa + CS
2 →
+">a+ROCS
2−]
This reaction is the basis of the manufacture of regenerated
cellulose
Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell wa ...
, the main ingredient of
viscose,
rayon
Rayon is a semi-synthetic fiber, made from natural sources of regenerated cellulose, such as wood and related agricultural products. It has the same molecular structure as cellulose. It is also called viscose. Many types and grades of viscose ...
and
cellophane. Both xanthates and the related
thioxanthate In chemistry, a thioxanthate is an organosulfur compound with the formula RSCS2X. When X is an alkali metal, the thioxanthate is a salt. When X is a transition metal, the thioxanthate is a ligand, and when X is an organic group, the compounds are ...
s (derived from treatment of CS
2 with sodium
thiolates) are used as flotation agents in mineral processing.
Sodium sulfide affords
trithiocarbonate Thiocarbonate describes a family of anions with the general chemical formula (''x'' = 0, 1, or 2):
*for ''x'' = 2 it is monothiocarbonate ion
*for ''x'' = 1 it is dithiocarbonate ion
*for ''x'' = 0 it is trithiocarbonate ion
Like the carbonate ...
:
:Na
2S + CS
2 →
+">a+sub>2
32−">S32−
Carbon disulfide does not hydrolyze readily, although the process is catalyzed by an
enzyme
Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
carbon disulfide hydrolase.
Reduction
Reduction of carbon disulfide with sodium affords
sodium 1,3-dithiole-2-thione-4,5-dithiolate
Sodium 1,3-dithiole-2-thione-4,5-dithiolate is the organosulfur compound with the formula Na2C3S5, abbreviated Na2dmit. It is the sodium salt of the conjugate base of the 1,3-dithiole-2-thione-4,5-dithiol. The salt is a precursor to dithiolene ...
together with sodium
trithiocarbonate Thiocarbonate describes a family of anions with the general chemical formula (''x'' = 0, 1, or 2):
*for ''x'' = 2 it is monothiocarbonate ion
*for ''x'' = 1 it is dithiocarbonate ion
*for ''x'' = 0 it is trithiocarbonate ion
Like the carbonate ...
:
: 4Na + 4CS
2 → Na
2C
3S
5 + Na
2CS
3
Chlorination
Chlorination of CS
2 provides a route to
carbon tetrachloride
Carbon tetrachloride, also known by many other names (such as tetrachloromethane, also recognised by the IUPAC, carbon tet in the cleaning industry, Halon-104 in firefighting, and Refrigerant-10 in HVACR) is an organic compound with the chemi ...
:
:CS
2 + 3
Cl2 → CCl
4 +
S2Cl2
This conversion proceeds via the intermediacy of
thiophosgene
Thiophosgene is a red liquid with the formula . It is a molecule with trigonal planar geometry. There are two reactive C–Cl bonds that allow it to be used in diverse organic syntheses.
Preparation
is prepared in a two-step process from carbon ...
, CSCl
2.
Coordination chemistry
CS
2 is a ligand for many metal complexes, forming pi complexes. One example is
CpCo(
η2-CS
2)(P
Me3).
Polymerization
CS
2 polymerizes upon photolysis or under high pressure to give an insoluble material called car-sul or "Bridgman's black", named after the discoverer of the polymer,
Percy Williams Bridgman. Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a
semiconductor
A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way ...
.
Uses
The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of
viscose rayon
Rayon is a semi-synthetic fiber, made from natural sources of regenerated cellulose, such as wood and related agricultural products. It has the same molecular structure as cellulose. It is also called viscose. Many types and grades of viscose f ...
and
cellophane film.
It is also a valued intermediate in chemical synthesis of
carbon tetrachloride
Carbon tetrachloride, also known by many other names (such as tetrachloromethane, also recognised by the IUPAC, carbon tet in the cleaning industry, Halon-104 in firefighting, and Refrigerant-10 in HVACR) is an organic compound with the chemi ...
. It is widely used in the synthesis of organosulfur compounds such as
xanthates, which are used in
froth flotation, a method for extracting metals from their ores. Carbon disulfide is also a precursor to
dithiocarbamates
In organic chemistry, a dithiocarbamate is a functional group with the general formula and structure . It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms (when only 1 oxygen is replaced the result is thiocar ...
, which are used as drugs (e.g.
Metam sodium) and
rubber chemistry.
Niche uses
It can be used in
fumigation
Fumigation is a method of pest control or the removal of harmful micro-organisms by completely filling an area with gaseous pesticides—or fumigants—to suffocate or poison the pests within. It is used to control pests in buildings ( ...
of airtight storage warehouses, airtight flat storages, bins, grain elevators, railroad box cars, shipholds, barges and cereal mills. Carbon disulfide is also used as an insecticide for the fumigation of grains, nursery stock, in fresh fruit conservation and as a soil disinfectant against insects and
nematodes.
Health effects
Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.
Concentrations of 500–3000 mg/m
3 cause acute and subacute poisoning. These include a set of mostly neurological and psychiatric symptoms, called encephalopathia sulfocarbonica. Symptoms include acute
psychosis
Psychosis is a condition of the mind that results in difficulties determining what is real and what is not real. Symptoms may include delusions and hallucinations, among other features. Additional symptoms are incoherent speech and behavi ...
(manic
delirium
Delirium (also known as acute confusional state) is an organically caused decline from a previous baseline of mental function that develops over a short period of time, typically hours to days. Delirium is a syndrome encompassing disturbances ...
,
hallucinations
A hallucination is a perception in the absence of an external stimulus that has the qualities of a real perception. Hallucinations are vivid, substantial, and are perceived to be located in external objective space. Hallucination is a combinati ...
),
paranoic ideas, loss of appetite, gastrointestinal and sexual disorders, polyneuritis, myopathy, and mood changes (including irritability and anger). Effects observed at lower concentrations include neurological problems (
encephalopathy, psychomotor and psychological disturbances,
polyneuritis
Peripheral neuropathy, often shortened to neuropathy, is a general term describing disease affecting the peripheral nerves, meaning nerves beyond the brain and spinal cord. Damage to peripheral nerves may impair sensation, movement, gland, or or ...
, abnormalities in nerve conduction), vision problems (burning eyes, abnormal light reactions, increased ophthalmic pressure), heart problems (increased deaths for heart disease,
angina pectoris,
high blood pressure
Hypertension (HTN or HT), also known as high blood pressure (HBP), is a long-term medical condition in which the blood pressure in the arteries is persistently elevated. High blood pressure usually does not cause symptoms. Long-term high bl ...
), and reproductive problems (increased miscarriages,
immobile or
deformed sperm), and decreased immune response.
Occupational exposure to carbon disulfide is also associated with
cardiovascular disease
Cardiovascular disease (CVD) is a class of diseases that involve the heart or blood vessels. CVD includes coronary artery diseases (CAD) such as angina and myocardial infarction (commonly known as a heart attack). Other CVDs include stroke, hea ...
, particularly
stroke
A stroke is a disease, medical condition in which poor cerebral circulation, blood flow to the brain causes cell death. There are two main types of stroke: brain ischemia, ischemic, due to lack of blood flow, and intracranial hemorrhage, hemorr ...
.
In 2000, the WHO believed that health harms were unlikely at levels below 100 μg/m
3, and set this as a guideline level. Carbon sulfide can be smelled at levels above 200 μg/m
3, and the WHO recommended a sensory guideline of below 20 μg/m
3. Exposure to carbon disulfide is well-established to be harmful to health in concentrations at or above 30 mg/m
3 Changes in the function of the central nervous system have been observed at concentrations of 20–25 mg/m
3. There are also reports of harms to health at 10 mg/m
3, for exposures of 10–15 years, but the lack of good data on past exposure levels make the association of these harms with concentrations of 10 mg/m
3 findings uncertain. The measured concentration of 10 mg/m
3 may be equivalent to a concentration in the general environment of 1 mg/m
3.
Environmental sources
The primary source of carbon disulfide in the environment is rayon factories.
Most global carbon disulfide emissions come from
rayon
Rayon is a semi-synthetic fiber, made from natural sources of regenerated cellulose, such as wood and related agricultural products. It has the same molecular structure as cellulose. It is also called viscose. Many types and grades of viscose ...
production, as of 2008.
[ Other sources include the production of cellophane, carbon tetrachloride,] carbon black, and sulfur recovery. Carbon disulfide production also emits carbon disulfide.[
, about 250 g of carbon disufide is emitted per kilogram of rayon produced. About 30 g of carbon disufide is emitted per kilogram of carbon black produced. About 0.341 g of carbon disufide is emitted per kilogram of sulfur recovered.][
Japan has reduced carbon disulfide emissions per kilogram of rayon produced, but in other rayon-producing countries, including China, emissions are assumed to be uncontrolled (based on global modelling and large-scale free-air concentration measurements). Rayon production is steady or decreasing except in China, where it is increasing, .] Carbon black production in Japan and Korea uses incinerators to destroy about 99% of the carbon disulfide that would otherwise be emitted.[ When used as a solvent, Japanese emissions are about 40% of the carbon disulfide used; elsewhere, the average is about 80%.][
Most rayon production uses carbon sulfide.][ One exception is rayon made using the ]lyocell
Lyocell, originally trademarked in 1982 as Tencel, is a form of regenerated cellulose. It consists of cellulose fibers, made by dissolving pulp and then reconstituting it by dry jet-wet spinning. The fiber is used to make textiles for clothing a ...
process, which uses a different solvent; the lyocell process is not widely used, because it is more expensive than the viscose process. Cuprammonium rayon also does not use carbon disulfide.
Historic and current exposure
Industrial workers working with carbon disulfide are at high risk. Emissions may also harm the health of people living near rayon plants.
Concerns about carbon disulfide exposure have a long history.[Lay, Manchiu D. S.; Sauerhoff, Mitchell W.; Saunders, Donald R.; "Carbon Disulfide", in ''Ullmann's Encyclopedia of Industrial Chemistry'', Wiley-VCH, Weinheim, 2000 ] Around 1900, carbon disulfide came to be widely used in the production of vulcanized rubber
Vulcanization (British: Vulcanisation) is a range of processes for hardening rubbers. The term originally referred exclusively to the treatment of natural rubber with sulfur, which remains the most common practice. It has also grown to inclu ...
. The psychosis produced by high exposures was immediately apparent (it has been reported with 6 months of exposure). Sir Thomas Oliver
Sir Thomas Oliver, (1853–1942) was a Scottish physician and expert on industrial hygiene, particularly in the mining industry and antimony workers. He was President of the College of Medicine 1926 to 1934 and President of the Royal Institute ...
told a story about a rubber factory that put bars on its windows so that the workers would not jump out to their deaths. Carbon disulfide's use in the US as a heavier-than-air burrow poison for Richardson's ground squirrel also lead to reports of psychosis. No systematic medical study of the issue was published, and knowledge was not transferred to the rayon industry.[
The first large epidemiological study of rayon workers was done in the US in the late 1930s, and found fairly severe effects in 30% of the workers. Data on increased risks of heart attacks and strokes came out in the 1960s. ]Courtaulds
Courtaulds was a United Kingdom-based manufacturer of fabric, clothing, artificial fibres, and chemicals. It was established in 1794 and became the world's leading man-made fibre production company before being broken up in 1990 into Courtaulds ...
, a major rayon manufacturer, worked hard to prevent publication of this data in the UK.[ Average concentrations in sampled rayon plants were reduced from about 250 mg/m3 in 1955-1965 to about 20–30 mg/m3 in the 1980s (US figures only?).] Rayon production has since largely moved to the developing world, especially China, Indonesia and India.[
Rates of disability in modern factories are unknown, .] Current manufacturers using the viscose process do not provide any information on harm to their workers.
See also
* Carbon monosulfide
Carbon monosulfide is a chemical compound with the formula CS. This diatomic molecule is the sulfur analogue of carbon monoxide, and is unstable as a solid or a liquid, but it has been observed as a gas both in the laboratory and in the interst ...
* Carbon subsulfide
Carbon subsulfide is an organic, sulfur-containing chemical compound with the formula and structure . This deep red liquid is immiscible with water but soluble in organic solvents. It readily polymerizes at room temperature to form a hard bla ...
* Carbon diselenide
* 1949 Holland Tunnel fire, accident with truck carrying carbon disulfide.
References
External links
Australian National Pollutant Inventory: Carbon disulfide
* ttps://web.archive.org/web/20120305094145/http://www.innomotionengg.com/ Inno Motion Engineering* Agency for Toxic Substances & Disease Registr
Public Health Statement for Carbon Disulfide
1996.
by the National Institute for Occupational Safety and Health
*
{{DEFAULTSORT:Carbon Disulfide
Sulfides
Inorganic carbon compounds
Inorganic sulfur compounds
Inorganic solvents
Hazardous air pollutants
Neurotoxins
Dichalcogenides
Occupational safety and health
Foul-smelling chemicals