carbon disulfide

In 1796, the German chemist Wilhelm August Lampadius (1772–1842) first prepared carbon disulfide by heating pyrite with moist charcoal. He called it "liquid sulfur" (flüssig Schwefel).{{cite journal |last1=Lampadius |title=Etwas über flüssigen Schwefel, und Schwefel-Leberluft |journal=Chemische Annalen für die Freunde der Naturlehre, Arzneygelährtheit, Haushaltungskunst und Manufacturen (Chemical Annals for the Friends of Science, Medicine, Economics, and Manufactures)|date=1796 |issue=2 |pages=136–137 |url=https://books.google.com/books?id=gqk5AAAAcAAJ&pg=PA136 |trans-title=Something about liquid sulfur and liver-of-sulfur gas (i.e., hydrogen sulfide) |language=de}} The composition of carbon disulfide was finally determined in 1813 by the team of the Swedish chemist Jöns Jacob Berzelius (1779–1848) and the Swiss-British chemist Alexander Marcet (1770–1822).{{cite journal |last1=Berzelius |first1=J. |last2=Marcet |first2=Alexander |title=Experiments on the alcohol of sulphur, or sulphuret of carbon |journal=Philosophical Transactions of the Royal Society of London |date=1813 |volume=103 |pages=171–199 |doi=10.1098/rstl.1813.0026 |s2cid=94745906 |doi-access=free }} Their analysis was consistent with an empirical formula of CS₂.(Berzelius and Marcet, 1813), p. 187.

Small amounts of carbon disulfide are released by volcanic eruptions and marshes. CS₂ once was manufactured by combining carbon (or coke) and sulfur at 800–1000 °C.{{cite journal | last=Warnecke | first=Friedrich | title=Die gewerbliche Schwefelkohlenstoffvergiftung | journal=Archiv für Gewerbepathologie und Gewerbehygiene | publisher=Springer Science and Business Media LLC | volume=11 | issue=2 | year=1941 | issn=0340-0131 | doi=10.1007/bf02122927 | pages=198–248 | bibcode=1941IAOEH..11..198W | s2cid=72106188 | language=de}}

:C + 2S → CS₂

A lower-temperature reaction, requiring only 600 °C, utilizes natural gas as the carbon source in the presence of silica gel or alumina catalysts:

:2 CH₄ + S₈ → 2 CS₂ + 4 H₂S

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.{{cite web |url=http://www.ihs.com/products/chemical/planning/ceh/carbon-disulfide.aspx |title=Carbon Disulfide report from IHS Chemical |access-date= June 15, 2013 }} United States production in 2007 was 56,000 tonnes.{{cite web |url=http://www.icis.com/Articles/2008/09/08/9154319/chemical-profile-carbon-disulfide.html |title=Chemical profile: carbon disulfide from ICIS.com |access-date= June 15, 2013 }}

Carbon disulfide can dissolve a variety of nonpolar chemicals including phosphorus, sulfur, selenium, bromine, iodine, fats, resins, rubber, and asphalt.{{cite web |url=http://www.akzonobel.com/sulfurderivatives/products/carbon_disulfide/ |title=Carbon Disulfide |publisher=Akzo Nobel |access-date=2010-12-16 |archive-date=2017-09-03 |archive-url=https://web.archive.org/web/20170903211829/https://www.akzonobel.com/sulfurderivatives/products/carbon_disulfide/ |url-status=dead }}

In March 2024, possible traces of CS₂ were detected in the atmosphere of the temperate mini-Neptune planet TOI-270 d by the James Webb Space Telescope.{{Citation |last1=Benneke |first1=Björn |title=JWST Reveals CH$_4$, CO$_2$, and H$_2$O in a Metal-rich Miscible Atmosphere on a Two-Earth-Radius Exoplanet |date=2024-03-05 |last2=Roy |first2=Pierre-Alexis |last3=Coulombe |first3=Louis-Philippe |last4=Radica |first4=Michael |last5=Piaulet |first5=Caroline |last6=Ahrer |first6=Eva-Maria |last7=Pierrehumbert |first7=Raymond |last8=Krissansen-Totton |first8=Joshua |last9=Schlichting |first9=Hilke E.|arxiv=2403.03325 }}

Combustion of CS₂ affords sulfur dioxide according to this ideal stoichiometry:

:CS₂ + 3{{nbsp}}O₂ → CO₂ + 2{{nbsp}}SO₂

For example, amines afford dithiocarbamates:{{cite journal | last1=Yokoyama | first1=Masataka | last2=Imamoto | first2=Tsuneo | title=Organic Reactions of Carbon Disulfide | journal=Synthesis | publisher=Georg Thieme Verlag KG | volume=1984 | issue=10 | year=1984 | issn=0039-7881 | doi=10.1055/s-1984-30978 | pages=797–824}}

:2{{nbsp}}R₂NH + CS₂ → [R₂NH₂⁺][R₂NCS₂⁻]

Xanthates form similarly from alkoxides:

:RONa + CS₂ → [Na⁺][ROCS₂⁻]

This reaction is the basis of the manufacture of regenerated cellulose, the main ingredient of viscose, rayon, and cellophane. Both xanthates and the related thioxanthates (derived from treatment of CS₂ with sodium thiolates) are used as flotation agents in mineral processing.

Upon treatment with sodium sulfide, carbon disulfide affords trithiocarbonate:

:Na₂S + CS₂ → [Na⁺]₂[CS₃²⁻]

Carbon disulfide does not hydrolyze readily, although the process is catalyzed by an enzyme carbon disulfide hydrolase.

Compared to the isoelectronic carbon dioxide, CS₂ is a weaker electrophile. While, however, reactions of nucleophiles with CO₂ are highly reversible and products are only isolated with very strong nucleophiles, the reactions with CS₂ are thermodynamically more favored allowing the formation of products with less reactive nucleophiles.{{Cite journal|last1=Li|first1=Zhen|last2=Mayer|first2=Robert J.|last3=Ofial|first3=Armin R.| last4=Mayr|first4=Herbert|date=2020-04-27|title= From Carbodiimides to Carbon Dioxide: Quantification of the Electrophilic Reactivities of Heteroallenes|journal=Journal of the American Chemical Society|volume=142|issue=18|pages=8383–8402|doi=10.1021/jacs.0c01960|pmid=32338511|bibcode=2020JAChS.142.8383L |s2cid=216557447}}

Reduction of carbon disulfide with sodium affords sodium 1,3-dithiole-2-thione-4,5-dithiolate together with sodium trithiocarbonate:{{cite journal|journal=Org. Synth.|year=1996|volume=73|page=270|doi=10.15227/orgsyn.073.0270|title=4,5-Dibenzoyl-1,3-dithiole-1-thione}}

: 4{{nbsp}}Na + 4{{nbsp}}CS₂ → Na₂C₃S₅ + Na₂CS₃

Chlorination of CS₂ provides a route to carbon tetrachloride:

:CS₂ + 3 Cl₂ → CCl₄ + S₂Cl₂

This conversion proceeds via the intermediacy of thiophosgene, CSCl₂.

CS₂ is a ligand for many metal complexes, forming pi complexes. One example is CpCo(η²-CS₂)(PMe₃).{{cite journal |last=Werner |first=Helmut |title=Novel Coordination Compounds formed from CS₂ and Heteroallenes |journal=Coordination Chemistry Reviews |year=1982 |volume=43 |pages=165–185 |doi=10.1016/S0010-8545(00)82095-0 }}

CS₂ 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.{{cite journal |last1=Bridgman |first1=P.W. |title=Explorations toward the limit of utilizable pressures |journal=Journal of Applied Physics |date=1941 |volume=12 |issue=6 |pages=461–469|doi=10.1063/1.1712926 |bibcode=1941JAP....12..461B }} Trithiocarbonate (-S-C(S)-S-) linkages comprise, in part, the backbone of the polymer, which is a semiconductor.{{cite journal |title=Carbon dioxide and carbon disulfide as resources for functional polymers |first1=Bungo |last1=Ochiai |first2=Takeshi |last2=Endo |journal=Progress in Polymer Science |volume=30 |issue=2 |pages=183–215 |doi=10.1016/j.progpolymsci.2005.01.005 |year=2005 }}

The principal industrial uses of carbon disulfide, consuming 75% of the annual production, are the manufacture of viscose rayon and cellophane film.

It is also a valued intermediate in chemical synthesis of carbon tetrachloride. 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, which are used as drugs (e.g. Metam sodium) and rubber chemistry.

File:Carbon disulfide insecticide ad, 1896 - The American elevator and grain trade (IA CAT31053470064) (page 3 crop).jpg

It can be used in fumigation of airtight storage warehouses, airtight flat storage, bins, grain elevators, railroad box cars, ship holds, barges, and cereal mills.{{Greenwood&Earnshaw2nd|page=}} 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.{{cite book |last1=Worthing |first1=Charles R. |last2=Hance |first2=Raymond J. |title=The Pesticide Manual, A World Compendium |publisher=British Crop Protection Council |year=1991 |edition=9th |isbn=9780948404429 |url-access=registration |url=https://archive.org/details/pesticidemanualw0000unse }}

It can also be used for the Barking dog reaction.

Carbon disulfide has been linked to both acute and chronic forms of poisoning, with a diverse range of symptoms.{{Cite web|url=https://www.atsdr.cdc.gov/phs/phs.asp?id=472&tid=84#bookmark05|title=ATSDR - Public Health Statement: Carbon Disulfide|website=www.atsdr.cdc.gov|access-date=2020-01-17|archive-date=2019-12-14|archive-url=https://web.archive.org/web/20191214052436/https://www.atsdr.cdc.gov/PHS/PHS.asp?id=472&tid=84#bookmark05|url-status=dead}}

Concentrations of 500–3000 mg/m³ cause acute and subacute poisoning. These include a set of mostly neurological and psychiatric symptoms, called encephalopathia sulfocarbonica. Symptoms include acute psychosis (manic delirium, hallucinations), 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, abnormalities in nerve conduction), hearing problems, vision problems (burning eyes, abnormal light reactions, increased ophthalmic pressure), heart problems (increased deaths for heart disease, angina pectoris, high blood pressure), reproductive problems (increased miscarriages, immobile or deformed sperm), and decreased immune response.{{cite book |title=Air Quality Guidelines |date=2000 |publisher=WHO Regional Office for Europe, Copenhagen, Denmark |edition=2 |url=https://www.euro.who.int/__data/assets/pdf_file/0019/123058/AQG2ndEd_5_4carbodisulfide.PDF |access-date=31 July 2021 |chapter=Chapter 5.4 : Carbon disulfide |archive-date=18 October 2022 |archive-url=https://web.archive.org/web/20221018194943/https://www.euro.who.int/__data/assets/pdf_file/0019/123058/AQG2ndEd_5_4carbodisulfide.PDF |url-status=dead }}{{Cite report |url=https://www.cdc.gov/niosh/docs/2018-124/ |title=Preventing hearing loss caused by chemical (ototoxicity) and noise exposure. |date=2018-03-01 |publisher=U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control and Prevention, National Institute for Occupational Safety and Health |doi=10.26616/nioshpub2018124 |language=en|doi-access=free }}

Occupational exposure to carbon disulfide is also associated with cardiovascular disease, particularly stroke.{{cite web |url=http://www.sbu.se/en/publications/sbu-assesses/occupational-health-and-safety--chemical-exposure/ |title=Occupational health and safety – chemical exposure |publisher=Swedish Agency for Health Technology Assessment and Assessment of Social Services (SBU) |website=www.sbu.se |language=en |access-date=2017-06-07 |archive-url=https://web.archive.org/web/20170606093333/http://www.sbu.se/en/publications/sbu-assesses/occupational-health-and-safety--chemical-exposure/ |archive-date=2017-06-06 |url-status=dead }}

In 2000, the WHO believed that health harms were unlikely at levels below 100 μg/m³, and set this as a guideline level.{{needs update|date=November 2023}} Carbon disulfide can be smelled at levels above 200 μg/m³, and the WHO recommended a sensory guideline of below 20 μg/m³. Exposure to carbon disulfide is well-established to be harmful to health in concentrations at or above 30 mg/m³. Changes in the function of the central nervous system have been observed at concentrations of 20–25 mg/m³. There are also reports of harms to health at 10 mg/m³, 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/m³ findings uncertain. The measured concentration of 10 mg/m³ may be equivalent to a concentration in the general environment of 1 mg/m³.

The primary source of carbon disulfide in the environment is rayon factories. Most global carbon disulfide emissions come from rayon production, as of 2008. Other sources include the production of cellophane, carbon tetrachloride,{{cite web |url=https://www.dir.ca.gov/dosh/DoshReg/CarbonDisulfide5155-4-08.doc|type=DOC|title=Carbon Disulfide Health Effects Assessment for HEAC Discussion April 2008|date=April 2008|website=Division of Occupational Safety and Health|publisher=State of California Department of Industrial Relations|access-date=24 March 2023}} carbon black, and sulfur recovery. Carbon disulfide production also emits hydrogen sulfide.

{{as of|2004}}, about 250 g of carbon disulfide is emitted per kilogram of rayon produced. About 30 g of carbon disulfide is emitted per kilogram of carbon black produced. About 0.341 g of carbon disulfide 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, {{as of|lc=yes|2004}}.{{cite journal |last1=Blake |first1=Nicola J. |title=Carbonyl sulfide and carbon disulfide: Large-scale distributions over the western Pacific and emissions from Asia during TRACE-P |journal=Journal of Geophysical Research |date=2004 |volume=109 |issue=D15 |pages=D15S05 |doi=10.1029/2003JD004259|bibcode=2004JGRD..10915S05B |s2cid=43793469 |url=https://scholars.unh.edu/cgi/viewcontent.cgi?article=1072&context=earthsci_facpub |doi-access=free }} 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.{{cite news |last1=Swan |first1=Norman |last2=Blanc |first2=Paul |title=The health burden of viscose rayon |url=http://www.abc.net.au/radionational/programs/healthreport/the-health-burden-of-viscose-rayon/8286870 |work=ABC Radio National |date=20 February 2017 |language=en|access-date=24 March 2023}}{{cite magazine|title=Bamboo Boom: Is This Material for You?|author=Nijhuis, Michelle |magazine=Scientific American Special Editions|volume=19|issue=2|pages=60–65|url=https://www.scientificamerican.com/article/bamboo-boom/|access-date=24 March 2023|year=2009|bibcode=2009SciAm..19f..60N}} One exception is rayon made using the lyocell process, which uses a different solvent; {{as of|lc=yes|2018}} the lyocell process is not widely used, because it is more expensive than the viscose process.{{cite journal |title=Regenerated cellulose by the Lyocell process, a brief review of the process and properties :: BioResources |journal=BioRes |url=https://bioresources.cnr.ncsu.edu/resources/regenerated-cellulose-by-the-lyocell-process-a-brief-review-of-the-process-and-properties/ |date=2018}}{{cite thesis |last1=Tierney |first1=John William |title=Kinetics of Cellulose Dissolution in N-MethylMorpholine-N-Oxide and Evaporative Processes of Similar Solutions |date=2005 |url=https://trace.tennessee.edu/cgi/viewcontent.cgi?referer=&httpsredir=1&article=3796&context=utk_gradthes}} Cuprammonium rayon also does not use carbon disulfide.

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 {{doi| 10.1002/14356007.a05_185}}{{Cite book|title=The Golden Thread: How Fabric Changed History|last=St. Clair|first=Kassia|publisher=John Murray|year=2018|isbn=978-1-4736-5903-2|location=London|pages=213–215|oclc=1057250632}}{{cite book |last1=Blanc, M.D. |first1=Paul David |title=Fake Silk / The Lethal History of Viscose Rayon |date=15 November 2016 |publisher=Yale University Press |isbn=9780300204667 |url=https://yalebooks.yale.edu/book/9780300204667/fake-silk |access-date=17 December 2020 |quote=in 1915,...[of 16] carbon disulfide poisoning cases....one worker had been briefly committed to an asylum and several others had experienced nervous system complaints...}}{{rp|79}} Around 1900, carbon disulfide came to be widely used in the production of vulcanized rubber. The psychosis produced by high exposures was immediately apparent (it has been reported with 6 months of exposure). Sir Thomas Oliver told a story about a rubber factory that put bars on its windows so that the workers would not jump out to their deaths.{{rp|17|\}} Carbon disulfide's use in the US as a heavier-than-air burrow poison for Richardson's ground squirrel also led 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, 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?{{globalize inline|US|date=October 2021}}). Rayon production has since largely moved to the developing world, especially China, Indonesia and India.

Rates of disability in modern factories are unknown, {{as of|lc=yes|2016}}.{{cite journal |doi= 10.1126/science.aak9834|pmid=27884997|title=Toxic textiles|year= 2016 |last1= Monosson |first1= Emily |journal= Science|volume= 354|issue= 6315 |page=977|bibcode= 2016Sci...354..977M|s2cid=45869497}} Current manufacturers using the viscose process do not provide any information on harm to their workers.

• Carbon monosulfide
• Ethenedithione
• Carbon subsulfide
• Carbon diselenide
• Carbon dioxide
• 1949 Holland Tunnel fire, accident with truck carrying carbon disulfide.

{{reflist}}

{{Commons category|Carbon disulfide}}

{{EB1911 poster|Carbon Bisulphide}}

• [http://www.npi.gov.au/substances/carbon-disulfide/index.html Australian National Pollutant Inventory: Carbon disulfide]
• [https://www.cdc.gov/niosh/npg/npgd0104.html CDC - NIOSH Pocket Guide to Chemical Hazards - Carbon Disulfide]
• [https://web.archive.org/web/20120305094145/http://www.innomotionengg.com/ Inno Motion Engineering]
• Agency for Toxic Substances & Disease Registry [https://www.atsdr.cdc.gov/phs/phs.asp?id=472&tid=84#bookmark05 Public Health Statement for Carbon Disulfide] {{Webarchive|url=https://web.archive.org/web/20191214052436/https://www.atsdr.cdc.gov/PHS/PHS.asp?id=472&tid=84#bookmark05 |date=2019-12-14 }}, 1996.
• [https://www.cdc.gov/niosh/topics/carbon-disulfide/default.html Resources on Carbon Disulfide] by the National Institute for Occupational Safety and Health
• {{cite book |last1=Blanc |first1=Paul David |title=Fake silk : the lethal history of viscose rayon |date=2016 |publisher=Yale University Press |location=New Haven |isbn=9780300204667 |pages=328 |url=https://yalebooks.yale.edu/book/9780300204667/fake-silk}}

{{Carbon compounds}}

{{Sulfides}}

{{Authority control}}

{{DEFAULTSORT:Carbon Disulfide}}

Category:Sulfides

Category:Inorganic carbon compounds

Category:Inorganic sulfur compounds

Category:Inorganic solvents

Category:Neurotoxins

Category:Dichalcogenides

Category:Chemical hazards

Category:Foul-smelling chemicals

Category:IV-VI semiconductors