| Revision as of 21:39, 17 January 2011 edit67.253.246.228 (talk)No edit summary← Previous edit |
Latest revision as of 10:28, 26 November 2024 edit undo194.190.252.20 (talk) Phosphorus trichloride reduces sulfur dichloride, so PCl5 is added to stabilize SCl2 |
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| verifiedrevid = 393532629 |
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| verifiedrevid = 408467094 |
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| Name = Sulfur dichloride |
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| Name = Sulfur dichloride |
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| ImageFile = Sulfur-dichloride-2D-dimensions.png |
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| ImageFile = Sulfur-dichloride-2D-dimensions.png |
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| ImageSize = 160px |
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| ImageSize = 160px |
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| ImageName = Structure and dimensions of the sulfur dichloride molecule |
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| ImageName = Structure and dimensions of the sulfur dichloride molecule |
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| ImageFileL1 = Sulfur-dichloride-3D-balls.png |
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| ImageFileL1 = Sulfur-dichloride-3D-balls.png |
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| ImageSizeL1 = 120px |
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| ImageSizeL1 = 120px |
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| ImageNameL1 = Ball-and-stick model of sulfur dichloride |
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| ImageNameL1 = Ball-and-stick model of sulfur dichloride |
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| ImageFileR1 = Sulfur-dichloride-3D-vdW.png |
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| ImageFileR1 = Sulfur-dichloride-3D-vdW.png |
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| ImageSizeR1 = 110px |
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| ImageSizeR1 = 110px |
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| ImageNameR1 = Space-filling model of sulfur dichloride |
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| ImageNameR1 = Space-filling model of sulfur dichloride |
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| IUPACName = Sulpur dichloride<br/>Sulfur(II) chloride<br/>Dichlorosulfane |
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| IUPACName = {{ubl|Dichlorosulfane|Sulfur dichloride|Sulfur(II) chloride}} |
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| OtherNames = Sulpur chloride |
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| OtherNames = {{ubl|Chloro thiohypochlorite|Dichloro sulfide|Sulphur chloride}} |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| SMILES = ClSCl |
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| CASNo = 10545-99-0 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 10545-99-0 |
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| ChemSpiderID = 23682 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| RTECS = WS4500000 |
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| RTECS = WS4500000 |
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| EINECS = 234-129-0 |
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| EINECS = 234-129-0 |
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| UNNumber = 1828 |
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| UNNumber = 1828 |
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| PubChem = 25353 |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 8Q6684WQ9H |
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| SMILES = ClSCl |
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| InChI = 1/Cl2S/c1-3-2 |
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| InChIKey = FWMUJAIKEJWSSY-UHFFFAOYAS |
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| StdInChI = 1S/Cl2S/c1-3-2 |
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| StdInChIKey = FWMUJAIKEJWSSY-UHFFFAOYSA-N |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = SCl<sub>2</sub> |
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| Formula = {{chem2|SCl2}} |
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| S=1|Cl=2 |
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| MolarMass = 102.97 g mol<sup>−1</sup> |
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| Appearance = red liquid with pungent odour |
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| Appearance = Cherry-red liquid |
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| Odour = Pungent |
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| Density = 1.621 g cm<sup>−3</sup>, liquid |
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| Density = 1.621 g/cm<sup>3</sup> |
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| Solubility = hydrolysis |
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| Solubility = Insoluble, reacts slowly |
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| MeltingPt = −121.0 °C (152.15 K) |
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| MeltingPtC = −121.0 |
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| BoilingPt = 59 °C (332.15 K) (decomp.) |
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| BoilingPtC = 59 |
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| RefractIndex = 1.5570 |
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| BoilingPt_notes = (decomposes) |
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| RefractIndex = 1.5570 |
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| MagSus = −49.4·10<sup>−6</sup> cm<sup>3</sup>/mol |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| Coordination = C<sub>2v</sub> |
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| Coordination = C<sub>2v</sub> |
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| MolShape = Bent |
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| MolShape = Bent |
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| Dipole = |
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| Dipole = |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| GHSPictograms = {{GHS05}}{{GHS07}}{{GHS09}} |
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| EUIndex = 016-013-00-X |
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| GHSSignalWord = Danger |
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| EUClass = Corrosive ('''C''')<br/>Irritant ('''Xi''')<br/>Dangerous for the environment ('''N''') |
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| HPhrases = {{H-phrases|314|335|400}} |
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| RPhrases = {{R14}}, {{R34}}, {{R37}}, R50 |
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| PPhrases = {{P-phrases|260|261|264|271|273|280|301+330+331|303+361+353|304+340|305+351+338|310|312|321|363|391|403+233|405|501}} |
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| SPhrases = {{S1/2}}, {{S26}}, {{S45}}, {{S61}} |
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| NFPA-H = 3 |
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| NFPA-H = 3 |
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| NFPA-F = 1 |
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| NFPA-F = 1 |
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| NFPA-R = 2 |
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| NFPA-R = 1 |
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| NFPA-O = W |
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| NFPA-S = |
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| Autoignition = 234 ºC |
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| AutoignitionPtC = 234 |
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| PEL = |
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| PEL = |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherFunctn = ]<br/>]<br/>] |
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| OtherFunction = {{ubl|]|]|]}} |
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| OtherCpds = ]<br/>]<br/>] |
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| OtherCompounds = {{ubl|]|]|]|]}} |
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'''Sulfur dichloride''' is the ] with the ] SCl<sub>2</sub>. This cherry-red liquid is the simplest sulfur chloride and one of the most common. It is used as a precursor to ]s.<ref>Schmidt, M.; Siebert, W. "Sulphur" ''Comprehensive Inorganic Chemistry'' Vol. 2, ed. A.F. Trotman-Dickenson. 1973.</ref> |
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'''Sulfur dichloride''' is the ] with the ] {{chem2|SCl2}}. This cherry-red liquid is the simplest sulfur chloride and one of the most common, and it is used as a precursor to ] compounds. It is a highly corrosive and toxic substance, and it reacts on contact with water to form chlorine-containing acids. |
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==Chlorination of sulfur== |
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==Chlorination of sulfur== |
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SCl<sub>2</sub> is produced by the chlorination of either elemental ] or ]. The process occurs in a series of steps, some of which are: |
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{{chem2|SCl2}} is produced by the chlorination of either elemental ] or ].<ref>F. Fehér "Dichloromonosulfane" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 370.</ref> The process occurs in a series of steps, some of which are: |
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::S<sub>8</sub> + 4 Cl<sub>2</sub> → 4 S<sub>2</sub>Cl<sub>2</sub>; ΔH = −58.2 kJ/mol |
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:{{chem2|S8 + 4 Cl2 → 4 S2Cl2}}; ''ΔH'' = −58.2 kJ/mol |
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::S<sub>2</sub>Cl<sub>2</sub> + Cl<sub>2</sub> → 2 SCl<sub>2</sub>; ΔH = −40.6 kJ/mol |
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:{{chem2|S2Cl2 + Cl2 ↔ 2 SCl2}}; ''ΔH'' = −40.6 kJ/mol |
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The addition of ] to S<sub>2</sub>Cl<sub>2</sub> has been proposed to proceed via a mixed valence intermediate Cl<sub>3</sub>S-SCl. SCl<sub>2</sub> undergoes even further chlorination to give SCl<sub>4</sub>, but this species is unstable at near room temperature. It is likely that several S<sub>x</sub>Cl<sub>2</sub> exist where x > 2. |
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The addition of ] to {{chem2|S2Cl2}} has been proposed to proceed via a ] intermediate {{chem2|Cl3S\sSCl}}. {{chem2|SCl2}} undergoes even further chlorination to give ], but this species is unstable at near room temperature. It is likely that several {{chem2|S_{''n''}Cl2}} exist where ''n'' > 2. |
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], S<sub>2</sub>Cl<sub>2</sub>, is the most common impurity in SCl<sub>2</sub>. Separation of SCl<sub>2</sub> from S<sub>2</sub>Cl<sub>2</sub> is possible via distillation with ] to form an ] of 99% purity |
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], {{chem2|S2Cl2}}, is the most common impurity in {{chem2|SCl2}}. Separation of {{chem2|SCl2}} from {{chem2|S2Cl2}} is possible via distillation with ] to form an ] of 99% purity, however sulfur dichloride loses chlorine slowly at room temperature and reverts to disulfur dichloride. Pure samples may be stored in sealed glass ] which develop a slight positive pressure of chlorine, halting the decomposition. |
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==Use of SCl<sub>2</sub> in chemical synthesis== |
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==Use of {{chem2|SCl2}} in chemical synthesis== |
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*SCl<sub>2</sub> is used in ]. It adds to ] to give chloride-substituted thioethers. Illustrative applications are its addition to ] to give a bicyclic ]<ref>{{OrgSynth | last = Bishop | first = Roger | title = 9-Thiabicyclo[3.3.1]nonane-2,6-dione | volume = 70 | pages = 120 | collvol = 9 | collvolpages = 692 | year = 1992 | prep = cv9p0692}}</ref> and ] to give ] S(CH<sub>2</sub>CH<sub>2</sub>Cl)<sub>2</sub>.<ref>R. J. Cremlyn “An Introduction to Organosulfur Chemistry” John Wiley and Sons: Chichester (1996). ISBN 0 471 95512 4.</ref> |
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{{chem2|SCl2}} is used in ]. It adds to ] to give chloride-substituted thioethers. Illustrative is its addition to ] to give a bicyclic ]<ref>{{OrgSynth | last = Bishop | first = Roger | title = 9-Thiabicyclo[3.3.1]nonane-2,6-dione | volume = 70 | pages = 120 | collvol = 9 | collvolpages = 692 | year = 1992 | prep = cv9p0692}}</ref> A well tested method for the production of the ] ], is the addition of ethylene to sulfur dichloride:<ref>R. J. Cremlyn “An Introduction to Organosulfur Chemistry” John Wiley and Sons: Chichester (1996). {{ISBN|0-471-95512-4}}.</ref> |
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:{{chem2|SCl2 + 2 C2H4 -> (ClC2H4)2S}} |
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SCl<sub>2</sub> is also a precursor to several inorganic sulfur compounds. Treatment with fluoride salts gives ]. Reaction with ammonia affords sulfur nitrides related to ]. With H<sub>2</sub>S, SCl<sub>2</sub> reacts to give "lower" sulfanes such as S<sub>3</sub>H<sub>2</sub>. |
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{{chem2|SCl2}} is also a precursor to several inorganic sulfur compounds. Treatment with fluoride salts gives ] via the decomposition of the intermediate ]. With {{chem2|H2S}}, {{chem2|SCl2}} reacts to give "lower" sulfanes such as {{chem2|S3H2}}. |
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Reaction with ammonia affords sulfur nitrides related to ]. Treatment of {{chem2|SCl2}} with primary amines gives ]s. One example is di-''t''-butylsulfurdiimide.<ref name= Kresze>{{cite journal | doi = 10.1002/anie.196701491| pmid = 4962859| title = New Methods of Preparative Organic Chemistry V: Organic Syntheses with Imides of Sulfur Dioxide| journal = Angewandte Chemie International Edition in English| volume = 6| issue = 2| pages = 149–167| year = 1967| last1 = Kresze| first1 = G.| last2 = Wucherpfennig| first2 = W.}}</ref> |
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==Safety considerations== |
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==Safety considerations== |
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SCl<sub>2</sub> hydrolyzes with release of ]. Old samples contain Cl<sub>2</sub>. |
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{{chem2|SCl2}} ] with release of ]. Old samples contain {{chem2|Cl2}}.{{citation needed|date=August 2019}} |
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==References== |
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==References== |
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{{reflist}} |
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{{sulfur compounds}} |
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{{Chlorides}} |
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