Difference between revisions of "Sulfuryl chloride"

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| MeltingPt_ref =  
 
| MeltingPt_ref =  
 
| MeltingPt_notes =  
 
| MeltingPt_notes =  
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| Odor = Pungent, suffocating
 
| pKa =  
 
| pKa =  
 
| pKb =  
 
| pKb =  
 
| Solubility = Reacts
 
| Solubility = Reacts
| SolubleOther = Miscible with glacial [[acetic acid]], [[benzene]], [[carbon tetrachloride]], [[chloroform]], [[dichloromethane]], [[toluene]]
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| SolubleOther = Reacts with [[alcohol]]s, [[amine]]s, [[ester]]s<br>Miscible with glacial [[acetic acid]], [[benzene]], [[carbon tetrachloride]], [[chloroform]], [[dichloromethane]], [[toluene]]<br>Soluble in [[hydrogen cyanide]], liq. [[sulfur dioxide|SO<sub>2</sub>]], [[Tin(IV) chloride|SnCl<sub>4</sub>]]<br>Immiscible with conc. [[sulfuric acid]]
 
| Solvent =  
 
| Solvent =  
| VaporPressure =  
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| VaporPressure = 106.5 mmHg (at 20 °C)
 
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| Section3 = {{Chembox Structure
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| DeltaGf =  
 
| DeltaGf =  
 
| DeltaHc =  
 
| DeltaHc =  
| DeltaHf =  
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| DeltaHf = 393 kJ/mol
 
| Entropy =  
 
| Entropy =  
| HeatCapacity =  
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| HeatCapacity = 131.6 J·K<sup>−1</sup>·mol<sup>−1</sup>
 
   }}
 
   }}
 
| Section5 = {{Chembox Explosive
 
| Section5 = {{Chembox Explosive
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'''Sulfuryl chloride''' is a water sensitive inorganic compound with the formula SO<sub>2</sub>Cl<sub>2</sub>. Sulfuryl chloride is sometimes confused with [[thionyl chloride]] (SOCl<sub>2</sub>), however the properties of the two chemicals are very different, as sulfuryl chloride is a source of chlorine, while thionyl chloride is a source of chloride ions.
+
'''Sulfuryl chloride''' is a water sensitive inorganic compound with the formula '''SO<sub>2</sub>Cl<sub>2</sub>'''. Sulfuryl chloride is sometimes confused with [[thionyl chloride]] (SOCl<sub>2</sub>), however the properties of the two chemicals are very different, as sulfuryl chloride is a source of chlorine, while thionyl chloride is a source of chloride ions.
  
 
==Properties==
 
==Properties==
 
===Chemical===
 
===Chemical===
 +
Sulfuryl chloride reacts exothermically with water to form [[hydrogen chloride]] and [[sulfuric acid]]:
  
 +
:2 H<sub>2</sub>O + SO<sub>2</sub>Cl<sub>2</sub> → 2 HCl + H<sub>2</sub>SO<sub>4</sub>
 +
 +
It will chlorinate various organic compounds, such as alkanes, alkenes, alkynes, aromatics, ethers. It will also chlorinate the metal center from organometallic compounds, when it is in a lower oxidation state.
  
 
===Physical===
 
===Physical===
Sulfuryl chloride is a colorless to yellowish liquid, with a strong poignant smell reminiscent of burned matches. It readily hydrolyzes in water.
+
Sulfuryl chloride is a colorless to yellowish liquid, with a strong poignant smell reminiscent of burned matches. It readily hydrolyzes in water and reacts with some organic solvents.
  
 
==Availability==
 
==Availability==
Delete this section if not applicable
+
Sulfuryl chloride is sold by various chemical suppliers, but it is extremely difficult for the amateur chemist to acquire it.
  
 
==Preparation==
 
==Preparation==
Sulfuryl chloride can be made by reacting [[sulfur dioxide]] and [[chlorine]].
+
Sulfuryl chloride can be made by reacting [[sulfur dioxide]] and [[chlorine]]. The reaction is generally done without a solvent. [[Activated carbon]] or graphite is used as a catalyst, though UV light can speed up the reaction.<ref>F. Fehér (1963). "Sulfuryl Chloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY,NY: Academic Press. pp. 382–384</ref>
 +
 
 +
: SO<sub>2</sub> + Cl<sub>2</sub> → SO<sub>2</sub>Cl<sub>2</sub>
 +
 
 +
If the reaction is done without a catalyst, at low temperatures, no product is obtained.<ref>Schulze, H.; Journal fuer Praktische Chemie (Leipzig); vol. 24; (1881); p. 168 - 183</ref>
 +
 
 +
It can also be prepared by reacting [[disulfur dichloride]] with [[sulfur dioxide]], at 170 °C. Elemental [[sulfur]] is produced as a byproduct.<ref>Besson, A.; Fournier, L.; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 150; (1910); p. 1752 - 1754</ref>
 +
 
 +
: S<sub>2</sub>Cl<sub>2</sub> + SO<sub>2</sub> → SO<sub>2</sub>Cl<sub>2</sub> + 2 S
 +
 
 +
Chlorination of [[chlorosulfuric acid]] will yield sulfuryl chloride. Various reagents, such as [[antimony(III) chloride]], [[bismuth chloride]], [[tin(IV) chloride]] can be used. Yields are given as 90%.<ref>Ruff, O.; Ber.; vol. 34; (1901); p. 3509 - 3515</ref> If [[mercury]] or [[mercury(II) sulfate]] are used instead, the yield is only around 60%.<ref>Bert, L.; Bulletin de la Societe Chimique de France; vol. 31; (1922); p. 1264 - 1270</ref><ref>North, H. B.; Journal of the American Chemical Society; vol. 32; (1910); p. 184 - 187</ref>
 +
 
 +
: 4 SOCl<sub>2</sub> + Hg → S<sub>2</sub>Cl<sub>2</sub> + HgCl<sub>2</sub> + 2 SO<sub>2</sub>Cl
 +
 
 +
[[Aluminium chloride]] will react with [[sulfur trioxide]] to yield sulfuryl chloride.<ref>Rose, H.; Annalen der Physik (Weinheim, Germany); vol. 44; (1838); p. 291 - 327</ref><ref>Beckmann, E.; Z. Anorg. Chem.; vol. 77; (1912); p. 90 - 102 ; (from Gmelin)</ref>
 +
 
 +
Oxidation of [[thionyl chloride]] with certain metal oxides, like [[manganese dioxide]], [[lead(II,IV) oxide]], [[lead(IV) oxide]], [[barium peroxide]],  also yields sulfuryl chloride. Reaction takes place at 150 °C over several hours:<ref>[https://pubs.acs.org/doi/10.1021/ja02194a004 H. B. North and A. M. Hageman, J. Am. Chem. Soc. 1913, 35, 5, 543–546]</ref>
 +
 
 +
: 2 SOCl<sub>2</sub> + MnO<sub>2</sub> → SO<sub>2</sub>Cl<sub>2</sub> + MnCl<sub>2</sub> + SO<sub>2</sub>
 +
: 4 SOCl<sub>2</sub> + Pb<sub>3</sub>O<sub>4</sub> → SO<sub>2</sub>Cl<sub>2</sub> + 3 PbCl<sub>2</sub> + 3 SO<sub>2</sub>
 +
: 2 SOCl<sub>2</sub> + PbO<sub>2</sub> → S<sub>2</sub>Cl<sub>2</sub> + PbCl<sub>2</sub> + 3 SO<sub>2</sub>Cl<sub>2</sub>
 +
: 2 SOCl<sub>2</sub> + BaO<sub>2</sub> → S<sub>2</sub>Cl<sub>2</sub> + BaCl<sub>2</sub> + 3 SO<sub>2</sub>Cl<sub>2</sub>
 +
 
 +
If [[mercury(II) oxide]] is used, a large excess of thionyl chloride must be used. If equimolar amounts of HgO and thionyl chloride are used instead, only sulfur dioxide is produced.<ref>[https://pubs.acs.org/doi/10.1021/ja01920a004 North, H. B.; Journal of the American Chemical Society; vol. 32; (1910); p. 184 - 187]</ref>
 +
 
 +
: 5 SOCl<sub>2</sub> + HgO → S<sub>2</sub>Cl<sub>2</sub> + HgCl<sub>2</sub> + 3 SO<sub>2</sub>Cl<sub>2</sub>
 +
: SOCl<sub>2</sub> + HgO → HgCl<sub>2</sub> + SO<sub>2</sub>
 +
 
 +
A less known route is given in literature as the reaction between [[sulfur trioxide]] and [[chromyl chloride]].<ref>S: MVol.B3; 131, page 1807 - 1808; (from Gmelin)</ref><ref>Luchinskii, G. P.; Likhacheva, A. I.; Zhurnal obshchei Khim. (russ.); vol. 7; (1937); p. 405 - 414</ref>
 +
 
 +
: SO<sub>3</sub> + CrO<sub>2</sub>Cl<sub>2</sub> → SO<sub>2</sub>Cl<sub>2</sub> + CrO<sub>3</sub>
 +
 
 +
Thermal decomposition of sodium chlorosulfate (sodium salt of chlorosulfuric acid) is claimed to yield sulfuryl chloride:<ref>Luchinskii, G. P.; Zhurnal obshchei Khim. (russ.); vol. 8; (1938); p. 1864 - 1869</ref>
 +
 
 +
: 2 NaSO<sub>3</sub>Cl → SO<sub>2</sub>Cl<sub>2</sub> + Na<sub>2</sub>SO<sub>4</sub>
 +
 
 +
Other sources indicate that sodium pyrosulfate is produced as side product.<ref>Puskaric, E.; Heubel, J.; Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques; vol. 267; (1968); p. 965 - 967</ref><ref>Puskaric, E.; Jaeger, R. de; Heubel, J.; Revue de Chimie Minerale; vol. 12; (1975); p. 374 - 381</ref>
  
 
==Projects==
 
==Projects==
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==Handling==
 
==Handling==
 
===Safety===
 
===Safety===
Sulfuryl is extremely corrosive and toxic. It hydrolyzes in water.
+
Sulfuryl is extremely corrosive and toxic. It fumes in (moist) air and hydrolyzes in water.
  
 
===Storage===
 
===Storage===
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===Disposal===
 
===Disposal===
Sulfuryl chloride can be neutralized with an alkaline solution.
+
Sulfuryl chloride can be neutralized with an alkaline solution. The reaction will release plenty of corrosive fumes, so it's best to do this outside.
  
 
==References==
 
==References==
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[[Category:Materials that react with water]]
 
[[Category:Materials that react with water]]
 
[[Category:Materials unstable in basic solution]]
 
[[Category:Materials unstable in basic solution]]
 +
[[Category:Corrosive chemicals]]
 
[[Category:Things that can kill you very quickly]]
 
[[Category:Things that can kill you very quickly]]
 
[[Category:Things that should NOT be messed with except by professionals]]
 
[[Category:Things that should NOT be messed with except by professionals]]
 
[[Category:Choking agents]]
 
[[Category:Choking agents]]
 +
[[Category:Irritants]]
 +
[[Category:Liquids]]

Latest revision as of 20:39, 6 August 2023

Sulfuryl chloride
Names
IUPAC name
Sulfuryl chloride
Other names
Sulfonyl chloride
Sulfur dichloride dioxide
Sulfuric chloride
Sulfuroyl dichloride
Properties
SO2Cl2
Molar mass 134.9698 g/mol
Appearance Colorless liquid with a strong pungent odor
Yellowish upon standing
Odor Pungent, suffocating
Density 1.67 g/cm3 (at 20 °C)
Melting point −54.1 °C (−65.4 °F; 219.1 K)
Boiling point 69.4 °C (156.9 °F; 342.5 K)
Reacts
Solubility Reacts with alcohols, amines, esters
Miscible with glacial acetic acid, benzene, carbon tetrachloride, chloroform, dichloromethane, toluene
Soluble in hydrogen cyanide, liq. SO2, SnCl4
Immiscible with conc. sulfuric acid
Vapor pressure 106.5 mmHg (at 20 °C)
Thermochemistry
393 kJ/mol
Hazards
Safety data sheet ScienceLab
Flash point Non-flammable
Related compounds
Related compounds
Thionyl chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Sulfuryl chloride is a water sensitive inorganic compound with the formula SO2Cl2. Sulfuryl chloride is sometimes confused with thionyl chloride (SOCl2), however the properties of the two chemicals are very different, as sulfuryl chloride is a source of chlorine, while thionyl chloride is a source of chloride ions.

Properties

Chemical

Sulfuryl chloride reacts exothermically with water to form hydrogen chloride and sulfuric acid:

2 H2O + SO2Cl2 → 2 HCl + H2SO4

It will chlorinate various organic compounds, such as alkanes, alkenes, alkynes, aromatics, ethers. It will also chlorinate the metal center from organometallic compounds, when it is in a lower oxidation state.

Physical

Sulfuryl chloride is a colorless to yellowish liquid, with a strong poignant smell reminiscent of burned matches. It readily hydrolyzes in water and reacts with some organic solvents.

Availability

Sulfuryl chloride is sold by various chemical suppliers, but it is extremely difficult for the amateur chemist to acquire it.

Preparation

Sulfuryl chloride can be made by reacting sulfur dioxide and chlorine. The reaction is generally done without a solvent. Activated carbon or graphite is used as a catalyst, though UV light can speed up the reaction.[1]

SO2 + Cl2 → SO2Cl2

If the reaction is done without a catalyst, at low temperatures, no product is obtained.[2]

It can also be prepared by reacting disulfur dichloride with sulfur dioxide, at 170 °C. Elemental sulfur is produced as a byproduct.[3]

S2Cl2 + SO2 → SO2Cl2 + 2 S

Chlorination of chlorosulfuric acid will yield sulfuryl chloride. Various reagents, such as antimony(III) chloride, bismuth chloride, tin(IV) chloride can be used. Yields are given as 90%.[4] If mercury or mercury(II) sulfate are used instead, the yield is only around 60%.[5][6]

4 SOCl2 + Hg → S2Cl2 + HgCl2 + 2 SO2Cl

Aluminium chloride will react with sulfur trioxide to yield sulfuryl chloride.[7][8]

Oxidation of thionyl chloride with certain metal oxides, like manganese dioxide, lead(II,IV) oxide, lead(IV) oxide, barium peroxide, also yields sulfuryl chloride. Reaction takes place at 150 °C over several hours:[9]

2 SOCl2 + MnO2 → SO2Cl2 + MnCl2 + SO2
4 SOCl2 + Pb3O4 → SO2Cl2 + 3 PbCl2 + 3 SO2
2 SOCl2 + PbO2 → S2Cl2 + PbCl2 + 3 SO2Cl2
2 SOCl2 + BaO2 → S2Cl2 + BaCl2 + 3 SO2Cl2

If mercury(II) oxide is used, a large excess of thionyl chloride must be used. If equimolar amounts of HgO and thionyl chloride are used instead, only sulfur dioxide is produced.[10]

5 SOCl2 + HgO → S2Cl2 + HgCl2 + 3 SO2Cl2
SOCl2 + HgO → HgCl2 + SO2

A less known route is given in literature as the reaction between sulfur trioxide and chromyl chloride.[11][12]

SO3 + CrO2Cl2 → SO2Cl2 + CrO3

Thermal decomposition of sodium chlorosulfate (sodium salt of chlorosulfuric acid) is claimed to yield sulfuryl chloride:[13]

2 NaSO3Cl → SO2Cl2 + Na2SO4

Other sources indicate that sodium pyrosulfate is produced as side product.[14][15]

Projects

  • Make chlorobenzene
  • Make alkyl chlorides

Handling

Safety

Sulfuryl is extremely corrosive and toxic. It fumes in (moist) air and hydrolyzes in water.

Storage

Sulfuryl chloride should be stored in glass bottles, preferably amber glass, away from any moisture, best in a corrosive chemicals cabinet.

Disposal

Sulfuryl chloride can be neutralized with an alkaline solution. The reaction will release plenty of corrosive fumes, so it's best to do this outside.

References

  1. F. Fehér (1963). "Sulfuryl Chloride". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry, 2nd Ed. Vol. 1. NY,NY: Academic Press. pp. 382–384
  2. Schulze, H.; Journal fuer Praktische Chemie (Leipzig); vol. 24; (1881); p. 168 - 183
  3. Besson, A.; Fournier, L.; Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences; vol. 150; (1910); p. 1752 - 1754
  4. Ruff, O.; Ber.; vol. 34; (1901); p. 3509 - 3515
  5. Bert, L.; Bulletin de la Societe Chimique de France; vol. 31; (1922); p. 1264 - 1270
  6. North, H. B.; Journal of the American Chemical Society; vol. 32; (1910); p. 184 - 187
  7. Rose, H.; Annalen der Physik (Weinheim, Germany); vol. 44; (1838); p. 291 - 327
  8. Beckmann, E.; Z. Anorg. Chem.; vol. 77; (1912); p. 90 - 102 ; (from Gmelin)
  9. H. B. North and A. M. Hageman, J. Am. Chem. Soc. 1913, 35, 5, 543–546
  10. North, H. B.; Journal of the American Chemical Society; vol. 32; (1910); p. 184 - 187
  11. S: MVol.B3; 131, page 1807 - 1808; (from Gmelin)
  12. Luchinskii, G. P.; Likhacheva, A. I.; Zhurnal obshchei Khim. (russ.); vol. 7; (1937); p. 405 - 414
  13. Luchinskii, G. P.; Zhurnal obshchei Khim. (russ.); vol. 8; (1938); p. 1864 - 1869
  14. Puskaric, E.; Heubel, J.; Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques; vol. 267; (1968); p. 965 - 967
  15. Puskaric, E.; Jaeger, R. de; Heubel, J.; Revue de Chimie Minerale; vol. 12; (1975); p. 374 - 381

Relevant Sciencemadness threads