Sulfur tetrachloride

Sulfur tetrachloride
Names
	IUPAC name Sulfur(IV) chloride
Identifiers
CAS Number	13451-08-6;
3D model (JSmol)	Interactive image;
ECHA InfoCard	100.149.178
PubChem CID	13932016;
CompTox Dashboard (EPA)	DTXSID20552819 ;
	InChI InChI=1/Cl4S/c1-5(2,3)4;
	SMILES ClS(Cl)(Cl)Cl;
Properties
Chemical formula	SCl4
Molar mass	173.87
Appearance	White powder
Melting point	−31 °C (−24 °F; 242 K)
Boiling point	−20 °C (−4 °F; 253 K) (decomposes)
Solubility in water	soluble in water
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H314, H400
Precautionary statements	P260, P264, P273, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P391, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Sulfur tetrachloride is an inorganic compound with chemical formula SCl₄. It has only been obtained as an unstable pale yellow solid. The corresponding SF₄ is a stable, useful reagent.

Preparation and structure

It is obtained by treating sulfur dichloride with chlorine at 193 K:

SCl₂ + Cl₂ → SCl₄

It melts with simultaneous decomposition above −20 °C.^[1]

Its solid structure is uncertain. It is probably the salt SCl₃⁺Cl⁻, since related salts are known with noncoordinating anions.^[2]^[3] In contrast to this tetrachloride, SF₄ is a neutral molecule.^[4]

Reactions

It decomposes above −30 °C (242 K) to sulfur dichloride and chlorine.

SCl₄ → SCl₂ + Cl₂

It hydrolyzes readily:

SCl₄ + H₂O → SOCl₂ + 2 HCl

Sulfur tetrachloride reacts with water, producing hydrogen chloride and sulfur dioxide through the hydrolysis process. Thionyl chloride is an implied intermediate.^[5]

SCl₄ + 2 H₂O → SO₂ + 4 HCl

It can be oxidized by nitric acid:

SCl₄ + 2 HNO₃ + 2 H₂O → H₂SO₄ + 2 NO₂↑ + 4 HCl

References

^ Georg Brauer: Handbuch der Präparativen Anorganischen Chemie. (in German)
^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
^ Christian, Beverly H.; Collins, Michael J.; Gillespie, Ronald J.; Sawyer, Jeffery F. (1986). "Preparations, Raman spectra, and crystal structures of (SCl3)(SbCl6), (SeCl3)(SbCl6), (SBr1.2Cl1.8)(SbCl6), (TeCl3)(AlCl4) (Triclinic modification), (TeCl3)(SbF6), (TeCl3)(AsF6), and (TeF3)2(SO4)". Inorganic Chemistry. 25 (6): 777–788. doi:10.1021/ic00226a012.
^ Goettel, James T.; Kostiuk, Nathan; Gerken, Michael (2013). "The Solid-State Structure of SF₄: The Final Piece of the Puzzle". Angewandte Chemie International Edition. 52 (31): 8037–8040. doi:10.1002/anie.201302917. PMID 23784951.
^ Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, 101. Auflage, de Gruyter Verlag 1995 ISBN 3-11-012641-9 (in German)

[brauer-1] Georg Brauer: Handbuch der Präparativen Anorganischen Chemie. (in German)

[2] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.

[3] Christian, Beverly H.; Collins, Michael J.; Gillespie, Ronald J.; Sawyer, Jeffery F. (1986). "Preparations, Raman spectra, and crystal structures of (SCl3)(SbCl6), (SeCl3)(SbCl6), (SBr1.2Cl1.8)(SbCl6), (TeCl3)(AlCl4) (Triclinic modification), (TeCl3)(SbF6), (TeCl3)(AsF6), and (TeF3)2(SO4)". Inorganic Chemistry. 25 (6): 777–788. doi:10.1021/ic00226a012.

[Goettel-4] Goettel, James T.; Kostiuk, Nathan; Gerken, Michael (2013). "The Solid-State Structure of SF₄: The Final Piece of the Puzzle". Angewandte Chemie International Edition. 52 (31): 8037–8040. doi:10.1002/anie.201302917. PMID 23784951.

[5] Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, 101. Auflage, de Gruyter Verlag 1995 ISBN 3-11-012641-9 (in German)

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