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
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
R-phrases (outdated)	R14, R34, R50
S-phrases (outdated)	(S1/2), S26, S45, S61
	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:

{\begin{matrix}{}\\{\ce {{SCl2}+Cl2->[{\text{193 K}}]SCl4}}\\{}\end{matrix}}

(1)

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.

{\begin{matrix}{}\\{\ce {SCl4->[{\text{-15 }}^{\circ }{\ce {C}}]{SCl2}+Cl2}}\\{}\end{matrix}}

(2)

It hydrolyzes readily:

{\ce {{SCl4}+ H2O -> {SOCl2}+ {2HCl}}}

(3)

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

{\ce {{SCl4}+ 2H2O -> {SO2}+ {4HCl}}}

(4)

Oxidized by nitric acid:

{\ce {{SCl4}+ {2HNO3}+ 2H2O -> {H2SO4}+ 2NO2 (^) + {4HCl}}}

(5)

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. "Preparations, Raman spectra, and crystal structures of (SCl₃)(SbCl₆), (SeCl₃)(SbCl₆), (SBr_1.2Cl_1.8)(SbCl⁶), (TeCl₃)(AlCl₄) (triclinic modification), (TeCl₃)(SbF₆), (TeCl₃)(AsF₆), and (TeF₃)₂(SO₄)" Inorganic Chemistry 1986, volume 25, 777-88. doi:10.1021/ic00226a012
Goettel, J. T., Kostiuk, N. and Gerken, M. (2013), The Solid-State Structure of SF₄: The Final Piece of the Puzzle . Angew. Chem. Int. Ed., 52: 8037–8040. doi:10.1002/anie.201302917
Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, 101. Auflage, de Gruyter Verlag 1995 ISBN 3-11-012641-9 (in German)

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[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. "Preparations, Raman spectra, and crystal structures of (SCl₃)(SbCl₆), (SeCl₃)(SbCl₆), (SBr_1.2Cl_1.8)(SbCl⁶), (TeCl₃)(AlCl₄) (triclinic modification), (TeCl₃)(SbF₆), (TeCl₃)(AsF₆), and (TeF₃)₂(SO₄)" Inorganic Chemistry 1986, volume 25, 777-88. doi:10.1021/ic00226a012

[Goettel-4] Goettel, J. T., Kostiuk, N. and Gerken, M. (2013), The Solid-State Structure of SF₄: The Final Piece of the Puzzle . Angew. Chem. Int. Ed., 52: 8037–8040. doi:10.1002/anie.201302917

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