Absorbing Markov chain

Template:Chembox Sulfur tetrachloride is an inorganic compound with chemical formula SCl₄. It is an unstable pale yellow solid, decomposing to sulfur dichloride and chlorine at temperatures above 242K. It is obtained by treating sulfur dichlorides with chlorine at 193K:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{2}}+\mathrm{C}{\mathrm{l}}_{\mathrm{2}}\stackrel{193K}{\to }\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}$

Its solid structure is uncertain. It is probably the salt SCl₃⁺Cl^-, since related salts are known.

Characteristics

Sulfur tetrachloride is stable in solid state below -30 °C, and it decomposes to chlorine and sulfur when temperature rises. In solid state, there is a white, finely powdered substance. It melts with simultaneous decomposition if higher than -20 °C. Sulfur tetrachloride reacts with water, producing hydrogen chloride and sulfur dioxide through the hydrolysis process.

Gas phase SCl₄ has a seesaw molecular geometry as evidenced from microwave spectroscopy and electron diffraction. The liquid has a fluxional trigonal bipyramidal geometry with rapid exchange of the axial and equatorial fluorine atoms on the NMR timescale at room temperature. For the solid state a structure has been reported consisting of a SCl₄ seesaw geometry linked in a three-dimensional network by weak S-F interactions, two per per molecule.

Reactions

• Decomposition:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}\stackrel{-15^{o}C}{\to }\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{2}}+\mathrm{C}{\mathrm{l}}_{\mathrm{2}}$

• Reacting with water in air:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}+{\mathrm{H}}_{\mathrm{2}}\mathrm{O}\stackrel{}{\to }\mathrm{S}\mathrm{O}\mathrm{C}{\mathrm{l}}_{\mathrm{2}}+\mathrm{2}\mathrm{H}\mathrm{C}\mathrm{l}$

• Treated with water:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}+\mathrm{2}{\mathrm{H}}_{\mathrm{2}}\mathrm{O}\stackrel{}{\to }\mathrm{S}{\mathrm{O}}_{\mathrm{2}}+\mathrm{4}\mathrm{H}\mathrm{C}\mathrm{l}$

• Oxidized by nitric acid:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}+\mathrm{2}\mathrm{H}\mathrm{N}{\mathrm{O}}_{\mathrm{3}}+\mathrm{2}{\mathrm{H}}_{\mathrm{2}}\mathrm{O}\stackrel{}{\to }{\mathrm{H}}_{\mathrm{2}}\mathrm{S}{\mathrm{O}}_{\mathrm{4}}+\mathrm{2}\mathrm{N}{\mathrm{O}}_{\mathrm{2}}\mathrm{\uparrow }+\mathrm{4}\mathrm{H}\mathrm{C}\mathrm{l}$

• Reacting with sodium hydroxide:

$\mathrm{S}\mathrm{C}{\mathrm{l}}_{\mathrm{4}}+\mathrm{6}\mathrm{N}\mathrm{a}\mathrm{O}\mathrm{H}\stackrel{}{\to }\mathrm{N}{\mathrm{a}}_{\mathrm{2}}\mathrm{S}{\mathrm{O}}_{\mathrm{3}}+\mathrm{4}\mathrm{N}\mathrm{a}\mathrm{C}\mathrm{l}+\mathrm{3}{\mathrm{H}}_{\mathrm{2}}\mathrm{O}$

References

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