Sulfur dichloride
Encyclopedia
Sulfur dichloride is the chemical compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....

 SCl2. This cherry-red liquid is the simplest sulfur chloride and one of the most common. It is used as a precursor to organosulfur compounds.

Chlorination of sulfur

SCl2 is produced by the chlorination of either elemental sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...

 or disulfur dichloride
Disulfur dichloride
Disulfur dichloride is the chemical compound with the formula S2Cl2 . Some alternative names for this compound are sulfur monochloride , disulphur dichloride and sulphur monochloride...

. The process occurs in a series of steps, some of which are:
S8 + 4 Cl2 → 4 S2Cl2; ΔH = −58.2 kJ/mol
S2Cl2 + Cl2 → 2 SCl2; ΔH = −40.6 kJ/mol

The addition of Cl2
Chlorine
Chlorine is the chemical element with atomic number 17 and symbol Cl. It is the second lightest halogen, found in the periodic table in group 17. The element forms diatomic molecules under standard conditions, called dichlorine...

 to S2Cl2 has been proposed to proceed via a mixed valence intermediate Cl3S-SCl. SCl2 undergoes even further chlorination to give SCl4, but this species is unstable at near room temperature. It is likely that several SxCl2 exist where x > 2.

Disulfur dichloride
Disulfur dichloride
Disulfur dichloride is the chemical compound with the formula S2Cl2 . Some alternative names for this compound are sulfur monochloride , disulphur dichloride and sulphur monochloride...

, S2Cl2, is the most common impurity in SCl2. Separation of SCl2 from S2Cl2 is possible via distillation with PCl3
Phosphorus trichloride
Phosphorus trichloride is a chemical compound of phosphorus and chlorine, having chemical formula PCl3. Its shape is trigonal pyramidal. It is the most important of the three phosphorus chlorides. It is an important industrial chemical, being used for the manufacture of organophosphorus compounds...

 to form an azeotrope
Azeotrope
An azeotrope is a mixture of two or more liquids in such a ratio that its composition cannot be changed by simple distillation. This occurs because, when an azeotrope is boiled, the resulting vapor has the same ratio of constituents as the original mixture....

 of 99% purity

Use of SCl2 in chemical synthesis

  • SCl2 is used in organic synthesis
    Organic synthesis
    Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...

    . It adds to alkenes to give chloride-substituted thioethers. Illustrative applications are its addition to 1,5-cyclooctadiene
    1,5-Cyclooctadiene
    1,5-Cyclooctadiene is the organic compound with the chemical formula C8H12. Generally abbreviated COD, this diene is a useful precursor to other organic compounds and serves as a ligand in organometallic chemistry.- Synthesis :...

     to give a bicyclic thioether
    Thioether
    A thioether is a functional group in organosulfur chemistry with the connectivity C-S-C as shown on right. Like many other sulfur-containing compounds, volatile thioethers have foul odors. A thioether is similar to an ether except that it contains a sulfur atom in place of the oxygen...

     and ethylene
    Ethylene
    Ethylene is a gaseous organic compound with the formula . It is the simplest alkene . Because it contains a carbon-carbon double bond, ethylene is classified as an unsaturated hydrocarbon. Ethylene is widely used in industry and is also a plant hormone...

     to give sulfur mustard
    Sulfur mustard
    The sulfur mustards, or sulphur mustards, commonly known as mustard gas, are a class of related cytotoxic, vesicant chemical warfare agents with the ability to form large blisters on exposed skin. Pure sulfur mustards are colorless, viscous liquids at room temperature...

     S(CH2CH2Cl)2.


SCl2 is also a precursor to several inorganic sulfur compounds. Treatment with fluoride salts gives SF4
Sulfur tetrafluoride
Sulfur tetrafluoride is the chemical compound with the formula SF4. This species exists as a gas at standard conditions. It is a corrosive species that releases dangerous HF upon exposure to water or moisture...

. Reaction with ammonia affords sulfur nitrides related to S4N4
Tetrasulfur tetranitride
Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This gold-poppy coloured solid is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for...

. With H2S, SCl2 reacts to give "lower" sulfanes such as S3H2.

Safety considerations

SCl2 hydrolyzes with release of HCl
Hydrogen chloride
The compound hydrogen chloride has the formula HCl. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric humidity. Hydrogen chloride gas and hydrochloric acid are important in technology and industry...

. Old samples contain Cl2.
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