Chemical elements
  Sulphur
    Isotopes
    Energy
    Extraction
    Refining
    Applications
    Allotropy
    Crystalline
    Amorphous Sulphur
    Colloidal Sulphur
    Physical Properties
    Chemical Properties
    Detection
    Estimation
    Compounds
      Hydrogen Sulphide
      Metal Polysulphides
      Hydrogen Polysulphides
      Hydrogen Pentasulphide
      Hydrogen Trisulphide
      Hydrogen Disulphide
      Sulphur Monofluoride
      Sulphur Tetrafluoride
      Sulphur Hexafluoride
      Sulphur Monochloride
      Sulphur Dichloride
      Sulphur Tetrachloride
      Sulphur Monobromide
      Thionyl Fluoride
      Sulphuryl Fluoride
      Fluorosulphonic Acid
      Thionyl Chloride
      Sulphuryl Chloride
      Sulphur Oxytetrachloride
      Pyrosulphuryl Chloride
      Chlorosulphonic Acid
      Thionyl Bromide
      Sodium Sulphoxylate
      Sulphur Dioxide
      Sulphurous Acid
      Sulphites
      Sulphur Trioxide
      Pyrosulphuric Acid
      Pyrosulphates
      Sulphuric Acid
      Persulphuric Anhydride
      Persulphuric Acid or Perdisulphuric Acid
      Perdisulphates
      Permonosulphuric Acid
      Amidopermonosulphuric Acid
      Thiosulphuric Acid
      Thiosulphates
      Polythionic Acids
      Dithionic Acid
      Trithionic Acid
      Trithionates
      Tetrathionic Acid
      Tetrathionates
      Pentathionic Acid
      Pentathionates
      Wackenroders Solution
      Hexathionic Acid
      Polythionic Acids
      Sulphur Sesquioxide
      Hydrosulphurous Acid
      Hydrosulphites
      Nitrogen Sulphide
      Nitrogen Persulphide
      Nitrogen Pentasulphide
      Sulphammonium
      Hexasulphamide
      Nitrogen Chlorosulphide
      Trithiazyl Chloride
      Thiotrithiazyl Chloride
      Dithiotetrathiazyl Chloride
      Nitrogen Bromosulphide
      Thiotrithiazyl Bromide
      Thiotrithiazyl Iodide
      Thiotrithiazyl Nitrate
      Thiotrithiazyl Hydrogen Sulphate
      Thiotrithiazyl Thiocyanate
      Thionylamide
      Sulphamide
      Imidodisulphamide
      Sulphimide
      Sulphonic Acids
      Amidosulphonic Acid
      Imidosulphonic Acid
      Nitrilosulphonic Acid
      Hydroxylamine-monosulphonic Acid
      Nitrososulphonic Acid
      Hydroxylamine-disulphonic Acid
      Hydroxylamine-isodisulphonic Acid
      Hydroxylamine-trisulphonic Acid
      Dihydroxylamidosulphonic Acid
      Sulphazinic Acid
      Sulphazotinic Acid
      Dehydrosulphazotinic Acid
      Nitrosulphonic Acid
      Nitrosulphonyl Chloride
      Nitrosulphonic Anhydride
      Nitrosulphuric Acid
      Nitrosodisulphonic Acid
      Sulphonitronic Acid
      Sulphates of Hydroxylamine
      Hydroxylamine Dithionate
      Hydrazine Dithionate
      Hydrazine Amidosulphonate
      Carbon Subsulphide
      Carbon Monosulphide
      Carbon Disulphide
      Thioformaldehyde
      Thiocarbonic Acid
      Ammonium thiocarbonate
      Thiolcarbonic Acid
      Xanthic Acid
      Perthiocarbonic Acid
      Sodium perthiocarbonate
      Carbonyl Sulphide
      Thiocarbonyl Chloride
      Thiocarbonyl Tetrachloride or
      Carbon Hexachlorosulphide
      Trichloromethyl Disulphide
      Thiocarbonyl Sulphochloride
      Carbon Bromosulphide
      Amino-derivatives of Thiocarbonic Acid
      Dithiocarbamic Acid
      Thiocarbamide
      Azidodithiocarbonic Acid
      Thiocyanogen
      Cyanogen Monosulphide
      Cyanogen Trisulphide
      Sulphur Thiocyanate
      Disulphur Dithiocyanate
      Thiocyanic Acid
      Thiocyanates
      Dithiocyanic Acid
      Trithiocyanuric Acid
      Perthiocyanic Acid
      Perthiocyanogen
      Sulphates

Sulphur Tetrachloride, SCl4






When a mixture of sulphur monochloride with liquid chlorine is kept in a sealed tube, slow combination ensues, with formation of Sulphur Tetrachloride, SCl4. At ordinary temperatures the rate of combination is very slow, but it is hastened by a moderate rise in temperature.

The product is a brownish-red liquid at ordinary temperatures; when cooled it exhibits in a marked manner the phenomenon of "suspended transformation," and generally does not solidify above -70° C., the yellowish-white solid obtained below this temperature melting at -30.5° C. A few degrees above the melting-point the dissociation pressure reaches one atmosphere, so that dissociation into sulphur monochloride and chlorine, probably with the production of sulphur dichloride as an intermediate stage, occurs exceedingly readily, and at the ordinary temperature the liquid contains only a small proportion of the tetrachloride, the dissociation products preponderating (see the following).

Water causes immediate and almost quantitative decomposition of sulphur tetrachloride, with formation of hydrochloric and sulphurous acids, the latter standing in the same relation to sulphur tetrachloride as carbonic acid to carbon tetrachloride and silicic acid to silicon tetrachloride:

SCl4 + 3H2O = H2SO3 + 4HCl.

With anhydrous ammonia the tetrachloride reacts to form nitrogen sulphide:

12SCl4 + 16NH3 = 3N4S4 + 48HCl + 2N2.

With an equimolecular proportion of sulphur trioxide, interaction occurs forming thionyl chloride, sulphur dioxide and chlorine:

SCl4 + SO3 = SOCl2 + SO2 + Cl2,

but an excess of sulphur trioxide leads to simultaneous formation of pyrosulphuryl chloride:

SCl4 + 2SO3 = S0Cl2 + S2O5Cl2. Sulphur dioxide does not exert any action on sulphur tetrachloride, but above 0° C. chlorosulphonic acid yields the same products as those given in the first equation for the action of sulphur trioxide, whilst below 0° C. the product is sulphur oxytetrachloride, S2O3Cl4.

Many chlorides, especially those of the metals, combine with sulphur tetrachloride to produce unstable crystalline additive compounds; thus, iodine trichloride, antimony pentachloride, titanium tetrachloride, stannic chloride, ferric chloride, and also arsenic fluoride, yield crystalline products containing the added molecule SCl4; this provides strong evidence of the definite existence of this chloride of sulphur.

In its action on organo-magnesium compounds, sulphur tetrachloride behaves as if it consists only of sulphur dichloride and chlorine, and its reactions with sulphur trioxide (see before) appear to be capable of a similar interpretation; in these cases it is indeed possible that sulphur dichloride and chlorine, present as products of dissociation, are the actual agents in the chemical change.


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