Chemical elements
  Phosphorus
    Isotopes
    Energy
    Preparation
    Applications
    Physical Properties
    Chemical Properties
      Alkali Phosphides
      Alkaline Earth Phosphides
      Copper Silver and Gold Phosphides
      Zinc Group Phosphides
      Aluminium Phosphide
      Titanium Group Phosphides
      Tin Phosphides
      Lead Phosphides
      Arsenic Phosphides
      Antimony Phosphides
      Bismuth Phosphides
      Chromium Phosphides
      Molybdenum and Tungsten Phosphides
      Manganese Phosphides
      Iron Phosphides
      Cobalt Phosphides
      Phosphonium Chloride
      Phosphonium Bromide
      Phosphonium Iodide
      Hydrogen Phosphides
      Alkylphosphines
      Phosphorus Trifluoride
      Phosphorus Pentafluoride
      Phosphorus Trifluorodichloride
      Phosphorus Trifluorodibromide
      Fluophosphoric Acid
      Phosphorus Dichloride
      Phosphorus Trichloride
      Phosphorus Pentachloride
      Phosphorus Chlorobromides
      Phosphorus Chloroiodides
      Phosphorus Tribromide
      Phosphorus Pentabromide
      Phosphorus Diiodide
      Phosphorus Triiodide
      Phosphorus Oxytrifluoride
      Phosphorus Oxychloride
      Pyrophosphoryl Chloride
      Metaphosphoryl Chloride
      Phosphoryl Monochloride
      Phosphoryl Dichlorobromide
      Phosphoryl Chlorodibromide
      Phosphoryl Tribromide
      Metaphosphoryl Bromide
      Phosphoryl Oxyiodides
      Phosphorus Thiotrifluoride
      Phosphorus Thiotrichloride
      Phosphorus Thiotribromide
      Mixed Phosphorus Thiotrihalides
      Phosphorus Suboxides
      Phosphorus Trioxide
      Phosphorus Dioxide
      Phosphorus Pentoxide
      Hypophosphorous Acid
      Phosphorous Acid
      Meta- and Pyro-phosphorous Acids
      Hypophosphoric Acid
      Tetraphosphorus Trisulphide
      Diphosphorus Trisulphide
      Tetraphosphorus Heptasulphide
      Phosphorus Pentasulphide
      Phosphorus Oxysulphides
      Phosphorus Thiophosphites
      Phosphorus Thiophosphates
      Phosphorus Selenophosphates
      Phosphorus Sulphoselenides
      Diamidophosphorous Acid
      Phosphorus Triamide
      Monamidophosphoric Acid
      Diamidophosphoric Acid
      Triamidophosphoric Acid
      Dimetaphosphimic Acid ≡P=
      Trimetaphosphimic Acid
      Tetrametaphosphimic Acid
      Penta- and Hexametaphosphimic Acid
      Monamidodiphosphoric Acid
      Diamidodiphosphoric Acid
      Triamidodiphosphoric Acid
      Nitrilotrimetaphosphoric acid
      Monothioamidophosphoric Acids
      Thiophosphoryl Nitride
      Di- Tri-imido- and -amido-thiophosphates
      Imidotrithiophosphoric Acid =
      Phosphorus Chloronitrides
      Triphosphonitrilic Chloride
      Tetraphosphonitrilic Chloride
      Pentaphosphonitrilic Chloride
      Hexaphosphonitrilic Chloride
      Heptaphosphonitrilic Chloride
      Triphosphonitrilic Bromide
      Phosphorus Halonitrides
      Phosphorus Nitride
      Phosphine
      Pyrophosphoric Acid
      Phosphoric acids
    Slow Oxidation
    Phosphatic Fertilisers

Phosphorus Chloronitrides






It was shown by Liebig in 1832 that when PCl5 was treated with dry ammonia and the product heated, a white stable sublimate was obtained. The empirical formula PNCl2 was assigned to this substance by Laurent, while Gladstone and Holmes on account of its high vapour density represented it as (PNCl2)3.


Preparation

Equal mols of PCl5 and NH4Cl may be heated to 150° C. in a sealed tube which is opened occasionally to permit the escape of hydrogen chloride formed according to the equation

nPCl5 + nNH4Cl = nPNCl2 + 4nHCl

The product was extracted with petroleum ether and the insoluble part distilled up to nearly a red heat. The distillate, after washing with hot water, was redistilled under reduced pressure, and yielded the fractions described below. Alternatively, 120 to 130 grams of ammonium chloride may be added to 400 grams of phosphorus pentachloride dissolved in a litre of sym-tetrachloroethane, and the mixture boiled under a reflux condenser guarded by a calcium chloride drying tube until hydrogen chloride is no longer evolved. This requires about 20 hours. The ammonium chloride is filtered off and the solvent distilled away in a water-pump vacuum. The residue, about 220 grams of a pasty material, is freed from oil by suction and by washing with benzene at 0° C. This leaves about 100 grams of a crystalline powder which is recrystallised from benzene and fractionated at a low pressure. The fractions may be recrystallised from benzene.

When the powder is heated above 255° C. it changes to a colourless transparent solid, while at 350° C. there is produced a colourless elastic mass which resembles rubber in appearance and in its property of swelling when placed in benzene.

Melting- and boiling-points of the phosphorus chloronitrides or phosphonitrilic chlorides

Formula(PNCl2)3(PNCl2)4(PNCl2)5(PNCl2)6
Melting-point, ° C114123.54191
Boiling-point (13 mm.), ° C127188224262
Boiling-point (760 mm.), ° C256.5328.5PolymerisesPolymerises
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