Chemical elements
    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
      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
      Pyrophosphoric Acid
      Phosphoric acids
    Slow Oxidation
    Phosphatic Fertilisers

Phosphorus Thiophosphates

The general methods of preparation recall those used in the preparation of phosphates, sulphides being used in place of oxides, with protection of the product from oxidation or hydrolysis:—

  1. The heating of metallic sulphides with phosphorus penta-sulphide gives the most highly thionised thiophosphates. The poly-sulphides which are formed at the same time may be removed by alcohol. From the solutions dithiophosphates may be isolated.

    3M2S + P2S5 = 2M3PS4
  2. The heating of metallic chlorides with phosphorus penta-sulphides gives thiophosphates together with PSCl3.
  3. By the action of alkalies on thiohalides. PSCl3 is the chloride of monothiophosphoric acid, and with alkalies it gives monothio-phosphates.

By fusing crystalline sodium sulphide with phosphorus penta- sulphide and dissolving the product in a little water, crystals of tri-sodium tetrathio-orthophosphate were obtained.

3(Na2S.9H2O) + P2S5 =2(Na3PS4.8H2O) + 11H2O

The crystals were needle-shaped or tabular, in the monoclinic system. The corresponding potassium salt, K3PS4, was obtained as a yellow crystalline mass by fusing KCl with P2S5.

These thiophosphates are hydrolysed in dilute solution with evolution of H2S. They can be dissolved unchanged in alkalies. With salts of the heavy metals they give precipitates which are decomposed on warming, giving H2S. They are easily oxidised by nitric acid, potassium dichromate, etc. with deposition of sulphur. When treated with solutions of sulphides, e.g. BaS, the trithiophosphates were produced, as represented by the equation

2Na3PS4 + 3BaS + 2H2O = Ba3(PS3O)2 + 3Na2S + 2H2S

Dithiophosphates, M3(PS2O2), were also produced by this reaction.

Other tetrathiophosphates which have been prepared by the foregoing methods are Cu3PS4 (CuCl and P2S5), Ag3PS4 (AgCl and P2S5), Hg3(PS4)2 (HgS and P2S5), Pb3(PS4)2 (PbCl2 and P2S5), Fe3(PS4)2 (FeS and P2S5), Ni3(PS4)2 (NiCl2 and P2S5).

The preparation of barium trithiophosphate has been described above. The magnesium salt, Mg3(PS3O)2.20H2O, was prepared by the action of the tetrathiosodium salt on magnesium hydrosulphide. The ammonium salt, (NH4)3(PS3O).H2O, was prepared by the action of water on ammonium imidothiophosphate. From a solution of this compound by interaction with salts of various metals, e.g. CuSO4, their trithiophosphates have been prepared.

Trisodium dithiophosphate, Na3(PS2O2).11H2O, has been prepared from P2S5 and a rather concentrated solution of sodium hydroxide. The solution was heated to 50° to 55° C. until the trithio-salt was decomposed. The salt was precipitated by alcohol, and when recrystallised from water appeared as colourless six-sided prisms. The ammonium salt, (NH4)3(PS2O2).2H2O, was prepared similarly from aqueous ammonia and P2S5. From these soluble thiophosphates those of the heavy metals may be obtained by double decomposition.

Trisodium monothiophosphate was obtained from the solution of mixed thiophosphates by heating to 90° C. in order to decompose dithiophosphate. On cooling, the crystalline salt Na3(PSO3).12H2O separated in six-sided tables, melting at 60° C. This salt was also prepared from PSCl3 as follows:—

PSCl3 + 6NaOH = Na3(PSO3) + 3NaCl + 3H2O.

Ammonium dihydromonothiophosphate was prepared by the hydrolysis of imidotrithiophosphoric acid, thus

H3[P(NH)S3] + 3H2O = (NH4)H2(PSO3) +2H2S

The salt was repeatedly precipitated by alcohol and dissolved in water. A similar or identical salt having the constitution SP(OH)2(ONH4) was prepared by the action of phosphorus pentasulphide on acetoxime in carbon disulphide solution. The part insoluble in CS2 was extracted with alcohol, boiled and crystallised from cold water in monoclinic prisms.

From the alkali monothiophosphates those of other bases have been obtained by precipitation.

A series of pyrothiophosphates, M2P2S7 (in which M is a divalent metal), has been prepared by the methods already described. The free acids decompose immediately on liberation, but a mixture of them has been prepared as a yellow oil having the composition H4P2O2S5 by the action of liquid hydrogen chloride on ammonium trithiophosphate at low temperatures.

Esters of the thiophosphoric acids have been prepared, e.g. ethyl tetrathiophosphate, (C2H5)3PS4.

Detection of Thiophosphates

Many of the reactions already described, such as the production of H2S and phosphoric acid when these salts are treated with acids, will serve to detect the thiophosphates. The alkali and ammonium salts are soluble, the others mostly insoluble. Calcium, barium and strontium monothiophosphates, barium and strontium dithiophosphates and barium trithiophosphate are insoluble, the other alkaline earth salts soluble. Thiophosphate solutions mixed with alkali sulphides give a green colour with ferric chloride. Monothiophosphates give a blue precipitate with cobalt sulphate soluble in excess of the cobalt salt, dithiophosphates a green precipitate soluble in excess of dithiophosphate, and trithiophosphates a brown solution. Several other tests have been described.
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