Nitrogen sulphides

Hopper, Study Explosive Properties of Nitrogen Sulphide and Compositions Containing It , PATR 919 (1938) 14) Ibid, PATR 978... 

Nitrogen sulphide, N4S4, m.p. 178°C, was prepared by Soubeiran [115] by the action of ammonia on sulphur chloride dissolved in benzene... 

Nitrogen sulphide is insoluble in water, slightly soluble in alcohol and ether, somewhat soluble in carbon disulphide and benzene. At room temperature it is hydrolysed to some extent by water to form free sulphur, sulphur dioxide and ammonia. Its specific gravity is 2.22. 

Nitrogen sulphide is less sensitive to friction and impact than mercury fulminate. It is a weaker initiator than mercury fulminate, its rate of acceleration being considerably less than that of the latter. Its ignition temperature is 207°C. It is exceptionally strongly endothermic, its heat of formation (—AH ) being —138.8 kcal/mole (Berthelot and Vieille [116]). 

In many patents nitrogen sulphide is recommended as a filling for fuses, primers etc. but in spite of this it has not been used in practice. 

Thionyl fluoride has also been obtained in excellent yield by the interaction of liquid hydrogen fluoride and nitrogen sulphide in the presence of a little copper oxide, the reaction being best effected in a copper bomb at 100° C. The gas, which issues on opening the bomb, can be collected in a receiver cooled by liquid air.1... 

Trithionic acid is found together with sulphuric, sulphurous and thiosulphuric acids in the reaction product from the decomposition of nitrogen sulphide, N4S4, with water. ... 

Nitrogen Sulphide or Sulphur Nitride, N4S4.—Preparation.— Nitrogen sulphide may be prepared by the action of dry ammonia on sulphur dichloride dissolved in either carbon disulphide 3 or benzene 4... 

The ammonium chloride separates out in flakes, the solution becoming orange-red in colour. Since it is less soluble in carbon disulphide than sulphur, the nitrogen sulphide may be extracted from the product by fractional crystallisation from that solvent. 

The hydrogen sulpiride may be removed as silver sulphide, whilst the nitrogen sulphide in the filtrate can be isolated by extraction with carbon disulphide. 

Nitrogen sulphide is only sparingly soluble in alcohol,2 ether, wood spirit and turpentine it is hydrolysed by water or moist air with formation of ammonium thiosulphate, ammonium trithionate and ammonia ... 

Solutions of metallic iodides in anhydrous ammonia form precipitates with nitrogen sulphide in ammoniacal solution. Lead iodide thus forms the compound lead dithiodi-imide, PbN2S2.NH3, which crystallises in olive-green prisms, turning orange on exposure to the air. Hydrochloric acid reacts quantitatively with this lead compound according to the equation ... 

Ruff and Geisel 3 assume that the compound of nitrogen sulphide with ammonia dissociates in anhydrous ammonia solution forming (A), N S NHa, and (b), S S(NH)a, of which the former yields an insoluble mercuric salt, N S NHg, and the latter an insoluble lead salt,... 

Heated to 120° C. in a closed platinum vessel, hydrogen fluoride and nitrogen sulphide unite to form a red liquid, which readily decomposes into its constituents. In the presence of traces of moisture, thionyl fluoride is formed. Dry hydrogen chloride reacts with nitrogen sulphide according to the equation 1... 

Nitrogen sulphide acts slowly on the acids of the paraffin series. In the case of acetic acid there is an evolution of sulphur dioxide, and sulphur and ammonium sulphate are obtained, as well as small quantities of free nitrogen. Considerable quantities of acetamide and diacetamide are also formed.7 The sulphide is indifferent towards primary and secondary bases of the aromatic scries and towards all tertiary bases.8 Nitrogen sulphide has been claimed to assist the vulcanisation of rubber. 

Constitution.—According to Sehenck,9 and Clever and Muthmann,10 nitrogen sulphide has the constitution... 

The pentasulphide may be prepared by heating together yellow nitrogen sulphide and carbon disulphide under pressure ... 

Examination of the absorption of light of various wave-lengths by solutions of hydrogen sulphide and nitrogen sulphide in liquid ammonia shows that several compounds must exist. 

Hexasulphamide, S6NH2.—In the preparation of nitrogen sulphide, N4S4, from ammonia and sulphur monochloride, as already described (p. 283), the mother-liquor may, on concentration, yield hexasulphamide in addition to nitrogen pentasulphide. Hexasulphamide crystallises in colourless, square plates, melting at 105° C. It is insoluble in water... 

The chlorosulphide is reconverted into nitrogen sulphide by the action of cold ammonia. When treated with dry hydrogen chloride in benzene solution it yields a bright yellow compound which is only slightly decomposed by cold water but immediately by lukewarm water. 

With concentrated nitric acid, thiotrithiazyl chloride yields thiotrithiazyl nitrate, N3S4.NOa.7 Like nitrogen sulphide, with dilute aqueous alkali it yields sulphite and thiosulphate.8 When thiotrithiazyl chloride is boiled with alcohol and the resulting solution treated with a few drops of alcoholic potash, an intense violet-red coloration is produced. Ammonia gas is rapidly absorbed by the dry compound, which then explodes violently after a few minutes. If thiotrithiazyl chloride is suspended in chloroform and submitted to the action of a stream of ammonia gas, the liquid becomes orange-red ammonium chloride and ammonium sulphide are produced and nitrogen sulphide is regenerated.0... 

Sulphur and NItrogen —Nitrogen Sulphides, Sulphammonium, Hoxasulpli-amido, Cliloro- and Bromo-sulphides, Thiazyl Salta—Amides of the Sulphur Oxy-acids—Sulphonic Acids—Sulphur Compounds of Hydroxylaimno and Hydrazine. 

For sulphur nitride, see nitrogen sulphide for selenium, nitride, see nitrogen selenide and for tellurium nitride, see nitrogen telluride. J. von Liebig 26 obtained a brown powder by igniting chromium chloride in ammonia, and he thought the product was elemental chromium. A. Schrotter showed that the product is chromium nitride, Cr2N2 or CrN. 

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