Phosphorus Sesquisulphide

Phosphorus sesquisulphide P4S3 [1314-85-8] M 220.1, m 172°. Extracted with CS2, filtered and evapd to dryness. Placed in H2O, and steam was passed through for an hour. The H2O was then removed, the solid was dried, followed by crystallisation from CS2 [Rogers and Gross JACS 74 5294 7952]. 

Phosphorus sesquisulphide was offidally introduced into France Ijy Sevfcne and Cahen for the manul cture of strike anywhere ... 

The examination of phosphorus sesquisulphide is carried out first, by the smell (odour of phosphorus) and then by Mitacherlich s test (r/, detection of phosphorus in match-heads, p. 134), or by the method of Schenck and Scharff. These methods are exact and permit the detection of very small traces. 

These serve, on the one hand, to increase the flection, and on the other to retard the explosion on igniting the match-head, so that the flame has time to act on the other materials, sulphur, paraffin, etc., which propagate the combustion. Brown umber is a variety of clay colour by the oxides of iron and manganese. Venetian red is ferric oxide, FctOa, and is obtained by the calcination of green vitriol. The use of chalk u 1 Riling material is now rare. Zinc oxide is employed chiefly In the compositions of matches containing phosphorus sesquisulphide, red phosphorus and the like. 

Even before Sdv and Cihen, Rais had recommended fusing together sulphur and red phosphorus, but the result was not equivalent to phosphorus sesquisulphide. The Sdvkte-Cahen process was taken up by the French Government, and it is said that the French public did not notice any diflerence on the Introduction of the socalled S. and C. matches, containing this substitute for phosphorus. 

In Schloesing s test for free white phosphorus in phosphorus sesquisulphide the latter is shaken with light petroleum (b. pt. 45 to dissolve free phosphorus. The liquid is quickly filtered and an aliquot part evaporated in a vacuum at 15 to 20 The residue is oxidised with nitric acid and the phosphorus estimated. In order simply to detect the presence of phosphorus, the residue after evaporating off the petroleum is shaken with fine sand in a flask in the dark and carefully examined for phosphorescent glow,... 

On the one hand, the examination of phosphorus sesquisulphide, which is frequently present, is, according to Friedheim, difficxilt, because the sulphur-phosphorus compounds gradually decompose into compounds containing less sulphur, with separation of white phosphorus, and on the other hand, the detection of pho horus in matches in presence of potassium chlorate cannot be carried out by the ordinary methods of analysis. 

To test for ordinary phosphorus in the presence of phosphorus sulphide (phosphorus sesquisulphide, P4S1),. the following process, due to R. Schenck and E. Scharff, can be employed. This method is based on the property of ordinary phosphorus, when oxidised to phosphorus trioxide, of ionising the air, which then becomes capable of conducting electricity. Phosphorus and sulphur compounds, even if they luminesce, do not produce this effect. 

According to C. Van Eijk, a tube containing phosphorus sesquisulphide is not luminescent below 70 , but if o 02 per cent, of white phosphorus be present a glow appears below 60 . An alternative plan is to extract with carbon disulphide, evaporate off the solvent, and distil the residue with a solution of lead acetate. Sesquisulphide of phosphorus is decomposed, and luminescence appears only in the presence of white phosphbrus. 

The relatively non-poisonous red phosphorus was discovered in 1845 (Anton Schrotter in Vienna) and had been used since 1851-1852 (some sources say the Paris Exhibition of 1855), either in the match itself or within the material of the surface upon which the match was rubbed ("safety matches"). However, "friction matches" incorporating white phosphorus continued to be made for a least another half-century and it wasn t until the reatisation, in 1898 (Sevene and Cahen in France), that the non-poisonous phosphorus sesquisulphide (P4S3 previously discovered by Berzelius) could be used successfully as a substitute, that an agreement (eventually in Europe, the "Berne Convention 1906" in USA, the "Esch" law and "Match Act" of 1912) finally put an end to the use of white phosphorus in the match industry. 

Strike-anywhere matches syn. block matches do not require a prepared surface and can be ignited on almost any dry surface. They often contain phosphorus sesquisulphide, which ignites easily by friction, or potassium chlorate, a strong oxidizer, which encourages the shank to bum. Fusee matches are strike-anywhere matches with bulbous heads that bum intensely with little flame and are difficult to blow out (e.g., matchsticks impregnated with potassium nitrate and tipped with sulphur). 

Matches, Strike anywhere or Fusee. They usually contain phosphorus sesquisulphide, potassium chlorate and other ingredients. The strike-anywhere matches are readily ignited by friction on almost any dry surface. ICAO A2... 

The first successful phosphorus-containing striking matches were invented by Sauria in 1831, and the use of the element in match compositions was introduced in England and France abont 1838. Phosphorus sesquisulphide, discovered by Letnoine in 1864, eventually replaced the toxic white form of the element. Safety matches incorporating red phosphorus were introduced by Sevene and Cahen in 1898. Self-igniting sea flares incorporating calcium phosphide were patented by Holmes and Player in 1876. 

Tetraphosphorus trisulphide, P4S3 and tetraphosphorus heptasulphide, P4S7, can be prepared by heating stoichiometric amounts of red phosphorus and sulphur above 180°C in an inert atmosphere. Tetraphosphorus trisulphide (also known as phosphorus sesquisulphide) was discovered in 1864 by Lemoine [20] and it is an important component of matches. 

Phosphorus trichloride will reduce many oxides, some violently, in reactions such as (4.210)-(4.213), but is itself reduced by antimony, arsenic or arsene (4.214, 4.215), and by hydrogen at elevated temperatures (4.216). Phosphine, PH3, is produced by reaction with LiAlH4 (4.135), and phosphorus sesquisulphide, P4S3 is among the products of reaction between PCI3 and H2S in the presence of a base [8]. 

The use of Sauria-type formulations led initially to many match workers contracting phossy jaw and children being poisoned by ingestion of match heads. By the end of the century, however, white P had been replaced by the much less toxic red P and by phosphorus sesquisulphide, P4S3. Today, the use of white P in match formulations is banned almost everywhere in the world, and the condition known as phossy jaw is virtually unknown [8]. 

Highly inflammable yellow powder which can ignite by friction. Irritant, corrosive and toxic by inhalation. Liberates toxic H2S on contact with moisture. Phosphorus sesquisulphide, P4S3, has very similar properties. 

Phosphorus sesquisulphide P4S3, free from yellow and white phosphoms [1341]... 

Arsenic monosulphide AsS (or AS2S2), phosphorus sulphides, phosphorus sesquisulphide P4S3 and phosphorus trisulphide P4S6 have no action on aluminium at room temperamre. 

In the presence of water, phosphorus trisulphide P4S6 decomposes under formation of phosphoric acid and thus attacks aluminium. On the other hand, phosphorus sesquisulphide P4S3 is insoluble in water and does not attack aluminium even in the presence of humidity. 

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