Besides which we will cite the following data given by various observers: heat of fusion for P (that is, for 31 parts of phosphorus by weight) -0·15 thousand calories; the conversion of yellow into red phosphorus for P, from +19 to +27 thousand calories; P + H_{ 3} = 4·3, HI + PH_{ 3} = 24, PH_{ 3} + HBr = 22 thousand calories.
At the ordinary temperature (20° C.) phosphorus is not oxidised by pure oxygen; oxidation only takes place with a slight rise of temperature, or the dilution of the oxygen with other gases (especially nitrogen or hydrogen), or a decrease of pressure.
[4 bis] Ordinary phosphorus takes fire at a temperature (60°) at which no other known substance will burn. Its application to the manufacture of matches is based on this property. In order to illustrate the easy inflammability of common (yellow) phosphorus, its solution in carbon bisulphide may be poured over paper; this solvent quickly evaporates, and the free phosphorus spread over a large surface takes fire spontaneously, notwithstanding the cooling effect produced by the evaporation of the bisulphide. The majority of _phosphorus matches_ are composed of common phosphorus mixed with some oxidising substance which easily gives up oxygen, such as lead dioxide, potassium chlorate, nitre, &c. For this purpose common phosphorus is carefully triturated under warm water containing a little gum; lead dioxide and potassium nitrate are then added to the resultant emulsion, and the match ends, previously coated with sulphur or paraffin, are dipped into this preparation. After this the matches are dipped into a solution of gum and shellac, in order to preserve the phosphorus from the action of the air. When such a match containing particles of yellow phosphorus is rubbed over a rough surface, it becomes (especially at the point of rupture of the brittle gummy coating) slightly heated, and this is sufficient to cause the phosphorus to take fire and burn at the expense of the oxygen of the other ingredients.
The heads of the 'safety' matches do not contain any phosphorus, but only substances capable of burning and of supporting combustion. Red phosphorus is spread over a surface on the box, and it is the friction against this phosphorus which ignites the matches. There is no danger of the matches taking fire accidentally, nor are they poisonous.[5] This red phosphorus is prepared by heating the ordinary phosphorus at 230° to 270°; it is evident that this must be done in an atmosphere incapable of supporting combustion--for example, in nitrogen, carbonic anhydride, steam, &c. On a large scale, ordinary phosphorus is placed in closed iron vessels,[5 bis] and immersed in a bath of different proportions of tin and lead, by which means the temperature of 250° necessary for the conversion is easily attained. It is kept at this temperature for some time. The temperature is at first cautiously raised, and the air is thus partially expelled by the heat, and also by the evolution of steam (the phosphorus is damp when put in), whilst the remaining oxygen is also partially absorbed by the phosphorus, so that an atmosphere of nitrogen is produced in the iron vessel. Red phosphorus enters into all the reactions proper to yellow phosphorus, only with greater difficulty and more slowly;[6] and, as its vapour tension (volatility) is less than that of the yellow variety, it may be supposed that a polymerisation takes place in the passage of the yellow into the red modification, just as in the passage of cyanogen into paracyanogen, or of cyanic acid into cyanuric acid (Chapter IX. Notes 39 bis and 48).