condenser, where it is condensed. It is then cast under water.
The calcium silicate remains in the furnace in the form of a
liquid slag, which may be run off, so that the action is practically
continuous. Kaolin may with advantage be used in addition
to or in part substitution for sand, because the double silicate
thus formed is more fusible than the single silicate of lime.
The alternating current is generally used, the action not being
electrolytic. One of the special advantages of the electrical
over the older process is that the distilling vessels have a longer
life, owing to the fact that they are not externally heated, and so
subjected to a relatively high temperature when in contact with
the corrosive slag formed in the process. The Readman-Parker
process (see Jour. Soc. Chem. Ind., 1891, x. 445) appears to
be very generally adopted. Readman, experimenting with a
Cowles furnace in Staffordshire in 1888, patented his process,
and in the same year Parker and Robinson, working independently,
patented a similar one. The two inventors then cooperated,
an experimental plant was run successfully, and the
patents were taken over by the leading manufacturers. With
the object of obtaining a valuable by-product in place of the
slag produced in this furnace, several patentees (e.g. Hilbert
and Frank, Billaudot, Bradley and Jacobs, and others) have
sought to combine the manufacture of calcium carbide and
phosphorus by using only calcium phosphate and carbon,
effecting direct reduction by carbon at a high temperature.
The crude phosphorus is purified by melting under water and then filtering through animal black and afterwards through chamois leather, or by treating it, when molten, with chromic acid or a mixture of potassium bichromate and sulphuric acid; this causes the impurities to rise to the surface as a scum which can be skimmed off. It is usually sent on the market in the form of sticks, which were at one time prepared by sucking the molten material up glass tubes; but the dangers to the workmen and other disadvantages of this method have led to its replacement by a continuous process, in which the phosphorus leaves the melting-pot for a pipe surrounded by water, in which it solidifies and can be removed as a continuous rod.
Properties.—When perfectly pure phosphorus is a white, transparent, waxy solid, but as usually prepared it is yellowish owing to the presence of the allotropic “ red phosphorus,” J. Böeseken (Abs. Jour. Chem. Soc., 1907, ii. 343, 760) prepares perfectly pure phosphorus by heating the crude product with chromic acid solution, washing and drying in a vacuum, first at 40°, then at 80°. It remains colourless in vacuum tubes in the dark, but on exposure it rapidly turns yellow. At 25° to 30° C. it is soft and flexible, but it hardens when strongly cooled, and can then only be cut with difficulty. The fracture is distinctly crystalline; large crystals, either regular dodecahedra or octahedral, may be obtained by crystallization from carbon bisulphide, sulphur chloride, &c., or by sublimation. It is a non-conductor of electricity. Its density at 0° is 1.836; this regularly diminishes up to the melting-point, 44.3°, when a sudden drop occurs. Molten phosphorus is a viscid, oily, highly refractive liquid, which may be supercooled to 32° before solidification. It boils at 200°, forming a colourless vapour which just about the boiling-point corresponds in density to tetratomic molecules, P4; at 1500° to 1700°, however, Biltz and Meyer detected dissociation into P2 molecules. Beckmann obtained P4 molecules from the boiling-point of carbon bisulphide solutions, and Hertz arrived at the same conclusion from the lowering of the freezing-point in benzene solution; E. Paternò and Nasini, however, detected dissociation. Phosphorus is nearly insoluble in water, but dissolves in carbon bisulphide, sulphur chloride, benzene and oil of turpentine.
The element is highly inflammable, taking fire in air at 34° and burning with a bright white flame and forming dense white clouds of the pent oxide, in perfectly dry air or oxygen, however, it may be distilled unchanged, H. B. Baker showing that a trace of water vapour was necessary for combination to occur. When exposed to the air a stick of phosphorus undergoes slow combustion, which is revealed by a greenish-white phosphorescence when the stick is viewed in the dark. This phenomenon was minutely studied by Boyle, who found that solutions in some essential oils (oil of cloves) showed the same character, whilst in others (oils of mace and aniseed) there was no phosphorescence. He also noticed a strong garlic-like odour, which we now know to be due to ozone. Frederick Slare noticed that the luminosity increased when the air was rarefied, an observation confirmed by Hawksbee and Homberg, and which was possibly the basis of Berzelius's theory that the luminosity depended on the volatility of the element and not on the presence of oxygen. Lampadius, however, showed that there was no phosphorescence in a Torricellian vacuum; and other experimenters proved that oxygen was essential to the process. It depends on the partial pressure of the oxygen and also on temperature. In compressed air at ordinary temperature there is no glowing, but it may be brought about by heating. Again, in oxygen under ordinary conditions there is no phosphorescence, but if the gas be heated to 25° glowing occurs, as is also the case if the pressure be diminished or the gas diluted. It is also remarkable that many gases and vapours, e.g. Cl, Br, I, NH3, N2O, NO2, H2S, SO2, CS2, CH4, C2H4, inhibit the phosphorescence.
The theory of this action is not settled. It is certain that the formation of hydrogen peroxide and ozone accompany the glowing, and in 1848 Schonbein tried to demonstrate that it depended on the ozone. E. Jungfleisch (Comptes rendus, 1905, 140, p. 444) suggested that it is due to the combustion of an oxide more volatile than phosphorus, a view which appears to be supported by the observations of Scharff (Zeit. physik. Chem., 1908, 62, p. 178) and of L. and E. Bloch (Comptes rendus, 1908, 147, p. 842).
The element combines directly with the halogens, sulphur and selenium, and most of the metals burn in its vapour forming phosphides. When finely divided it decomposes water giving hydrogen phosphide; it also reduces sulphurous and sulphuric acids, and when boiled with water gives phosphine and hypophosphorous acid; when slowly oxidized under water it yields hypophosphoric acid.
Allatropio Phosphorus.—Several allotropic forms of phosphorus have been described, and in recent years much work has been done towards settling their identities. When the ordinary form immersed in water is exposed to light, it gradually loses its transparency and becomes coated with a thin film. This substance was regarded as an allotrope, but since it is not produced in non-aerated water it is probably an oxide. More important is the so-called “ red phosphorus,” which is produced by heating yellow phosphorus to about 230° for 24 hours in an inert atmosphere, or in closed vessels to 300°, when the change is effected in a few minutes. E. Kopp in 1844 and B. C. Brodie in 1853 showed that a trace of iodine also expedited the change. The same form is also produced by submitting ordinary phosphorus to the silent electric discharge, to sunlight or the ultraviolet light. Since this form does not inflame until heated to above 350°, it is manufactured in large quantities for consumption in the match industry. The process consists in heating yellow phosphorus in iron pots provided with air-tight lids, which, however, bear a long pipe open to the air. A small quantity of the phosphorus combines with the oxygen in the vessel, and after this the operation is practically conducted in an atmosphere of nitrogen with the additional safety from any risk of explosion. The product is ground under water, and any unchanged yellow form is eliminated by boiling with caustic soda, the product being then washed and dried and finally packed in tin boxes. The red variety is remarkably different from the yellow. It is a dark red microcrystalline powder, insoluble in carbon bisulphide, oil of turpentine, &c, and having a density of 2.2, It is stable to air and light, and does not combine with oxygen until heated to above 350° in air or 260° in oxygen, forming the pent oxide. It is also non-poisonous. When heated in a vacuum to 530° it sublimes, and on condensation forms microscopic needles.
Hittorf's phosphorus is another crystalline allotrope formed by heating phosphorus with lead in a sealed tube to redness, and removing the lead by boiling the product with nitric and
