Chapter 77

PHOSPHORUS.

NOTE.--Phosphorus should be kept in water, and handled with forceps, never with the fingers, except under water, as it is liable to burn the flesh and produce ulcerating sores. Pieces not larger than half a pea should be used, and every bit should finally be burned.

197. Solution and Combustion. Experiment 112. -Put 1 or 2 pieces of P into an evaporating- dish, and pour over them 5 or 10cc.CS2 carbon disulphide. This will be enough for a class. When dissolved, dip pieces of unglazed paper into it, and hold these in the air, looking for any combustion as they dry. The P is finely divided in solution, which accounts for its more ready combustion then. Notice that the paper is not destroyed. This is an example of so-called "spontaneous combustion." The burning- point of P, the combustible, in air, the supporter, is about 60 degrees.

198. Combustion under Water.

Experiment 113. -Put a piece of P in a t.t. which rests in a receiver, add a few crystals KClO3 and 5cc. H2O. Now pour in through a thistle-tube 1cc.or more of H2SO4. Look for any flame. H2SO4 acts very strongly on KClO3. What is set free? From this fact explain the combustion in water.

199. Occurrence.--P is very widely disseminated, but not abundant, and is found only in compounds, the chief of which is calcium phosphate Ca3(PO4)2. It occurs in granite and other rocks, as the mineral apatite, in soils, in plants, particularly in seeds and grains, and in the bones, brains, etc., of vertebrates. From the human system it is excreted by the kidneys as microcosmic salt, HNaNH4PO4; and when the brain is hard- worked, more than usual is excreted. Hence brain-workers have been said to "burn phosphorus."

200. Sources.--Rocks are the ultimate source of this element. These, by the action of heat, rain, and frost, are disintegrated and go to make soils. The rootlets of plants are sent through the soil, and, among other things, soluble phosphates in the earth are absorbed, circulated by the sap, and selected by the various tissues. Animals feed on plants, and the phosphates are circulated through the blood, and deposited in the osseous tissue, or wherever needed.

Human bones contain nearly 60 per cent of Ca3(PO4)2; those of some birds over 80 per cent.

The main sources of phosphates and P are the phosphate beds of South Carolina, the apatite beds of Canada, and the bones of animals.

201. Preparation of Phosphates and Phosphorus.--Bone ash, obtained by burning or distilling bones, and grinding the residue, is treated with H1SO4, and forms soluble H4Ca(PO4)2, superphosphate of lime, and insoluble CaSO4.

Ca3(PO4)2 + 2 H2SO4 = H4Ca(PO04)2 + 2 CaSO4. This completes the process for fertilizers. If P is desired, the above is filtered; charcoal, a reducing agent, is added to the filtrate; the substance is evaporated, then very strongly heated and distilled in retorts, the necks of which dip under water. It is then purified from any uncombined C by melting in hot water and passing into molds in cold water.

The work is very dangerous and injurious, on account of the low burning-point of P, and its poisonous properties. While its compounds are necessary to human life, P itself destroys the bones, particularly the jaw bones, of the workers in it.

Between 1,000 and 2,000 tons are made yearly, mostly for matches, but almost all at two factories, one in England, and one in France. 202. Properties.--P is a colorless, transparent solid, when pure; the impure article is yellowish, translucent, and waxy. It is insoluble in water, slightly soluble in alcohol and ether, and it readily dissolves in CS2, oil of turpentine, etc. Fumes, having a garlic odor, rise when it is exposed to the air, and in the dark it is phosphorescent, emitting a greenish light.

203. Uses. -The uses of this element and its compounds are for fertilizers, matches, vermin poisons, and chemical operations.

204. Matches.-The use of P for matches depends on its low burning-point. Prepared wood is dipped into melted S, and the end is then pressed against a stone slab having on it a paste of P, KClO3, and glue. KNO3 is often used instead of KClO3. In either case the object is to furnish O to burn P. Matches containing KClO3 snap on being scratched, while those having KNO3 burn quietly. The friction from scratching a match generates heat enough to ignite the P, that enough to set the S on fire, and the S enough to burn the wood. Give the reaction for each. Paraffine is much used instead of S. Safety matches have no P, and must be scratched on a surface of red P and Sb2S3, or on glass.

205. Red Phosphorus.-Two or three allotropic forms of P are known, the principal one being red. If heated between 230 degrees and 260 degrees, away from air, the yellow variety changes to red, which can be kept at all temperatures below 260 degrees. Above that it changes back. Red P is not poisonous, ignites only at a high temperature, and is not phosphorescent, like the yellow. 206. Spontaneous Combustion of Phosphene, or Hydrogen Phosphide, PH3.

Experiment 114.--Put into a 20cc.flask 1 g. P and 50cc.saturated solution NaOH or KOH. Connect with the p.t. by a long d.t., as in Figure 44, the end of which must be kept under water. Pour 3 or 4cc.of ether into the flask, to drive out the air. It is necessary to exclude all air, as a dangerously explosive mixture is formed with it. Heat the mixture, and as the gas passes over and into the air, it takes fire spontaneously, and rings of smoke successively rise. It will do no harm if, on taking away the lamp, the water is drawn back into the flask; but in that case the flask should be slightly lifted to prevent breakage by the sudden rush of water. On no account let the air be drawn over.

The experiment has no practical value, but is an interesting illustration of the spontaneous combustion of PH3 and of vortex rings. What are the products of the combustion? An admixture of another compound of P and H causes the combustion.