CHAPTER XXXIX. 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.