White phosphorus

“ White or yellow phosphorus shall not be employed in the production of matches and other lighting substances. Lighting substances made with white phosphorus shall not be kept for sale, or sold, or otherwise brought on the market. ”

“ It is stated that one pound of phosphorus is sufficient for 1,000,000 matches, though the proportion varies greatly. In France there are consumed for this purpose 70,000 pounds of phosphorus every year. The largest makers are in Austria, two of whom use twenty tons of phosphorus per annum, and produce nearly 45,000,000,000 matches. One firm in New York uses annually 700,000 feet of choice white-pine timber, 100,000 pounds of sulphur, and 150 tons of straw-board for their boxes. ”

“ At the ordinary temperature, therefore, white phosphorus must be considered as the less stable (metastable) form, for although it can exist in contact with red phosphorus for a long period, its vapour pressure, as we have seen, is greater than that of the red modification, and also, its solubility in different solvents is greater [71] than that of the red modification; as we shall find later, the solubility of the metastable form is always greater than that of the stable.
The relationships which are met with in the case of phosphorus can be best represented by the diagram, Fig. 11. ”

“ White phosphorus may be fatal if ingested, even in small quantities [5] . Phosphorus vapor is toxic; work in a contained atmosphere with adequate care. SAMPLING: 1. 2. 3. 4.
Calibrate each personal sampling pump with a representative sampler in line. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump with flexible tubing. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 5 to 100 L. Cap the samplers and pack securely for shipment. ”

“ Q. What is phosphorus?
A. A pale amber-coloured substance, [Pg 284] resembling wax in appearance. The word is derived from two Greek words, which mean “to produce or carry light.” (φῶς-φέρεινφῶς) .
Q. How is phosphorus obtained?
A. By heating bones to a white heat; by which means the animal matter and charcoal are consumed, and what is left is called “phosphate of lime.” ”

“ When the sulphate of potash is combined with sulphate of alumina, it forms common alum.
10. Phosphorus is a soft pale yellow substance which readily takes fire in the air, and gives off, while burning, a dense white smoke. The white fumes which form this smoke are a compound of [Pg 53] phosphorus with oxygen obtained from the air, and are called phosphoric acid. In the ash of plants the phosphorus is found in the state of phosphoric acid, though it probably does not all exist in the living plant in that state. ”

“ First Experiment.
To prepare nitrogen gas, it is only necessary to place a little dry phosphorus in a Berlin porcelain cup on a wine glass, and to stand them in a soup plate containing water. The phosphorus is set on fire with a hot wire, and a gas jar or cylindrical jar is then carefully placed over it, so that the welt of the jar stands in the water in the soup plate. At first, expansion takes place in consequence of the heat, but this effect is soon reversed, as the oxygen is converted into a solid by union with the phosphorus, forming a white smoke, which gradually disappears. (Fig. 106.) ”

“ There are five combinations, of phosphorus and oxygen:—1. the white oxide; 2. the red oxide; 3. hypophosphorous acid; 4. phosphorous acid; 5. phosphoric acid. The last is the only one of interest in the arts. It may be obtained from the syrupy superphosphate of lime above described, by diluting it with water, saturating with carbonate of ammonia; evaporating, crystallizing, and gently igniting the salt in a retort. The ammonia is volatilized, and may be condensed into water by a Woulfe’s apparatus, while the phosphoric acid remains in the bottom of the retort. ”

“ Cut a small piece from an ordinary stick of phosphorus under water, take care to dry it properly with a cloth, and after placing it in a deflagrating spoon, remove the stopper from the gas-jar, as there is no fear of the oxygen rushing away, because it is somewhat heavier than atmospheric air; and then, after placing the spoon with the phosphorus in the neck of the jar, apply a heated wire and pass the spoon at once into the middle of the oxygen; in a few seconds a most brilliant light is obtained, and the jar is filled with a white smoke ”

“ Dissolve the precipitate off the filter with dilute ammonia, and run the solution into the original beaker. Run in from a burette, slowly and with stirring, "magnesia mixture," using about 15 c.c. for each 0.1 gram of phosphoric oxide. Allow to stand for one hour. The white crystalline precipitate contains the phosphorus as ammonium-magnesium phosphate.
Phosphate of lead is decomposed by sulphuric acid; the lead is converted into the insoluble lead sulphate, and the phosphoric acid is dissolved. Phosphate of copper and phosphate of iron may be treated with sulphuretted hydrogen ”

“ Yet, if we would allow room for emotion in research, we could still be excited about the wondrous substance that chemical and biological work continues to reveal as vitally important. It is a fundamental plant nutrient, an essential part in nerve and brain substance, a decisive factor in muscle action and cell growth, and also a component in fast-acting, powerful poisons. The importance of phosphorus was gradually recognized and the means by which this took place are characteristic and similar to other developments in the history of science. ”

“ In this strange association of inorganic salts with human temperaments, the role of iron phosphate as a producer of courage is particularly interesting. What would a modern philosopher conclude if he followed the development of insight into the composition and function of complex phosphate compounds in organisms?
From Inorganic to Organic Phosphates
By the middle of the 19th century, the source of phosphorus in natural phosphates and the chemistry of its oxidation products had been established. ”

“ On the small scale, common phosphorus may be converted into amorphous phosphorus by simply exposing it for 50 or 60 hours to a temperature of about 473° Fahr., in any suitable vessel from which the air is kept excluded by a stream of carbonic acid, or any other gas which is unable to act chemically on the phosphorus. ”

“ There were many disadvantages in the use of this yellow phosphorus. First of all, it is a poisonous substance; and what is more, the vapour of the phosphorus was liable to affect the workpeople engaged in the manufacture of lucifer matches with a bad disease of the jaw, and which was practically, I am afraid, incurable. A very great chemist, Schrötter, discovered that phosphorus existed under another form, some of which I have here. ”

“ Figure 23.—Melvin Calvin (b. 1911) received the Nobel Prize in Chemistry in 1961 for his research in photosynthesis, in which he specified the function of phosphoglyceric acid as an intermediate in the synthesis of carbohydrates from carbon dioxide and water by green plants.
The story of phosphorus, which began 300 years ago, has acquired new importance in this century. Many scientists have contributed to it: 13 of them have received Nobel Prizes for work directly bearing on the chemical and biological importance of phosphorus compounds. ”

“ At about that time (1833) , the Duke of Richmond proved that the fertilizing value of bones resided not in the gelatin, nor in the calcium, but in the phosphoric acid. Thus, he confirmed what Théodore de Saussure had said in 1804, that “we have no reason to believe” that plants can exist without phosphorus. Unknowingly at first, the farmer had supplied this element by means of the organic fertilizers he used: manure, excrements, bones, and horns. Now, with the value of phosphorus known, a search began for mineral phosphates to be applied as fertilizers. ”

“ Red phosphorus (sometimes wrongly called amorphous phosphorus) is partially formed when ordinary phosphorus [153] remains exposed to the action of light for a long time. It is also formed in many reactions; for example, when ordinary phosphorus combines with chlorine, bromine, iodine, or oxygen, a portion of it is converted into red phosphorus. Schrötter, in Vienna, investigated this variety of phosphorus, and pointed out by what methods it may be produced in considerable quantities. Red phosphorus is a powdery red-brown opaque substance of specific gravity 2·14. ”

“ Manufacture of phosphorus with the assistance of electricity. Readman and Parker have recently devised a process for the manufacture of phosphorus on a large scale in a continuously working apparatus by means of a powerful electric current, such as is yielded by a larger dynamo. The mixture used for the operation differs from the ordinary one of calcium phosphate and charcoal, in that it contains in addition a slag-forming body—a flux—silicic acid (quartz sand) being at first used for the purpose. ”

“ As the green colour is more or less interfered with by the presence of organic matters, he passes the gas through a solution of nitrate of silver; the resulting precipitate [Pg 270] is then placed in another hydrogen apparatus, as just mentioned, and the colour of the flame of the issuing gas noted. Phosphorus may become decomposed in the body; and as phosphoric acid is taken in most articles of food, the only satisfactory evidence of phosphorus having been taken is to produce it in its free state, or at least to exhibit its luminosity. ”

“ During the intervening three centuries numerous other chemical miracles have been found, yet phosphorus retains a special aura of universal importance in chemistry. Many investigators have occupied themselves with this element and its diverse chemical compounds. Further enlightenment and insight into the ways of nature can be expected from these efforts. ”

“ So much for the metals in soils; but, important as they are, plants can not live on them alone. Among the nonmetallic bodies phosphorus stands high among essentials, and for it we are indebted to the sea and the interior of the earth. Many living creatures extract phosphorus from the sea water—combine it chiefly with lime, and use the phosphate for making skeletons or shells, as the case may be. ”

“ This is not to be wondered at in view of the fact that 85 per cent. of the phosphorus ingested in the form of hypo­phosphite is excreted unchanged, and there is no proof that even the remaining 15 per cent. is available to the organism. It is doubtful if there are any conditions in which the body suffers from lack of phosphorus. Even should such conditions exist, phosphorus, in the form that it occurs in the ordinary foods, or as phosphates, is more efficient in supplying the deficit than hypo­phosphites that must be oxidized before utilization and which are only about 15 per cent. ”

“ For not only the two pounds of lime, but the pound and a half of phosphorus, and the far less quantity of iron, are as essential as the 106 lbs. of oxygen.
What is most curious about phosphorus is that, being a powerful and terrible poison, the body can contain such a lot of it without suffering injury. Sufficient is scattered among the bones, the flesh, the nervous system, and the various organs to kill off a whole village, or to supply it with all the matches it requires. For the body contains sufficient phosphorus to make 8,064 boxes of matches containing 60 matches each. ”

“ It is unaffected by light when pure, but if phosphorus be present, even in minute quantity, it turns yellow and ultimately dark red. It oxidizes on exposure to air to the pentoxide, and with a brilliant inflammation when thrown into oxygen at 50°–60°. It slowly reacts with cold water to form phosphorous acid; but with hot water it is energetically decomposed, giving much red phosphorus or the suboxide being formed with an explosive evolution of spontaneously inflammable phosphoretted hydrogen; phosphoric acid is also formed. ”

“ To prevent the melting of the lead the pans are bricked in under a very flat arch, so that the fire gases are forced to pass close over the liquor, the pans being kept constantly full. When crystallization is complete the liquor is drawn off and the pans are refilled.
In the manufacture of phosphorus there is left after every distillation a residue of basic calcium phosphate, and it is advisable to decompose it with hydrochloric acid, this being effected in a vat lined with lead or coated with paraffine. ”

“ The gas is soluble in water, and makes its presence known in certain sulphur springs. The colour imparted to egg-spoons and fish-knives and forks sometimes is due to the presence of metallic sulphides. The solution is called hydro-sulphuric acid.
Phosphorus occurs in very small quantities, though in the form of phosphates we are acquainted with it pretty generally, and as such it is absorbed by plants, and is useful in agricultural operations. In our organization—in the brain, the nerves, flesh, and particularly in bones—phosphorus is present, and likewise in all animals. ”

“ Phosphates as Plant Nutrients
One hundred years after the discovery of “cold light,” the presence of phosphorus in plants and animals was ascertained, and its form was established as a compound of phosphoric acid. This knowledge had little practical effect until the “nature” of the acid, in its various forms, was explained through the work of Thomas Graham. ”