Phosgene

“ If sulphur is heated in a stream of phosphine, hydric sulphide and sulphur phosphide are the products. Oxides of the metals, heated with phosphine, yield phosphides with formation of water. Iodine, warmed in phosphine, gives white crystals of iodine phosphonium, and biniodide of phosphorus, 5I + 4PH3 = 3PIH4 + PI2. Chlorine inflames the gas, the final result being hydric chloride and chloride of phosphorus, PH3 + 8Cl = 3ClH + PCl5. One of the most important decompositions for our purpose is the action of phosphine on a solution of nitrate of silver ”

“ Solid Phosphoretted Hydrogen, P4H2, first obtained by Le Verrier (loc. cit.) , is formed by the action of phosphorus trichloride on gaseous phosphine (Besson, Comptes rendus, 111, p. 972) ; by the action of water on phosphorus di-iodide and by the decomposition of calcium phosphide with hot concentrated hydrochloric acid. It is a yellow solid, which is insoluble in water. It burns when heated to about 200° C. Oxidizing agents decompose it with great violence. When warmed with alcoholic potash it yields gaseous phosphine, hydrogen and a hypophosphite. It reduces silver salts. ”

“ 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. ”

“ Now (like sulphur, present in the albuminoid base) , phosphorus is an element which, besides having several allotropic forms, has a great affinity for oxygen; and an organic compound into which it enters, beyond the instability otherwise caused, has a special instability caused by its presence. The tendency to undergo change will therefore be great when the proportion of the phosphorized component is great. Hence the statement that "the chemical differences between chromatin and cytoplasm, striking and constant as they are, are differences of degree only;" ”

“ The hard part of bone is about nine-tenths phosphate, and phosphorus is an element of molecules organized into muscle and nerve.
The proportion of phosphates in the crust of the earth below organic remains is very slight, insufficient for the support of the higher forms of vegetable or animal life. It has been concentrated and gathered into the soil by the selective agency of the organic world, as it continues to be concentrated from the soil by each individual plant, and from vegetable products by each individual animal. ”

“ Phosphorus itself is a remarkable substance, much resembling sulphur, but much more inflammable. It has been procured chiefly, till of late, from urine, but now more generally from bones, by means of the vitriolic acid, which unites with the calcareous earth of which bones consist, and sets at liberty the phosphoric acid, or the base of that acid, with which it was naturally combined. The acid thus procured, mixed [Pg 60] with charcoal, and exposed to a strong heat, makes phosphorus. ”

“ 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. ”

“ In the system of chemistry, as it developed in the first half of the 19th century, the new development can be characterized as the turn from inorganic to organic phosphates, from the substance of minerals and strong chemical interactions to the components in which phosphate groups remained combined with carbon-containing substances.
Phosphatides and Phosphagens
The important phosphorus compounds in organisms are much more complex than the simple salts, to which Nietzsche attributed such influence on man’s character. ”

“ Thus, from phosphatides, phosphoric acid is generated, and they could also be called phosphagens. Since 1926, however, the name phosphagens has been reserved for a group of organic substances that release their phosphoric acid very readily. The link between phosphorus and carbon is provided by oxygen in the phosphatides, by nitrogen in the phosphagens. In vertebrates, the basis for the phosphoric acid is creatine, whereas invertebrates have arginine instead.
Creatine Phosphate
Arginine phosphate Nuclein and Nucleic Acids
All parts of an organism are essential for life. ”

“ 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. ”

“ 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. ”

“ Of more importance is the fact, now known, that little phosphorus, if any, is assimilated from the hypo­phosphites—far less than from phosphorus compounds of ordinary food.93 There is no justification for giving hypo­phosphites for the sake of their phosphorus content. For various reasons, however—partly from force of habit and partly because of the power of advertising—many physicians still prescribe hypo­phosphite preparations, and consequently, they are still included in the Pharmacopeia and in textbooks on materia medica and therapeutics. ”

“ It was formerly obtained from urine, as that fluid contains some phosphoric salts. It is now prepared from bones. These are burnt to an ash, and diluted sulphuric acid is poured on it; the phosphoric acid it contains is then disengaged, and remains in the fluid. The sulphate of lime is then separated, the fluid boiled to dryness, and the dry mass is mixed with charcoal, and distilled in the open fire.
The phosphoric pencil, for writing on a wall, paper, &c. to be luminous in the dark, is nothing more than a bit of phosphorus put into a quill. ”

“ 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. ”

“ The tertiary phosphines are characterized by their readiness to pass into derivatives containing pentavalent phosphorus, and consequently they form addition compounds with sulphur, carbon bisulphide, chlorine, bromine, the halogen acids and the alkyl halides with great readiness. On oxidation they yield phosphine oxides, R3P·O. The quaternary phosphonium salts resemble the corresponding nitrogen compounds. They are stable towards aqueous alkalis, but on digestion with moist silver oxide yield the phosphonium hydroxides, which are stronger bases than the caustic alkalis. ”

“ In the first place, the phosphatic minerals found in the archæan rocks are considered derivative from organic remains, as to-day phosphorus as a phosphate results from animal secretions, though phosphorus is omnipresent in the plant-world, and the ashes of various vegetables yield from eight per cent, to fifty-three per cent, of phosphoric acid, while the annual shipment of flour and wheat from our shores represents thousands of tons of this element. ”

“ Verification of the Strength of the Standard Solution of Phosphoric Acid.—The strength of the standard solution of phosphoric acid is verified by evaporating a known volume, fifty cubic centimeters for example, with a solution of ferric hydroxid containing a known quantity of ferric oxid. The mass having been evaporated to dryness, and ignited in a platinum crucible, gives an increase in the weight of the iron oxid exactly equal to the amount of anhydrous phosphoric acid contained therein, both the nitric acid and ammonia being driven off by the heat. ”

“ LII. is extremely interesting in reference to the dogma that phosphorus is a necessary ingredient in living matter. Solutions of the ammonic tartrate in distilled water have been twice analyzed for me by a skilled chemist, without revealing the least trace either of phosphorus or sulphur. This result is very remarkable when compared with the amount of living matter which may so soon appear in such a solution: the number of the organisms and the rapidity of their evolution, being almost equal to that which occurs in a similar solution to which a phosphate has been added. ”

“ An artificial phosphate is thus prepared: Melt in an oven a mixture of 100 parts of phosphorite, ground coarsely, 70 parts of acid sulphate of soda; 20 parts of carbonate of lime; 22 parts of sand, and 607 parts of charcoal. Run the molten matter into a receiver filled with water; on cooling it will become granular. Rake out the granular mass from the water, and after drying, grind to a fine powder. The phosphate can be kept for a long time without losing its quality, for it is neither caustic nor hygroscopic. ”

“ It seems very extraordinary, on first sight, that phosphorus, which forms so important an element of all bones, and from which it is extracted, should be so destructive to its life when coming in contact with it, but the physiological explanation of the seeming anomaly is this: the fumes of the phosphorus destroy the periosteum, or the vascular lining of all living bone, and by which it is nourished. ”

“ A characteristic reaction is the formation of a red precipitate of cuprous hydride, Cu2H2, when heated with copper sulphate solution to 60°. It is a monobasic acid forming salts which are permanent in air, but which are gradually oxidized in aqueous solution. On heating they yield phosphine and leave a residue of pyrophosphate, or a mixture of meta- and pyrophosphates, with a little phosphorus. They react as reducing agents. On boiling with caustic potash they evolve hydrogen, yielding a phosphate. ”

“ Of other phosphorus compounds we may here notice Gengembre’s discovery of phosphuretted hydrogen (phosphine) in 1783, the analogy of which to ammonia was first pointed out by Davy and supported at a later date by H. Rose; liquid phosphuretted hydrogen was first obtained by Thénard in 1838; and hypophosphorous acid was discovered by Dulong in 1816. Of the halogen compounds of phosphorus, the trichloride was discovered by Gay Lussac and Thénard, while the pentachloride was obtained by Davy. The oxychloride, bromides, and other compounds were subsequently discovered ”

“ Nearly all the phosphorus accessible on the planet has been a constituent of living bodies. Its proportion in the soil is a main factor in the growth of cereal grains. Already, and with the stretch of land to the westward, bone-earth and phosphatic guanos are well known in American markets. When phosphates fail at the root of the plant, grain fails at the mill; and when, from waste at the mill, phosphates fail in the bread, the bones and the teeth fail in growing bodies. ”

“ The reagent is prepared by dissolving a freshly made precipitate of iron phosphate from ten grams of ferric chlorid in 400 cubic centimeters of an aqueous solution of forty grams of glacial phosphoric acid. A gentle heat promotes the solution of the phosphate.
In the case of a fertilizer supposed to contain leather, about one gram of the material is treated with thirty cubic centimeters of water and a few drops of sulfuric acid. The mixture is boiled and poured on a filter. To a portion of the filtrate some of the solution of iron phosphate is added, and the mixture made alkaline with ammonia. ”

“ Nitric acid is easily reduced to nitrogen, whilst phosphoric acid is reduced with very much greater difficulty. All the compounds of phosphorus are less volatile than those of nitrogen. Nitric acid, HNO3, is easily distilled; metaphosphoric acid, HPO3, is generally said to be [157] non-volatile; triethylamine, N (C2H5) 3, boils at 90°, and triethylphosphine, P (C2H5) 3, at 127°.
Phosphorus not only combines easily and directly with oxygen, but also with chlorine, bromine, iodine, sulphur, and with certain metals, and red phosphorus when heated combines with hydrogen also. ”

“ In luminous insects and deep-sea fish the power of emitting light appears to have a special significance, and very elaborate mechanisms have been developed. The pale glow of phosphorescence has a certain resemblance to the light emitted by phosphorus, and it was an early suggestion that the phenomenon in living organisms was due to that substance. Phosphorus, however, and its luminous compounds are deadly poisons to all living tissues, and never occur in them in the course of natural metabolism, and the phosphorescence of life cannot therefore be assigned to the oxidation of phosphorus. ”