Phosphine

“ 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. ”

“ Blood takes up far more phosphine than water. Dybskowsky found that putting the coefficient of solubility of phosphine in pure water at ·1122 at 15°, the coefficient for venous blood was ·13, and for arterial 26·73; hence the richer the blood is in oxygen the more phosphine is absorbed. It seems probable that the poisonous gas reacts on the oxyhæmoglobin of the blood, and phosphorous acid is formed. This is supported by the fact that a watery extract of such blood reduces silver nitrate, and has been also found feebly acid. ”

“ Phosphuretted Hydrogen.—Phosphine (PH3) , mol. weight 34, specific gravity 1·178, percentage composition, phosphorus 91·43, hydrogen 8·57 by weight. The absolutely pure gas is not spontaneously inflammable, but that made by the ordinary process is so. It is a colourless, highly poisonous gas, which does not support combustion, but is itself combustible, burning to phosphoric acid (PH3 + 2O2 = PO4H3) . Extremely dangerous explosive mixtures may be made by combining phosphine and air or oxygen. Phosphine, when quite dry, burns with a white flame, but if mixed with aqueous vapour, it is green ”

“ 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. ”

“ 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 ”

“ Blondlot and Dusart evolve hydrogen from zinc and dilute sulphuric acid, and pass the gas into silver nitrate; if the gas is pure, there is of course no reduction; the liquid to be tested is then added to the hydrogen-generating liquid, and if phosphorous or hypophosphorous acids be present, a black precipitate of phosphor-silver will be produced. To prove that this black precipitate is neither that produced by SH2, nor by antimony nor arsenic, the precipitate is collected and placed in the apparatus to be presently described, and the spectroscopic appearances of the phosphine flame observed. ”

“ It may also be reparcd by leading a current of dry air into phosphorus trichloride at 60° and passing the vapours into water at 0°, the crystals thus formed being drained, washed with ice-cold water and dried in a vacuum. The crystals melt at 70°. The acid is very deliquescent, and oxidizes on exposure to air to phosphoric acid. It decomposes on heating into phosphine and phosphoric acid. It is an energetic reducing agent; for example, when boiled with copper sulphate metallic copper is precipitated and hydrogen evolved. ”

“ Calibrate daily with at least six working standards. a. Add 10 mL of acidic permanganate solution and 1 mL of ferrous reagent to a 125-mL separatory funnel. b. Add 2 to 400 μL of the standard phosphate solution to cover the range 0.1 to 10 μg of PH 3. Add 8 to 9 mL of water to make the total volume of the solution (permanganate solution, ferrous solution, phosphate solution and water) equal to 20 mL. Prepare at least six calibration standards and a blank containing no phosphate. c. Add 7.5 mL of molybdate reagent and 25 mL of toluene-isobutanol solvent to the funnel. ”

“ Phosphene, fos′fēn, n. a brilliant coloured spectrum seen when the finger is pressed into the internal corner of the eye. [Gr. phōs, light, phainein, to shine.]
Phosphorus, fos′fō-rus, n. the morning-star: a yellowish substance, like wax, inflammable and giving out light in the dark.—n. Phos′phate, a salt formed by the combination of phosphoric acid with a base.—adj. Phosphat′ic, of the nature of, or containing, a phosphate.—ns. Phos′phide, a compound formed of phosphorus and some other element, as copper or iron; Phos′phite, a salt of phosphorous acid ”

“ When phosphorus is heated to the temperature of 148°, it takes fire, burns with a bright flame, and gives out a great quantity of white smoke. Phosphorus enters into combination with oxygen, azote, hydrogen, and carbon. Phosphorus is soluble in oils, and, when thus dissolved, forms what has been called liquid phosphorus, which may be rubbed on the face and hands without injury. It dissolves too in ether; and a very beautiful experiment consists in pouring this phosphoric ether in small portions, and in a dark place, on the surface of hot water. ”

“ In a few minutes the retort will be filled with a white cloud; then the gas generated will begin to bubble at the end of the saucer; a minute more, each bubble, as it issues from the boiling fluid, will spontaneously take fire as it comes into the air, forming at the same time the philosopher’s ring of phosphoric acid. Care is required in handling phosphorus; but our young chemical readers will, we think, not forego this wonderful experiment for the want of due attention; for, without proper care on their part, we must give up showing them wonders even greater than these. ”

“ 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. ”

“ 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. ”

“ George Maclean, of Princeton, in a communication to the editors of the American Journal of Science, that on one occasion, after some experiments with phosphuretted hydrogen, prepared from phosphorus and solution of potash, on retiring to bed, he found his body to be luminous with a glow like that of phosphorus exposed to the air. Some of the gas, escaping combustion, or the product of its burning, must have been absorbed into the system, and the phosphorus afterward separated at the surface have there undergone eremacausis. ”

“ 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. ”

“ 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.) ”

“ It isn't phosphorus that most of us need, but brains to burn it in. A man might as well light a fire in a carriage, because coal makes an engine go, as hope to mend the pace of his dull pate by eating fish for the sake of the phosphates.
The question still remains, How did the salt originally get there? After all, when we say that it was produced, as rock-salt, by evaporation of the water in inland seas, we leave unanswered the main problem, How did the brine in solution get into the sea at all in the first place? ”

“ 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. ”

“ This is prepared on a commercial scale by heating phosphate rock (which contains calcium phosphate) with sand and coke in an electric furnace. Phosphorus occurs in two forms, white and red. White phosphorus, which is formed when the vapor of the [Pg 287] substance is quickly cooled, is, in the pure state, almost colorless, melts at 44° C., boils at 287° C., is readily soluble in various solvents, and is luminous in the air, at the same time emitting fumes (the oxidation product, phosphorus pentoxide) . On gentle warming in the air, it takes fire and burns with a brightly luminous flame. ”

“ The identity of Phlogiston in all combustible bodies was founded upon observations and experiments of so decisive a nature, that after the existence of the principle itself was admitted, they could not fail to be satisfactory. When phosphorus is made to burn, it gives out a strong flame, much heat is evolved, and the phosphorus is dissipated in fumes, which, if properly collected, will quickly absorb 420 moisture from the atmosphere, and produce an acid liquid known by the name of phosphoric acid. ”

“ 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;" ”

“ 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. ”