Discoveries and Inventions of the Nineteenth Century

from the lid, and is connected with a worm surrounded by cold water, for the purpose of condensing the aniline which is vapourized in the process. The aniline, containing a due amount of toluidine, is mixed in this apparatus with about one and a half times its weight of a saturated solution of arsenic acid (H3AsO4). The fire is lighted and kept up for several hours: water first, and lastly aniline, distil over. When the operation is ended, steam is blown through the apparatus, thus carrying off an additional portion of aniline. The crude product is then boiled with water, the solution filtered, 790and common salt added, which precipitates an impure magenta. This is afterwards dissolved and recrystallized several times. The crystals of this magenta—like those of many of the coal-colour products—have a peculiar greenish metallic lustre; they dissolve in warm water, forming a deep purplish-red solution. The chemical composition of magenta has been investigated by Dr. Hofman, who found it to be a salt of an organic base, to which he gave the name of “rosaniline.” This rosaniline is easily obtained from magenta by addition to its solution of an alkali. While all its salts are intensely coloured, rosaniline itself is a perfectly colourless substance, becoming reddened by exposure to the air, as it absorbs carbonic acid, thus passing to the condition of a salt. Rosaniline, then, displays its chromatic powers only when it is combined with an acid. This property is sometimes shown at lectures in a striking manner by dipping a piece of paper into a colourless solution of rosaniline, and exposing it to the air, when, as the rosaniline absorbs carbonic acid, the paper changes from white to red. A more elegant form of the same experiment is to dip a white rose into a solution of rosaniline containing a little ammonia. As the ammonia escapes, or is expelled by a current of warm air, the same kind of action occurs, and the white rose changes to red—as if by magic, the emblem of the House of York is transformed into the badge of Lancaster! The chemical nature of rosaniline is regarded as analogous to that of ammonia—it is, in fact, looked upon by chemists as a sort of ammonia, in each particle of which some atoms of hydrogen have been replaced by certain groups of carbon and hydrogen atoms—some of these groups being derived from the aniline and others from the toluidine. The particular salt of rosaniline which constitutes the crude product of the action on the aniline and toluidine, depends on the substance employed to effect the oxidation. If a chloride, the resulting product is chloride of rosaniline; if a nitrate, it is the nitrate; and so on. The magenta which is formed in the first instance by the process we have described is an arseniate of rosaniline; but in the subsequent processes, it is converted into the chloride—the salt usually sold as magenta. Other salts of rosaniline are made on the large scale—especially the acetate, the beautiful crystals of which have the advantage of being very soluble. Magenta attaches itself strongly to animal fibres, but the colour is somewhat fugacious under the action of sunlight. It is used not only as a dye, but more largely as the raw material from which a number of other beautiful colours are obtained. For this reason it is manufactured on an enormous scale, thousands of tons being produced annually, and the money value of the colour produced from it must be reckoned by thousands of pounds. Yet aniline was a few years ago merely a curiosity never met with out of the laboratory of the scientific chemist. It is stated that a single firm now makes more than twelve tons of aniline weekly, and on its premises may be seen tanks, in each of which 30,000 gallons of magenta solution is depositing its crystals. If a salt of rosaniline be heated with aniline, the colour changes gradually through purple to blue, while ammonia is at the same time given off. This is the colour known as aniline blue, “bleu du Lyons,” &c. In its preparation it has been found that the best results are obtained by employing the salt of some weak acid—acetate of rosaniline, for example—and pure aniline, that is, aniline free from toluidine. The operation is conducted in iron pots very similar to those used in making magenta, but smaller. These pots are not set over a fire, but a number of them are placed in a large vessel containing oil, by which they can be 791maintained at a regulated temperature when the oil is heated. The crude product undergoes several purifications, and the aniline blue is supplied in commerce in powder, or dissolved in spirits of wine. It is insoluble in water, and this has been an obstacle to its employment; but recently a similar substance has been obtained in a soluble form, and is extensively used for dyeing wool, under the name of “Nicholson’s blue.” Other blues have been similarly prepared, and from the same two substances, magenta and aniline, a colour known as “violet imperial” was formerly made in very large quantities, but it has been superseded by the colours about to be described. It may be well to mention that these blues and violets have been found to contain bases formed of rosaniline, in which one, two, or three atoms of hydrogen are replaced by the group C6H5. This group of atoms will be noticed to belong to aniline, and chemists have named it phenyl, and, therefore, bases of these coloured salts are respectively named phenyl-rosaniline, di-phenyl-rosaniline, tri-phenyl-rosaniline. But Dr. Hofman found that other groups of atoms besides C6H5 may be made to take the place of H in rosaniline. By acting on rosaniline or its salts with iodides of ethyl, C2H5I, or iodide of methyl, CH3I, he obtained a beautiful series of violets, of which many shades could be produced, varying from red-purple to blue. These are the colours so well known as Hofman’s violets, and are prepared on the large scale by heating a solution of magenta (chloride of rosaniline) in alcohol or wood spirit, with the iodide of ethyl or the iodide of methyl. The nature and proportions of the ingredients are regulated according to the tint required. The vessels are hermetically closed during the heating, which is accomplished by steam admitted into a steam-jacket surrounding the vessel. The crude product has to be separated from the substances with which it is mixed, and the colouring matter is finally obtained, presenting in the solid state the peculiar semi-metallic lustre so characteristic of these products. Like the other colours, Hofman’s violets are salts of colourless bases, which, as indicated above, are substitution products of rosaniline. The tints they produce incline to red, violet, or blue, according as one, two, or three hydrogen atoms are replaced by the ethyl or methyl groups. Colours have also been obtained from mauve and iodide of ethyl—for example, the dye known in commerce as “dahlia.” Other colours are procured from magenta by treating it with various compounds: one such is the “Britannia violet,” discovered also by Mr. Perkin, who procures it from magenta and a hydrocarbon-bromide derived from the action of bromine or common turpentine. This is a very useful colour, and is largely used in dyeing and printing violets, of which any shades may be obtained. Another derivative of rosaniline is the aniline green. It is obtained by dissolving the rosaniline salt in dilute sulphuric acid, adding crude aldehyde (a substance obtained by acting with oxidizing agents on alcohol). The mixture is heated until a sample dissolves in acidulated water with a blue tint; it is poured out into boiling water containing in solution hyposulphite of sodium, boiled, the liquid filtered; and the green dye, if required in the solid state, is precipitated by carbonate of sodium. Aniline green dyes wool and silk, the latter especially, of a magnificent green; perhaps as beautiful a colour as any of the coal-tar series, and one which has the singular advantage among greens of looking as beautiful in artificial light as in daylight. The manner in which this dye was discovered is somewhat curious. It is related by Mr. Perkin of a dyer, named Chirpin, that he was trying to render permanent a blue colouring matter, which had been found 792could be produced from rosaniline by the action of aldehyde and sulphuric acid. After a number of fruitless attempts at fixing it, he confided his perplexities to a photographic friend, who evidently thought that if it was possible to fix a photograph, anything else might be fixed in like manner, for he recommended his confidant to try hyposulphite of sodium. On making the experiment, however, the dyer did not succeed in fixing his blue, but converted it into the splendid aldehyde green. Like other colouring matters we have described, this is a salt of a colourless base containing sulphur. Like rosaniline, the colourless base takes on the characteristic colour of its salts by merely absorbing carbonic acid from the air. Again, by a modification of the process for producing the Hofman violets, another green of an entirely different constitution may be obtained. It is bluer in tint than the former, and is much used for cotton and silks, under the name of “iodine green.” In the manufacture of magenta there is formed a residuum or bye-product, consisting of a resinous, feebly basic substance, from which Nicholson obtained a dye, imparting to silk and wool a gorgeous golden yellow colour. This dye cannot be obtained directly, but is always produced in greater or less quantity when magenta is made on the large scale, and is separated during the purification. By first dyeing the silk or wool with magenta, and then with this dye, which is commercially known as “phosphine,” brilliant scarlet tints are obtained. The yellow colours have been found to be salts of a base termed chrysaniline, a sort of chemical relative of rosaniline, as may be seen in comparing the formulæ which represent their constitution, with which we place also the symbol for another substance obtained by submitting rosaniline to the influence of nascent hydrogen. This body, leucaniline, again yields rosaniline very readily when the hydrogen is removed by oxidizing agents. It will be noticed that the three bodies form a series the members of which differ only by H2, thus indicating their close relationship. C20H17N3 Chrysaniline. C20H19N3 Rosaniline. C20H21N3 Leucaniline. Some idea will have been obtained from the foregoing particulars of the great colour-supplying capabilities of aniline; but we have not yet exhausted the utility of this interesting substance. It is probable that the letters on the page now under the reader’s eye owe their blackness to an aniline product. For after all the salts furnishing the lovely tints we have mentioned have been extracted, there is in their manufacture a final residuum, and from this an intense black is obtained, which is largely used in the manufacture of printing-ink. We have mentioned phenol as a substance yielding colours. Phenol is the body now so well known as a disinfectant under the name of “carbolic acid,” a name given to it by its discoverer, Runge, who prepared it from coal-tar, in 1834. Phenol forms colourless crystals, which dissolve to some extent in water, and very readily in alcohol. It is a powerful antiseptic, that is, it arrests the process of putrefaction in animal or vegetable bodies, and it is also highly poisonous. The constitution of phenol is given by the formula C6H5 OH, in which the reader will recognize the same group of atoms already indicated as entering into the aniline derivatives. From some of these phenol may in fact be obtained, and although it cannot be formed directly from benzol, phenol can be made to furnish benzol. When 793crude phenol is treated with a sulphuric acid and oxalic acid, a substance is obtained which presents itself as a brittle resinous mass of a brown colour, with greenish metallic