Part 97

The operation is effected in the apparatus represented in Fig. 355. It consists of a large iron cylinder, within which works a paddle on a vertical revolving spindle, which, being hollow, is also a pipe to convey high pressure steam within the apparatus. Fig. 356 is a section of the hollow spindle, in which _f_ is the pivot at the bottom of the cylinder on which it turns; _d_ is the stirring paddle; _e_ is an aperture admitting the steam from the pipe, _c_, forming the shaft of the paddle, which is made to revolve by the bevil-wheel. The steams enters by the elbow-pipe, which has a nozzle ground to fit the head of the vertical revolving pipe, upon which it is pressed down by the screw. When the materials have been introduced into the cylinder, the stirrer is set in motion, and superheated steam is sent down the pipe; the aniline is volatilized and passes with the steam through the pipe, which is connected with a worm surrounded by cold water. The aniline is purified by another distillation over lime or soda. When pure, aniline is a colourless, somewhat oily-looking liquid, of a feeble aromatic odour. Under the influence of light and air it becomes of a brownish tint, in which condition it usually presents itself in commerce. It scarcely dissolves in water, but is readily soluble in alcohol, ether, &c.

It was Mr. Perkin who, in 1856, first obtained from aniline a substance practically available for dyeing. Let it be noticed that when Mr. Perkin discovered _aniline purple_, he was not engaged in searching for dye-stuffs, but was carrying on a purely scientific investigation as to the possibility of artificially preparing quinine. With this view, having selected a substance into the composition of which nitrogen, hydrogen, and carbon enter in exactly the same proportions as they occur in quinine, but differing from it by containing no oxygen, he thought it not improbable that by oxidizing this body he might obtain quinine. In this he was disappointed, for the result was a dirty reddish-brown powder. Being desirous, however, of understanding more fully the nature of this reddish powder, he proceeded to try the effects of oxidation on other similarly constituted but more simple bodies. For this purpose he fortunately selected _aniline_, which, when treated with sulphuric acid and bichromate of potash, he found to yield a perfectly black product. Persevering in his experiments by examining this black substance, he obtained, by digesting it with spirits of wine, the now well-known “aniline purple.” Mr. Perkin, having determined to make the aniline purple on the large scale, patented his process, and succeeded in overcoming the many obstacles incident to the establishment of a new manufacture requiring as its raw material products not at that time met with as commercial articles. The process is now carried on the large scale by mixing sulphuric acid and aniline in the proportions in which they combine to form the sulphate of aniline, and dissolving by boiling with water in a large vat. Bichromate of potash is dissolved in water in another large vat. When both solutions are cold, they are mixed together in a still larger vessel and allowed to stand a day or two. A fine black powder settles on the bottom of the vessel in large quantities; this is collected in filters, washed with water, and dried. This powder is not aniline purple alone, but a mixture of this with other products, presenting a very unpromising appearance; but when it has been digested for some time with diluted methylated spirit, all the colouring matter is dissolved out, and is obtained from the solution by placing the latter in a still, where the spirit is distilled off and collected for future use, while all the colouring matter remains behind, held in solution by the water. From this aqueous solution the mauve is thrown down by adding caustic soda. It is collected, washed, and drained until of a pasty consistence, in which condition it is sent into the market. It can be obtained in crystals, but the commercial article is seldom required in this form, as the additional expense is not compensated by any superiority in the practical applications of the colour. Mauve is readily soluble in spirits of wine, but not very soluble in water. Its tinctorial power is so great that _one-tenth of a grain_ suffices to impart quite a deep colour to a gallon of water. Silk and woollen fabrics have an extraordinary attraction for this colouring matter, which attaches itself very firmly to their fibres. If some white wool is dipped into even a very dilute solution, the colour is quickly absorbed. Mauve is more permanent than any other coal-tar colour, being little affected by the prolonged action of light.

Mauve is chemically a salt of a base which has been termed “mauveine.” Mauveine itself is a nearly black crystalline powder, which forms solutions of a dull blue-violet tint, but when an acid is added to such a solution the tint is at once changed to purple. Mauveine is a powerful base, displacing ammonia from its compounds. The commercial crystallized mauve is the acetate of mauveine.

The process by which Mr. Perkin originally obtained mauve from aniline evidently depends upon the well-known oxidizing property of bichromate of potash, and experiments were accordingly made with other, oxidizing bodies and aniline; in fact, patents were taken out for the use of nearly every known oxidizing chemical. Three years after Mr. Perkin’s discovery of mauve, M. Verguin, of Lyons, obtained, by treating _crude_ aniline with chloride of tin, the bright red colouring matter now known as magenta. It was found also that crude aniline, when treated with other metallic chlorides, nitrates, or other salts, which are oxidizing agents less powerful than bichromate of potash, yields this bright red colouring matter. A process patented by Medlock, in 1860, in which arsenic acid is the oxidizing agent, has almost entirely superseded, in England at least, all the others yet proposed for the manufacture of magenta. It is not a little remarkable that magenta would not have been discovered had M. Verguin and others operated on _pure_ aniline instead of on the ordinary commercial article. For it was found subsequently by Dr. Hofman that pure aniline cannot be made to yield magenta: the presence of another body is necessary. A reference to the table of coal-tar constituents will show that there is a hydro-carbon named “toluol.” This substance is of a similar nature to benzol, and has a boiling-point so little above that of benzol, that in the rough methods of separation usually employed, a notable quantity of toluol is carried over with the benzol, and is always present in the commercial article. In the processes which benzol undergoes for conversion into aniline, the toluol accompanies it in a series of parallel transformations, resulting in the production of a base termed “toluidine”—similar to aniline—being, however, in its pure state a solid at ordinary temperatures. We write down the symbols representing the composition of the bodies formed in the two cases in order to clearly show this:

Benzol C_{6}H_{6} Nitro-benzol C_{6}H_{5}(NO_{2}) Aniline C_{6}H_{5}NH_{2} Toluol C_{7}H_{8} Nitro-toluol C_{7}H_{7}(NO_{2}) Toluidine C_{7}H_{7}NH_{2}

This aniline prepared from commercial benzol always contains some toluidine; and it is essential for the production of magenta that this substance should be operated on along with the aniline. Whether the presence of some toluidine is also necessary for the production of mauve and other colours is not yet known, but they are always prepared from commercial benzol. It is certain that pure aniline yields no magenta, neither does pure toluidine; but a mixture supplies it in abundance. For the preparation of magenta the best proportions for this mixture would be about three parts of aniline to one of toluidine; but, in practice, it is not necessary to obtain the two substances separately, as benzol, mixed with a sufficient quantity of toluol, may be obtained by regulating the distillation. The apparatus used in the production of magenta is shown in Fig. 352. It consists of a large iron pot set over a furnace in brickwork, and having a lid with a stuffing-box, through which passes a spindle carrying a stirrer. A bent tube rises 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 (H_{3}AsO_{4}). 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, and 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 maintained 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 C_{6}H_{5}. 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 C_{6}H_{5} may be made to take the place of H in rosaniline. By acting on rosaniline or its salts with iodides of ethyl, C_{2}H_{5}I, or iodide of methyl, CH_{3}I, 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 could 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 H_{2}, thus indicating their close relationship.

C_{20}H_{17}N_{3} Chrysaniline. C_{20}H_{19}N_{3} Rosaniline. C_{20}H_{21}N_{3} 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 C_{6}H_{5} 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 crude 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 lustre. This substance is called _rosolic acid_ by chemists, but in commerce it is known as _aurine_, and is used for dyeing silk of an orange colour, which, however, is not very permanent. But by heating rosolic acid with liquid ammonia, a permanent red dye is procured which has been termed _peonine_, and has been much used for woollen goods. But it lately had the reputation of exerting a poisonous action, producing blistering and sores when stockings or other articles dyed with it were worn in contact with the skin. It is now, therefore, less extensively employed. _Coralline_, another body identical with or very similar to the former, is similarly prepared from rosolic acid by heating it with ammonia under pressure.

Again, by heating coralline with aniline, a blue dye, known as “azurine,” or “azuline,” was formerly made in large quantities; but it has been supplanted by the aniline blues already described.

When phenol is acted upon by nitric acid new compounds are produced, standing in the same relation to phenol as nitro-benzol does to benzol. The final result of the action of nitric acid on phenol is _picric acid_, called also “carbazotic acid,” and, more systematically, “tri-nitro-phenol;” for it is regarded as phenol in which three of the hydrogen atoms have been replaced by the group NO_{2} thus, C_{6}H_{2}(NO_{2})_{3} OH. It forms bright yellow-coloured crystals, and its solution readily imparts a bright pure yellow colour to wool, silk, &c. It received the name of picric acid (πικρος, _bitter_) from the exceedingly bitter taste of even an extremely diluted solution. It is said that picric acid is employed as an adulterant in bitter ale instead of hops. Now, the colouring power of picric acid is so great, that even the minute quantity which could be used to impart bitterness to beer is recognizable by dipping a piece of white wool into the beer, when, if picric acid be present, the wool acquires a clear yellow tint. Besides its employment as a yellow, it is useful for procuring green tints by combination with the blues. Picric acid again furnishes, by treatment with _cyanide of potassium_, a deep red colour, consisting of an acid which, when combined with ammonia, furnishes a magnificent colouring material—which is, in fact, _murexide_, a dye identical with the famous Tyrian purple of the ancients, and formerly obtainable only from certain kinds of shell-fish.