In a former chapter some slight reference has been made to those bye-products of coal-tar which have proved so valuable in the production of the aniline dyes. It is thought that the subject is of so interesting a nature as to deserve more notice than it was possible to bestow upon it in that place. With abstruse chemical formulae and complex chemical equations it is proposed to have as little as possible to do, but even the most unscientific treatment of the subject must occasionally necessitate a scientific method of elucidation.

The dyeing industry has been radically changed during the last half century by the introduction of what are known as the artificial dyes, whilst the natural colouring matters which had previously been the sole basis of the industry, and which had been obtained by very simple chemical methods from some of the constituents of the animal kingdom, or which were found in a natural state in the vegetable kingdom, have very largely given place to those which have been obtained from coal-tar, a product of the mineralised vegetation of the carboniferous age.

The development and discovery of the aniline colouring matters were not, of course, possible until after the extensive adoption of house-gas for illuminating purposes, and even then it was many years before the waste products from the gas-works came to have an appreciable value of their own. This, however, came with the increased utilitarianism of the commerce of the present century, but although aniline was first discovered in 1826 by Unverdorben, in the materials produced by the dry distillation of indigo (Portuguese, anil, indigo), it was not until thirty years afterwards, namely, in 1856, that the discovery of the method of manufacture of the first aniline dye, mauveine, was announced, the discovery being due to the persistent efforts of Perkin, to whom, together with other chemists working in the same field, is due the great advance which has been made in the chemical knowledge of the carbon, hydrogen, and oxygen compounds. Scientists appeared to work along two planes; there were those who discovered certain chemical compounds in the resulting products of reactions in the treatment of existing vegetation, and there were those who, studying the wonderful constituents in coal-tar, the product of a past age, immediately set to work to find therein those compounds which their contemporaries had already discovered. Generally, too, with signal success.

The discovery of benzene in 1825 by Faraday was followed in the course of a few years by its discovery in coal-tar by Hofmann. Toluene, which was discovered in 1837 by Pelletier, was recognised in the fractional distillation of crude naphtha by Mansfield in 1848. Although the method of production of mauveine on a large scale was not accomplished until 1856, yet it had been noticed in 1834, the actual year of its recognition as a constituent of coal-tar, that, when brought into contact with chloride of lime, it gave brilliant colours, but it required a considerable cheapening of the process of aniline manufacture before the dyes commenced to enter into competition with the old natural dyes.

The isolation of aniline from coal-tar is expensive, in consequence of the small quantities in which it is there found, but it was discovered by Mitscherlich that by acting upon benzene, one of the early distillates of coal-tar, for the production of nitro-benzole, a compound was produced from which aniline could be obtained in large quantities. There were thus two methods of obtaining aniline from tar, the experimental and the practical.

In producing nitrobenzole (nitrobenzene), chemically represented as (C₆H₅NO₂), the nitric acid used as the reagent with benzene, is mixed with a quantity of sulphuric acid, with the object of absorbing water which is formed during the reaction, as this would tend to dilute the efficiency of the nitric acid. The proportions are 100 parts of purified benzene, with a mixture of 115 parts of concentrated nitric acid (HNO₃) and 160 parts of concentrated sulphuric acid. The mixture is gradually introduced into the large cast-iron cylinder into which the benzene has been poured. The outside of the cylinder is supplied with an arrangement by which fine jets of water can be made to play upon it in the early stages of the reaction which follows, and at the end of from eight to ten hours the contents are allowed to run off into a storage reservoir. Here they arrange themselves into two layers, the top of which consists of the nitrobenzene which has been produced, together with some benzene which is still unacted upon. The mixture is then freed from the latter by treatment with a current of steam. Nitrobenzene presents itself as a yellowish oily liquid, with a peculiar taste as of bitter almonds. It was formerly in great demand by perfumers, but its poisonous properties render it a dangerous substance to deal with. In practice a given quantity of benzene will yield about 150 per cent of nitrobenzene. Stated chemically, the reaction is shown by the following equation:

C6H6    	    +       HNO3       =        C6H5NO2      +        H2O
(Benzene)       (Nitric acid)       (Nitrobenzene)         (Water)

The water which is thus formed in the process, by the freeing of one of the atoms of hydrogen in the benzene, is absorbed by the sulphuric acid present, although the latter takes no actual part in the reaction.

From the nitrobenzene thus obtained, the aniline which is now used so extensively is prepared. The component atoms of a molecule of aniline are shown in the formula C₆H₅NH₂. It is also known as phenylamine or amido-benzole, or commercially as aniline oil. There are various methods of reducing nitrobenzene for aniline, the object being to replace the oxygen of the former by an equivalent number of atoms of hydrogen. The process generally used is that known as Bechamp’s, with slight modifications. Equal volumes of nitrobenzene and acetic acid, together with a quantity of iron-filings rather in excess of the weight of the nitrobenzene, are placed in a capacious retort. A brisk effervescence ensues, and to moderate the increase of temperature which is caused by the reaction, it is found necessary to cool the retort. Instead of acetic acid hydrochloric acid has been a good deal used, with, it is said, certain advantageous results. From 60 to 65 per cent. of aniline on the quantity of nitrobenzene used, is yielded by Bechamp’s process.

Stated in a few words, the above is the process adopted on all hands for the production of commercial aniline, or aniline oil. The details of the distillation and rectification of the oil are, however, as varied as they can well be, no two manufacturers adopting the same process. Many of the aniline dyes depend entirely for their superiority, on the quality of the oil used, and for this reason it is subject to one or more processes of rectification. This is performed by distilling, the distillates at the various temperatures being separately collected.

When pure, aniline is a colourless oily liquid, but on exposure rapidly turns brown. It has strong refracting powers and an agreeable aromatic smell. It is very poisonous when taken internally; its sulphate is, however, sometimes used medicinally. It is by the action upon aniline of certain oxidising agents, that the various colouring matters so well known as aniline dyes are obtained.

Commercial aniline oil is not, as we have seen, the purest form of rectified aniline. The aniline oils of commerce are very variable in character, the principal constituents being pure aniline, para- and meta-toluidine, xylidines, and cumidines. They are best known to the colour manufacturer in four qualities

(a) Aniline oil for blue and black.

(b) Aniline oil for magenta.

(c) Aniline oil for safranine.

(d) Liquid toluidine.

From the first of these, which is almost pure aniline, aniline black is derived, and a number of organic compounds which are further used for the production of dyes. The hydrochloride of aniline is important and is known commercially as “aniline salt.”

The distillation and rectification of aniline oil is practised on a similar principle to the fractional distillation which we have noticed as being used for the distillation of the naphthas. First, light aniline oils pass over, followed by others, and finally by the heavy oils, or “aniline-tailings.” It is a matter of great necessity to those engaged in colour manufacture to apply that quality oil which is best for the production of the colour required. This is not always an easy matter, and there is great divergence of opinion and in practice on these points.

The so-called aniline colours are not all derived from aniline, such colouring matters being in some cases derived from other coal-tar products, such as benzene and toluene, phenol, naphthalene, and anthracene, and it is remarkable that although the earlier dyes were produced from the lighter and more easily distilled products of coal-tar, yet now some of the heaviest and most stubborn of the distillates are brought under requisition for colouring matters, those which not many years ago were regarded as fit only to be used as lubricants or to be regarded as waste.

It is scarcely necessary or advisable in a work of this kind to pursue the many chemical reactions, which, from the various acids and bases, result ultimately in the many shades and gradations of colour which are to be seen in dress and other fabrics. Many of them, beautiful in the extreme, are the outcome of much careful and well-planned study, and to print here the complicated chemical formulae which show the great changes taking place in compounds of complex molecules, or to mention even the names of these many-syllabled compounds, would be to destroy the purpose of this little book. The Rosanilines, the Indulines, and Safranines; the Oxazines, the Thionines: the Phenol and Azo dyes are all substances which are of greater interest to the chemical students and to the colour manufacturer than to the ordinary reader. Many of the names of the bases of various dyes are unknown outside the chemical dyeworks, although each and all have complicated; reactions of their own. In the reds are rosanilines, toluidine xylidine, &c.; in the blues phenyl-rosanilines, diphenylamine, toluidine, aldehyde, &c.; violets rosaniline, mauve, phenyl, ethyl, methyl, &c.; greens iodine, aniline, leucaniline, chrysotoluidine, aldehyde, toluidine, methyl-anilinine, &c.; yellows and orange leucaniline, phenylamine, &c.; browns chrysotoluidine, &c.; blacks aniline, toluidine, &c.

To take the rosanilines as an instance of the rest.

Aniline red, magenta, azaleine, rubine, solferino, fuchsine, chryaline, roseine, erythrobenzine, and others, are colouring matters in this group which are salts of rosaniline, and which are all recognised in commerce.

The base rosaniline is known chemically by the formula C₂₀H₁₉N₃, and is prepared by heating a mixture of magenta aniline, toluidine, and pseudotoluidine, with arsenic acid and other oxidising agents. It is important that water should be used in such quantities as to prevent the solution of arsenic acid from depositing crystals on cooling. Unless carefully crystallised rosaniline will contain a slight proportion of the arseniate, and when articles of clothing are dyed with the salt, it is likely to produce an inflammatory condition of skin, when worn. Some years ago there was a great outcry against hose and other articles dyed with aniline dyes, owing to the bad effects which were produced, and this has no doubt proved very prejudicial to aniline dyes as a whole.

Again, the base known as mauve, or mauveine, has a composition shown by the formula C₂₇H₂₄N₄. It is produced from the sulphate of aniline by mixing it with a cold saturated solution of bichromate of potash, and allowing the mixture to stand for ten or twelve hours. A blue-black precipitate is then formed, which, after undergoing a process of purification, is dissolved in alcohol and evaporated to dryness. A metallic-looking powder is then obtained, which constitutes this all-important base. Mauve forms with acids a series of well-defined salts and is capable of expelling ammonia from its combinations. Mauve was the first aniline dye which was produced on a large scale, this being accomplished by Perkin in 1856.

The substance known as carbolic acid is so useful a product of a piece of coal that a description of the method of its production must necessarily have a place here. It is one of the most powerful antiseptic agents with which we are acquainted, and has strong anaesthetic qualities. Some useful dyes are also obtained from it. It is obtained in quantities from coal-tar, that portion of the distillate known as the light oils being its immediate source. The tar oil is mixed with a solution of caustic soda, and the mixture is violently agitated. This results in the caustic soda dissolving out the carbolic acid, whilst the undissolved oils collect upon the surface, allowing the alkaline solution to be drawn from beneath. The soda in the solution is then neutralised by the addition of a suitable quantity of sulphuric acid, and the salt so formed sinks while the carbolic acid rises to the surface.

Purification of the product is afterwards carried out by a process of fractional distillation. There are various other methods of preparing carbolic acid.

Carbolic acid is known chemically as C₆H₅(HO). When pure it appears as colourless needle-like crystals, and is exceedingly poisonous. It has been used with marked success in staying the course of disease, such as cholera and cattle plague. It is of a very volatile nature, and its efficacy lies in its power of destroying germs as they float in the atmosphere. Modern science tells us that all diseases have their origin in certain germs which are everywhere present and which seek only a suitable nidus in which to propagate and flourish. Unlike mere deodorisers which simply remove noxious gases or odours; unlike disinfectants which prevent the spread of infection, carbolic acid strikes at the very root and origin of disease by oxidising and consuming the germs which breed it. So powerful is it that one part in five thousand parts of flour paste, blood, &c., will for months prevent fermentation and putrefaction, whilst a little of its vapour in the atmosphere will preserve meat, as well as prevent it from becoming fly-blown. Although it has, in certain impure states, a slightly disagreeable odour, this is never such as to be in any way harmful, whilst on the other hand it is said to act as a tonic to those connected with its preparation and use.

The new artificial colouring matters which are continually being brought into the market, testify to the fact that, even with the many beautiful tints and hues which have been discovered, finality and perfection have not yet been reached. A good deal of popular prejudice has arisen against certain aniline dyes on account of their inferiority to many of the old dye-stuffs in respect to their fastness, but in recent years the manufacture of many which were under this disadvantage of looseness of dye, has entirely ceased, whilst others have been introduced which are quite as fast, and sometimes even faster than the natural dyes.