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The existence of naphthalene in coal-tar was made known in 1820 by Garden, who gave it this name because the oils obtained from the tar by distillation went under the general designation of naphtha. The greater portion of the hydrocarbon is contained in the carbolic oil, and is separated and purified in the manner described. A further quantity of impure naphthalene separates out from the next fraction—the creosote oil, and this is similarly washed and purified by distillation. The large quantity of naphthalene existing in tar has already been referred to, but although it is such an important constituent, it was only late in the history of the colour industry that it found any extensive application. In early times it was regarded as a nuisance, and was burnt as fuel, or for the production of a dense soot, which was condensed to form lampblack. It will be remembered that the first of the coal-tar colours made required only the light oils. There are at present only a few direct uses for naphthalene, but one of its applications is sufficiently important to be mentioned.

The hydrocarbon is a white crystalline solid melting at 80° C., and boiling at 217° C. Although it has a high boiling-point, it passes readily into vapour at lower temperatures, and the vapour on condensation forms beautiful silvery crystalline scales. This product is “sublimed naphthalene.” The vapour of naphthalene burns with a highly luminous flame, and if mixed with coal-gas, it considerably increases the luminosity of the flame. Advantage is taken-of this in the so-called “albo-carbon light,” which is the flame of burning coal-gas saturated with naphthalene vapour. The burner is constructed so that the gas passes through a reservoir filled with melted naphthalene kept hot by the flame itself ([Fig. 9]).

Fig. 9.—Albo-carbon Burner.

To appreciate properly the value of those discoveries which have enabled manufacturers to utilize this hydrocarbon, it is only necessary to recall to mind the actual quantity produced in this country. Supposing that ten million tons of coal are used annually for gas-making, and that the 500,000 tons of tar resulting therefrom contain only eight per cent. of naphthalene, there would be available about 40,000 tons of this hydrocarbon annually. Great as have been the recent advancements in the utilization of naphthalene derivatives, there is still a larger quantity of this hydrocarbon produced than is necessary to supply the wants of the colour-manufacturer. From this last statement it will be inferred that naphthalene is now a source of colouring-matters. Let us consider how this has been brought about.

The phenols of naphthalene are called naphthols—they bear the same relationship to naphthalene that carbolic acid bears to benzene. Owing to the structure of the naphthalene molecule there are two isomeric naphthols, whereas there is only one phenol. The naphthols—known as alpha- and beta-naphthol, respectively—are now made on a large scale from naphthalene, by heating the latter with sulphuric acid; at a low temperature the alpha sulpho-acid is produced, and at a higher temperature the beta sulpho-acid, and these acids on fusion with caustic soda furnish the corresponding naphthols. Similarly there are two amidonaphthalenes, known as alpha- and beta-naphthylamine respectively. As aniline is to benzene, so are the naphthylamines to naphthalene. The alpha-compound is made in precisely the same way as aniline, viz. by acting upon naphthalene with nitric acid so as to form nitronaphthalene, and then reducing the latter with iron dust and acid. Beta-napthylamine cannot be made in this way; it is prepared from beta-naphthol by heating the latter in presence of ammonia, when the hydroxyl becomes replaced by the amido-group in accordance with a process patented in 1880 by the Baden Aniline Company. The principle thus utilized is the outcome of the scientific work of two Austrian chemists, Merz and Weith. Setting out from the naphthols and naphthylamines we shall be led into industrial developments of the greatest importance.

The first naphthalene colour was a yellow dye, discovered by Martius in 1864, and manufactured under the name of “Manchester yellow.” It is, chemically speaking, dinitro-alpha-naphthol; but it was not at first made from naphthol, as the latter was not at the time a technical product. It was made from alpha-naphthylamine by the action of nitrous and nitric acids. When a good method for making the naphthol was discovered in 1869, the dye was made from this. The process is just the same as that employed in making picric acid; the naphthol is converted into a sulpho-acid, and this when acted upon by nitric acid, gives the colouring-matter. Manchester yellow is now largely used for colouring soap, but as a dye-stuff it has been improved upon in a manner that will be readily understood. The original colouring-matter being somewhat fugitive, it was found that its sulpho-acid was much faster. This sulpho-acid cannot be made by the direct action of sulphuric acid upon the colouring-matter—as in the case of acid yellow or acid magenta—but by acting upon the naphthol with very strong sulphuric acid, three sulphuric acid residues or sulpho-groups enter the molecule, and then on nitration only two of these are replaced by nitro-groups, and there results a sulpho-acid of dinitro-alpha-naphthol. This was discovered in 1879 by Caro, and introduced as “acid naphthol yellow.” It is now one of the standard yellow dyes.