Page:EB1911 - Volume 06.djvu/614

 body or whole. The word is used, especially in a political sense, of an alliance or temporary union for joint action of various powers or states, such as the coalition of the European powers against France, during the wars of the French Revolution; and also of the union in a single government of distinct parties or members of distinct parties. Of the various coalition ministries in English history, those of Fox and North in 1782, of the Whigs and the Peelites, under Lord Aberdeen in 1852–1853, and of the Liberal Unionists and Conservatives in Lord Salisbury’s third ministry in 1895, may be instanced.

COAL-TAR, the black, viscous, sometimes semi-solid, fluid of peculiar smell, which is condensed together with aqueous “gas liquor” when the volatile products of the destructive distillation of coal are cooled down. It is also called “gas-tar,” because it was formerly exclusively, and even now is mostly, obtained as a by-product in the manufacture of coal-gas, but the tar obtained from the modern coke-ovens, although not entirely identical with gas-tar, resembles it to such an extent that it is worked up with the latter, without making any distinction in practice between the two kinds. Some descriptions of gas-tar indeed differ very much more than coke-oven tar from pure coal-tar, viz. those which are formed when bituminous shale or other materials, considerably deviating in their nature from coal, are mixed with the latter for the purpose of obtaining gas of higher illuminating power.

It may be generally said that for the purpose of tar-distillers the tar is all the more valuable the less other materials than real coal have been used by the gas-maker. All these materials—bog-head shale, bituminous lignite and so forth—by destructive distillation yield more or less paraffinoid oils, which render the purification of the benzols very difficult and sometimes nearly impossible for the purposes of the manufacturer of coal-tar colours.

Neither too high nor too low a temperature should have been observed in gas-making in order to obtain a good quality of tar. Since in recent times most gas retorts have been provided with heating arrangements based on the production of gaseous fuel from coke, which produce higher temperatures than direct firing and have proved a great economy in the process of gas-making itself, the tar has become of decidedly inferior quality for the purposes of the tar-distillers, and in particular yields much less benzol than formerly.

Entirely different from gas-tar is the tar obtained as a by-product from those (Scottish) blast furnaces which are worked with splint-coal. This tar contains very little aromatic hydrocarbons, and the phenols are of quite a different character from those obtained in the working of gas-tar. The same holds good of oil-gas tars and similar substances. These should not be worked up like gas-tars.

The ordinary yield of tar in the manufacture of coal-gas is between 4 and 5% of the weight of the coal. Rather more is obtained when passing the gas through the apparatus of E. Pelouze and P. Audouin, where it is exposed to several shocks against solid surfaces, or by carrying on the process at the lowest possible temperature, as proposed by H. J. Davis, but this “carbonizing process” can only pay under special circumstances, and is probably no longer in practical use.

All coal-tars have a specific gravity above that of water, in most cases between 1·12 and 1·20, but exceptionally up to 1·25. The heavier tars contain less benzol than the lighter tars, and more “fixed carbon,” which remains behind when the tars are exhausted of benzol and is a decidedly objectionable constituent. All tars also mechanically retain a certain quantity of water (or rather gas-liquor), say, 4% on the average, which is very obnoxious during the process of distillation, as it leads to “bumping,” and therefore ought to be previously removed by prolonged settling, preferably at a slightly elevated temperature, which makes the tar more fluid. The water then rises to the top, and is removed in the ordinary way or by special “separators.”

The tar itself is a mixture of exceedingly complex character. The great bulk of its constituents belongs to the class of “aromatic” hydrocarbons, of very different composition and degrees of volatility, beginning with the simplest and most volatile, benzene (C6H6), and ending with an entirely indistinguishable mass of non-volatile bodies, which compose the pitch left behind in the tar-stills. The hydrocarbons mostly belong to the benzene series CnH2n–6, the naphthalene series CnH2n–12, and the anthracene and phenanthrene series CnH2n–18. Small quantities of “fatty” (“aliphatic”) hydrocarbons are never absent, even in pure tars, and are found in considerable quantities when shales and similar matters have been mixed with the coal in the gas-retorts. They belong mostly to the paraffins CnH2n+2, and the olefines CnH2n. The “asphalt” or soluble part of the pitch is also a mixture of hydrocarbons, of the formula CnH2n; even the “carbon,” left behind after treating the pitch with all possible solvents is never pure carbon, but contains a certain quantity of hydrogen, although less than any of the volatile and soluble constituents of the tar.

Besides the hydrocarbons, coal-tar contains about 2% of the simpler phenols CnH2n–7OH, the best known and most valuable of which is the first of the series, (q.v.) C6H5OH, besides another interesting oxygenized substance, cumarone C8H6O. The phenols, especially the carbolic acid, are among the more valuable constituents of coal-tar. Numerous sulphur compounds also occur in coal-tar, some of which impart to it their peculiar nauseous smell, but they are of no technical importance or value.

Still more numerous are the nitrogenated compounds contained in coal-tar. Most of these are of a basic character, and belong to the pyridine and the quinoline series. Among these we find a somewhat considerable quantity of aniline, which, however, is never obtained from the tar for commercial purposes, as its isolation in the pure state is too difficult. The pyridines are now mostly recovered from coal-tar, but only in the shape of a mixture of all members of the series which is principally employed for denaturing alcohol. Some of these nitrogenated compounds possess considerable antiseptic properties, but on the whole they are only considered as a contamination of the tar-oils.

Applications of Coal-Tar in the Crude State.—Large quantities of coal-tar are employed for various purposes without submitting it to the process of distillation. It is mostly advisable to dehydrate the tar as much as possible for any one of its applications, and in some cases it is previously boiled in order to remove its more volatile constituents.

No preparation whatever is needed if the tar is to be used as fuel, either for heating the gas-retorts or for other purposes. Its heating-value is equal to the same weight of best coal, but it is very difficult to burn it completely without producing a great deal of evil-smelling smoke. This drawback has been overcome by employing the same means as have been found suitable for the combustion of the heavy petroleum residues, called “masut,” viz. converting the tar into a fine spray by means of steam or compressed air. When the gas-maker cannot conveniently or profitably dispose of his tar for other purposes, he burns it by the above means under his retorts.

Several processes have also been patented for producing illuminating gas from tar, the most notable of which is the Dinsmore process. This process has been adversely criticized by very competent gas-makers, and no great success can be expected in this line.

Coal-tar is very much employed for painting wood, iron, brickwork, or stone, as a preventive against the influence of weather or the far more potent action of corrosive chemicals. This, of course, can be done only where appearance is no object, for instance in chemical works, where all kinds of erections and apparatus are protected by this cheap kind of paint. Coal-tar should not be used for tarring the woodwork and ropes of ships, a purpose for which only wood-tar has been found suitable.

One of the most considerable outlets for crude tar is in the manufacture of roofing-felt. This industry was introduced in Germany upwards of a hundred years ago, even before coal-tar was available, and has reached a very large extension both in that country and in the United States, where most of the gas-tar seems to be devoted to this purpose. In the United Kingdom