ork, Del Maine New Jer Assistant Bishop the se passed a lume of g teach by the in com f Christ Louse of in the on called English De Lord s of the al conEngland ountain piritasi bishop gative 137,000 ad, wa erbury upport of the enedic d br great e year Leeds, and in He Con er, sa ess to this rinity eries o the the at Cambridge, Oxford, and Manchester. The Bishop of Gloucester and Bristol was the president; and among. the distinguished members who attended, were the Bishops of Chichester, Ely, Bath and Wells, Kilmore, Guyana, the Earl of Harrowby, Lord Lyttleton, Mr. Beresford Hope, Archdeacon Denison, Dr. Pusey, Canon M'Neile. All parties were again represented, though the High Church party was obviously in the ascendency. On several important topics, as the increase of the episcopate and the restoration of church synods, all the speakers were agreed, thus indicating clearly the current of public opinion in the Church of England. 23 later an oily liquid was at different times sepa- ANILINE, OR COAL-TAR COLORS. Pur- Brief references to the aniline colors occur in Aniline was first obtained in separate form by Unverdorben, in 1826. He isolated it from mong other products of the distillation of animal matters, as a heavy but volatile oily liquid, which he named crystalline. Later it was produced by Fritsche, of St. Petersburg, by the action of caustic potash on indigo. After this, Zimin, of St. Petersburg, by a process consisting essentially in acting upon nitro-benzole with Elphide of ammonium, produced the same body, which he named "benzidum." And still In the early part of 1856, Mr. Perkin was experimenting on a compound of toluidine, in the hope of forming quinine artificially. Failing in this, he tried the action of bichromate of potash, acidulated with sulphuric acid, on the sulphate of aniline. The result was a black precipitate of unpromising appearance, but which, on examination, was found to yield the dye already mentioned. This, known as mauve, phenamine, indisine, &c., is more correctly termed aniline purple, or, as some dealers prefer to say, aniline violet. The interest created by the introduction of this new color naturally Prof. Hofmann, in a note to the Royal directed the attention of chemists again to its Society, June, 1858, mentioned the formation of a crystalline derivative from aniline, by action on the latter of bi-chloride of carbon, the reaction being accompanied by the appearance of a magnificent crimson color. This appears to have been the first notice of the aniline crimson (aniline red), subsequently named by its discoverer rosaniline; although it is also stated that Natanson had observed this coloring matter, as formed from aniline, in 1856. As, however, very little of the pigment was obtained source. by Hofmann, and the products of the reaction were very complex, the examination was at the time discontinued. But practical men seized and acted on the hint; and M. Verguin, of Lyons, first succeeded in preparing the crimson dye on a large scale, by acting on aniline with bi-chloride of tin. Its manufacture and application in dyeing were rapidly developed in France, among others by Verguin and the Rénard brothers, and in England especially by the house of Simpson, Maule & Nicholson. To this color, or to particular hues of it, have been given by different manufacturers a variety of names, such as magenta, roseine, fuchsine (now somewhat commonly, but improperly, changed to fuchsia, and by Prof. Dussauce to futschine), &c. From the first discovery of a brilliant dye from aniline, it became of course a matter of interest to be able to produce the latter material in large quantities, and more cheaply than could before be done; and as these objects were presently accomplished by operating on benzole, it will be important here briefly to trace the relations and show the nature of this substance. When bituminous coal, placed in gas-retorts, is distilled by application of a high heat, some 40 per cent. of it is volatilized and driven out of the retorts, the remaining 60 per cent. constituting the coke; and the volatilized portion being made to pass through the "hydraulic main" and a succession of other condensers, its condensible or liquid and solid matters are chiefly arrested in these, while the mixed illuminating gases and some impurities pass on to the proper reservoir. The condensed portions altogether constitute the coal-tar. This consists mainly of bodies which, when isolated, have the form of oils (the coal-oils), and of a tarry or pitchy residue, from which many solids, crystallizable or otherwise, can be separated. From the entire coal-tar some forty or more distinct chemical substances (solids, liquids, and gases) have, upon analysis of it, been obtained. When coal-tar is by itself placed in a retort, and redistilled, the temperature being slowly and gradually raised, the products that are first for a time obtained are oils, those which pass over at temperatures successively higher being of different composition, and more and more dense or heavy. The oils which thus volatilize at temperatures reaching to about 212° F., and which are usually collected together, constitute the "light oil" or "crude coal-naphtha." This, in commerce, is more commonly known as benzole or benzine, although the single oil which (when pure) properly takes these names, forms only a certain percentage of its whole bulk. Among the many products which the entire coal-tar, upon analysis, yields, are the solid, as naphthaline, paranaphthaline, cumidine, paraffine, &c.; the liquid bases, as methylamine, aniline, chinoline, toluidine, &c.; the liquid acids, as the rosolic, brunolic, phenic or carbolic, &c.; the liquid neutral bodies, as water, ben zole, toluole, cumole, &c.; and gases, as ammo nia, &c. The quantity of aniline thus directl separable from coal-tar is, however, small, an the process is not remunerative. The light coal-oil or naphtha is a yellow o brownish liquid, and when purified, has a spe cific gravity of from .70 to .85. The amount of benzole proper contained in the naphtha varies in different samples, being in some very small. Benzole, first separated by Faraday from oil-gas, was so named by Mitscherlich (1834), as being procured by him from benzoic acid, distilled with baryta. The fact of its forming a considerable portion of coal-naphtha was later shown by Mansfield, an English chemist; though the practical method of procuring it was brought out on the continent, about 1850. French chemists named the substance benzine; and under this name, and that of "benzine-collas," it became familiarly known as useful for removing grease from cloth, &c. Benzole, as obtained from naphtha, is not usually entirely free from mixture with oils homologous with it, as toluole, &c. At ordinary temperatures it is a colorless, highly mobile liquid, of an aromatic odor, and at 59° F. has a specific gravity of about .85. Its composition is represented by C12H6. Mitscherlich found that the strongest nitric acid readily attacks benzole, one equivalent of its hydrogen becoming replaced by one of hyponitric acid, and a new compound-a heavy, yellowish oily liquid-being produced, the composition of which is, therefore, C12H.NO.. This he termed nitro-benzole. In preparing it, the reaction just stated is secured by simply allowing a fine stream of benzole and another of concentrated nitric acid to run together in a worm or long glass tube, kept well cooled, the resulting product being then treated with water and carbonate of soda. Nitro-benzole has the odor of oil of bitter almonds, and has hence become much used, under the name of "essence of mirbane," for scenting soaps and for other like uses. Zinin's mode of procuring aniline from this oil by sulphide of ammonium has been already referred to; but as it was not economical, many other methods were tried, among these being that by means of nascent hydrogen, set free by zinc and an acid, and that with acetate of iron. By a modification of the last-named reagent, introduced by M. Béchamp, the process being distinguished as that with "ferrous acetate," it is, that aniline can be cheaply prepared by the ton, and that all the aniline of commerce is now obtained, In this process, 2 parts of nitro-benzole, 2 of concentrated acetic acid, and 3 of iron filings, are placed together in a retort: the application of heat is unnecessary, the chemical reaction giving rise to sufficient heat to distill over a mixture which is found to contain aniline, its acetate, and some nitro-benzole. Redistilling, and treating the distillate with fused caustic potash, the aniline separates as an oily layer. A further portion of it can be obtained from the residue in the retort; and the entire quantity is finally to be distilled again and rectified. The aniline of commerce is never pure. As benzole (C12H1), in the ordinary modes of separation, always holds and carries with it some portion of at the least-toluole (CH), so, when nitro-benzole is prepared, there is formed at the same time with it nitro-toluole; and finally, in the change in which, as commonly stated, nitro-benzole is converted into aniline, the nitro-toluole mixed with the former is in the mean time and by a like reaction converted into toluidine (C1.H,N). The commercial aniline is always a mixture of at least these two substances, and very probably contains minute quantities of still other homologues of aniline proper. This very impurity of aniline, it will presently be seen, is essential to the production of the coloring matters. Dr. Phipson gives the boiling-point of pure aniline as 359°.6, and that of toluidine as 388°.4 F.; and he states that the anilines sought for the manufacture of the dyes are those having their boiling-points between about 365° and 410° F., and which are neceesarily, therefore, mixtures. usually vary with the nature of the oxidizer employed; and the consequence has been the issuing of a proportionately large number of patents, and also much litigation between different claimants. Perkin's aniline purple is a material quite unlike in composition to the crimson or rosaniline of Hofmann, with its derivatives. The former appears, according to a late statement of its discoverer, to consist essentially of mauveine (CHN), which plays with acids the part of a powerful base. The aniline crimson was at first never obtained pure, and accounts of its composition varied Mr. Nicholson first procured it in the pure state, by acting on the boiling solution of the compound formed by the crimson dye with acetic acid (a form in which the material is quite generally used in dyeing), by means of ammonia. The basic substance is deposited from the liquid, on cooling, in the form of needles and plates, which, so far as entirely pure, are perfectly white or colorless. Dr. Phipson, however, cites M. Preisser as having shown, some years ago, that most coloring matters in the pure state have no more color than white sugar. For the name, roseine, As met with in commerce, aniline is a col- which Nicholson gave to this pure crimson dye, orless, oily liquid, which sinks in water, and i. e., magenta, but which is now appropriated to has a vinous odor, and an acid, burning taste. another of these dyes, Hofmann, who analyzed It is very slightly soluble in water, but readily the former, substituted rosaniline. This body, so in alcohol or ether. These qualities, also, in in the white crystalline, i. e., pure form, is in much the same degree, belong to pure aniline; reality a hydrate of the true base; and in this, however, being lighter, and having a Hofmann's latest expressions of it would be lower boiling-point. Its specific gravity is represented by C0H1N3, H2O, equivalent to 1.028. The formation of aniline from nitro- CHNO. It forms with acids numerous benzole takes place by substitution of an equiva- perfectly crystallizable salts, which possess the lent of amide in the former for that of hypo- vivid crimson color of the dye; and as it enters nitric acid; so that its formula is C..H.N. It into these it contains no oxygen, and is repreis a powerful organic base, having a resem- sented by C.H19Ns. The magenta dyes in blance to certain vegetable alkaloids, and com- practical use are always some one or more of. bining with many acids to form salts. A such salts; in the latter of which the color characteristic quality of this base, that of seems to be developed. When the pure white striking a fine purple blue with bleaching crystals, however, of rosaniline are exposed to powder and other oxidizing agents, and the the atmosphere, they rapidly turn pink, and observation of which finally led to the de- ultimately dark red, no perceptible alteration velopment of the aniline dyes, has been al- of weight attending this change; and when ready mentioned. dissolved in alcohol, they impart to the liquid a deep-red color. Heated to 212° F. the base loses a minute quantity of water; and at temperatures above 266° it is decomposed, leaving a quantity of carbon and an oily liquid containing much aniline. The rosaniline base appears capable of forming three classes of salts, containing respectively one, two, and three equivalents of acid; the monacid salts are stable, and the dyes belong to this class. The crystals of these salts, red when seen in thin plates by transmitted light, are by reflected light of a rich greenish metallic lustre. Being very hygroscopic, they require to be kept from the air. Some other derivatives of coal-tar besides aniline have been made to yield dyes; as, certain homologues of aniline, and also chinoline, naphthaline, carbolic acid, &c. The "coal-tar colors" are thus much more numerous than the "aniline colors," strictly so called; although the latter expression appears sometimes to be used as equivalent to the former. Since the time when Verguin and the Rénard brothers brought out the aniline crimson, by action of a chloride of tin on aniline, other chemists and manufacturers in different European countries have produced the crimson or particular hues of it by the employment of a variety of other oxidizing agents, among these being chlorides of lime, carbon, mercury, iron, and perhaps others of the metals, and also nitrate of mercury, nitric acid, bichromate of potash, ozone, arsenic acid, &c. The hues obtained After Prof. Hofmann had been for some time engaged in the investigation of rosaniline, he discovered that during the oxidation of aniline there was formed another base, also a coloring matter, and of a beautiful yellow color, which in fact accompanies rosaniline in all the usual modes of production, and can be obtained from the residue that remains after the extraction of the latter, by passing through it a current of steam, condensing, and adding nitric acid. The nitrate of the base is thus formed, and being extremely insoluble in water, is at once precipitated. The base, isolated, is in form of a yellow powder, and from its color the discoverer named it chrysaniline. It is very soluble in alcohol and ether. Its composition is C..H1N.; i. e., rosaniline-2 H. Again, rosaniline acted on by nascent hydrogen (the dye being dissolved in hydrochloric acid, and zinc added), gives rise to a third base, and to this, as being perfectly colorless both in itself and in its salts, Hofmann gave the name of leucaniline. Its composition is C40H1N3; i. e., rosaniline + 2 H. This substance, however, when long exposed to the air becomes slightly red, and still more so when heated. It long passed as a fact that the magenta or crimson dye was a product of the oxidation of the aniline proper contained in the impure aniline of commerce. More recently, however, Hofmann tried upon pure aniline the usual reaction, and found that the crimson dye could not be obtained from it. As was natural, he next tried pure toluidine, but still no rosaniline was produced. But upon mixing the two materials, both pure, the reaction of a suitable oxidizer at once gave the coloring matter. He infers that to the formation of rosaniline both toluidine and aniline proper must contribute, a portion of their hydrogen being meantime given up to the oxygen of the reagent used: the result may be thus represented-2 (C1,H,N) + (C12H,N)-7 HC40H19N3. Quite recently, also, MM. Laurent and Casthelez have succeeded in converting nitro-benzole by a single operation into aniline crimson. This they effect by mixing the former with iron and hydrochloric acid, or with protochloride of iron, and then heating. At first, aniline and perchloride of iron result; and when the mixture is heated, the perchloride reacts on the aniline, producing rosaniline. Some of the facts here stated in relation to rosaniline and the related substances were given in the preceding volume of this CYCLOPEDIA: such are here repeated only so far as is requisite to a sufficiently connected and clear view of the entire subject. In the same place will be found a brief account of the aniline blue, with a reference to the analogous colors in which the phenyle-radical of that substance is replaced by ethyle, methyle, and amyle, respectively, and also to the cyanine, obtained from chinoline. Aniline yields other dyes than those yet named, as the green, or emeraldine, &c.; and several dyes are in use which are procured from certain other derivatives of coal-tar; among the latter being picric acid, and (it would appear) azuline, &c. As might be expected, however, in the beginning of a branch of industry of such extent, a considerable variety of usage and oven much confusion still exist among manufacture and dealers in reference to the very names the various colors obtained from coal-tar pro ucts. In such a state of things, a systemat and complete classification of the new dyes as yet scarcely practicable. Some of the mor important of the coal-tar dyes, however, whethe yet practically in use or not so, require furthe and special notice: of such a list is here given 1. Aniline purple (Perkin's purple, mauve, com mon aniline violet, imperial violet, pensée, &c).Obtained as a black precipitate, by mixing equiva lents of solutions of sulphate of aniline and bichrowashed with water, and dried, digested in naphtha mate of potash, and allowing to stand; the precipitate till this ceases to be colored brown, then repeatedly boiled in alcohol to extract the coloring matter; the latter left upon distilling off the alcohol: thus prepared it is not pure. When purified, and dried, it is obtained as a brittle substance, having a beautiful bronze-colored surface. As one test, a little of the alcoholic solution being evaporated on a glass plate, and viewed by transmitted light, appears of a beautiful bluish-violet color. Many characteristic reactions are given; but of these, or those of the dyes yet to be named, space does not here allow. The color imparted by this dye is a bluish or deep violet. The name mauve (French, for mallow,) was given from a resemblance (supposed, at least) of the color to that of the petals of the plant in question. It is stated that much of the mauve now seen is an imitation, with a dye obtained by a new process from archil. While there are two unlike colors which pass among dealers and dyers as solferino, one of them is a purple or violet, of different shades, and is stated to the writer to be identical with Perkin's purple. 2. Violine.-A product of the oxidation of aniline, first obtained by Dr. David Price, by means of the action of binoxide of lead on a solution of two equivalents of sulphuric acid and one of aniline in water. Dried from alcoholic solution at the close of the process (not here given in full), it resembles the aniline purple dye, but has a more coppery appearance. Very soluble in alcohol, insoluble in ether. afterwards by Dr. Price. The latter obtained it by 3. Roseine.-First noticed by Mr. C. G. Williams, acting on a boiling solution of sulphate of aniline with binoxide of lead, filtering, &c. Dried, a dark, brittle substance, of slightly metallic lustre; dissolved in alcohol, gives a fine crimson. The three coloring matters thus far named are closely allied. 4. Aniline crimson (aniline red, aniline pink, rosaniline, magenta, fuchsine, roseine, &c).-The history of its discovery, as well as an account of its composition, has been given, and the sorts of reagents that produce it from aniline have been named. Béchamp CH, N2, this, when the base is free, being associated considers the formula of anhydrous fuchsine as with H.O, giving CH, NO. Perkin, and after him Dussauce, give quite fully the modes of preparing the dye with bichloride of tin, and with nitrate of mercury. As met with in commerce, the coloring matter, when not pulverized, is in small irregular masses or lumps, having a golden-green semi-metallic lustre, but which, in thin plates and by transmitted light, are red. A light and slightly bluish magenta is the other color to which the name of solferino is sometimes given. This, however, is not a proper violet or purple, but a distinct and bright crimson. 5. Chrysaniline (phosphine).-As already stated, a residual product, formed at the same time with rosaniline, and removed from the residue left in preparing that dye, by passing through it a current of steam. It dyes a golden yellow, as its two namesfrom xpvoos, gold, and phosphorus-respectively indicate. 6. Aniline blue (bleu de Paris, bleu de Lyon, opal blue).-A dye produced under circumstances somewhat similar to those giving the crimson: as described by MM. Persoz, De Luynes, and Salvetat, it is formed by heating in sealed tubes, for 30 hours, 9 parts bichloride of tin with 16 parts aniline, to about 3560 F. It crystallizes from its alcoholic solution in fine needles somewhat resembling the ammoniacal sulphate of copper. It is soluble in water, wood-spirit, and acetic acid. This blue is very beautiful, and several fine and durable tints of it appear now to be produced at Lyons, if not elsewhere. 7. Aniline green (emeraldine).—A substance long known in the laboratory, as forming on the outside of vessels in the vicinity of aniline. It may be obtained by oxidizing aniline with chloric acid, or a salt of that body with perchloride of iron. Dried, it has an olive-green color. It is soluble, and somewhat changed, in sulphuric acid; insoluble in water, alcohol, ether, and benzole. It appears to be now successfully used as a dye. Among dyes directly obtained from aniline, there is said also to be a black, and the writer has seen browns and scarlets said to be derived from the same material; but of these no account has been met with. 8. Nitroso-phenyline (comp., C,H,N,O). Obtained by action of nascent hydrogen on an alcoholic solution of di-nitro-benzole. It gives crimson-colored solutions, but not so brilliant as those of rosaniline. 9. Di-nitraniline (C,H,N,O2).—Obtained from dinitro-phenyle citra-conamide, by carbonate of soda. Pure, it is found in yellow tabular crystals. It can be made to dye silk yellow. 10. Nitro-phenyline diamine.-Obtained from the last named, by sulphide of ammonium, in form of red, acicular crystals, which give an orange solution with water. It is capable of dyeing silk of a clear golden color. 11. Picric, or Di-nitro-phenic acid (C12H,N3O14).— A long-known product, obtainable by action of heated nitric acid on aniline, indigo, carbolic acid, salicine, silk, aloes, and a number of other substances; and which was first introduced as a dye about 1855, by MM. Guinon, Marnas, and Bonney, silk dyers of Lyons. It is prepared on the large scale from carbolic acid, and also from certain gum-resins. Pure and dry, it is of a light primrose-yellow color, crystallizing in shining famine. Its taste is extremely bitter. It dissolves in water. Cheap and inferior imitations of it are in the market. 12. Rosolic acid (C2H22O4).--Obtained by Dr. H. Muller from crude phenate of lime. Pure, it is a dark, amorphous mass, showing the greenish metallic lustre of cantharides; and in thin layers, by transmitted light, of a golden metallic color. It is said to be disused since the discovery of rosaniline. 13. Cyanine (chinoline blue).-Obtained from chinoline, a constituent of the mixed product known as quinoline or leucoline (from coal-tar). A very delicate, pure blue, but extremely fugitive, and not yet successfully employed. A chinoline violet, and green, are similarly liable to objection. 14. Azuline. This is a very beautiful blue dye, introduced during the year 1861 by Guinon, Marnas, and Bonney. It is obtained from coal-tar, but from which of its derivatives, or what the process, is as yet kept secret. The dye is in amorphous masses, of a coppery lustre. The color it gives, though not as fine as that of chinoline blue, is far superior to the Prus sian blue. is capable of dyeing silk of a color like that of annoto. 18. Nitroso-naphthaline.-A product of the action of nitrous acid on naphthalamine. With much hydrochloric or sulphuric acid, it dyes silk a beautiful violet, but which fades at once unless so much of the acid be left as to rot the silk. 19. Naphthamein.-This dyes silk or cotton of a purple color, but very inferior. 20. Tar Red.-Discovered by Mr. Clift, of Manchester, 1853. It is obtained by exposing for about three weeks to the air a mixture of the more volatile parts of basic oils of coal-tar and hypochlorite of lime. With different mordants it yields different colors. The irregularity which as yet prevails in the naming and classification of the coal-tar colors, is illustrated in the sets of samples of colors produced that are furnished to dealers. The Fuchsine Société, and advertising a capital of manufacturing firm in Lyons, known as La $4,000,000, furnishes to importers in New York samples bearing the following names: fuchsine, bleu de lumiére (very light), bleu de Lyon (in three shades, darker and darker, marked T, R, and E-light, reddish, and deep), violet Hofmann (two shades, R and B-reddish and bluish), violet (R and B), and dahlia imperial, a fine reddish violet. Other sets of specimens vary again more or less from these. Simpson, Maule and Nicholson furnish, to illustrate Dr. Phipson's paper on the subject, opal blue, chrysaniline, rosaniline, Hofmann's patent violet, regina purple, and imperial violet. ("Popular Science Review," July, 1863.) Hofmann's violet is a very brilliant and fine reddish violet, though the shades produced by different makers differ somewhat; and the dye is now one of the most expensive. It is said to be also called primula, Alexandria violet, and imperial purple. The so-called (imported) Humboldt purple, if not identical with this, is at least quite similar to it. Aniline colors are now manufactured in this country, from imported aniline, by the "Holliday Chemical and Color Co.," of Brooklyn (Eastern District), N. Y. Of the magenta or crimson dye they produce three hues, which they term the Empire red (the dye soluble in cold water), the Keystone (bluish), and the Bay State (reddish); of the violet, three hues, the Manhattan (reddish), the Knickerbocker (bluish), and the Humboldt (bluish, more deep); and of the blue, two hues, the Union (reddish, or deep), and the Washington, (greenish, or "night" shade). Most of these the company's agents hold at this time at $9, in gold. It would appear, also, that some of the aniline and other coal-tar colors have been already produced in this country from products separated from petroleum - especially from the naphtha and the residuum. It is stated that the "Humboldt Petroleum Co.," of New York, have works for this manufacture now in process of erection, at Plummer, on Cherry Run, Venango Co., Pa. It has been stated to the writer that the company have already produced from petroleum several superior dyes, and-a very important point, if con |