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The boiling points, which vary essentially from those of the ethylene series with the same composition, do not rise so rapidly as in the latter, their course being not regular either in one or the other. Markownikoff has recently abandoned his standpoint, since further investigations, especially of the socalled octanaphthene, which he made with the assistance of J. Spady, proved it actually to be a hexahydroxylole.' This view is also supported by the results obtained by M. Konowaloff2 in bromizing nonanaphthene.

According to Markownikoff and Oglobin, the portion of the so-called naphthenes in Baku oils amounts to at least 80 per cent. They further showed that American oils also do not consist exclusively of saturated hydrocarbons-which, however, has never been maintained—but contain small quantities of naphthene and naphthylene." They also found naphthene in Hanover oil. Lachowicz established the presence of hydrogenized hydrocarbons, especially of hydrotoluole, in Galician petroleum, and, according to him, Galician crude oil, as regards the content of naphthene, stands between Baku and Pennsylvania oils.

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According to Le Bel' the crude oils of Becherelli and Tschungnelek (Crimea, Russia) closely resemble the Baku oils. Dr. G. Kraemer was at first inclined to consider the 1 Ber. d. Deutsch. Chem. Gesel., 1887, 20, 1850. 2 Jour. der Russ. Phys.-Chem. Ges., 1887 (1), pp. 255 to 257. Schuetzenberger and Jonine established the C1 H2 combinations in question in American oils. Engineering, 42, 579. Sitzbr. Ver. zur Beförderung des Gewerbefleisses, 1885, 292.

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naphthenes a mixture of methanes with aromatic bodies, but in one of his most recent articles published jointly with W. Böttcher,' he acknowledges the existence and independence of the hexahydrides of the aromatic series. The two authors mentioned above found that in the more strongly resinified, denser Oelheim oil, most of the naphthenes occur in the portion indifferent towards mineral acids (methane and naphthene), while in the lighter oils from Tegernsee and Pechelbronn, there is a decided preponderance of methanes.

In the crude oils of the Pechelbronn flowing wells, of Schwabweiler, of Oelheim and of Tegernsee, Engler showed the presence of mesitylene and pseudocumol in the form of nitro-derivatives and bromo-derivatives. He did not search for the other members of the benzole series, his object being to establish the presence of such aromatic bodies in German oils, as their presence proves that petroleum must have been formed. by dry distillation.

All chemists who have investigated the naphthenes, now declare them to be hexahydrides of the aromatic series (CH−6+H).

3. Benzole Series: CH2n+6. (To the group of the aromatic

Hydrocarbons.)

The specific gravity of the members of this series is about 0.86; the most important are:

[blocks in formation]

The benzoles are quite widely diffused in petroleum, though

1 Ber. deutsch. Chem. Ges., 20, 590 to 598.

they are always present only in very small quantities. Thus, for instance, Pawlesky found in the benzine obtained from Galician petroleum about 4 per cent. benzoles and paraxylol. Since, however, the yield of benzine from Galician oil is at the utmost about 10 per cent., the content of benzoles referred to crude oils is about 0.4 per cent. Engler determined the content of pseudocumol and mesitylene in American petroleum as 0.2 per cent.

Besides these normal series, isomeric bodies are also found in petroleum or its distillates. Of these combinations the follow

ing have thus far been established:

Benzole was found in Galician distillates by Palewsky' and Lachowicz; in Baku crude oil, by Markownikoff; in crude oil from Zarskiji Kolodzi (Goverment Tiflis), by Beilstein and Kurbatoff; in Rangoon oil, by Warren de la Rue and H.. Müller, and in Pennsylvania oil, by Schorlemmer.

Toluole was found in all oils given under benzole by the investigators mentioned there.

Xylole was prepared from Rangoon oil by Warren de la Rue and Müller, and from Pennsylvania crude oil by Schorlemmer. Isoxylole (boiling point 141° C) was established in the distillates of Galician crude oils by Palewsky and by Lachowicz, in Caucasian crude oil by Dr. Kraemer, and in Baku crude oil by Markownikoff. Paraxylol (boiling point 137° C.) was obtained by Palewsky from Galician distillates.

Cumol was found by Warren de la Rue and H. Müller in Rangoon oil, S. F. Peckham also mentioning isocumol. Pseudocumol (boiling point 166° C.) was found in Caucasian oil by Markownikoff and Oglobin, and in oils from America (very likely Pennsylvania), Alsace, Hanover, Galicia and Italy (Terra de Lavore) by Engler. Mesitylene (C9H12, boiling point 163° C.) was established in Galician crude oil by Lachowicz, and in crude oils from America, Alsace, Hanover, Galicia and Italy by Engler. Markownikoff found it in Baku oil. The above mentioned benzoles also occur, according to Schultz and others, in coal tar.

1 Ber. deutsch. chem. Ges. 18, 1915. 2 Ber. deutsch. Chem. Ges. 18, 2234.

Besides the above-mentioned aromatic combinations, there are also found in the fractions of Caucasian petroleum, boiling between 2480 and 420.8° F., durole, isodurole, diethyltoluole, isocambylbenzole and other combinations after the type CH16.

According to Beilstein and Kurbatoff, aromatic hydrocarbons are also said to be present in the Hanover crude oil and, according to Schorlemmer,' also in Candian oils. Pelouze, Warren, N. Tate, M. Murphy, C. F. Chandler, Bolley and Schwarzenbach searched in vain for benzoles in Pennsylvania crude oils.

4. Other Series of Hydrocarbons.

Besides the previously-mentioned hydrocarbons, the presence of others in the fractions boiling at a high temperature has been partially established, and partially conjectured for more or less good reasons. They are of no special importance, on account of their rarity and the extraordinarily small quantities in which they occur.

A. Acetylene Series: CH-2.

From the behavior of some fractions of the Baku oil towards certain reagents (potassium permanganate, nitric acid, mercuric iodide), Mendelejeff inferred the presence of hydrocarbons of this series. Later on they were also found in very small quantities by Markownikoff and Oglobin."

B. Camphene Series: (Ca H2—4.)

According to investigations by the two last-named chemists, this series is present in very small quantity in Baku oil. Boussingault produced from the maltha and asphalt of Pechelbronn, at 572° F., fractions which he called petrolene, and considered as the fluid part of all asphalts (the solid part he called asphaltine). He gave it the formula C10H16, whereby he placed

1 London Chem. News, 11, 255; Trans. Royal Soc. (5) 14, 186. 2 Chem. Centr. Blatt, 1881, 609; Ber. deutsch. chem. Ges. 18, 2234; Chem. Industrie, 1882, 5, 189. 8 Ann. Chim. Phys., 61, 141; 73, 442.

this body in the camphene series, especially amongst the terpenes. He determined the boiling point=536° F., and the vapor-density 9.415. Warren in a private communication to Prof. Dana' points out that the vapor-density could only be 8.49, and that petrolene is a mixture consisting chiefly of ethylenes.

Völkel' subjected tough bitumen from Travers (Switzerland) to distillation in iron cylinders, and obtained six fractions whose contents of carbon and hydrogen were nearly the same, but whose boiling points were between 1940 and 482° F., and the densities (at 59° F.) between 0.784 and 0.867. The temperature and volume weights rose gradually. He arrived at the common formula C6H10, and considered the fractions as polymeric bodies of C12H20, for which reason they would have to be placed in the camphene series. In this case also we have very likely to do with mixtures.

Nendtwich claims to have found solid petrolene in maltha from Pecklenicza near Murakoz (Hungary). Kraemer conjec tures that small quantities of terpenes or polyterpenes must be present in heavy petroleum, since the viscous condition of the fractions of heavy oils boiling at high temperatures can only be thus satisfactorily explained. They may partially be originally present in the petroleum and partially be formed during distillation.

The above-mentioned investigations allow of the conjecture that the camphenes may be present in greater abundance in maltha and asphalt. Further careful investigation is, however, necessary to definitely settle this question.

C. Combinations rich in Carbon.

Markownikoff and Oglobin have separated in the fractions boiling at over 410° F., very small quantities of hydrocarbons

1Dana, System of Mineralogy, 730. 2 Annal. Chim. Phys., 87, 143, 1862. 'The densities are throughout greater than those of the members of the ethylene series of the same boiling point, nor do they correspond with the napthalene series. Haidinger's Berichte, 3, 271; Jahrb. geol. Reichs-Anst. 7, 743.

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