THE Franklin Institute is not responsible for the statements and opinions advanced by contributors to the Journal. CHEMICAL SECTION. DR. W. C. DAY, President, in the Chair. [The President announced the paper for the evening, and introduced the speaker.] COMPOSITION OF THE AMERICAN SULPHUR PETROLEUMS. BY CHARLES F. MABERY, Professor of Chemistry, Case School of Applied Science. [Concluded from vol. cxxxix, p. 424.] OHIO PETROLEUM. Aside from our own publications on the sulphur compounds in Ohio oil (Proc. Amer. Acad, 25, 218; Amer. Chem. Journ. 16, 83), and those of Orton (Ohio State Geological Reports for 1886, 1888, 1890; and United States Geological Report, 1886-87), I have seen no published statements concerning the composition of the Ohio sulphur petroleum. The crude oil, that has formed the basis of this work, was received from the Peerless Refining Company, Findlay, O., VOL. CXL. No. 835. I which controls a large section of oil territory. This oil was somewhat thicker in consistency than Pennsylvania oil, with a slight odor of hydric sulphide, and it contained a small quantity of water which was slowly removed by fused calcic chloride. Its specific gravity at 20° was found to be 0.838. A determination of sulphur gave 072 per cent., a value somewhat higher than we have hitherto obtained, o'55 per cent. Markownikoff and Ogloblin obtained in Apsheron petroleum 0.064 per cent. and in the Transcaspian oil o'16 per cent. A combustion in oxygen with a layer of plumbic peroxide in front to retain the sulphur (Warren, Proc. Amer. Acad., 6, 472) gave the following percentages of carbon and hydrogen: Carbon, 84'57; Hydrogen, 13.62. Bromine absorption in the crude oil and in some of the fractions was determined by the method given in Allen's Commercial Organic Analysis, Vol. II, page 388, with the following results: A determination of the bromine absorption in the crude oil gave 61 per cent. The distinctive qualities of Ohio oil appear also in the proportions which distill at different temperatures; 800 grams of the crude oil distilled in the following proportions, beginning at 110°: 110°-150° 150°-220° 220°-257° 257°-300° 300°-350° Residue Ο ΙΟ 0'38 0'37 0'37 0'54 sulphur The distillates below 225° were not appreciably decomposed, since they were free from color and odors resulting from decomposition. At somewhat higher temperatures the distillates were colored, with characteristic penetrating odors. It was, therefore, evident that in the refinery distillation of Ohio oils cracking begins in the vicinity of 250°. There is evidence that certain extremely unstable constituents of the crude oils, when separated, decompose on standing, and no doubt similar decompositions take place, perhaps more slowly, when they are dissolved in other portions of the oils. At the beginning of the distillation, hydric sulphide appears to some extent, but the higher fractions are nearly free from it. Considerable sulphur is lost during distillation, as shown by analyses of the crude oil and of products obtained from it. In determining experimentally what became of the sulphur evolved, it appeared to escape mainly as hydric sulphide, with the separation in small quantity of free sulphur and perhaps in still smaller quantities as volatile sulphur compounds. The ash obtained by igniting the residue from the distillation of the volatile portions of petroleum, has frequently been examined. Traces of metals, gold, silver and copper have been found, as well as the oxides of calcium, iron and aluminum. In the ash of Caucasus petroleum Markownikoff and Ogloblin found substantially the same composition, and the quantity of ash calculated for the original quantity of crude oil amounted to o'09 per cent. In the coke from Ohio petroleum, we have found 95.06 per cent. of carbon, 4'85 per cent. of hydrogen, and o'11 per cent. of ash. It has already been mentioned that all petroleums are regarded by some chemists as having a similar composition, the difference in properties depending upon a variation in the proportions of the constituents. The Caucasus petroleum contains but a small proportion of the series CnH2n+2' and the Pennsylvania oil, so far as it has been examined, contains the series CH2, in much smaller proportions than the Russian oil. Referring the sulphur in Ohio petroleum to the average composition of the compounds containing it, the sulphur derivatives should amount to at least five per cent. of the crude oil. Such a proportion of sulphur compounds must necessarily exert an important influence on the properties of the crude oil as well as of the products ob 2n tained from it. To ascertain, therefore, the relation in which the Ohio sulphur oil stands to the other two petroleums in question, it seemed necessary to submit the Ohio product to an examination for all constituents. We have undertaken to determine first the presence of the hydrocarbons CnH2n+2, with the approximate quantity of each member of this series, except those with low boiling points. HYDROCARBONS CnH2n + 2• For the separation of the members of this series, we procured twenty-five liters of the most volatile refinery distillates collected from a 300-barrel still. This product was subjected to distillation in quantities of eight liters each, with the aid of a Warren condenser filled with a mixture of salt and ice, ice alone or water dependent upon the boiling point of the distillate collected, placing in front of the condenser another containing the freezing mixture. To collect any gas that might escape during the distillation, a delivery tube dipping beneath an inverted receiver filled with water was connected to the bottle receiving the distillate. first, a very small quantity of gas collected, which burned with a smoky flame, but none afterward. In refinery distil lation of the Ohio oil, gases escape in considerable quantities before distillates condense, but we have not yet examined them. With the exception of hydric sulphide, probably these gases do not differ essentially from those which are evolved at the beginning of the distillation of Pennsylvania oil. I am not aware that the composition of the gas from Ohio oil wells has been determined, but it is probably not very different from that of the gas issuing from the Pennsylvania wells which Sadtler (Amer. Chem., 7, 97) found to consist principally of methane, with smaller quantities of ethane, hydrogen, carbon dioxide and nitrogen. In the gas from the Canadian wells at Enniskillen, Fouqué (Compt. Rend. 67, 1045) found marsh gas, ethane, and small quantities of carbonic dioxide. The first distillates were subjected to further distillation. until a considerable quantity collected that distilled tolerably constant within narrow limits of temperature, corre sponding to the boiling points of the hydrocarbons. Between 0° and 1o, 35 grams collected, which distilled for the most part at 0°, barometer 741 mm., corresponding to the boiling point of butane. At 70-90, 20 grams of a distillate collected, corresponding to the hydrocarbon which was separated by Warren from Pennsylvania petroleum, and which he regarded as one of the butanes. Of the two possible butanes there can be no doubt that one boils at 0°, and Butlerow (Ann. Chem. Pharm. 144, 10) obtained from isobutyl alcohol a butane to which he assigned as the boiling point —17°.5. Since, therefore, there seems to be some question concerning the product which he collected at 8°, more of this distillate will be procured for the study of its chemical behavior to ascertain whether it be a definite compound. Between 29° and 30°, barometer 747 mm., the distillate amounted to 75 grams, and a vapor density determination gave the value required for isopentane; found 252, required for pentane, 2:49. At 37°-38°, 75 grams distilled, and this product gave as its vapor density, 2:49; required for normal pentane, 2:49. At 60°-61°, 50 grams collected, which gave a vapor density required for isohexane; found, 2'94; required, 2.98. The quantity of product collected at 67°-68° gave as its vapor density, 3'00; required for normal hexane, 2'98. On account of the manner in which these distillates were collected, the weights afford no information concerning the proportions in which they are contained in the crude oil, although they are evidently present in much smaller quantities than in Pennsylvania oil. For the separation of the hydrocarbons with higher boiling points, the fraction 150° from the crude oil distilled in vacuo, was submitted to further distillation under atmospheric pressure. 415 kilos of crude Findlay oil was distilled under a tension of 50 mm., and products separated within the limits -100°, 100°-150°, 150°-200°, 200°-250°, 250°-350°, and the residue above 350°, which was preserved. These products collected with but slight decomposition and without the disagreeable odors characteristic of refinery distillates. On account of the reduced pressure, doubtless some of the more volatile constituents were lost, and in |