54 PROCEEDINGS OF THE AMERICAN ACADEMY. 



ties of bromine absorbed in the fractions collected in vacuo is suggest- 

 ive. It cannot be caused by decomposition, but it seems to be due 

 rather to the reduction in boiling points by which certain compounds 

 capable of absorbing bromine are carried over at lower temperatures, 

 and doubtless too with less decomposition. The increased absorp- 

 tion above 250° may indicate cracking, or the presence of normal con- 

 stituents that absorb bromine. Since the difference in tlie amounts 

 absorbed in the Canadian oil in vacuo and under atmospheric pressure 

 is not large except in the residues, and the conditions much less favor- 

 able for cracking in the vacuum distillates, it would seem that the 

 absorptive capacity is due to normal constituents of the crude oil. 



The fraction 150°-200°, containing 0.47 per cent of sulphur, ab- 

 sorbed 4.59 per cent of bromine. A portion was treated with alco- 

 holic mercuric chloride, washed, dried, and it was then found to contain 

 0.063 per cent of sulphur. A determination of the amount of bromine 

 it absorbed gave 2.8 per cent. Tliis result is evidently independent of 

 the sulphur compounds. It must indicate either normal constituents 

 of the oil with an affinity for bromine, or the presence of decomposi- 

 tion products due to cracking. 



Another portion of the same fraction was agitated with concentrated 

 sulphuric acid, and the quantity of bromine then absorbed was equiv- 

 alent to 1.15. Since mercuric chloride has been shown to remove 

 nearly all the sulphur compounds from the lower fractions, and sul- 

 phuric acid only partially, it is still further evident that there are pres- 

 ent in this fraction other bodies capable of absorbing bromine, perhaps 

 unsaturated hydrocarbons, either contained in the crude oil or result- 

 ing from decomposition during distillation. 



The distillates collected in vacuo showed but slight indications of 

 decomposition ; they were only slightly discolored, except the residue 

 above 350°. In prolonged distillation the higher fractions gradually 

 become colored by polymerization or other decomposition. Even the 

 residue above 350° showed scarcely any odor, and it had apparently 

 undergone but little decomposition. The distillates above 150° and 

 the residue above 350° are reserved for further study. 



As in the study of Ohio petroleum, the lower members of the series 

 C„H2„ + 2 were sought for in the most volatile refinery distillate. 

 Twenty litres of the veiy first distillate from Petrolia crude oil was 

 submitted to distillation, and the vapors collected in a Warren condenser 

 filled with a freezing mixture or with water, according to the boiling 

 points of the distillates, and with a condensing worm in front filled with 

 the freezing mixture. Distillates were collected below 45°, and the dis- 



