[ 111 
VII. On the Normal Paraffins. By C. Schorlemmer, F.B.S. 
Received December 20, 1871, — Read February 1, 1872. 
In the year 1858 Bertiiolet proved that the compound CH 3 Cl, obtained by the action 
of chlorine upon marsh-gas, was identical with methyl chloride, by converting it into 
methyl alcohol and other methyl compounds. Since that time the researches of Pelouze 
and Cahours, as well as my own, have shown that this method is a general one, and 
that by means of it the corresponding alcohol may be prepared from any paraffin. 
On oxidizing some of the alcohols obtained by this method, acids were formed con- 
taining the same number of carbon atoms in the molecule as the alcohols themselves 
contained, from which it would appear that these alcohols were primary alcohols. 
Pelouze and Caiiours, however, stated that the octyl alcohol which was obtained 
from octane contained in petroleum was identical with the so-called capryl alcohol pre- 
pared from castor-oil, and Chapman afterwards came to the same conclusion. At that 
time it was believed that capryl alcohol was a primary alcohol. However, by the study 
of its oxidation products I found this not to be the case, but that this alcohol belongs 
to the group of secondary alcohols, being methyl-hexyl carbinol*. It was therefore 
necessary to repeat the experiments of Pelouze and Cahours and Chapman, and to 
study carefully the oxidation products of the alcohol from petroleum, which none of 
these chemists had done. The result of my investigation was that this alcohol is a 
mixture of methyl-hexyl carbinol with a primary octyl alcohol f. 
This observation made it highly probable that, by acting with chlorine upon the paraf- 
fins, primary and secondary chlorides are formed at the same time ; and the more so, as I 
had formerly found an acetone amongst the oxidation products of the amyl alcohol from 
petroleum, the origin of which I was then at a loss to explain J. As I have already 
stated in a preliminary note, further experiments with hexane fully confirmed the cor- 
rectness of my supposition. 
The reasons why, in my former researches, I overlooked the secondary compounds are 
the following : — 
The mixture from which the chlorides had to be isolated contained, besides large 
quantities of unattacked hydrocarbon, also higher chlorinated products. The difference 
between the boiling-points of the two chlorides is about 10°, but by far the greatest 
portion distils within these limits at a nearly constant temperature ; and as by fractional 
distillation the boiling-point becomes yet more constant, and the quantity of liquid dis- 
tilling at this temperature increases, I believed I had obtained a pure compound, and 
considered the smaller quantities of liquids boiling a little above and below the constant 
* Proc. Roy. Soc. vol. xvi. p. 376. f Ibid. vol. xviii. p. 25. % Ibid. vol. xvi. p. 372. 
