112 
ME. C. SCHOKLEMMER ON THE NORMAL PARAEEINS. 
point to consist of mixtures of the chloride with the paraffin, or with higher chlorinated 
products. 
To convert the chlorides into the alcohols, they were first heated with potassium 
acetate ; during this operation a large quantity of the secondary chloride splits up into 
hydrochloric acid and an olefine, from which the acetic ethers formed had again to be 
separated by fractional distillation. From the highest boiling fraction, which of course 
consisted chiefly of the primary acetate, the alcohol was then prepared ; but the quantity 
obtained was so small, that the acid formed by oxidizing it could not be isolated, and 
its existence was only proved by analyzing the silver salt, in the preparation of which 
the small quantity of the acetone remained in aqueous solution and was thus over- 
looked. 
As soon as I had ascertained that by acting with chlorine upon the paraffins a mix- 
ture of primary and secondary chlorides is formed, the problem next to be solved was 
under what conditions the one or the other is formed. 
In order to obtain decisive results, it was first of all required to work with large quan- 
tities of a hydrocarbon ; and I chose for my first experiments the hexyl hydride or 
hexane , C 6 H 14 , from petroleum, a hydrocarbon which can be obtained most easily 
in a sufficient quantity. The hexane was treated with chlorine under the following 
conditions : — 
(1) Dry chlorine was passed into the well-cooled hydrocarbon in diffused daylight. 
(2) It was acted upon in the cold by chlorine in presence of iodine. 
(3) Chlorine was passed into the vapour of the boiling hydrocarbon. 
(4) Chlorine was passed into the vapour in the presence of iodine. 
The result was that in all four cases, as first product, a mixture of primary and 
secondary hexyl chlorides was formed. Further, it was found that when chlorine acts 
on the liquid hydrocarbon, or when iodine is present, always large quantities of higher 
chlorinated products are formed, but that by passing chlorine to the vapour, the forma- 
tion of these bodies can be almost completely avoided. In investigating the other 
paraffins, to be described further on, I always used the latter method. 
The apparatus employed consisted of a large flask, which, by means of a cork, was con- 
nected on one side with the chlorine apparatus by a tube reaching to the lower end of 
the neck, and on the other side with a reversed Liebig’s condenser, the upper end of 
which was further connected with absorption-bottles containing caustic soda solution, 
and in. which the hydrocarbon which was carried away by the current of hydrochloric 
acid was condensed. On passing a moderately strong current of dry chlorine into the 
vapour of the gently boiling hydrocarbon, the colour of the chlorine disappears instan- 
taneously, and the chloride formed is seen to flow back in. oily streaks on the side of the 
vessel. The operation was interrupted in the evening, the hydrocarbon not acted upon 
distilled off, and treated repeatedly in the same way until a sufficient quantity of the 
chlorides had been formed. The latter were then heated with the required quantity of 
potassium acetate, and an equal volume of glacial acetic acid in sealed tubes to 190° to 
