312 MR C. G. WILLIAMS ON THE VOLATILE BASES 



distillate could be procured for nearly fifty degrees above that point, until after 

 several rectifications, when it was found that fractions could be obtained at 

 every ten degrees from about 300° to 500° F. (183° to 260° C.) It was therefore 

 determined to submit the whole of the chinoline in my possession to a systematic 

 fractionation ; and by the use of very small retorts, and tolerably perfect conden- 

 sation, I was enabled to effect ten fractionations even of the smaller portions ; 

 and with the distillates of the higher boiling points, which were larger in quantity 

 than the others, twelve, and in some cases even thirteen were effected. Altogether 

 this procedure involved, with those afterwards found necessary, at least 200 dis- 

 tillations. By this means, fractions were obtained as low as between 310° and 

 320° F. (154° to 160° C), and as high as 520° F. (271° C). When it is considered 

 that the boiling point of chinoline is 460° F. (238 J C), it will be seen that it was 

 not going too far to conclude that evidence was obtained of the correctness of the 

 suspicion previously mentioned ; and it is submitted, that the following experi- 

 ments prove that cinchonine by distillation with potash yields at least seven bases 

 instead of one, as has been generally believed. It might be imagined that they 

 would all be found to consist of homologues of chinoline, but it will be shown 

 that this is not the case, and that two distinct series are present, one homologous 

 with chinoline, and the other isomeric with the aniline series, and identical in 

 composition with the group found by Dr Anderson in bone oil,* and afterwards 

 by myself in the naphtha, from the bituminous shale of Dorsetshire.! 



Before proceeding to the details of the experiments, it is proper to mention, 

 that although the researches were commenced in London, and afterwards partially 

 carried on in my own laboratory in Glasgow, that on becoming assistant to Dr 

 Anderson, he not only permitted me to make comparative experiments with his 

 bases, but gave me every possible opportunity of pursuing the investigation. In 

 my first experiments, and before I had any considerable quantity of chinoline at 

 my disposal, I endeavoured to obtain some insight into the nature of the fluid by 

 fractionally crystallizing the platinum salts according to the method described in 

 a paper on the presence of pyridine in the basic portion of the naphtha from the 

 Dorsetshire shale.! 



The results, which are given below, were too remarkable not to be carried out 

 more in detail ; but the large quantity of platinum required to effect a perfect 

 separation, prevented me from availing myself of this method of working, and I 

 was forced to fall back upon the tedious and wasteful process of fractional distil- 

 lation. 



To obtain the platinum salts, a certain quantity of hydrochlorate of chinoline, 

 freed from pyrrol, by boiling its acid solution for a long time, was evaporated on 

 the water-bath, as long as water came off, but it could not be obtained in a per- 



* Trans. Royal Soc. Edin., vol. xvi., part iv. f Quart. Jour. Chem. Soc, Lond., July 1854. 



+ Phil. Mag., September 1854. 



