THE ALUMNI JOURNAL. 



Ill 



washed till practically exhausted- The 

 filtrate is warmed, dilute sulphuric acid 

 added in quantity just sufficient to pre- 

 cipitate the barium, the solution filtered 

 and set to evaporate, sufficient ammonia 

 being added to nearly neutralize. When 

 concentrated to 8 c.c. (.05 grm. ammon- 

 ium oxalate added) it is allowed to cool, 

 mixed with i c.c. alcohol and i c.c. ether 

 and then ammonia added till no further 

 precipitate is produced, and a distinct 

 odor of ammonia is present after stirring, 

 and breaking down any lumps that may 

 have formed. After four or five hours 

 the precipitate is collected on counter- 

 poised filters, washed with morphiated 

 water and dried. It is then powdered, 

 washed with chloroform, dried and 

 weighed. A weighed portion of the pre- 

 cipitate is neutralized with standard acid 

 and the percentage calculated. The 

 former method gives a purer morphia 

 precipitate which on that account is more 

 easily accurately neutralized than that 

 obtained in the latter method. On the 

 other hand the neutralization of the so- 

 lution before concentrating, in order to 

 precipitate resinoid, etc., must be care- 

 fully conducted. Should the addition of 

 ammonia be carried rather far, acetic 

 acid must be added to perceptibly acid 

 reaction, so as to ensure that all the 

 morphine is in solution. 



The method (B ) has the advantage of 

 being more expeditious, and requiring 

 less work than probably any of the others. 

 The precipitated morphine, however, 

 contains much impurity, rendering the 

 exact neutralization with standard acid 

 somewhat difficult. Yet it is a good 

 practical process, and sufficiently accu- 

 rate for most purposes. It may be modi- 

 fied so as to give a purer morphine by 

 first exhausting the opium with water 

 and then adding the barium chloride to 

 the filtrate. This necessitates an addit- 

 ional filtration, but gives an ultimate 



precipitate containing less color and im- 

 purity. In the case of a comparatively 

 pure morphine, such as is usually ob- 

 tained in the B.P. or U.S. P. processes, 

 it may make little practical difference, 

 whether the correction is by treatment 

 with lime-water or by acidyfying with 

 standard acid; but in the case of a less 

 pure precipitate the difference is very 

 marked, as the following figures show. 

 The purified precipitate obtained in 

 method (B) above described, indicated by 

 washing with baryta water 94 per cent, 

 of morphine, while by titration with ^-^ 

 acid it indicated only 83 per cent. The 

 same precipitate, after washing with 

 morphiated spirit, indicated by titration 

 87 8 per cent, of morphine, showing that 

 that method of purification is of very 

 limited value in such a case. It is in- 

 teresting to note that Dr. Squibb in his 

 "Ephenieris" and Dr. Geisler at the 

 New York meeting have both given 

 numbers which confirm the truth of a 

 note I published (Pharm. Jour.) some 

 years ago, to the effect that the formula 

 of hydrated morphine is Bg(H20)9, and 

 not BHoO as generally stated. Dr. Geis- 

 ler found 6.8 per cent, as the average 

 loss on drying, Bs(H.,0)9 requiring 7.1, 

 and BHoO requiring 5.9. This gives 305 

 as the equivalent instead of 303. 



It was suggested by Rutherford Hill 

 at one of the evening meetings of the 

 Pharmaceutical Society, that amylic al- 

 cohol might afford a good means of sepa- 

 rating the morphine in the assay of opium 

 That is a well-known method of separat- 

 ing small amounts of morphine and sim- 

 ilar alkaloids in the analysis of medicines. 

 I have tried it in several different ways, 

 wet and dry, with quite unsuccessful re- 

 sults, largely due to the fact that mor- 

 phine is very sparingly soluble in that 

 menstruum. It .seems scarcely possible 

 to devise an amylic alcohol method which 

 will offer any advantages either as to ac- 



