CRYSTALLINE CONSTITUENTS OF OPIUM. 211 



bable. The alleged absence of chlorine must also be considered as in the highest 

 degree questionable ; indeed Couerbe appears to have relied entirely on the action 

 of oxide of silver in removing the chlorine he found in the crude substance, and does 

 not appear to have tested by heating with lime, and hence has overlooked the sub- 

 stitution chlorine which his substance undoubtedly contained. Nor is this surpris- 

 ing, for his paper was written at a time when the law of substitution was un- 

 known, and little attention had been paid to the organic chlorine compounds. 



I have already mentioned that if the current of chlorine is passed through fused 

 opianyl for too long a time, no crystals are deposited, and a substance resembling 

 Canada balsam is obtained, which is no doubt identical with the resinous matter 

 which Couerbe got mixed with the crystals of his mechloic acid. This substance 

 is insoluble in water, but highly soluble in alcohol and ether, and deposited in an 

 amorphous condition when these menstrua are evaporated. When treated with 

 potash it dissolves, and the fluid on saturation with an acid yields a pulverulent 

 precipitate, soluble in alcohol, and giving irregular crystals on evaporation. This 

 substance I at first suspected might be mechloic acid, but it is entirely different, 

 contains abundance of chlorine, and is obviously a further substitution product, 

 although it was not obtained of definite constitution. A single analysis gave — 



{4*540 grains, dried at 212°, gave 

 8-295 ... carbonic acid, and 

 1-535 ... water. 



Carbon, . . . 45-82 



Hydrogen, . . . 3-75 



This lies nearly half-way between the numbers of chloropianyl and those re- 

 quired for a product containing two equivalents of chlorine. 



Couerbe gives for his resinous substance the formula C 10 H 5 8 ; but if we as- 

 sume it to have contained chlorine, his analysis would agree pretty well with 

 the formula C 20 H 3 Cl 2 3 . His numbers, recalculated with the correct atomic 

 weight of carbon, are given below, and compared with that formula. 



Couerbe. Calculation. 



Carbon, 



. 46-93 



45-53 



45-63 



^9n 



120 



Hydrogen, 



3-72 



3-83 



3-04 



H 8 



8 



Chlorine, 



• 



• • • 



26-99 



Cl 2 



71 



Oxygen, 







... 



24-34 



° 8 



64 



100-00 268 



It is highly probable that this substance actually did contain chlorine, but the 

 approximation to the formula is possibly only fortuitous. 



Action of Bromine on Opianyl. 



When bromine Avater is dropped into an aqueous solution of opianyl, crystal- 

 vol. xxi. part i. 3 L 



