274 



HOLIEES. 



Table XR'. — Action of iodine vapor in the sulphate of morphine and codeine. 



Morphine sulphate. Codeine sulphaie. 



Time in . 

 days. 



Gain in 

 weight. 



Atoms of 

 iodine 



per mole- 

 cule al- 

 kaloid. 



Atoms 01 

 kaloid. 





Gram. 



1 



0.0019 



2 



0.0036 



3 



O.0083 



4 







10 

 27 

 39 



S7 

 121 

 '144 



0.0049 

 0.0061 

 0.0081 

 0.0321 

 0.0676 

 0.1706 

 0.2030 

 0.2079 



0.048 

 0.065 

 0.0S3 



0.12 

 0.1-5 



o.ao 



0.80 

 1.69 

 4.27 

 5. OS 



5.21 



Gram. 





0.0061 



0.09 



0.0101 



0.15 



0.0178 



0.26 



0.0272 



0.40 



0.0^3 



0.51 



0.0a20 



0.75 



0.0962 



1.40 



0.3288 



4.78 



0.5133 



■ 7.47 



0.5350 



7.78 



0.5096 



7.42 



0.5006 



7.2$ 



' These results also are scmewhat high, since no correction has been applied for the 

 change in the equilibrium of the balance during the experiments. 



The sample of heroin sulphate referred to above took up iodine very 

 much faster than either of the other sulphates, and it seems very probable 

 that pure heroin sulphate would absorb iodine more rapidly than the 

 sulphates of the other alkaloids. Codeine sulphate has certainly a 

 greater affinity for iodine than has morphine sulphate. 



It is obvious also upon comparison of the results obtained with the 

 free bases and with their salts that the free bases have a greater affinity 

 for iodine than their salts, absorbing iodine to a greater degree and 

 with considerably greater rapidity. The introduction of the acid group 

 has a marked effect in diminishing the reactivity of the compound with 

 iodine. It will be remembered that the same effect was observed in 

 aqueous solutions and indeed the reactions observed in the desiccators 

 appear to be parallel with them. The color of the periodide became 

 darker in every case as more iodine was absorbed and the final product 

 was always a black, pitchy or tar-like compound. 



COXCLUSIOSS. 



It has been shown that the alkaloids morphine, codeine, and heroin, as 

 well as their salts, have a remarkable affinity for iodine, the combination 

 occurring under a wide range of circumstances whenever the reacting 

 substances are brought together. 



Iodine will combine with these alkaloids in the absence of any solvent, 

 in solutions of organic solvents and ia aqueous solutions, whether the 



