upon b 

 For this 



-Phosphorus Oxychloride. 



Art. XL VI. — Communications from the Laboratory of Williams 

 College. No. YL — Concerning Phosphorus Oxychloride; by 

 Ira Eemsen. 



The fact was recently established* that carbon monoxide, 

 though it must be considered as an unsaturated compound, 

 does not readily combine with the oxygen from ozone to form 

 the saturated dioxide. Indeed it was impossible to discover 

 any conditions under which such a combination takes place. 

 Although it is known that ozone does readily oxydize many 

 substances, it seemed to me desirable to further test its action 

 odies which are generally recognized as unsaturated. 

 5 purpose I have first employed phosphorus trichloride 

 L the hope of obtaining the oxychloride, POCI3. The method 

 vyf formation of the oxychloride thus indicated would be inter- 

 esting from more than one stand-point, as will be pointed out 



It has already been shown by Brodief that, when oxygen is 

 passed into phosphorus trichloride at the boiling temperature 

 of the latter, a partial transformation into the oxychloride takes 

 place; and Michaelis:}: subsequently showed that this transfor- 

 mation or oxydatiou is exceedingly incomplete, even though 

 the process be continued for two or three days. An analogous 



formed. It is plain that, in both of these experin 

 the forces which opposes the combination is that which binds 

 together the atoms of oxygen in the molecule of oxygen, and 

 the atoms of sulphur in the molecule of sulphur; and hence, 

 if we could employ free atoms of oxygen or sulphur instead of 

 their molecules, we would expect the action to take place much 

 more readily. In the case of sulphur, it is not possible, as far 

 as we know at present, to obtain free atoms or unstable 

 molecules which by their breaking up yield free atoms. In 

 ozone, however, we "have such an unstable molecule of oxygen. 

 As we have seen in the experiment with carbon monoxide, 

 above referred to, ozone does not always appear to furnish free 

 atoms of oxygen when we might expect it to, and hence the 

 formation of phosphorus oxychloride by the action of ozone 

 could not be predicted with any certainty. Experiment proved, 

 however, that the formation actually does take place with 



§ Berliner Berichte, ii, 638. 



