Section III., 1915 [203] Trans. R.S.C. 



Liquid Chlorine as a Solvent: Cryoscopic Determinations at 

 Low Temperature. 



By P. Waentig and D. McIntosh, F.R.S.C. 



(Read May Meeting, 1915). 



During the last few years many investigations of the basic proper- 

 ties of oxygen and of its tetravalence have been made. It has 

 been shown that the halogen hydrides unite with organic substances 

 containing oxygen — such as ether — yielding compounds of the general 

 type C4H10O, HX. To bring these results in agreement with our 

 views on valence, tetravalent oxygen has been assumed, and for the 

 compounds the formulae =0<x and =0 = XH have been suggested. 



Physico-chemical studies show that the former is to be preferred, 

 since in solution the oxygen compound moves to the cathode under an 

 electrical stress, i.e., it must be part of the positively charged ion. 

 The conductivity measurements prove, however, that in a solution of 

 a halogen acid these compounds are much more complex than the 

 formula given above would indicate. 



Somewhat similar combinations made with the halogens and 

 alcohol, ethers and ethereal salts show compounds of the types, 

 C H4 O, X, C4H10 O, X2, and CH3 GOOC2H5, X3, so that a hydroxyl 

 atom is balanced by one, an ethereal or ke tonic oxygen by two, and the 

 three oxygen atoms of an ester by three halogen atoms. The constitu- 

 tions of the compounds are as doubtful as those with the halogen acids. 

 Some chemists give to them the simple formula C4H10O, X2 in the case 

 of the ether combination. With the alcohol complexes the formula 

 must be doubled, and with ethyl alcohol the most probable constit- 

 tion is C2H60 = C1-C1 = O CaHg. 



With all the oxonium compounds the constitutions are far from 

 satisfactorily explained. The chlorine compounds dissolved in lique- 

 fied chlorine must be simpler than the corresponding compounds with 

 the halogen acids since the former show no electrical conductivity, 

 and therefore no ionization. Mr. Maass^ and one of us have attempted 

 to add to our knowledge by investigating the freezing point curves of 

 a number of these systems. The slopes of the curves showed that 

 all types were largely broken down in solution. In the hope of gaining 

 some further knowledge of these complexes, cryoscopic determinations 



1 Jour. Am. Chem. Soc. 33, p. 71, 1911; 34, p. 1273, 1912. 



