362 



Wc must I'tiKillii .sfi// jtiilat out hcfi' tlmt in coiUrddisluictioii inltli 



■'7. . . r- '".I 



I'l/iiii/xiii (()) ///,(' ijnolii'iit iH. t'li/Kition (17j (IimI , at equation 



(18) Is till' ratio of coiici'iUration of A and B in (in drhitrnri/ .solu- 

 tion, in ivldvh. A and B an- in intenuil cqiiiHljriwn. 



4. The ridation. for ihr casr of polymery. 



Up to now Ave have sii[)posed that A and B are isomers, but 

 the same considerations are valid for the case of polymery. 



Put the case that Jj is a polymer of A, and that the internal 

 equilibrium is represented by : 



B:^2A 

 then the just given derivation may be applied also here. We must 

 oidy bear in mind that to get a relation that is analogous to equa- 

 tion (16) i. e. in which the expression for the equilibrium constant 

 in the liquid- and gasphase occurs, we must apply Henry's law to 

 those concentrations of A and B which occur in the equation for 

 the equilibrium constant. Hence we consider the concentration -x^ of 

 A, and y of B. 



In this way we then get the I'elation : 



— = 17^- — ■•ir (^0) 



This equation expresses, indeed, the same thing as equation (16), 

 which holds for isomers, I tut dilfers from it in shape. Of course 

 this equation, too, can only be applied to the ideal case, and only 

 then, vwritteii in the form: 



it can be used to examine which modification is the stable one at 

 a certain temperature. This is however, only po.isihle ndie)i we knoy 

 the .size of tin' different l-inils of oiolecuks. Now the great advantage 

 of equation (J is evident, as this can be applied, without the size 

 of liie molecules of ..4 and B being known. 



In this communication 1 have tried to treat the problem in the 

 simplest way possible; in the next the relations considered here will 

 be derived by a thermodynamic way, and there the significance of 

 the phenomena known in practice which seem in conflict with this 

 theory, will also be pointed out. 



Am.sterdani, 23 .lune 1915. Anorg. Chem. Laboratory 



of the University. 



