340 BULLETIN OP THE UNIVERSITY OF WISCONSIN. 



discussed by Reychler 1 , whose conclusion is that, "above every- 

 thing else we notice that the hypothesis of free ions is in op- 

 position to thermo-chemical observations" 2 . 



The attempts to harmonize the theory of electrolytic dissocia- 

 tion with the law of mass action have signally failed in the 

 case of the electrolytes par excellence,, as is well known, in spite 

 of the fact that very earnest endeavors have been made in this 

 direction for over a decade. In the case of weak organic acids, 

 to be sure, a tolerable agreement between the law of mass 

 action and the dissociation theory has been found by Ostwald. 

 The fact that the dissociation hypothesis cannot be brought into 

 harmony with the law of mass action is one of the strongest 

 arguments against the theory. It is really unfortunate that 

 in discussing problems of equilibrium into which strong elec- 

 trolytes enter (their solubility for instance) the adherents of 

 the dissociation theory should go right ahead with their mathe- 

 matical equations and deductions as though the theory were in 

 full accord with the law of mass action 3 . 



The chemical reactiveness of electrolytes has been explained 

 by attempting to ascribe to the ions a peculiarly strong chemical 

 activity on account of the electrical charges that are supposed 

 to reside upon them. 4 The fact that a goodly number of sub- 

 stances will not react with each other when water is not present 

 and that they do react in aqueous solution, or at any rate 

 when moist, has been called into requisition in this connection. 

 While this behavior may be claimed to agree with the disso- 

 ciation theory, it cannot be used as an argument to support the 

 latter; for it is clear that many pure substances and mixtures 



1 Outlines of Physical Chemistry. (Translated by McCrae.) Whittaker and Co. 

 (1899), page 214. 



2 The italics are Keychler's. 



9 Compare for instance the general and unqualified statements concerning the 

 so-called solubility product contained in Ostwald's "Scientific Foundations of 

 Analytical Chemistry," which the author applies to electrolytes, to most of which, 

 certainly, it does not apply unqualifiedly. 



*A recent statement of H. C. Jones illustrates the extreme views that are en- 

 tertained by some regarding this matter. He concludes a review of the work 

 done on the dissociating power of solvents (Amer. Chem. Jour. 25, 232 (1901) ) with 

 the statement, "The chemistry of atoms and molecules has thus given place 

 to the chemistry of ions". 



