Equilibrium in Mixed Electrolytes. 



345 



The additional salt in each of these three cases of isomeric 

 mixture prevented the mixture from at once attaining a fixed 

 or final chemical and molecular constitution. 



N.B. Compare the results with those of Tables III. and IV. 



Table III. — Influence of Time. 



After standing 24 hours. 



Mixtures. 



E.M.F. 



Cl+(KBr+KI). 

 Br+(KCl+KI). 

 I + (KCl+KBr). 



1-37868 



Calculated 

 E.M.F. 



1-2376 

 1-3101 

 1-2806 



Change of 

 E.M.F. 



Gain -14108 

 „ -0685 

 „ -0980 



Per 



cent. 



11-37 



5-22 

 765 



By standing a sufficient period of time at ordinary atmo- 

 spheric temperature, the first two solutions of Table II. lost 

 energy, and acquired the same chemical and molecular 

 composition as the third one, i. e., the one having the smallest 

 electromotive force ; these two mixtures therefore were in an 

 unstable condition. 





Table IV. — Influence of Heating. 







Mixtures. E.M.F. 



Calculated 

 E.M.F. 



Change of 

 E.M.F. 



Per 



cent. 



After heating. 



)> >> 



Cl + (KBr+KI). 1-3701 

 Br+(KCl+KI). 1-3844 

 I + (KCl4-KBr). 1-35294 



1-2376 

 1*3101 



1-2806 



Gain -1325 = 

 „ -0743 

 „ '0723 



10-70 

 567 

 5-65 



Each mixture, newly made, was heated to 90° G. during 

 15 minutes in a stoppered glass flask and then cooled. In 

 each case the percentage of gain of electromotive force which 

 had occurred during the mixing was largely reduced, but 

 least so with the last liquid. These results indicate that all 

 three of these mixtures were more or less unstable, the first 

 one the most and the last one the least so, that neither of 

 them had completely attained the most fixed chemical and 

 molecular condition, and that heating caused a rapid change 

 in each to a fixed state. The chemical change and the final 

 state arrived at evidently depend upon the temperature ; 

 even at 16° C. a slow change occurs, see Table III. 

 Table V. — Influence of Doubling the Amount of the Halogen. 



Mixtures. 



E.M.F. 



2Cl+(KBr+KI). 

 2Br + (KCl + KI). 



1-62178 



Calculated 

 E.M.F. 



1-3113 

 1-5684 



Change of 

 E.M.F. 



Per 



cent. 



Gain '31048 

 •05338 



23-67 



340 



