Reaction before Complete Equilibrium. 4<^ 



equation, the point of equilibrium, and especially that, owing 

 to the interference of external factors such as the surrounding 

 temperature, &c, the obtained points of equilibrium are not 

 the real ones but only apparent points of equilibrium. It 

 is evident that chemical equilibrium in heterogeneous systems has 

 also only one point where it is real, and this is where equilibrium 

 is real for cell its constituent reactions. Since now the real 

 point of equilibrium is certainly not reached by the physical 

 reactions, it follows that chemical equilibrium in heterogeneous 

 systems is also only an apparent one, and the obtained results 

 concerning equilibrium will, according to the arrangements 

 of the experiment, always differ from one another, and always 

 only approximate more or less to those results which are the 

 correct ones. Having, namely, for equilibrium of the physical 

 reactions the equation 



M = c(t -t)(t-^t ov +K)-c / O-*)=0 



CIT 



instead of 



C —= c (t -t)(t-t ov +K) = 0, 



the- values of p T , pr at equilibrium will always differ from 

 P , P/, and, according to the laws of action of mass, there 

 will always be a redistribution between the quantities of each 

 kind of molecules constituting the system in the homogeneous 

 part, so as to correspond to the given values p T , pr» Look- 

 ing thus away from the form of the equations for velocity of 

 reaction themselves, which show that a system can arrive at 

 its point of real equilibrium only in an infinite time, and 

 giving our attention to the more serious source of error arisino- 

 from external influences, it is evident that to secure success in 

 this region of research all the steps necessary to secure 

 correct equilibrium for the physical reactions must be taken 

 in the first instance. Only after this is done shall we be able 

 from the equations concerning the velocity of reaction to 

 calculate how far we succeeded in approaching the real point of 

 equilibrium after a given time t 2 —Tx. Should the nature of 

 the phenomenon, or of the problem, on some occasions require 

 very great accuracy in the method employed, we shali 

 have here, as in the case of delicate freezing-points, or of 

 solubility measurements, to make also detailed investigation 

 of the values C, c", t — t, ~l—t ov + K, t g — t, &c, as this 

 alone will enable us here as there to discriminate between 

 correct and incorrect results, independently of the assertions 

 of every investigator. 

 Davy Faraday Laboratory, 

 lloyal Institution, May 1902. 



Phil. Mag. S, 6. Vol. 4. No. 22. Oct. 1902. 2 K 



