476 Dr. Meyer Wilderman on the Velocity of 



K!" can be put = c(to — t) we shall get above, below, and at 

 equilibrium 



© = o'(<.-*)(2, + K) and (J) =c"(t -t)(tr + K) 



for the partial velocities of ice melting and ice separation, i. e., 

 we shall get the result that the velocity-constants of each 

 reaction c(t — t), c f/ (t — t) decrease with rise of temperature 

 below the point of equilibrium, become = zero at equilibrium, and 

 then increase with the rise of temperature above t lie point of equili- 

 brium. No such conceptions can be entertained for one moment. 

 It is a thermodynamic impossibility that the velocity-constant 

 of a reaction should change in this manner and become 

 zero at any temperature. If such an interpretation of c(t — t) 

 should be made here, it is to be made in all cases of complete 

 equilibrium, &c, whore a similar equation holds good. Now 

 I found on the basis of careful experiments that the velocity 

 of separation of salt from a supersaturated solution becomes 

 greater the higher the temperature, and it is a very well- 

 known fact that the velocity of solution of a salt in water 

 or unsaturated solution becomes greater the higher the tem- 

 perature. But granting even that such interpretation of 

 K f// , K7 K", were possible, what is the result? Since at 

 equilibrium K' or c (t o — t) = 0, and K" or c"(t o — t)=0, 

 and therefore also K"' becomes =zero, we get the result that 

 the constant of equilibrium K //x , which is to regulate the two 

 opposite reactions at equilibrium, does not exist at all — is zero 

 —the two opposite reactions, which are to explain equilibrium 

 dynamically as counterbalancing each other, do not exist 

 at equilibrium at all, and with it the whole foundation for 

 such a conception falls to pieces. Now, if there are no 

 two opposite reactions at equilibrium, why should we 

 assume the same before equilibrium, and under assumptions 

 which seem to us quite unnatural. Indeed, while in the 

 case of chemical reactions it seems quite natural to assume 

 that two opposite reactions are taking place simultaneously, it 

 is difficult to assume the same for complete equilibrium and 

 for the point of transition ; it is difficult to think that below 

 0° ice melts, above 0° ice separates, that an unsaturated 

 solution can separate salt or that an unsaturated vapour has 

 the property to condense to a liquid ; in the notion of an 

 unsaturated solution or vapour, moreover, the idea is con- 

 tained that the solid salt or the liquid cannot co-exist 

 with them together, can not only not be formed, but must go 

 first into solution or evaporate, and the solution must first 

 become saturated, or the vapour saturated, before such a 



