On the Statistical Basis of the Theory of Electrolytes

摘要

In the following paper the author investigates how far the various statistical‐thermodynamic methods hitherto proposed are suitable for application to strong electrolytes. The significance of the ionic radius is, in many instances, far more important than has hitherto been assumed. When the influence of the ionic radius is negligible conditions are derived from dimensional considerations which considerably restrict the functional form of the free energy. Furthermore, proceeding from conditions of integrability, thermodynamics appreciably limits the number of possible expressions for the ionic potential. The disregarding of these limitations has been responsible for certain paradoxes in the literature on this subject. A new fluctuation formula for the electric potential of the ions is derived and conclusions are drawn from it as to the correctness of existing theories. In connection with this last a deduction proposed by Fowler is reviewed. Kramers' theory of electrolytes is tested with respect to its agreement with the theorems here developed. Finally, a review of the statistical and thermodynamical basis of Bjerrum's theory of ionic association is presented.