Statistical Thermodynamics of Bolaform and Dipolar Ionic Solutions by the Mayer Method

Abstract

We have applied the ring-diagram approximation of the Mayer ionic solution theory to solutions containing bolaform ions and to solutions containing dipolar ions. For the former case we derive a simple expression for the activity coefficient of the counterion to the bolaform ion. This expression has the property of increasing with the length of the bolaform ion from the Debye—Hückel limiting value for a uni-divalent salt (zero length) to the limiting value for a uni-univalent salt (infinite length). For dipolar ions we recover as a limiting case an expression derived by Kirkwood by classical means. We also derive a term accounting for dipolar ion—dipolar ion interactions, which is comparable to one obtained by Fuoss for a different model.