We argue that Bjerrum's approach to ion pairing is inappropriate for the size-asymmetric primitive model in the neighborhood of its critical point, and propose a new approach based on the Stillinger-Lovett pairing procedure. The new approach recursively scales up the ion size until linear approximations are suitable for analyzing such a model. To locate the critical point, a residual van der Waals interaction between pairs is added, with an energy cutoff adjusted to match the critical temperature of the restricted primitive model. The locations and downward trends of Tc and ρc with asymmetry are found to compare favorably with simulations.
ASJC Scopus subject areas
- Physics and Astronomy(all)