We put forth the idea of treating coexisting phases as a composite system and express its free energy as the average of its constitutent free energies weighted by their respective volume proportions. As a result, the theoretical study of charged colloidal phase separation in the presence of electrolytes reduces to optimizing solely the entities pertaining to colloids and small ions. As concrete illustrations, we demarcated the boundaries of coexisting phases for the simplest colloidal dispersion driven by salts at moderate to high concentrations and compared the results with those obtained in the usual manner to numerically show the robust efficiency of the present theory. Also, for a charged colloidal dispersion at very low ionic strength, we crosshatched both the homogeneous one phase and coexisting phases, and used the domains of coexisting phases to interpret an anomalous “transition” of phase diagrams exhibited in dilute colloidal dispersions induced by salts on dilution.

• Received 23 March 2004

DOI:https://doi.org/10.1103/PhysRevE.70.051402