Isotropic-nematic phase separation in asymmetrical rod-plate mixtures

Recent experiments on mixtures of rodlike and platelike colloidal particles have uncovered the phase behavior of strongly asymmetrical rod-plate mixtures. In these mixtures, in which the excluded volume of the platelets is much larger than that of the rods, an extended isotropic (I)–plate-rich nematic (N−)–rod-rich nematic (N+) triphasic equilibrium was found. In this paper, we present a theoretical underpinning for the observed phase behavior starting from the Onsager theory in which higher virial terms are incorporated by rescaling the second virial term using an extension of the Carnahan–Starling excess free energy for hard spheres (Parsons’ method). We find good qualitative agreement between our results and the low concentration part of the experimental phase diagram.