Equation of State of Charged Rod Dispersions

Abstract

We study the accuracy of the theory of Stroobants, Lekkerkerker, and Odijk [Macromolecules 1986, 19, 2232−2238, called SLO theory, to describe the thermodynamic properties of an isotropic fluid of charged rods. By incorporation of the effective diameter of the rods according to SLO theory into scaled particle theory (SPT), we obtain an expression for the rod concentrationdependent free volume fraction and the osmotic pressure of a collection of charged hard spherocylinders. The results are compared to Monte Carlo simulations. We find close agreement between the simulation results and the SLO-SPT predictions for not too large values of the Debye length and for high rod charge densities. The deviations increase with rod density, particularly at concentrations above which isotropic−nematic phase transitions are expected.