Equation of State of Charged Rod Dispersions

TL;DR

This paper evaluates the SLO theory's effectiveness in predicting the thermodynamic behavior of charged rod dispersions by integrating it with scaled particle theory and comparing results to Monte Carlo simulations.

Contribution

It introduces a combined SLO-SPT approach to accurately model the free volume and osmotic pressure of charged rods, extending the applicability of existing theories.

Findings

Good agreement with simulations at low Debye lengths and high charge densities.

Deviations grow at higher concentrations, especially near phase transition points.

The combined theory provides a reliable tool for certain parameter ranges.

Abstract

We study the accuracy of the theory of Stroobants, Lekkerkerker and Odijk, called SLO theory (Macromolecules 19 (1986) 2232-2238), 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 concentration-dependent 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.