Equation of state of charged colloidal suspensions and its dependence on the thermodynamic route

Abstract

The thermodynamic properties of highly charged colloidal suspensions in contact with a salt reservoir are investigated in the framework of the renormalized Jellium model (RJM). It is found that the equation of state is very sensitive to the particular thermodynamic route used to obtain it. Specifically, the osmotic pressure calculated within the RJM using the contact value theorem can be very different from the pressure calculated using the Kirkwood-Buff fluctuation relations. On the other hand, Monte Carlo simulations show that both the effective pair potentials and the correlation functions are accurately predicted by the RJM. It is suggested that the lack of self-consistency in the thermodynamics of the RJM is a result of neglected electrostatic correlations between the counterions and coions.