The equation of state of colloidal dispersions

We present a comparison of experimentally and theoretically determined osmotic pressures for various colloidal dispersions. Experimental data is collected from several different silica and polystyrene dispersions. The theoretical pressure determinations are based on the Primitive Model combined with the Cell Model and the physical quantities are calculated exactly using Monte Carlo simulations in the canonical and grand canonical ensemble. The input to the simulations in terms of colloidal particle size, surface charge density etc are taken directly from experiments and the approach does not contain any adjustable parameters. The agreement between theory and experiment is excellent without any fitting parameters showing that the simplifications behind the primitive model and the cell model are physically sound. For one of the silica dispersions we have also investigated how various monovalent counterions influence the swelling properties. Within experimental errors, we are unable to detect any ion specificity, which is another support for the theoretical models used.