Virial expansion for charged colloids and electrolytes

Abstract:

Using a field-theoretic approach, we derive the first few coefficients of the exact low-density (“virial”) expansion of a binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). Our calculations are nonperturbative with respect to the diameters d₊ and d_- and charge valences q₊ and q_- of positive and negative ions. Consequently, our closed-form expressions for the coefficients of the free energy and activity can be used to treat dilute salt solutions, where typically d ₊∼d _- and q ₊∼q _-, as well as colloidal suspensions, where the difference in size and valence between macroions and counterions can be very large. We show how to map the TCPHC on a one-component hard-core plasma (OCPHC) in the colloidal limit of large size and valence ratio, in which case the counterions effectively form a neutralizing background. A sizable discrepancy with the standard OCPHC with uniform, rigid background is detected, which can be traced back to the fact that the counterions cannot penetrate the colloids. For the case of electrolyte solutions, we show how to obtain the cationic and anionic radii as independent parameters from experimental data for the activity coefficient.