Critical coagulation concentration of a salt-free colloidal dispersion

Both exact and approximate analytical solutions of the Poisson-Boltzmann equation for two planar, parallel surfaces are derived for the case when a dispersion medium contains counterions only, and the results obtained are used to evaluate the critical coagulation concentration of a spherical dispersion. A correction factor, which is a function of the valence of counterions, the surface potential of a particle, and the potential on the midplane between two particles at the onset of coagulation, is derived to modify the classic Schulze-Hardy rule for the dependence of the critical coagulation concentration on the valence of counterions. The correction factor is found to increase with the increase in the valence of counterions and/or with the increase in the surface potential. However, it approaches a constant value of 0.8390 if the surface potential is sufficiently high.