Ionic Specificity in Rapid Coagulation of Silica Nanoparticles

The Smoluchowski theory has been widely accepted as the basic theory to estimate the rapid coagulation rate of colloidal particles in electrolyte solutions. However, because the size and specificity of molecules and ions are not taken into account, the theory is applicable only if the particle size is large enough to neglect the effects caused by the structured layers composed of water molecules, ions, and hydrated ions adsorbed on the colloidal surface. In the present study, the rapid coagulation rates of silica nanoparticles in concentrated chloride and potassium solutions were measured by using a low-angle light-scattering apparatus, and the dependence of the experimental value of rapid coagulation rate, K_E^R, on the particle diameter, D_p, and also on the Gibbs free energy of hydration of ions, ΔG_hyd, was investigated extensively. The following were found. (1) When the particle size was small enough, the value of K_E^R reduced exponentially not only with the decreasing particle size but also with the increasing value of (-ΔG_hyd) of cations (counterions) in the case of chloride solutions and with that of anions (coions) in the case of potassium solutions. (2) Silica nanoparticles of D_p ≲ 70 nm in 1 M KNO₃ and KSCN solutions did not coagulate at all, although they coagulated at D_p ≳ 100 nm as in the other potassium solutions. These unexpected phenomena were explained by the proposed mechanisms.