Specific ion effects on particle aggregation induced by monovalent salts within the Hofmeister series

Ion specific effects of monovalent salts on charging and aggregation for two types of polystyrene latex particles were investigated by electrophoresis and time-resolved light scattering. The chemical composition of the electrolytes was systematically varied in the experiments. Accordingly, NaH2PO4, NaF, NaCl, NaBr, NaNO3, and NaSCN were used to vary the anions and N(CH3)4Cl, NH4Cl, CsCl, KCl, NaCl, and LiCl for the cations. The salt concentration dependence of the electrophoretic mobilities indicates that the surface charge was screened by the counterions when their concentrations increased. For the SCN(-) ions, adsorption on positively charged particles leads to charge reversal. The aggregation rates are small at low electrolyte concentrations indicating stable dispersions under these conditions, and they increase with the salt concentration. When viscosity corrections are taken into account, no ion specific effects in the fast aggregation regime can be established. The slow and fast aggregation regimes are separated by the critical coagulation concentration (CCC). Within the experimental error, the CCCs are the same in systems containing different co-ions but the same counterions, with the exception of ammonium salts. However, the variation of counterions leads to different CCC values due to specific interaction of the counterions with the surface. These values follow the Hofmeister series for negatively charged sulfate latex particles, while the reversed order was observed for positively charged amidine latex. Comparison between experimental CCCs and those calculated by the theory of Derjaguin, Landau, Verwey, and Owerbeek reveals that variations in the surface charge due to ionic adsorption are mainly responsible for the ion specific effects in the aggregation process.