Particle Zeta Potentials Remain Finite in Saturated Salt Solutions

The zeta potential of a particle characterizes its motion in an electric field and is often thought to be negligible at high ionic strength (several moles per liter) due to thinning of the electrical double layer (EDL). Here, we describe zeta potential measurements on polystyrene latex (PSL) particles at monovalent salt concentrations up to saturation (∼5 M NaCl) using electrophoresis in sinusoidal electric fields and high-speed video microscopy. Our measurements reveal that the zeta potential remains finite at even the highest concentrations. Moreover, we find that the zeta potentials of sulfated PSL particles continue to obey the classical Gouy-Chapman model up to saturation despite significant violations in the model's underlying assumptions. By contrast, amidine-functionalized PSL particles exhibit qualitatively different behaviors such as zero zeta potentials at high concentrations of NaCl and KCl and even charge inversion in KBr solutions. The experimental results are reproduced and explained by Monte Carlo simulations of a simple lattice model of the EDL that accounts for effects due to ion size and ion-ion correlations. At high salt conditions, the model suggests that quantitative changes in the magnitude of surface charge can result in qualitative changes in the zeta potential-most notably, charge inversion of highly charged surfaces. These findings have important implications for electrokinetic phenomena such as diffusiophoresis within salty environments such as oceans, geological reservoirs, and living organisms.