Surface and zeta-potentials of silver halide single crystals: pH-dependence in comparison to particle systems

We have carried out surface and zeta-potential measurements on AgCl and AgBr single crystals. As for particle systems we find that, surprisingly and previously unnoted, the zeta-potential exhibits pH-dependence, while the surface potential does not. A possible interpretation of these observations is the involvement of water ions in the interfacial equilibria and in particular, stronger affinity of the hydroxide ion compared to the proton. The pH-dependence of the zeta-potential can be suppressed at sufficiently high silver concentrations, which agrees with previous measurements in particle systems where no pH-dependence was found at high halide ion concentrations. The results suggest a subtle interplay between the surface potential determining the halide and silver ion concentrations, and the water ions. Whenever the charge due to the halide and silver ions is sufficiently high, the influence of the proton/hydroxide ion on the zeta-potential vanishes. This might be related to the water structuring at the relevant interfaces which should be strongly affected by the surface potential. Another interesting observation is accentuation of the assumed water ion effect on the zeta-potential at the flat single crystal surfaces compared to the corresponding silver halide colloids. Previous generic MD simulations have indeed predicted that hydroxide ion adsorption is accentuated on flat/rigid surfaces. A thermodynamic model for AgI single crystals was developed to describe the combined effects of iodide, silver and water ions, based on two independently previously published models for AgI (that only consider constituent and background electrolyte ions) and inert surfaces (that only consider water and background electrolyte ions). The combined model correctly predicts all the experimentally observed trends.