The colloidal probe technique was used to measure the inner layer capacitance of an electrical double layer. In particular, the forces were measured between silica surfaces and sulfate latex surfaces in solutions of monovalent salts of different alkali metals. The force profiles were interpreted with Poisson-Boltzmann theory with charge regulation, whereby the diffuse layer potential and the regulation properties of the interface were obtained. While the diffuse layer potential was measured in this fashion in the past, we are able to extract the regulation properties of the inner layer, in particular, its capacitance. We find systematic trends with the type of alkali metal ion and the salt concentration. The observed trends could be caused by difference in ion hydration, variation of the binding capacitance, and changes of the effective dielectric constant within the Stern layer. Our results are in agreement with recent experiments involving the water-silica interface based on a completely independent method using X-ray photoelectron spectroscopy in a liquid microjet. This agreement confirms the validity of our approach, which further provides a means to probe other types of interfaces than silica.
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