The structure of the electrical double layer at the interface of planar electrodes and aqueous solutions is investigated. Electrical impedance spectroscopy is used to measure the impedance of aqueous solutions of sodium chloride and two different surfactants over a wide range of concentrations. The electrode capacitance is directly inferred from the admittance spectra, as well as by regression of the impedance spectra to an equivalent circuit. It is found that the electrode capacitance remains on the same order of magnitude over the entire range of investigated concentrations. This is contradictive to the predictions of the Gouy-Chapman-Stern theory which predicts that at low concentrations, the electrode capacitance should be determined by the diffuse layer. It is concluded that the Stern layer capacitance always dominates the electrode capacitance, even at very low concentrations, and the establishment of a diffuse layer capacitance 1 requires an ionic strength of around 1 mM.

The addition of surfactants can considerably impact the electrical characteristics of an interface, and the zeta potential measurement is the standard method for its characterization. In this article, a comprehensive study of the zeta potential of poly(methyl methacrylate) (PMMA) in contact with aqueous solutions containing an anionic, a cationic, or a zwitterionic surfactant at different pH and ionic strength values is conducted. Electrophoretic mobilities are inferred from electrophoretic light scattering measurements of the particulate PMMA. These values can be converted into zeta potentials using permittivity and viscosity measurements of the continuous phase. Different behaviors are observed for each surfactant type, which can be explained with the various adsorption mechanisms on PMMA. For the anionic surfactant, the absolute zeta potential value below the critical micelle concentration (CMC) increases with the concentration, while it becomes rather constant around the CMC. At concentrations above the CMC, the absolute zeta potential increases again. We propose that hydrophobic-based adsorption and, at higher concentrations, the competing micellization process drive this behavior. The addition of cationic surfactant results in an isoelectric point below the CMC where the negative surface charge is neutralized by a layer of adsorbed cationic surfactant. At concentrations near the CMC, the positive zeta potential is rather constant. In this case, we propose that electrostatic interactions combined with hydrophobic adsorption are responsible for the observed behavior. The zeta potential in the presence of zwitterionic surfactant is influenced by the adsorption, because of hydrophobic interactions between the surfactant tail and the PMMA surface. However, there is less influence, compared to the ionic surfactants. For all three surfactant types, the zeta potential changes to more-negative or less-positive values for alkaline pH values, because of hydroxide adsorption. An increase of the ionic strength decreases the absolute value of the zeta potential, because of the shielding effects.

Many unit operations required in microfluidics can be realised by electrokinetic phenomena. Electrokinetic phenomena are related to the presence of electrical surface charges of microfluidic substrates in contact with a liquid. As surface charges cannot be directly measured, the zeta potential is considered as the relevant parameter instead. PMMA is an attractive microfluidic substrate since micron-sized features can be manufactured at low costs. However, the existence of PMMA surface charges is not well understood and the zeta potential data found in the literature show significant disagreement. In this article, we present a thorough investigation on the zeta potential of PMMA. We use computations of the potential distribution in the electrical double layer to predict the influence of various electrolyte parameters. The generated knowledge is compared to extensive experiments where we investigate the influence of ionic strength, pH, temperature and the nature of the electrolyte. Our findings imply that two different mechanisms influence the zeta potential depending on the pH value. We propose pure shielding in the acidic and neutral milieus while adsorption of co-ions occurs along with shielding in the alkaline milieu.

This paper presents a new method to determine the zeta potential of porous substrates in contact with a liquid. Electroosmosis, arising near the solid/liquid boundaries within a fully saturated porous substrate, pumps against the capillary pressure arising from the surface tension of a droplet placed in series with the pump. The method is based on measuring the liquid/gas interface deflection due to the imposed electric potential difference. The distinguishing features of our technique are accuracy, speed, and reliability, accomplished with a straightforward and cost-effective setup. In this particular setup, a bistable configuration of two opposing droplets is used. The energy barrier between the stable states defines the range of capillary resistance and can be tuned by the total droplet volume. The electroosmotic pump is placed between the droplets. The large surface area-to-volume ratio of the porous substrate enables the pumping strength to exceed the capillary resistance even for droplets small enough that their shapes are negligibly influenced by gravity. Using a relatively simple model for the flow within the porous substrate, the zeta potential resulting from the substrate-liquid combination is determined. Extensive measurements of a borosilicate substrate in contact with different aqueous electrolytes are made. The results of the measurements clarify the influence of the ionic strength and pH value on the zeta potential and yield an empirical relationship important to engineering approaches.

We investigate the electrokinetic flow and transport within a micro-electrophoresis device. A mathematical model is set up, which allows to perform two-dimensional, time-dependent finite-element simulations. The model reflects the dominant features of the system, namely electroosmosis, electrophoresis, externally-applied electrical potentials, and equilibrium chemistry. For the solution of the model equations we rely on numerical simulations of the core region, while the immediate wall region is treated analytically at leading order. This avoids extreme refinements of the numerical grid within the EDL. An asymptotic matching of both solutions and subsequent superposition, nevertheless, provides an approximation for the solution in the entire domain. The results of the simulations are verified against experimental observation and show good agreement.