Tomer Markovich

Surface tension of electrolyte solutions: A self-consistent theory

We study the surface tension of electrolyte solutions at the air/water and oil/water interfaces. Employing field-theoretical methods and considering short-range interactions of anions with the surface, we expand the Helmholtz free energy to first order in a loop expansion and calculate the excess surface tension. Our approach is self-consistent and yields an analytical prediction that reunites the Onsager-Samaras pioneering result (which does not agree with experimental data), with the ionic specificity of the Hofmeister series. We obtain analytically the surface-tension dependence on the ionic strength, ionic size and ion-surface interaction, and show consequently that the Onsager-Samaras result is consistent with the one-loop correction beyond the mean-field result. Our theory fits well a wide range of concentrations for different salts using one fit parameter, reproducing the reverse Hofmeister series for anions at the air/water and oil/water interfaces.

Charge regulation: A generalized boundary condition?

The three most commonly-used boundary conditions for charged colloidal systems are constant charge (insulator), constant potential (conducting electrode) and charge regulation (ionizable groups at the surface). It is usually believed that the charge regulation is a generalized boundary condition that reduces in some specific limits to either constant charge or constant potential boundary conditions. By computing the disjoining pressure between two symmetric planes for these three boundary conditions, both numerically (for all inter-plate separations) and analytically (for small inter-plate separations), we show that this is not, in general, the case. In fact, the limit of charge regulation is a separate boundary condition, yielding a disjoining pressure with a different characteristic separation-scaling. Our findings are supported by several examples demonstrating that the disjoining pressure at small separations for the charge regulation boundary-condition depends on the details of the dissociation/association process.

Surface tension of electrolyte interfaces: Ionic specificity within a field-theory approach

We study the surface tension of ionic solutions at air/water and oil/water interfaces by using field-theoretical methods and including a finite proximal surface-region with ionic-specific interactions. The free energy is expanded to first-order in a loop expansion beyond the mean-field result. We calculate the excess surface tension and obtain analytical predictions that reunite the Onsager-Samaras pioneering result (which does not agree with experimental data), with the ionic specificity of the Hofmeister series. We derive analytically the surface-tension dependence on the ionic strength, ionic size, and ion-surface interaction, and show consequently that the Onsager-Samaras result is consistent with the one-loop correction beyond the mean-field result. Our theory fits well a wide range of salt concentrations for different monovalent ions using one fit parameter per electrolyte and reproduces the reverse Hofmeister series for anions at the air/water and oil/water interfaces.

Bjerrum pairs in ionic solutions: A Poisson-Boltzmann approach

Ionic solutions are often regarded as fully dissociated ions dispersed in a polar solvent. While this picture holds for dilute solutions, at higher ionic concentrations, oppositely charged ions can associate into dimers, referred to as Bjerrum pairs. We consider the formation of such pairs within the nonlinear Poisson-Boltzmann framework and investigate their effects on bulk and interfacial properties of electrolytes. Our findings show that pairs can reduce the magnitude of the dielectric decrement of ionic solutions as the ionic concentration increases. We describe the effect of pairs on the Debye screening length and relate our results to recent surface-force experiments. Furthermore, we show that Bjerrum pairs reduce the ionic concentration in bulk electrolyte and at the proximity of charged surfaces, while they enhance the attraction between oppositely charged surfaces.

Surface Tension of Acid Solutions: Fluctuations beyond the Nonlinear Poisson–Boltzmann Theory

We extend our previous study of surface tension of ionic solutions and apply it to acids (and salts) with strong ion-surface interactions, as described by a single adhesivity parameter for the ionic species interacting with the interface. We derive the appropriate nonlinear boundary condition with an effective surface charge due to the adsorption of ions from the bulk onto the interface. The calculation is done using the loop-expansion technique, where the zero loop (mean field) corresponds of the full nonlinear Poisson-Boltzmann equation. The surface tension is obtained analytically to one-loop order, where the mean-field contribution is a modification of the Poisson-Boltzmann surface tension and the one-loop contribution gives a generalization of the Onsager-Samaras result. Adhesivity significantly affects both contributions to the surface tension, as can be seen from the dependence of surface tension on salt concentration for strongly absorbing ions. Comparison with available experimental data on a wide range of different acids and salts allows the fitting of the adhesivity parameter. In addition, it identifies the regime(s) where the hypotheses on which the theory is based are outside their range of validity.

Complex fluids with mobile charge-regulating macro-ions

We generalize the concept of charge regulation of ionic solutions, and apply it to complex fluids with mobile macro-ions having internal non-electrostatic degrees of freedom. The suggested framework provides a convenient tool for investigating systems where mobile macro-ions can self-regulate their charge (e.g. , proteins). We show that even within a simplified charge-regulation model, the charge dissociation equilibrium results in different and notable properties. Consequences of the charge regulation include a positional dependence of the effective charge of the macro-ions, a non-monotonic dependence of the effective Debye screening length on the concentration of the monovalent salt, a modification of the electric double-layer structure, and buffering by the macro-ions of the background electrolyte.

Ionic profiles close to dielectric discontinuities: Specific ion-surface interactions

We study, by incorporating short-range ion-surface interactions, ionic profiles of electrolyte solutions close to a non-charged interface between two dielectric media. In order to account for important correlation effects close to the interface, the ionic profiles are calculated beyond mean-field theory, using the loop expansion of the free energy. We show that how it is possible to overcome the well-known deficiency of the regular loop expansion close to the dielectric jump and treat the non-linear boundary conditions within the framework of field theory. The ionic profiles are obtained analytically to one-loop order in the free energy, and their dependence on different ion-surface interactions is investigated. The Gibbs adsorption isotherm as well as the ionic profiles is used to calculate the surface tension, in agreement with the reverse Hofmeister series. Consequently, from the experimentally measured surface tension, one can extract a single adhesivity parameter, which can be used within our model to quantitatively predict hard to measure ionic profiles.

Dielectric constant of ionic solutions: Combined effects of correlations and excluded volume

The dielectric constant of ionic solutions is known to reduce with increasing ionic concentrations. However, the origin of this effect has not been thoroughly explored. In this paper, we study two such possible sources: long-range Coulombic correlations and solvent excluded-volume. Correlations originate from fluctuations of the electrostatic potential beyond the mean-field Poisson-Boltzmann theory, evaluated by employing a field-theoretical loop expansion of the free energy. The solvent excluded-volume, on the other hand, stems from the finite ion size, accounted for via a lattice-gas model. We show that both correlations and excluded volume are required in order to capture the important features of the dielectric behavior. For highly polar solvents, such as water, the dielectric constant is given by the product of the solvent volume fraction and a concentration-dependent susceptibility per volume fraction. The available solvent volume decreases as a function of ionic strength due the increasing volume fraction of ions. A similar decrease occurs for the susceptibility due to the correlations between the ions and solvent, reducing the dielectric response even further. Our predictions for the dielectric constant fit well with experiments for a wide range of concentrations for different salts in different temperatures, using a single fit parameter related to the ion size.

Surface Pressure of Charged Colloids at the Air/Water Interface

Charged colloidal monolayers at the interface between water and air (or oil) are used in a large number of chemical, physical, and biological applications. Although considerable experimental and theoretical effort has been devoted in the past few decades to the investigation of such monolayers, some of their fundamental properties are not yet fully understood. In this article, we model charged colloidal monolayers as a continuum layer of finite thickness, with a separate charge distribution on the water and air sides. The electrostatic surface free energy and surface pressure are calculated via the charging method and within the Debye-Hückel approximation. We obtain the dependence of surface pressure on several system parameters: the monolayer thickness, its distinct dielectric permittivity, and the ionic strength of the aqueous subphase. The surface pressure scaling with the area per particle, a, is found to be between a-2 in the close-packing limit and a-5/2 in the loose-packing limit. In general, it is found that the surface pressure is strongly influenced by charges on the air side of the colloids. However, when the larger charge resides on the water side, a more subtle dependence on salt concentration emerges. This corrects a common assumption that the charges on the water side can always be neglected due to screening. Finally, using a single fit parameter, our theory is found to fit the experimental data well for strong- to intermediate-strength electrolytes. We postulate that an anomalous scaling of a-3/2, recently observed in low ionic concentrations, cannot be accounted for within a linear theory, and its explanation requires a fully nonlinear analysis.