Surface excess concentration electrolyte effect

Another interpretation of the electrocapillary curve is easily obtained from Equation (89). We wish to investigate the effect of changes in the concentration of the aqueous phase on the interfacial tension at constant applied potential. Several assumptions are made at this point to simplify the desired result. More comprehensive treatments of this subject may be consulted for additional details (e.g., Overbeek 1952). We assume that (a) the aqueous phase contains only 1 1 electrolyte, (b) the solution is sufficiently dilute to neglect activity coefficients, (c) the composition of the metallic phase (and therefore jt,Hg) is constant, (d) only the potential drop at the mercury-solution interface is affected by the composition of the solution, and (e) the Gibbs dividing surface can be located in such a way as to make the surface excess equal to zero for all uncharged components (T, = 0). With these assumptions, Equation (89) becomes... 

X is the concentration of the adsorbate A which is varied in order to study the effect of bulk concentration on the interfacial surface excess y is the concentration of the electrolyte whose activity is kept constant. The corresponding electrolyte concentration is kept reasonably high to provide electrical conductivity to the solution. For low values of x, the electrolyte concentration is constant. However, at higher concentrations of organic solute, the activity coefficient of the electrolyte varies with organic solute concentration. Thus, in general, the concentration of the electrolyte must also be varied in order to keep its activity constant. It is also important that the ions of the electrolyte not adsorb on the electrode to a significant extent. 

C104 ) is kept constant when the concentration of the adsorbing anion is changed. It is considered that the effect of the adsorption of the anion of the supporting electrolyte on the measured surface excess of the investigated anion can be minimized under this condition. In addition, it is assumed that in the presence of an excess of supporting electrolyte the measured surface excess is essentially equal to the surface concentration. 

The specific ion effects at the water/air interface have recently been reviewed by Jungwirth and Tobias (2006). Since the surface region of water with respect to air or water vapor differs in properties and structure from bulk water (Sect. 4.1), it is expected that ions react to these different environments by being either attracted to or repelled from the surface. In other words, ions may be sorbed at or desorbed from the surface of an electrolyte solution. The excess concentration Te (the amount of an electrolyte sorbed per unit increase of the surface energy) at the surface relative to the bulk is governed by the Gibbs adsorption law ... 

The repulsion between oil droplets will be more effective in preventing flocculation Ae greater the thickness of the diffuse layer and the greater the value of 0. the surface potential. These two quantities depend oppositely on the electrolyte concentration, however. The total surface potential should increase with electrolyte concentration, since the absolute excess of anions over cations in the oil phase should increase. On the other hand, the half-thickness of the double layer decreases with increasing electrolyte concentration. The plot of emulsion stability versus electrolyte concentration may thus go through a maximum. 

How can such problems be counterbalanced Since a large capacitance of a semiconductor/electrolyte junction will not negatively affect the PMC transient measurement, a large area electrode (nanostructured materials) should be selected to decrease the effective excess charge carrier concentration (excess carriers per surface area) in the interface. PMC transient measurements have been performed at a sensitized nanostructured Ti02 liquidjunction solar cell.40 With a 10-ns laser pulse excitation, only the slow decay processes can be studied. The very fast rise time cannot be resolved, but this should be the aim of picosecond studies. Such experiments are being prepared in our laboratory, but using nanostructured... 

The contribution of transport under the influence of the electric field (migration), which, if appreciable, should be subtracted from the total mass flux. The use of excess inert (supporting) electrolyte is recommended to suppress migration effects. However, it should be remembered that this changes the composition of the electrolyte solution at the electrode surface. This is particularly critical in the interpretation of free-convection results, where the interfacial concentration of the inert as well as the reacting ions determines the driving force for fluid motion. 

The various qualitative behaviors of the hydration force in different systems (either oscillatory [12] or monotonic [10], with various decay lengths (2—3 A [10] or about 10 A [13]), either independent of electrolyte concentration [10] or exhibiting strong specific ion effects [14]) appear to point out toward the existence of a number of different microscopic origins for the short range repulsions between surfaces immersed in water, in excess to those accounted by the DLVO theory. On the other hand, there are some striking similarities between the hydration forces in different systems. For example, the Molecular Dy-... 

---