Double-layer interactions, experimental measurements

Determination of the Electrophoretic Mobility, To evaluate the equation for the double-layer interaction (eq 5), the zeta potential, must be known it is calculated from the experimentally measured electrophoretic mobility. For emulsions, the most common technique used is particle electrophoresis, which is shown schematically in Figure 4. In this technique the emulsion droplet is subjected to an electric field. If the droplet possesses interfacial charge, it will migrate with a velocity that is proportional to the magnitude of that charge. The velocity divided by the strength of the electric field is known as the electrophoretic mobility. Mobilities are generally determined as a function of electrolyte concentration or as a function of solution pH. 

The electrical double layer has been dealt with in countless papers and in a number of reviews, including those published in previous volumes of the Modem Aspects of Electrochemistry series/ The experimental double layer data have been reported and commented on in several important works in which various theories of the structure of the double layer have been postulated. Nevertheless, many double layer-related problems have not been solved yet, mainly because certain important parameters describing the interface cannot be measured. This applies to the electric permittivity, dipole moments, surface density, and other physical quantities that are influenced by the electric field at the interface. It is also often difficult to separate the electrostatic and specific interactions of the solvent and the adsorbate with the electrode. To acquire necessary knowledge about the metal/solution interface, different metals, solvents, and adsorbates have been studied. 

It is noted that the molecular interaction parameter described by Eq. 52 of the improved model is a function of the surfactant concentration. Surprisingly, the dependence is rather significant (Eig. 9) and has been neglected in the conventional theories that use as a fitting parameter independent of the surfactant concentration. Obviously, the resultant force acting in the inner Helmholtz plane of the double layer is attractive and strongly influences the adsorption of the surfactants and binding of the counterions. Note that surface potential f s is the contribution due to the adsorption only, while the experimentally measured surface potential also includes the surface potential of the solvent (water). The effect of the electrical potential of the solvent on adsorption is included in the adsorption constants Ki and K2. 

The Stern theory is difficult to apply quantitatively because several of the parameters it introduces into the picture of the double layer cannot be evaluated experimentally. For example, the dielectric constant of the water is probably considerably less in the Stern layer than it would be in bulk because the electric field is exceptionally high in this region. This effect is called dielectric saturation and has been measured for macroscopic systems, but it is difficult to know what value of e6 applies in the Stern layer. The constant K is also difficult to estimate quantitatively, principally because of the specific chemical interaction energy . Some calculations have been carried out, however, in which the various parameters in Equation (97) were systematically varied to examine the effect of these variations on the double layer. The following generalizations are based on these calculations ... 

The net surface charge of a cell and the associated electrical double layer are important in interactions between cells and may influence the development of extracellular structure such as basement membranes. The net negative charge on cells also gives rise to an experimentally measurable electrophoretic mobility. 

Owing to their fundamental interest and their practical importance in issues such as colloid stability, much experimental effort has been devoted to the measurement of electric double layer and van der Waals interactions between macroscopic objects at close separations. Such measurements involve balancing the force(s) to be measured with an externally applied force. 

Halley and Mazzolo l develop>ed a flrst-principles-based direct dynamics method to examine the water/copper metal interface. Previous models on the electrochemical metal/ water interface published in the literature could not straightforwardly describe the asymmetry of the capacitance measured experimentally in the double layer. In approach taken by Halley and MazoUo, the electrons in the metal are modeled quantum mechanically using a jellium-type free electron model where only the s-electrons in copper are treated. Pseudopotentials are used to describe the electron interactions with water. The water solution phase is decoupled from the electronic structure and treated by molecular dynamics simulations with explicit water molecules using classical force fields. Gouy-Chapman theory is used to treat ionic screening. The electronic structure at the interface between the metal and the water is carefully matched by p>erforming electronic structure calculations on the metal substrate after each time step in the water MD simulation. The approach was used to examine the influence of applied potential on the structm-e of the metal-water... 

Orientation and interactions of adsorbed molecules From measurements of the differential capacitance of the electrode double layer or from electrocapillary measurements the surface concentration of the adsorbed molecules and the area A required for an adsorbed molecule in the electrode surface can be determined [18, 27, 28, 30, 69, 70]. Using data obtained for the crystal structure of bases the area which would be occupied by one adsorbed molecule in different surface orientations can be evaluated and compared with the experimentally-determined area A. From these calculations it has been concluded that at low surface concentrations (the so-called dilute adsorption region) the adsorbed bases lie flat at the electrode surface. In compact layer the adsorbed bases seem to adopt a perpendicular surface orientation [18, 45]. Similar reorientation from flat to perpendicular stance has been observed with... 

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