Adsorption surface free energy

Returning to more surface chemical considerations, most literature discussions that relate adhesion to work of adhesion or to contact angle deal with surface free energy quantities. It has been pointed out that structural distortions are generally present in adsorbed layers and must be present if bulk liquid adsorbate forms a finite contact angle with the substrate (see Ref. 115). Thus both the entropy and the energy of adsorption are important (relative to bulk liquid). The... 

While in previous ab initio smdies the reconstructed surface was mostly simulated as Au(lll), Feng et al. [2005] have recently performed periodic density functional theory (DFT) calculations on a realistic system in which they used a (5 x 1) unit cell and added an additional atom to the first surface layer. In their calculations, the electrode potential was included by charging the slab and placing a reference electrode (with the counter charge) in the middle of the vacuum region. From the surface free energy curves, which were evaluated on the basis of experimentally measured capacities, they concluded that there is no necessity for specific ion adsorption [Bohnen and Kolb, 1998] and that the positive surface charge alone would be sufficient to lift the reconstmction. 

Adsorption is accompanied by a loss of surface free energy. Free energy change is related to enthalpy, AH, and entropy, AS, changes by the Gibbs equation ... 

Busscher, H. J., H. M. Uyen, G. A. M. ICip, and J. Arends. 1987. Adsorption of aminefluorides onto glass and the determination of surface free energy, zeta potential and adsorbed layer thickness. Colloids and Surfaces 22 161-69. 

Using this approach, a model can be developed by considering the chemical potentials of the individual surfactant components. Here, we consider only the region where the adsorbed monolayer is "saturated" with surfactant (for example, at or above the cmc) and where no "bulk-like" water is present at the interface. Under these conditions the sum of the surface mole fractions of surfactant is assumed to equal unity. This approach diverges from standard treatments of adsorption at interfaces (see ref 28) in that the solvent is not explicitly Included in the treatment. While the "residual" solvent at the interface can clearly effect the surface free energy of the system, we now consider these effects to be accounted for in the standard chemical potentials at the surface and in the nonideal net interaction parameter in the mixed pseudo-phase. 

Equation (46), one form of the Gibbs equation, is an important result because it supplies the connection between the surface excess of solute and the surface tension of an interface. For systems in which y can be determined, this measurement provides a method for evaluating the surface excess. It might be noted that the finite time required to establish equilibrium adsorption is why dynamic methods (e.g., drop detachment) are not favored for the determination of 7 for solutions. At solid interfaces, 7 is not directly measurable however, if the amount of adsorbed material can be determined, this may be related to the reduction of surface free energy through Equation (46). To understand and apply this equation, therefore, it is imperative that the significance of r2 be appreciated. 

Adsorption reduces the imbalance of attractive forces which exists at a surface, and, hence, the surface free energy of a heterogeneous system. In this respect, the energy considerations relating to solid surfaces are, in principle, the same as those already discussed for liquid surfaces. The main differences between solid and liquid surfaces arise from the fact that solid surfaces are heterogeneous in respect of activity, with properties dependent, to some extent, on previous environment. 

From thermodynamics, the lowering of surface free energy due to surfactant adsorption is given by the Gibbs adsorption equation for a binary, isothermal system containing excess electrolyte ... 

As explained under the adsorption theory of adhesion,3 an adhesive must first wet the substrate and come into intimate contact with it. (A brief description of the adsorption theory of adhesion is presented in the section below.) The result of good wetting is simply that there is greater contact area between adherend and adhesive over which the forces of adhesion (e.g., van der Waals type of forces) may act. For good wetting, the surface free energy (surface tension yLV) of the liquid adhesive must be less than that (critical surface tension yc) of the solid adherend, or... 

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