Free energy mixing, surface phase

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. 

By analogy with the treatment of mixed micelles, we now assume that the free energy of mixing of the surface phase can be calculated using the standard regular solution expression for the activity coefficients in a binary mixture ... 

Using an automated film balance the behavior of mixed monomolecular films exhibiting deviations from ideality was studied. Particular attention was paid to condensation effects obtained when cholesterol is mixed with a more expanded component. The deviations at various film pressures are discussed in terms of the partial molecular areas of the film components. Slope changes in these plots are caused by phase transitions of the expanded monolayer component and do not indicate the formation of surface complexes. In addition, the excess free energies, entropies, and enthalpies of mixing were evaluated, but these parameters could be interpreted only for systems involving pure expanded components, for which it is clear that the observed condensation effects must involve molecular interactions. 

A thermodynamic treatment is first suggested on the basis of which one can explain the inclined phase transition that occurs in monolayers of insoluble surfactants. By minimizing the Helmholtz free energy of the monolayer, the equilibrium radius and the equilibrium area fraction of the LC islands are obtained as functions of the average molecular surface area A. The mixing entropy provides a negligible effect on... 

At the liquid-liquid interface between a hydrocarbon oil and water under mixing, the molecules encounter unbalanced attraction forces, pull inwardly, and contract as other molecules leave the interface for the interior of the bulk liquid. As a result, spherical droplets are formed. Customarily, the boundaries between a liquid and gas and between two liquids are the surface and the interface, respectively. The interfacial tension (or interfacial free energy) is defined as the work required to increase the interfacial area of one liquid phase over the other liquid phase isothermally and reversibly. Moving molecules away from the bulk to the surface or interfacial surface requires work (i.e., an increase in free energy). Water molecules and hydrocarbon oil molecules at the interface are attracted to the bulk water phase as a result of water-water interaction forces (i.e., van der Waals dispersion y and hydrogen bonding y ), to the bulk oil phase due to the oil-oil dispersion forces, y 1, and to the oil-water phase by oil-water interactions, y )W (i.e., dispersion forces). As mentioned in Chapter 3, the oil-water dispersion interactions are related to the geometric mean of the water-water and oil-oil dispersion interactions. The interfacial tension is written as ... 

Upon mixing two immiscible liquids, one of the two liquids (i.e., the dispersed phase) is subdivided into smaller droplets. The surface area and the interfacial free energy increase, and the system is then thermodynamically unstable. Without continuous mixing, the droplets will be stabilized throughout the dispersion medium by dissolving the surface-active agent. There are several theories for the stabilization of emulsions but a single theory cannot account for the stabilization of all emulsions. 

The mixing parameter Ae makes the CT free energy surfaces dependent on the gas-phase, adiabatic transition dipole moment. The standard extension... 

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