Interfacial free energy, microemulsion

Any surfactant adsorption will lower the oil-water interfacial tension, but these calculations show that effective oil recovery depends on virtually eliminating y. That microemulsion formulations are pertinent to this may be seen by reexamining Figure 8.11. Whether we look at microemulsions from the emulsion or the micellar perspective, we conclude that the oil-water interfacial free energy must be very low in these systems. From the emulsion perspective, we are led to this conclusion from the spontaneous formation and stability of microemulsions. From a micellar point of view, a pseudophase is close to an embryo phase and, as such, has no meaningful y value. 

Similar attempts were made by Likhtman et al. [13] and Reiss [14]. Reference 13 employed the ideal mixture expression for the entropy and Ref. 14 an expression derived previously by Reiss in his nucleation theory These authors added the interfacial free energy contribution to the entropic contribution. However, the free energy expressions of Refs. 13 and 14 do not provide a radius for which the free energy is minimum. An improved thermodynamic treatment was developed by Ruckenstein [15,16] and Overbeek [17] that included the chemical potentials in the expression of the free energy, since those potentials depend on the distribution of the surfactant and cosurfactant among the continuous, dispersed, and interfacial regions of the microemulsion. Ruckenstein and Krishnan [18] could explain, on the basis of the treatment in Refs. 15 and 16, the phase behavior of a three-component oil-water-nonionic surfactant system reported by Shinoda and Saito [19],... 

The earlier concepts of microemulsion stability stressed a negative interfacial tension and the ratio of interfacial tensions towards the water and oil part of the system, but these are insuflBcient to explain stability (13). The interfacial free energy, the repulsive energy from the compression of the diffuse electric double layer, and the rise of entropy in the dispersion process give contributions comparable with the free energy, and hence, a positive interfacial free energy is permitted. 

Stability of Microemulsions. The first attempt to describe the microemulsion stability in terms of different free energy components was made by Ruckenstein and Chi (55) who evaluated the enthalpic (Van der Waals potential, interfacial free energy and the potential due to the compression of the diffuse double layer) and entropic... 

Qualitatively the thermodynamics of microemulsions is well understood as the interplay between a small interfacial free energy and a small entropy of mixing. However, because of these contributions being small, other small effects, such as the influence of curvature on the interfacial tension and the influence of fluctuations, become important, and quantitative understanding still leaves a lot to be desired. 

In Sec. II we discuss the mechanism by which the interfacial tension may become ultralow. After that, in Sec. Ill we mention curvature effects of the oil/water interface. Subsequently, a number of models for thermodynamic calculations are described (Sec. IV). In Secs. V-VII we discuss droplet-type microemulsions in some detail. Section Vdescribes a thermodynamic formalism that incorporates the interfacial free energy (as influenced by the curvature) and the free energy of mixing of droplets and continuous medium and ultimately leads to equations for the size distribution of microemulsion droplets. This size distribution is important because measurable properties can be calculated... 

The energy requirements for the formation of macroemulsions can be quite substantial. The formation of small droplets requires that the system overcome both the adverse positive interfacial free energy between the two immiscible phases working toward drop coalescence and bulk properties of the dispersed phase such as viscosity. Microemulsions, on the other hand, form spontaneously or with very gentle agitation when the proper composition is reached. 

Specific roles of the so-called co-surfactants (commonly, but not necessarily alcohols) have been examined by various workers [122, 126, 136] some points are discussed here. For example, a critical thermodynamic analysis in conjunction with experimentations led Eicke [ 136] to the conclusion that a co-surfactant should decrease the interfacial free energy under isothermal conditions, while causing an uptake of water into the microemulsion and extension of its domain. The anionic surfactant AOT assists the formation of large reverse microemulsion domains (high water uptake) in different ternary systems without help from a co-surfactant (Section 2.2), but cationic surfactants do generally need this fourth component. In spite of this, enhanced solubilization by the addition of (small quantities of) a co-surfactant has been observed by various workers in AOT systems. Eicke [136] used cyclohexane, benzene, carbon tetrachloride and nitrobenzene in the system AOT/ isooctane/water and found considerable water uptake (the fraction of the oil phase, i.e. isooctane was 0.8 or more). With increasing polarizability or polarity of the CO-surfactant, the water uptake decreased. 

The change in interfacial free energy AG, is always positive in the formation of a microemulsion or a nanoemulsion as both y and AA are positive positive AA is due to an increase in the interfacial area between oil and water when droplets are formed. The entropy contribution -TAS is always negative as both T and AS are positive positive AS is due to an increase in the disorder of the... 

Mixtures of aqueous electrolytes, hydrocarbons, and amphiphilic compounds have been the subjects of extensive research, especially those systems forming amorphous isotropic solutions, called microemulsions. Several books and papers have treated this subject [1-5]. The term microemulsion was first introduced by Hoar and Schulman [5]. Microemulsions are thermodynamically stable, isotropic, transparent colloidal solutions of low viscosity, consisting of three components a surfactant (amphiphile), a polar solvent (usually water), and a nonpolar solvent (oil) [1-7]. The surfactant monomers in these fluids reside at oil water interface and effectively lower the interfacial-free energy, resulting in the formation of optically clear, thermodynamically stable formulations. The innate formation of colloidal particles is typically up to nanometer scale globular droplets each... 

These three-phase behavior systems have been found to be associated with ultealow interfacial tension and, thus, were the target of the enhanced oil-recovery research in the seventies. Note that the ultralow interfacial tension is perfectly consistent with the possibility of entropy stabilization of microemulsions, because it decreases the interfacial free energy term yAA [50]. 

This transition may j-.e. reducing the specific surface energy, f. The reduction of f to sufficiently small values was accounted for by Ruckenstein (15) in terms of the so called dilution effect". Accumulation of surfactant and cosurfactant at the interface not only causes significant reduction in the interfacial tension, but also results in reduction of the chemical potential of surfactant and cosurfactant in bulk solution. The latter reduction may exceed the positive free energy caused by the total interfacial tension and hence the overall Ag of the system may become negative. Further analysis by Ruckenstein and Krishnan (16) have showed that micelle formation encountered with water soluble surfactants reduces the dilution effect as a result of the association of the the surfactants molecules. However, if a cosurfactant is added, it can reduce the interfacial tension by further adsorption and introduces a dilution effect. The treatment of Ruckenstein and Krishnan (16) also highlighted the role of interfacial tension in the formation of microemulsions. When the contribution of surfactant and cosurfactant adsorption is taken into account, the entropy of the drops becomes negligible and the interfacial tension does not need to attain ultralow values before stable microemulsions form. 

Surfactants form semiflexible elastic films at interfaces. In general, the Gibbs free energy of a surfactant film depends on its curvature. Here we are not talking about the indirect effect of the Laplace pressure but a real mechanical effect. In fact, the interfacial tension of most microemulsions is very small so that the Laplace pressure is low. Since the curvature plays such an important role, it is useful to introduce two parameters, the principal curvatures... 

If the interfacial tension between two liquids is reduced to a sufficiently low value on addition of a surfactant, emulsification will readily take place, because only a relatively small increase in the surface free energy of the system is involved. If tt y0, a microemulsion may form (see page 269). 

---