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It is demonstrated that, while the Lifshitz-van der Waals (ylw) and the polar, Lewis acid-base ( ) surface tension components are additive, the Lewis acid-base electron-acceptor ( +) and electron-donor ( ~) surface tension parameters (which on account of the intrinsic asymmetry of their interactions are connected in a more complex manner) are not additive. Contact angle data cannot, in general, be correlated with a single surface tension property. The relation between contact angles and the three controlling parameters YgW, 7s> and § of a polar solid, S, cannot be established by means of one single equation. These three unknowns can, however, be determined by means of contact angle measurements with three different liquids L (of which two must be polar and H-bonding), which are completely characterized as to their respective ylW, Yl, and £ parameters by using a modified Young-Good-Girifalco-Fowkes equation 3 times.In view of these considerations, recent claims to have proven the applicability of a single "equation of state" are shown to be spurious. angle on a particular solid would be found to have the same surface tension. Table I shows that this is not the case. Water and glycerol form nearly the same contact angle on four of the solids. But the surface tensions of the two liquids differ by 12%, and the contact angles of the two liquids are significantly different on six other solids.Further, while glycerol spreads on flat surfaces of a gel encasing water (which could be expected), it is a curious finding that water also spreads on flat surfaces of a gel encasing glycerol (see Table II). It is not possible to explain this result by means of the equation of state.

An equation relating the free energies of cohesion of separate phases to the free energy of adhesion, and hence the surface tensions to the interfacial tensions, is proposed:-[AFaba/(Af'a0A/'b0)IA] = [( " -j--yb -7ab)/2(7a7b)1/!] = . The relations developed are confronted with experimental data on interfacial tensions.

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Following the development of a methodology for determining the apolar components as well as the electron donor and the electron acceptor parameters of the surface tension of polar surfaces, surfaces of a number of quite common materials were found to manifest virtually only electron donor properties and no, or hardly, any electron acceptor properties. Such materials may be called monopolar; they can strongly interact with bipolar materials (e.g., with polar liquids such as water); but one single polar parameter of a monopolar material cannot contribute to its energy of cohesion. Monopolar materials manifesting only electron acceptor properties also may exist, but they do not appear to occur in as great an abundance. Among the electron donor monopolar materials are: polymethylmethacrylate, polyvinylalcohol, polyethyleneglycol, proteins, many polysaccharides, phospholipids, nonionic surfactants, cellulose esters, etc. Strongly monopolar materials of the same sign repel each other when immersed or dissolved in water or other polar liquids. The interfacial tension between strongly monopolar surfaces and water has a negative value. This leads to a tendency for water to penetrate between facing surfaces of a monopolar substance and hence, to repulsion between the molecules or particles of such a monopolar material, when immersed in water, and thus to pronounced solubility or dispersibility. Monopolar repulsion energies can far outweigh Lifshitz-van der Waals attractions as well as electrostatic and "steric" repulsions. In aqueous systems the commonly observed stabilization effects, which usually are ascribed to "steric" stabilization, may in many instances be attributed to monopolar repulsion between nonionic stabilizing molecules. The repulsion between monopolar molecules of the same sign can also lead to phase separation in aqueous solutions (or suspensions), where not only two, but multiple phases are possible. Negative interfacial tensions between monopolar surfactants and the brine phase can be the driving force for the formation of microemulsions; such negative interfacial tensions ultimately decay and stabilize at a value very close to zero. Strongly monopolar macromolecules or particles surrounded by oriented water molecules of hydration can still repel each other, albeit to an attenuated degree. This repulsion was earlier perceived as caused by "hydration pressure". A few of the relevant colloid and surface phenomena are reviewed and re-examined in the light of the influence of surface monopolarity on these phenomena.

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