Molecular Interactions in Mixed Monolayers of Octadecanoic Acid and Three Related Amphiphiles.

Binary mixed monolayers of octadecanoic acid and three related amphiphilic compounds (octadecanamide, octadecylamine, octadecylurea) have been investigated at the air/water interface by surface pressure-area (Pi-Â) isotherms and their resistances to water evaporation (r). In addition, the excess free energies of mixing (DeltaG(E)) were calculated using the Goodrich method. Both the ln r vs x and DeltaG(E) vs x plots exhibit marked deviations from linearity, indicating a high degree of miscibility and nonideal behavior of the components in the mixed films. For all of these binary systems the excess free energies of mixing have been found to be minimum for a certain composition corresponding almost to a maximum in evaporation resistances. Weak interactions were detected in octadecanoic acid/octadecanamide monolayers, whereas significant condensation effects were observed in 1 : 1 mixed films containing octadecanoic acid and octadecylamine. This is attributed to an acid-base equilibrium followed by the formation of a well-ordered arrangement of COO(-) and NH(3)(+) head groups bound to each other by electrostatic forces. The unusual polymorphism of octadecylurea monolayers could be influenced by adding small amounts of octadecanoic acid. The formation of the low-temperature phase (beta-phase) is completely suppressed, if the acid content exceeds 8 mol%. The octadecanoic acid seems to induce the formation of the high-temperature phase (alpha-phase), which is characterized by a vertical orientation of the hydrocarbon chains. Copyright 2000 Academic Press.