Phases of monomolecular films

The analogy between three- and two-dimensional phase diagrams can be carried much further. Monomolecular amphiphilic films show ordered phases similar to three-dimensional systems [579], The phases of an amphiphilic monolayer can be detected most conveniently in pressure-area (7r-versus-OA) isotherms. These may look different for different substances. The behavior of simple amphiphilic molecules, like long-chain alcohols, amines, or acids, was extensively investigated (reviews Refs. [580,581]). In monolayers so-called mesophases can occur. In a mesophase the tail groups are ordered over relatively large areas, while the order in the hydrophilic head groups is only over a much smaller distances. 

Fatty acids, phospholipids, etc., on water often show the following phases [582-584] (Fig. 13.3)  

After passing a plateau at a critical film pressure nc the liquid-condensed phase is reached via a phase transition of first order. Here, the amphiphiles exhibit a tilted phase with a decreasing tilt angle (measured against the normal to the subphase). The film is relatively stiff but there is still some water present between the headgroups. 

Contaminations are also responsible for the second difference between real and ideal isotherms. At 7rc the isotherm is not perfectly horizontal but slightly tilted, in particular at elevated temperatures. Contaminations are expelled from the liquid condensed phase. Thus, when more and more of the monolayer goes into the liquid condensed phase, contaminations are enriched in the remaining liquid expanded phase. This reduces the two-dimensional 

The phase behavior of monolayers is determined by the molecular structure of the am-phiphile and the conditions of the subphase. Phospholipids, for example, attract each other because of van der Waals interactions between the alkyl chains. The longer the alkyl chains, the more strongly the phospholipids attract each other. Thus, the LE-LC transition pressure will decrease with increasing chain length (at constant temperature). Double bonds in the alkyl chains increase this phase transition pressure. Charges and oriented dipole moments (see Chapter 6) in the headgroups, lead to a repulsion between the phopholipids and increase the pressure at which the transition occurs. Salts in the subphase, screen this repulsion and decrease the transition pressure. 

---