Abstract
Abstract We aim to explain certain cooperative phenomena displayed by monolayers at the air/water or oil/water interfaces, consisting of molecules with polar headgroups immersed in water attached to hydrocarbon chains in the other medium. In addition to vapour-liquid transitions, the cooperative phenomena are continuous liquid condensed-liquid expanded transitions and, for bipolar molecules, extensive regions of negative thermal expansion in the surface pressure/area plane. A two-dimensional lattice gas model is postulated, in which each molecule can exist in either an upright monomer state with two distinct orientations or a laterally extended (dimer) state. A two-site cluster variation (Bethe) statistical approximation is used with nearest-neighbour interactions and a long-range interaction. Patterns of isotherms corresponding to four quite different types of monolayer behaviour are calculated.
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