Influence of temperature and alkyl chain length on phase behavior in Langmuir monolayers of some oxyethylenated nonionic surfactants

We study the surface phase behavior in Langmuir monolayers of a series of nonionic surfactants of the general formula Cn  E1 with n=14n=14, 16, and 18 by film balance and Brewster angle microscopy (BAM) over a wide range of temperatures. A cusp point followed by a pronounced plateau region in the pressure–area (π–Aπ–A) isotherms indicates a first-order phase transition in the coexisting state between a lower density liquid expanded (LE) phase and a higher density liquid condensed (LC) phase at the air–water interface. The formation of bright two-dimensional (2D) LC domains in a dark background visualized by BAM further confirms this observation. In addition to the cusp point at the onset of the LE–LC coexistence state, another cusp point followed by a small plateau is observed for the C14E1 and C18E1 monolayers, indicating a second phase transition between two condensed phases of different compressibility and tilt orientation of the molecules. This unusual two-step phase transition is explained by the Ostwald step rule. The C16E1 and C18E1 monolayers show a kink in their respective isotherms, after which the surface pressure increases steeply with only a little decrease in the molecular area, suggesting that the molecules undergo a transition from a tilted to an almost vertical orientation with respect to the water surface. The thermodynamic parameters for the condensation of the molecules in the LE–LC coexistence state were calculated by employing the 2D Clapeyron equation. The temperature coefficient of the critical surface pressure dπc/dTdπc/dT values shows a decreasing trend from C14E1 to C18E1, suggesting that the condensation process becomes less and less prone to thermal perturbation as the chain length increases. For all the amphiphiles, the ΔH values are found to be negative, suggesting an exothermic nature of condensation. The negative ΔS   values obtained from the relation ΔH/TΔH/T probably come from the restriction on the rotational and translational motion of the molecules constrained in a confined area in the LE–LC transition region.