Murakami Daiki, Takata Youichi, Matsubara Hiroki, Aratono Makoto, Takiue Takanori
Department of Chemistry and Physics of Condensed Matter, Graduate School of Science, Kyushu University, Fukuoka 812-8581, Japan.
J Phys Chem B. 2005 Dec 1;109(47):22366-70. doi: 10.1021/jp0581227.
The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC9OH), against water was measured as a function of the total molality and composition of the mixture at 298.15 K under atmospheric pressure. The existence of omega-dipole in HDFC9OH makes the interfacial density larger in the gaseous and expanded states and smaller in the condensed state compared to FDFC9OH. The phase diagram of adsorption (PDA) was constructed, and the excess Gibbs energy of adsorption (gH,E) was calculated at each state in order to discuss quantitatively the miscibility of FDFC9OH and HDFC9OH in the adsorbed film. We found that the gH,E value is negative in the gaseous state, while it is positive and increases with decreasing interfacial tension in the condensed state. These results are explained mainly by the balance of two effects induced by mixing of two alcohols: (1) Reduction of repulsive interaction between omega-dipoles aligning parallel in the adsorbed film because of the increase in mean distance between HDFC9OH molecules. (2) The loss of effective dispersion interaction between hydrophobic chains due to the fact that the oblique orientation of HDFC9OH molecules at the interface is mixed with the perpendicular one of FDFC9OH. We concluded that the factor (2) is negligible compared to the factor (1) in the gaseous and expanded films and exceeds the factor (1) in the condensed film, in which molecules are closely packed.
