Balancing Hydrophobic and Hydrophilic Forces at the Water/Vapor Interface: Surface Structure of Soluble Alcohol Monolayers†

Surface tension and surface specific vibrational techniques were used to study the structure of soluble alcohol monolayers adsorbed to the air/water interface. Surface tension measurements were used to determine terminal monolayer coverages of different alcohol isomers whereas the surface specific vibrational sum frequency generation probed the interfacial structure and organization. The alcohols studied ranged from heptanols to dodecanols with constitutional isomers having the −OH group in the 1, 2, 3, and 5 positions. Not surprisingly, linear isomers form tightly packed monolayers having molecular areas of ∼20 A2/molecule, a value close to the calculated cross section of linear, all-trans alkyl chains. The vibrational spectra of these monolayers consistently show features associated with monolayers having very little conformational disorder. For the 2- and 3-position isomers, surface tension measurements show surface coverages that were only half those of the linear isomers. Quantitative analyses of the...

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