Molecular orientation and multilayer formation in the adsorbed film of 1H,1H,10H,10H-perfluorodecane-1,10-diol at the hexane/water interface; Pressure effect on the adsorption of fluoroalkane-diol

Takanori Takiue, Tsubasa Fukuda, Daiki Murakami, Hiroyasu Sakamoto, Hiroki Matsubara, Makoto Aratono

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Abstract

The adsorption of 1H,1H,10H,10H-perfluorodecane-1,10-diol (FC 10diol) at the hexane solution/water interface was investigated by the measurement of interfacial tension γ as a function of pressure p and concentration m1 and the thermodynamic data analysis. The results obtained were compared with those of 1H,1H,2H,2Hperfluorodecanol (TFC10OH) in order to clarify the effect of molecular orientation on the structure and property of the adsorbed film from the viewpoint of volume change of adsorption. The interfacial pressure π versus mean area per adsorbed molecule A curve revealed two types of phase transitions among expanded, parallel condensed, and multilayer states. The A value in the condensed state and the transition pressure between the expanded and condensed states were larger for FC 10diol than for TFC10OH, which manifests the different molecular orientation that the dispersion interaction between hydrophobic chains is weaker in the parallel orientation of FC10diol than in the perpendicular orientation of TFC10OH. The partial molar volume of FC10diol in the condensed state ν1 H.C is slightly larger than that of TFC10OH, although the partial molar volume in the hexane solution is much smaller for FC10diol than for TFC10OH. This supports the view that the fluorocarbon chains of FC10diol remain in their contact with hexane even in the condensed film because of the parallel molecular orientation. The partial molar volume in the multilayer ν1 H,M was very close to the molar volume of solid FC10diol ν1S and smaller than that of ν1H.C at the condensed-multilayer phase transition, and increased gradually with molecular piling. This substantiates that FC10diol molecules are densely packed in a first few layers just above the phase transition and a little loosely packed in the upper layers of the multilayer with increasing molecular piling. Furthermore, the volume change associated with adsorption from the solid FC10diol Δν(S) evaluated from the γ versus p curve under the existence of solid deposit was positive and showed a minimum against concentration for the multilayer state. This is primarily due to the minimum in interfacial density at the solubility limit Γ1H,S and thus due to the minimum in ν1H,M.

Original languageEnglish
Pages (from-to)14667-14673
Number of pages7
JournalJournal of Physical Chemistry B
Volume113
Issue number44
DOIs
Publication statusPublished - May 11 2009

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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