Effect of Hydrophobic Chain Structure on Phase Transition and Domain Formation of Hybrid Alcohol Films Adsorbed at the Hexane/Water Interface

Kenta Mitani, Yosuke Imai, Toshiaki Ina, Kiyofumi Nitta, Hajime Tanida, Tomoya Uruga, Hiroki Matsubara, Makoto Aratono, Takanori Takiue

Research output: Contribution to journalArticle

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Abstract

The phase transition and domain formation of the adsorbed film of two kinds of hybrid alcohols (CF3(CF2)m-1(CH2)nOH, FmHnOH), 2-perfluorooctylethanol (F8H2OH) and 2-perfluorohexylhexanol (F6H6OH), as a mixture at the hexane/water interface was investigated by interfacial tensiometry and X-ray reflection. The interfacial tension γ versus total molality m curve of pure F8H2OH has a break point at high concentration, and thus, the mean area per molecule A changes discontinuously at high interfacial pressure π, corresponding to the phase transition between expanded and condensed films. The Fresnel divided reflectivity R/RF versus Qz plots in the expanded state was well-fitted by the domain model for incoherent interference to determine the interfacial coverage, which is the fraction of the interface covered by the condensed phase. This indicates that the expanded film is heterogeneous and consists of a condensed F8H2OH domain, the size of which is larger than the X-ray coherence length (∼5 μm). In the mixed system, the discontinuous change in A at the phase transition point becomes small with increasing the bulk composition of F6H6OH X2 in the mixture, and eventually the A value changes continuously; i.e, the phase transition becomes obscure in X2 ≥0.6. This behavior was linked to an increase in interfacial coverage with X2. Furthermore, the R/RF versus Qz plot was fitted by the domain model for coherent interference, suggesting that the size of the domain is smaller than 5 μm. These results are probably due to the reduction of domain line tension by preferential adsorption of F6H6OH at the F8H2OH domain boundary.

Original languageEnglish
Pages (from-to)12436-12445
Number of pages10
JournalJournal of Physical Chemistry B
Volume119
Issue number38
DOIs
Publication statusPublished - Sep 24 2015

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Phase Transition
Hexanes
Hexane
alcohols
Alcohols
Phase transitions
Water
water
X-Rays
X rays
Surface Tension
Adsorption
Surface tension
plots
interference
Pressure
Molecules
transition points
Chemical analysis
interfacial tension

All Science Journal Classification (ASJC) codes

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

Cite this

Effect of Hydrophobic Chain Structure on Phase Transition and Domain Formation of Hybrid Alcohol Films Adsorbed at the Hexane/Water Interface. / Mitani, Kenta; Imai, Yosuke; Ina, Toshiaki; Nitta, Kiyofumi; Tanida, Hajime; Uruga, Tomoya; Matsubara, Hiroki; Aratono, Makoto; Takiue, Takanori.

In: Journal of Physical Chemistry B, Vol. 119, No. 38, 24.09.2015, p. 12436-12445.

Research output: Contribution to journalArticle

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AU - Tanida, Hajime

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AB - The phase transition and domain formation of the adsorbed film of two kinds of hybrid alcohols (CF3(CF2)m-1(CH2)nOH, FmHnOH), 2-perfluorooctylethanol (F8H2OH) and 2-perfluorohexylhexanol (F6H6OH), as a mixture at the hexane/water interface was investigated by interfacial tensiometry and X-ray reflection. The interfacial tension γ versus total molality m curve of pure F8H2OH has a break point at high concentration, and thus, the mean area per molecule A changes discontinuously at high interfacial pressure π, corresponding to the phase transition between expanded and condensed films. The Fresnel divided reflectivity R/RF versus Qz plots in the expanded state was well-fitted by the domain model for incoherent interference to determine the interfacial coverage, which is the fraction of the interface covered by the condensed phase. This indicates that the expanded film is heterogeneous and consists of a condensed F8H2OH domain, the size of which is larger than the X-ray coherence length (∼5 μm). In the mixed system, the discontinuous change in A at the phase transition point becomes small with increasing the bulk composition of F6H6OH X2 in the mixture, and eventually the A value changes continuously; i.e, the phase transition becomes obscure in X2 ≥0.6. This behavior was linked to an increase in interfacial coverage with X2. Furthermore, the R/RF versus Qz plot was fitted by the domain model for coherent interference, suggesting that the size of the domain is smaller than 5 μm. These results are probably due to the reduction of domain line tension by preferential adsorption of F6H6OH at the F8H2OH domain boundary.

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