Effect of ω-hydrogenation on the adsorption of fluorononanols at the hexane/water interface

Miscibility in the adsorbed film of fluorononanols

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Abstract

The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its ω-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 ω-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 ω-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 FDFC 9OH. 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.

Original languageEnglish
Pages (from-to)22366-22370
Number of pages5
JournalJournal of Physical Chemistry B
Volume109
Issue number47
DOIs
Publication statusPublished - Dec 1 2005

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Surface Tension
Hydrogenation
Hexanes
Hexane
Adsorption
hydrogenation
solubility
Solubility
Atmospheric Pressure
adsorption
Water
Hydrophobic and Hydrophilic Interactions
water
Molecules
Surface tension
interfacial tension
Alcohols
dipoles
molecules
Gibbs free energy

All Science Journal Classification (ASJC) codes

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

Cite this

@article{f02ebfbfd7c64c5098c3d231b746a85b,
title = "Effect of ω-hydrogenation on the adsorption of fluorononanols at the hexane/water interface: Miscibility in the adsorbed film of fluorononanols",
abstract = "The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its ω-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 ω-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 ω-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 FDFC 9OH. 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.",
author = "Daiki Murakami and Youichi Takata and Hiroki Matsubara and Makoto Aratono and Takanori Takiue",
year = "2005",
month = "12",
day = "1",
doi = "10.1021/jp0581227",
language = "English",
volume = "109",
pages = "22366--22370",
journal = "Journal of Physical Chemistry B Materials",
issn = "1520-6106",
publisher = "American Chemical Society",
number = "47",

}

TY - JOUR

T1 - Effect of ω-hydrogenation on the adsorption of fluorononanols at the hexane/water interface

T2 - Miscibility in the adsorbed film of fluorononanols

AU - Murakami, Daiki

AU - Takata, Youichi

AU - Matsubara, Hiroki

AU - Aratono, Makoto

AU - Takiue, Takanori

PY - 2005/12/1

Y1 - 2005/12/1

N2 - The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its ω-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 ω-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 ω-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 FDFC 9OH. 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.

AB - The interfacial tension of the hexane solution of 1H,1H-perfluorononanol (FDFC9OH) and its ω-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 ω-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 ω-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 FDFC 9OH. 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.

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U2 - 10.1021/jp0581227

DO - 10.1021/jp0581227

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JF - Journal of Physical Chemistry B Materials

SN - 1520-6106

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