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

Takanori Takiue, Daiki Murakami, Takafumi Tamura, Hiroyasu Sakamoto, Hiroki Matsubara, Makoto Aratono

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Abstract

The interfacial tensions (γ) of the hexane solutions of 1H, 1H-perfluorononanol (FDFC9OH) and its ω-hydrogenated analogue 1H, 1H, 9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of ω-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (π) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given π in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1 -H - s1 O) and energy (u1 -H - u1 O) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u 1 -H - u1 O value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for ω-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower u1 -H value for HDFC9OH than for FDFC9OH. (2) The contact of ω-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1 O value of HDFC9OH is expected to be larger than that of FDFC9OH.

Original languageEnglish
Pages (from-to)14154-14159
Number of pages6
JournalJournal of Physical Chemistry B
Volume109
Issue number29
DOIs
Publication statusPublished - Jul 28 2005

Fingerprint

Hydrogenation
Hexanes
Hexane
Thermal effects
Adsorption
hydrogenation
temperature effects
Entropy
dipoles
Molecules
Temperature
adsorption
Water
entropy
water
molecules
Atmospheric Pressure
Surface Tension
Phase Transition
transition points

All Science Journal Classification (ASJC) codes

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

Cite this

@article{5d33c4761ad84554a7e7934a664b0b1c,
title = "Effect of ω-hydrogenation on the adsorption of fluorononanols at the hexane/water interface: Temperature effect on the adsorption of fluorononanols",
abstract = "The interfacial tensions (γ) of the hexane solutions of 1H, 1H-perfluorononanol (FDFC9OH) and its ω-hydrogenated analogue 1H, 1H, 9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of ω-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (π) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given π in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1 -H - s1 O) and energy (u1 -H - u1 O) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u 1 -H - u1 O value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for ω-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower u1 -H value for HDFC9OH than for FDFC9OH. (2) The contact of ω-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1 O value of HDFC9OH is expected to be larger than that of FDFC9OH.",
author = "Takanori Takiue and Daiki Murakami and Takafumi Tamura and Hiroyasu Sakamoto and Hiroki Matsubara and Makoto Aratono",
year = "2005",
month = "7",
day = "28",
doi = "10.1021/jp058118v",
language = "English",
volume = "109",
pages = "14154--14159",
journal = "Journal of Physical Chemistry B Materials",
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TY - JOUR

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

T2 - Temperature effect on the adsorption of fluorononanols

AU - Takiue, Takanori

AU - Murakami, Daiki

AU - Tamura, Takafumi

AU - Sakamoto, Hiroyasu

AU - Matsubara, Hiroki

AU - Aratono, Makoto

PY - 2005/7/28

Y1 - 2005/7/28

N2 - The interfacial tensions (γ) of the hexane solutions of 1H, 1H-perfluorononanol (FDFC9OH) and its ω-hydrogenated analogue 1H, 1H, 9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of ω-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (π) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given π in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1 -H - s1 O) and energy (u1 -H - u1 O) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u 1 -H - u1 O value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for ω-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower u1 -H value for HDFC9OH than for FDFC9OH. (2) The contact of ω-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1 O value of HDFC9OH is expected to be larger than that of FDFC9OH.

AB - The interfacial tensions (γ) of the hexane solutions of 1H, 1H-perfluorononanol (FDFC9OH) and its ω-hydrogenated analogue 1H, 1H, 9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of ω-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (π) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given π in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1 -H - s1 O) and energy (u1 -H - u1 O) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u 1 -H - u1 O value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for ω-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower u1 -H value for HDFC9OH than for FDFC9OH. (2) The contact of ω-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1 O value of HDFC9OH is expected to be larger than that of FDFC9OH.

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