Self-assembly in surfactant-based liquid mixtures: octanoic acid/Bis(2-ethylhexyl)amine systems.

The physico-chemical properties of Bis(2-ethylhexyl)amine (BEEA) plus octanoic acid (OA) mixtures have been investigated by IR, SAXS, WAXS, viscosimetry, and AC complex impedance spectroscopy in the whole composition range. Mainly driven by proton transfer from the acidic OA to the basic BEEA, the formation of stoichiometrically well-defined adducts takes place in the mixtures. This causes the slowing down of molecular dynamics and the increase in charge carrier number density. Interestingly, while the pure components possess no significant conductivity (about 10(-12) S cm(-1) at 25 °C), their mixtures show a composition-dependent enhanced conductivity (up to about 10(-5) S cm(-1)), i.e., more than seven orders of magnitude higher than that of the pure components. The comparison of the composition dependence of viscosity, direct-current conductivity, and static permittivity indicates the concurrence of contributions of different adducts and that the dynamics controlling molecular reorientation and momentum and charge transfer, even if ultimately related to the proton transfer from OA to BEEA, are different. The results can be used not only to design novel materials for application purposes, but also to shed more light on the principles regulating molecular self-assembly in surfactant-based liquid systems.

[1]  E. Caponetti,et al.  FT-IR and dielectric study of water/AOT liquid crystals , 2000 .

[2]  P. H. Kasai,et al.  Dimerization of Carboxylic Acids and Salts: An IR Study in Perfluoropolyether Media , 1997 .

[3]  C. King,et al.  Extraction of carboxylic acids with amine extractants. 2. Chemical interactions and interpretation of data , 1990 .

[4]  Shenhao Chen,et al.  Investigations of Triphenyl Phosphate and Bis-(2-ethylhexyl) Phosphate Self-Assembled Films on Iron Surface Using Electrochemical Methods, Fourier Transform Infrared Spectroscopy, and Molecular Simulations , 2007 .

[5]  R. Heacock,et al.  THE INFRARED SPECTRA OF SECONDARY AMINES AND THEIR SALTS , 1956 .

[6]  P. Calandra,et al.  Fast proton conduction in hydrogen bonded microheterogeneous systems: bis(2-ethylhexyl)phosphoric acid/N-methyl formamide liquid mixtures. , 2010, Journal of colloid and interface science.

[7]  Y. Arai,et al.  Fourier Transform Infrared Study on Hydrogen Bonding Species of Carboxylic Acids in Supercritical Carbon Dioxide with Ethanol , 1999 .

[8]  Friedrich Kremer,et al.  Broadband dielectric spectroscopy , 2003 .

[9]  V. T. Liveri,et al.  Physicochemical Properties of Copper(II) Bis(2-ethylhexyl) Sulfosuccinate Reversed Micelles , 1998 .

[10]  A. Mele,et al.  Self-assembly in surfactant-based liquid mixtures: bis(2-ethylhexyl)phosphoric acid/bis(2-ethylhexyl)amine systems. , 2010, Journal of colloid and interface science.

[11]  D. DeTar,et al.  Carboxylic acid-amine equilibria in nonaqueous solvents , 1970 .

[12]  Thomas O. Mason,et al.  Evaluating Dielectric Impedance Spectra using Effective Media Theories , 2000 .

[13]  R. Weiss,et al.  Amphotropic ionic liquid crystals with low order parameters , 2004 .

[14]  S. Greenbaum,et al.  Anhydrous proton-conducting polymeric electrolytes for fuel cells. , 2006, The journal of physical chemistry. B.

[15]  I. Honma,et al.  Anhydrous protonic conductivity of a self-assembled acid-base composite material , 2004 .