Aggregation behavior and electrical properties of amphiphilic pyrrole-tailed ionic liquids in water, from the viewpoint of dielectric relaxation spectroscopy

Abstract

The self-aggregation behavior of amphiphilic pyrrole-tailed imidazolium ionic liquids (Py(CH₂)₁₂mim⁺Br⁻: Py = pyrrole, mim = methylimidazolium) in water is investigated by dielectric spectroscopy from 40 Hz to 110 MHz. Dielectric determination shows that the critical micelle concentration (CMC) is 8.5 mM, which is lower than that for traditional ionic surfactants. The thermodynamic parameter of the micellization, the Gibbs free energy ΔG, was calculated for Py(CH₂)₁₂mim⁺Br⁻ and compared to those of the corresponding C(n)mim⁺Br⁻ (n = 12, 14). It was found that the main driven forces of the Py(CH₂)₁₂mim⁺Br⁻ aggregation were hydrophobic interaction and π-π interactions among the adjacent Py groups. Further, the structure of aggregation was speculated theoretically that Py groups partially insert into the alkyl chains and the staggered arrangement in micelles is formed. When the concentration of Py(CH₂)₁₂mim⁺Br⁻ is higher than CMC, two remarkable relaxations which originated from diffusion of counterions and interfacial polarization between the micelles and solution, were observed at about 1.3 MHz and 55 MHz. The relaxation parameters representing the real properties of the whole system were obtained by fitting the experimental data with Cole-Cole equation. A dielectric model characterizing the structure and electrical properties of spherical micelles was proposed by which the conductivity, permittivity and the volume fraction of micelles as well as electrical properties of solution were calculated from the relaxation parameters. An intriguingly high permittivity of about 150 for the micelle was found to be a direct consequence of the strong orientational order of water molecules inside the core of micelle, and essentially is attributed to the special structure of the micelle. Furthermore, the calculation of the interfacial electrokinetic parameters of the micelles, i.e., the surface conductivity, surface charge density and zeta potential, were also achieved based on the relaxation parameters and phase parameters from higher frequency relaxation. On the basis of the results obtained, the aggregation behaviours and interfacial electrokinetic properties of the special micelles are discussed.