Evidence for Ion Association at the Gas-Liquid Interface of the Mixture of 1-Butyl-3-methylimidazolium Hexafluorophosphate and Benzonitrile: A Sum Frequency Generation Spectroscopy and Surface Tension Study.

The gas-liquid interface for the mixtures of [BMIM][PF6] and benzonitrile is studied by sum frequency generation (SFG) spectroscopy and surface tension measurements as an important solute to reduce the viscosity of ionic liquids. Solvation of ionic compounds in bulk solvent is not necessarily the same as that at the surface due to the lower dielectric medium at the air/liquid interface. The results from the temperature-dependent SFG spectroscopy and surface tension study suggest that the ionic liquid in a benzonitrile solvent is associated as ion pairs at the surface rather than as dissociated─solvated─ions in the bulk solution. The influence of ionic liquids on the surface structure of benzonitrile is investigated from 0 to 1.0 mole fraction of benzonitrile. The CH stretching mode of vibration of benzonitrile in the SFG spectrum begins from a 0.2 mole fraction (x) of benzonitrile, and the intensity of the peak constantly increases on increasing the concentration of benzonitrile. However, the addition of benzonitrile does not result in extra peaks or shifting of the peak frequency to the spectra of [BMIM][PF6]. The surface tension measurements further support the presence of benzonitrile at the gas-liquid interface. The surface tension data of the mixture smoothly decrease as the benzonitrile concentration increases. The apparent tilt angle of the terminal methyl group of the cation of [BMIM][PF6] is calculated from SFG polarization spectra and shows an apparent lowering with the addition of benzonitrile. The effect of temperature on the surface structure of the binary mixture is also reported at four different temperatures between -15 and 40 °C for both the SFG spectroscopy and surface tension study. Benzonitrile shows different behavior in the mixture at higher temperatures than pure benzonitrile, as observed in the SFG spectra. In contrast, it does not show any CN peak in the mixture below 0.9 mole fraction. The temperature dependence of the interfacial tension is used to evaluate thermodynamic functions such as surface entropy and surface enthalpy. Both were found to be lowered with the increasing concentration of benzonitrile. Both spectroscopic and thermodynamic analyses indicate that the ionic liquid is highly associated as ion pairs and the benzonitrile is more ordered at the surface at concentration <0.4×.