Excess Thermodynamic Properties in Mixtures of a Representative Room-Temperature Ionic Liquid and Acetonitrile

The nature of the interactions between a representative room-temperature ionic liquid, namely 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM][BF₄]) and a common organic solvent, acetonitrile (CH₃CN) has been investigated by means of Brillouin light scattering, over the whole concentration range and in the temperature range from −20 to 45 °C. Negative deviations from the ideal behavior of both molar volumes and adiabatic compressibility have been observed. This result has been interpreted within the framework of a well-established theoretical model, namely a nonadditive hard-sphere mixture. Despite that similar findings were rationalized in terms of enhanced interactions between molecules, a more detailed analysis of excess thermodynamic functions indicates that they are mainly due to excluded volume effects and that the differences in local intermolecular interactions act as higher order contributions:  we have found that this can be a general feature of liquid mixtures. On this basis we present a reconsideration for excess thermodynamic data and for their role in providing direct information on intermolecular interactions.