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][BF(4)]) and a common organic solvent, acetonitrile (CH(3)CN) has been investigated by means of Brillouin light scattering, over the whole concentration range and in the temperature range from -20 to 45 degrees 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.
Istituto per i Processi Chimico-Fisici del CNR, Salita Sperone, Contrada Papardo, 98158 Messina, Italy.
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