Thermodynamics of mixtures containing a very strongly polar compound. 12. Systems with nitrobenzene or 1-nitroalkane and hydrocarbons or 1-alkanols

Abstract

Mixtures involving nitrobenzene and hydrocarbons, or 1-alkanols and 1-nitroalkane, or nitrobenzene have been investigated on the basis of a whole set of thermophysical properties available in the literature. The properties considered are: excess molar functions (enthalpies, entropies, isobaric heat capacities, and volumes), vapour-liquid and liquid-liquid equilibria, permittivities or dynamic viscosities. In addition, the mixtures have been studied by means of the application of the DISQUAC, ERAS, and UNIFAC models, and using the formalism of the concentration-concentration structure factor. The corresponding interaction parameters in the framework of the DISQUAC and ERAS models are reported. In alkane mixtures, dipolar interactions between 1-nitroalkane molecules are weakened when the size of the polar compound increases, accordingly with the relative variation of their effective dipolar moment. Dipolar interactions are stronger in nitrobenzene solutions than in those containing the smaller 1-nitropropane, although both nitroalkanes have very similar effective dipole moment (aromaticity effect). Systems with 1-alkanols are characterized by dipolar interactions between like molecules which sharply increases when the alkanol size increases. Simultaneously, interactions between unlike molecules become weaker, as the OH group is then more sterically hindered. Interactions between unlike molecules are stronger in systems with nitromethane than in nitrobenzene solutions. The replacement of nitromethane by nitroethane in systems with a given 1-alkanol leads to strengthen those effects related with the alcohol self-association. Permittivity data and results on Kirkwood’s correlation factors show that the addition of 1-alkanol to a nitroalkane leads to cooperative effects, which increase the dipolar polarization of the solution, in such way that the destruction of the existing structure in pure liquids is partially counterbalanced. This effect is less important when longer 1-alkanols are involved.