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 1alkanol 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.

Densities and Viscosities for the Binary Mixtures of n-Nonane with 1-Heptanol, 1-Octanol, 1-Nonanol, and 1-Decanol

“…In addition, the corresponding derived properties including excess molar volumes and viscosity deviations are beneficial to understand the molecular interactions of the substances. Consequently, the investigation of the viscosity and density of alkane/alcohol mixtures has attracted great interest during the last few years. , …”

Liquid–Liquid Equilibrium Data Correlation Using NRTL Model for Different Types of Binary Systems: Upper Critical Solution Temperature, Lower Critical Solution Temperature, and Closed Miscibility Loops

“…Maia et al [22] also determined LLE data for some aqueous binary systems including ionic liquids and they correlated these data using NRTL and e-NRTL equations with quadratic temperature dependence, but again all these systems belong to UCST type. González et al [23] provided the coexistence curves of LLE UCST type for mixtures containing aromatic nitriles and used DISQUAC group contribution model to calculate these data. The group contribution equation of state (GC-EoS) has been used to represent the LLE phase behaviour of UCST binary mixtures containing benzene + ionic liquid [24].…”