Thermodynamics of organic mixtures containing amines: V. Systems with pyridines

Binary mixtures containing pyridine (PY), or 2-methylpyridine (2MPY) or 3-methylpyridine (3MPY) or 4-methylpyridine (4MPY) and an organic solvent as benzene, toluene, alkane, or 1-alkanol are investigated in the framework of DISQUAC. The corresponding interaction parameters are reported. The model describes accurately a whole set of thermodynamic properties: vapor–liquid equilibria (VLE), liquid–liquid equilibria (LLE), solid–liquid equilibria (SLE), molar excess Gibbs energies (GE), molar excess enthalpies, (HE), molar excess heat capacities at constant pressure (CPE) and the concentration–concentration structure factor (SCC(0)). It is remarkable that DISQUAC correctly predicts the W-shaped curve of the CPE of the pyridine + n-hexadecane system. The model can be applied successfully to mixtures with strong positive or negative deviations from the Raoult's law. DISQUAC improves the theoretical results from UNIFAC (Dortmund version). The replacement of pyridine by a methylpyridine leads to a weakening of the amine–amine interactions, ascribed to the steric effect caused by the methyl group attached to the aromatic ring. This explains that for a given solvent (alkane, 1-alkanol) HE(pyridine) > HE(methylpyridine).