화학공학소재연구정보센터
Industrial & Engineering Chemistry Research, Vol.54, No.1, 550-559, 2015
Orientational Effects and Random Mixing in 1-Alkanol + Nitrile Mixtures
1-Alkanol + alkanenitrile or + benzonitrile systems have been investigated by means of the molar excess functionsenthalpies (H-m(E)), isobaric heat capacities (C-p,m(E)), volumes (V-m(E)), and entropiesand using the Flory model and the concentrationconcentration structure factor (S-CC(0)) formalism. From the analysis of the experimental data available in the literature, it is concluded that interactions are mainly of dipolar type. In addition, large H-m(E) values contrast with rather low V-m(E) values, indicating the existence of strong structural effects. H-m(E) measurements have been used to evaluate the enthalpy of the hydroxylnitrile interactions (Delta HOH-CN). They are stronger in methanol systems and become weaker when the alcohol size increases. In solutions with a given short chain 1-alkanol (up to 1-butanol), the replacement of ethanenitrile by butanenitrile weakens the mentioned interactions. Application of the Flory model shows that orientational effects exist in methanol or 1-nonanol, or 1-decanol + ethanenitrile mixtures. In the former solution, this is due to the existence of interactions between unlike molecules. For mixtures including 1-nonanol or 1-decanol, the systems at 298.15 K are close to their UCST (upper critical solution temperature), and interactions between like molecules are dominant. Orientational effects also are encountered in methanol or ethanol + butanenitrile mixtures because self-association of the alcohol plays a more important role. Aromaticity effect seems to enhance orientational effects. For the remainder of the systems under consideration, the random mixing hypothesis is attained to a rather large extent. Results from the application of the S-CC(0) formalism show that homocoordination is the dominant trend in the investigated solutions, and are consistent with those obtained from the Flory model.