2026-04-17T07:49:27Zhttps://riubu.ubu.es/oai/request

oai:riubu.ubu.es:10259/47042024-11-05T10:58:45Zcom_10259_4393com_10259_5086com_10259_2604col_10259_4394

Orientational Effects and Random Mixing in 1‑Alkanol + Nitrile Mixtures González López, Juan Antonio García de la Fuente, Isaías Cobos, José Carlos . Alonso Tristán, Cristina Sanz, Luis Felipe 1-Alkanol + alkanenitrile or + benzonitrile systems have been investigated by means of the molar excess functionsenthalpies (Hm E ), isobaric heat capacities (Cp,m E ), volumes (Vm E ), and entropiesand using the Flory model and the concentration−concentration structure factor (SCC(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 Hm E values contrast with rather low Vm E values, indicating the existence of strong structural effects. Hm E measurements have been used to evaluate the enthalpy of the hydroxyl−nitrile interactions (ΔHOH−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 SCC(0) formalism show that homocoordination is the dominant trend in the investigated solutions, and are consistent with those obtained from the Flory model. 2018-01-17T09:04:41Z 2018-01-17T09:04:41Z 2018-01-17T09:04:41Z 2015-01 info:eu-repo/semantics/article 0888-5885 http://hdl.handle.net/10259/4704 10.1021/ie504282s eng Industrial & Engineering Chemistry Research. 2015, V. 54, n. 1, p. 550–559 https://doi.org/10.1021/ie504282s info:eu-repo/semantics/openAccess American Chemical Society