58 research outputs found
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 (Hm E ), isobaric heat capacities (Cp,m
E ), volumes (Vm E ), and entropiesand 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
Volumetric Properties of the Mixture 2,5,8,11-Tetraoxadodecane C8H18O4 + C10H22 Decane (LB0725, VMSD1212)
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