Thermodynamics of mixtures with strongly negative deviations from Raoult's law. XV. Permittivities and refractive indices for 1-alkanol + n-hexylamine systems at (293.15-303.15) K. Application of the Kirkwood-Fröhlich model

Abstract

Relative permittivities at 1 MHz, $\varepsilon_{\text{r}}$, and refractive indices at the sodium D-line, $n_{\text{D}}$, are reported at 0.1 MPa and at (293.15-303.15) K for the binary systems 1-alkanol + n-hexylamine (HxA). Also, their corresponding excess functions are calculated and correlated. Positive values of the excess permittivities, $\varepsilon_{\text{r}}^{\text{E}}$, are encountered for the methanol system, whereas the remaining mixtures show negative values. This reveals that interactions between unlike molecules contribute positively to $\varepsilon_{\text{r}}^{\text{E}}$. This contribution is dominant for the methanol mixture, while those arising from the breaking of interactions between like molecules are prevalent for the remaining mixtures. At ${\phi}_1$ (volume fraction) = 0.5, $\varepsilon_{\text{r}}^{\text{E}}$ changes in the order: methanol > 1-propanol > 1-butanol > 1-pentanol < 1-heptanol. Similar variation with the chain length of the 1-alkanol is observed for mixtures such as 1-alkanol + heptane, or + cyclohexylamine, and can be explained in terms of the lower and weaker self-association of longer 1-alkanols. The effect of the replacement of HxA by cyclohexylamine, or by aniline, is also shown. Calculations on molar refractions indicate that dispersive interactions in the systems under study increase with the length of the 1-alkanol. The mixtures are studied by means of the application of the Kirkwood-Fr\"ohlich model, and the Kirkwood correlation factors, including the corresponding excess values, are reported.