Thermodynamics of mixtures with strongly negative deviations from Raoult's law. XVI. Permittivities and refractive indices for 1-alkanol + di-n-propylamine systems at (293.15-303.15) K. Application of the Kirkwood-Fr\"ohlich model

TL;DR

This study investigates the permittivities and refractive indices of 1-alkanol + di-n-propylamine mixtures, analyzing their excess functions and applying the Kirkwood-Fr"ohlich model to understand molecular interactions across various temperatures.

Contribution

It provides new experimental data and applies the Kirkwood-Fr"ohlich model to analyze molecular interactions in 1-alkanol + DPA mixtures, highlighting the effects of chain length and composition.

Findings

Positive excess permittivities in methanol mixture.

Stronger interactions in DPA solutions compared to HxA.

Variation of excess permittivities with chain length and composition.

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 + di-n-propylamine (DPA). Their corresponding excess functions are calculated and correlated. For the methanol mixture, positive values of the excess permittivities, $\varepsilon_{\text{r}}^{\text{E}}$, are found. Except at high concentrations of the alcohol in the 1-propanol mixture, the remaining systems show negative values of this property. This fact reveals that the creation of (1-alkanol)-DPA interactions contributes positively to $\varepsilon_{\text{r}}^{\text{E}}$, being this contribution dominant in the methanol mixture. At ${\phi}_1$ (volume fraction) = 0.5, $\varepsilon_{\text{r}}^{\text{E}}$ changes in the sequence: methanol > 1-propanol > 1-butanol > 1-pentanol < 1-heptanol. An analogous variation with the chain length of the 1-alkanol is observed in mixtures such as 1-alkanol + heptane, + cyclohexylamine or + n-hexylamine (HxA). Moreover, for a given 1-alkanol, $\varepsilon_{\text{r}}^{\text{E}}$ is larger for DPA than for HxA mixtures, suggesting that in DPA solutions multimers with parallel alignment of the molecular dipoles are favoured and cyclic multimers are disfavoured when compared to HxA mixtures. The ${(\partial{\varepsilon_{\text{r}}}/\partial T)}_p$ values are higher for the mixtures than for pure 1-alkanols, because (1-alkanol)-DPA interactions are stronger than those between 1-alkanol molecules. Molar refractions indicate that dispersive interactions in DPA systems increase with the chain length of the 1-alkanol and are practically identical to those in HxA solutions. The considered mixtures are treated by means of the Kirkwood-Fr\"ohlich model, reporting the Kirkwood correlation factors and their excess values.