Thermodynamics of mixtures with strongly negative deviations from Raoult's law. XVII. Permittivities and refractive indices for alkan-1-ol + N,N-diethylethanamine systems at (293.15-303.15) K. Application of the Kirkwood-Fr\"ohlich model

TL;DR

This study measures permittivities and refractive indices of alkan-1-ol + amine mixtures at various temperatures, analyzing their dielectric behavior and interactions using the Kirkwood-Fröhlich model, revealing how molecular structure influences mixture properties.

Contribution

It provides new dielectric data for alkan-1-ol + amine systems and applies the Kirkwood-Fröhlich model to interpret molecular interactions and structural effects.

Findings

Positive excess permittivities in methanol systems at high alcohol concentrations

Negative excess permittivities in other mixtures across all compositions

A correlation between molecular structure and dielectric behavior

Abstract

Relative permittivities at 1 MHz, $\varepsilon_{\text{r}}$, at 0.1 MPa and (293.15-303.15) K and refractive indices, $n_{\text{D}}$, at similar conditions have been measured for the alkan-1-ol (methanol, propan-1-ol, butan-1-ol, pentan-1-ol or heptan-1-ol) + N,N-diethylethanamine (TEA) systems. Positive values of the excess permittivities, $\varepsilon_{\text{r}}^{\text{E}}$ , are encountered for the methanol system at high alcohol concentrations. The remaining mixtures are characterized by negative $\varepsilon_{\text{r}}^{\text{E}}$ values over the whole composition range. At ${\phi}_1$ (volume fraction) = 0.5, $\varepsilon_{\text{r}}^{\text{E}}$ changes in the order: methanol > propan-1-ol > butan-1-ol < pentan-1-ol < heptan-1-ol. Mixtures formed by alkan-1-ol and an isomeric amine, hexan-1-amine (HxA) or N-propylpropan-1-amine (DPA) or cyclohexylamine, behave similarly. This has been explained in terms of the lower and weaker self-association of longer alkan-1-ols. From the permittivity data, it is shown that: (i) (alkan-1-ol)-TEA interactions contribute positively to $\varepsilon_{\text{r}}^{\text{E}}$; (ii) TEA is an effective breaker of the network of the alkan-1-ols; (iii) structural effects, which are very important for the volumetric and calorimetric data of alkan-1-ol + TEA systems, are also relevant when evaluating dielectric data. This is confirmed by the comparison of $\varepsilon_{\text{r}}^{\text{E}}$ measurements for alkan-1-ol + aliphatic amine mixtures; (iv) the aromaticity effect (i.e., the replacement of TEA by pyridine in systems with a given alkan-1-ol) leads to an increase of the mixture polarization. Calculations conducted in the framework of the Kirkwood-Fr\"ohlich model are consistent with the previous statements.