Dielectric and refractive index measurements for the systems 1-pentanol + 2,5,8,11,14-pentaoxapentadecane, or for 2,5,8,11,14-pentaoxapentadecane + octane at (293.15-303.15) K

Abstract

Relative permittivities, $\varepsilon_{r}$, and refractive indices, $n_{D}$, have been measured at (293.15-303.15) K, for the mixtures 1-pentanol + 2,5,8,11,14-pentaoxapentadecane (TEGDME) or TEGDME + octane. These data have been used, together with density measurements available in the literature, to calculate the correlation factors, $g_{K}$, according to the Kirkwood-Fr\"ohlich equations. The curves of the deviations of from the ideal behaviour, $\Delta\varepsilon_{r}$, of the 1-pentanol + TEGDME system are shifted to high mole fractions of the alcohol, and show a rather large minimum. The shape of the $\Delta\varepsilon_{r}$ curves of methanol + TEGDME or + polyethylene glycol dimethyl ether 250 (PEG-250) mixtures is similar. This reveals that polyethers can break the alcohol self-association even at high alkanol concentrations. The higher $\Delta\varepsilon_{r}$ values of the methanol solutions are ascribed to large self-association of this alcohol. The $\Delta\varepsilon_{r}$ curves of the 1-pentanol + dibutyl ether (DBE) system are nearly symmetrical, and the $\Delta\varepsilon_{r}$ values are higher than those of the corresponding TEGDME mixture. This indicates that effects related to the alcohol self-association are much more relevant in the DBE system. These findings are supported by $g_{K}$ and molar polarization data. Values of molar refraction of 1-pentanol systems reveal that dispersion forces become more important in the sequence: octane < DBE < TEGDME. Such forces are also more relevant in the 1-pentanol + TEGDME system than in the methanol + TEGDME solution. The comparison of $\varepsilon_{r}$ and $g_{K}$ data for TEGDME or DBE + octane mixtures shows than the polyether is a more structured liquid.