Thermodynamics of amide + amine mixtures. 3. Relative permittivities of N , N -dimethylformamide + N -propylpropan-1-amine, + N -butylbutan-1-amine, + butan-1-amine, or + hexan-1-amine systems at several temperatures

Abstract

Relative permittivities at 1 MHz, ε_r, and at (293.15-303.15) K, are reported for the binary systems N,N-dimethylformamide (DMF) + N-propylpropan-1-amine (DPA), + N-butylbutan-1-amine (DBA), + butan-1-amine (BA) or + hexan-1-amine (HxA). The values of the excess relative permittivities, ε_r^E, have also been determined for these solutions. The measurements were realized by means of a precision impedance analyser 4294A, to which a 16452A cell connected using a 16048G test lead, all of them from Agilent. The ε_r^E values are large and negative, and diminish when the size of the amine increases along a homologous series, which has been ascribed mainly to the rupture of interactions between like molecules along mixing. Calculations on excess molar orientational polarizabilities support this conclusion, indicating a dominant contribution to ε_r^E from the orientational polarizability of the molecules in the mixture. The analysis of excess relative Kirkwood correlation factors shows that the correlation between dipoles is effectively decreased along the mixing process.