Thermodynamics of amide + ketone mixtures. 1. Volumetric, speed of sound and refractive index data for N,N-dimethylformamide + 2-alkanone systems at several temperatures

Abstract

Densities, $\rho$, speeds of sound, $c$, and refractive indices, $n_{\text{D}}$, have been measured for the systems N,N-dimethylformamide (DMF) + propanone, + 2-butanone, or + 2-pentanone in the temperature ($T$) range from 293.15 to 303.15 K and at 298.15 K for the DMF + 2-heptanone mixture. Due to the high volatility of acetone, the corresponding $n_{\text{D}}$ measurements were developed at 293.15 K and 298.15 K. The direct experimental data were used to determine the excess molar volumes, $V_{\text{m}}^{\text{E}}$, and the excess refractive indices, $n_{\text{D}}^{\text{E}}$, at the working $T$. Values of the excess functions at 298.15 K, for the speed of sound, $c^{\text{E}}$, the isentropic compressibility, $\kappa_S^{\text{E}}$ and for the excess thermal expansion coefficient, $\alpha_p^{\text{E}}$, were also calculated. The investigated systems are characterized by strong amide-ketone interactions, which become weaker when the alkanone size is increased. This is supported by negative $V_{\text{m}}^{\text{E}}$ values; by the dependence on $T$ and pressure of $V_{\text{m}}^{\text{E}}$, and by positive $P_{\text{int}}^{\text{E}}$ (excess internal pressure) values. Analysis of the systems in terms of the Rao's constant indicates that there is no complex formation. In addition, negative $V_{\text{m}}^{\text{E}}$ values also reveal the existence of structural effects, which largely contribute to the excess molar enthalpy, $H_{\text{m}}^{\text{E}}$. $V_{\text{m}}^{\text{E}}$ and $H_{\text{m}}^{\text{E}}$ values increase with the chain length of the 2-alkanone. It allows to conclude that the relative $V_{\text{m}}^{\text{E}}$ variation with the ketone size is closely related to that of the interactional contribution to this excess function. Molar refraction values, $R_{\text{m}}$, show that dispersive interactions become more relevant for the systems including longer 2-alkanones.