Thermodynamics of amide+ketone mixtures. 2. Volumetric, speed of sound and refractive index data for N,N-dimethylacetamide+2-alkanone systems at several temperatures. Application of Flory's model to tertiary amide+n-alkanone systems

Abstract

Data on density, $\rho$, speed of sound, $c$, and refractive index, $n_{\text{D}}$, have been reported at (293-303.15) K for the N,N-dimethylacetamide (DMA) + CH$_3$CO(CH$_2$)$_{u-1}$CH$_3$ ($u$ = 1, 2, 3) systems, and at 298.15 K for the mixture with $u$ = 5. These data have been used to compute excess molar volumes, $V_{\text{m}}^{\text{E}}$, excess adiabatic compressibilities, $\kappa_S^{\text{E}}$, and excess speeds of sound $c^{\text{E}}$. Negative $V_{\text{m}}^{\text{E}}$ values indicate the existence of structural effects and interactions between unlike molecules. From excess molar enthalpies, $H_{\text{m}}^{\text{E}}$, available in the literature for N,N-dimethylformamide (DMF), or N-methylpyrrolidone (NMP) + n-alkanone systems, it is shown: (i) amide-ketone interactions are stronger in DMF systems than in those with NMP; (ii) they become weaker when $u$ increases in mixtures with a given amide. Structural effects largely contribute to $H_{\text{m}}^{\text{E}}$ and are more relevant in mixtures containing NMP. The application of the Flory's model reveals that the random mixing hypothesis is valid to a large extent for DMF solutions, while NMP systems are characterized by rather strong orientational effects. From values of molar refraction and of the product $P_{\text{int}} V_{\text{m}}$ (where $P_{\text{int}}$ is the internal pressure and $V_{\text{m}}$ the molar volume), it is concluded that dispersive interactions increase with $u$, or when DMF is replaced by DMA in mixtures with a fixed ketone.