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, nD, have been reported at (293–303.15) K for the N,Ndimethylacetamide (DMA) + CH3CO(CH2)_(u – 1)CH3 (u = 1, 2, 3) systems, and at 298.15 K for the mixture with u=5. These data have been used to compute excessmolar volumes, VmE, excess adiabatic compressibilities, kSE, and excess speeds of sound cE. Negative VmE values indicate the existence of structural effects and interactions between unlike molecules. From molar excess enthalpies, HmE, 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 HmE and are more relevant in mixtures containing NMP. The application of the Flory's model reveals that the random mixing hypothesis is valid in large extent for DMF solutions, while NMP systems are characterized by rather strong orientational effects. From values of molar refraction and of the product PintVm (where Pint is the internal pressure and Vm 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.