Thermoynamic properties (HmE, CP,mE, VmE, κTE) of binary mixtures {x1,3-Dioxane + (1−x)Cyclohexane} at 298.15 K

Molar excess enthalpies HmE, isobaric heat capacities CP,mE, volumes VmE and isothermal compressibilities κTE for the 1,3-dioxane(3DX) + cyclohexane mixture were measured at 298.15 K, in order to compare to those of the 1,4-dioxane(4DX) + cyclohexane mixture. HmE is endothermic and the maximum value about 1.5 kJ mol−1 at x ≈ 0.45, and lower than that of the 4DX mixture by about 80 J mol−1. VmE is positive over the whole concentration and the maximum value is about 0.85 cm3 mol−1 at x ≈ 0.45, and lower than that of the 4DX mixture. The above results suggest the energetic unstabilization, resulting in the volume expansion in the mixture. CP,mE shows the characteristic W-shaped concentration dependence, which has maximum at x ≈ 0.45 and two minima at x ≈ 0.1 and 0.9. The maximum CP,mE value for 3DX mixture shifts toward the positive side, compared to that of 4DX mixture. κTE were estimated from speeds of sound, densities, thermal expansion coefficients and isobaric heat capacities of the pure component liquids and the mixtures. The κTE result shows the positive concentration dependence over the whole composition range. The 3DX mixture has the similar thermodynamic properties to the 4DX mixture, despite that 4DX is the nonpolar solvent and 3DX is the dipolar liquid. this means that there exists the local dipolar interaction between 4DX molecules, and the prevalence of “microheterogeneity” in the both mixtures.