Composition of the Solvation Shell of the Selected Cyclic Ethers (1,4-Dioxane, 12-Crown-4, 15-Crown-5 and 18-Crown-6) in a Mixture of Formamide with Water at Four Temperatures.

The solution enthalpy of 15-crown-5 and 18-crown-6 ethers in the mixture of formamide (F) and water (W) was measured at four temperatures: 293.15 K, 298.15 K, 303.15 K, 308.15 K. The standard molar enthalpy of solution, ΔsolHo, depends on the size of cyclic ethers molecules and the temperature. With increasing temperature, the values of ΔsolHo become less negative. The values of the standard partial molar heat capacity Cp,2o of cyclic ethers at 298.15 K have been calculated. The Cp,2o=f(xW) curve shape indicates the hydrophobic hydration process of cyclic ethers in the range of a high-water content in the mixture with formamide. The enthalpic effect of preferential solvation of cyclic ethers was calculated and the effect of temperature on the preferential solvation process was discussed. The process of complex formation between 18C6 molecules and formamide molecules is observed. The cyclic ethers molecules are preferentially solvated by formamide molecules. The mole fraction of formamide in the solvation sphere of cyclic ethers has been calculated.