Densities and Molar Thermal Expansions of (Water + 1,4-Dioxane) Mixture over the Temperature Range from 274.15 to 333.15 K at Atmospheric Pressure─Comparison with Literature Data

Abstract

The densities of the mixture {water (1) + 1,4-dioxane (2)} were measured using a vibration density meter at temperatures from 274.15 to 333.15 K and atmospheric pressure over the entire composition range. The excess molar volume of the mixture and the partial molar volumes of water and 1,4-dioxane were calculated. The temperature of the maximum density of 1,4-dioxane aqueous solutions was determined. It is shown that the formation of the mixture occurs with a decrease in volume. The dependences of partial molar volumes on the concentration of water and 1,4-dioxane have extremums. The values of molar volumes of water and 1,4-dioxane exceed the corresponding limit partial molar volumes. An increase in the temperature or concentration of 1,4-dioxane increases the magnitude of the molar expansion of the mixture over the entire range of compositions. Replacing the intrinsic environment of a molecule in a solvate shell with molecules of another component leads to a decrease in the partial molar volume at infinite dilution. The obtained results were compared with the literature data.

Densities and Volumetric Properties of Water + 1,3-Dioxolane Mixtures at Temperatures of (274.15 to 323.15) K and Ambient Pressure

“…Shift in the temperature of the maximal density in the mixtures {water (1) + 1,3-dioxolane (2)}: black ■, water + 1,3-dioxolane; red ●, water + oxolane, ref ; and green ▲, water + 1,4-dioxane, ref . The points are the experimental data; the lines are the result of the approximation of the equation.…”

“…Excess molar volumes, V m E , of the mixtures of water + simple cyclic ether at 288.15 (filled symbols) and 333.15 K (open symbols) at atmospheric pressure: black ■, □ water + 1,3-dioxolane; red ●, ○ water + oxolane, ref ; and green ▲, △ water + 1,4-doxane, ref .…”

“…Comparison of partial molar volumes of water, V̅ 1 , and difference ( V̅ ̅̅ 2 ∞ – V̅ m,2 ) between the limiting partial molar volumes and molar volumes of 1,3-dioxolane in mixtures of water with cyclic ethers at 278.15 (filled symbols) and 333.15 K (open symbols) at atmospheric pressure: black ■, □ {water (1) + 1,3-dioxolane (2)}; red ●, ○ {water (1) + oxolane (2)}, ref ; and green ▲, △ {water (1) + 1,4-dioxane}, ref . Since 1,4-DO freezes, its molar volume at 278.15 K was found by the extrapolation of x 2 → 1.…”

“…The same dependence is characteristic of water + oxolane and water + 1,4-dioxane mixtures. 21,22 A comparison of the molar isobaric expansion values of pure cyclic ethers (Figure 8b For a more detailed analysis of the isobaric molar expansion, E P,m , of water + 1,3-dioxolane, the partial molar expansion of the mixture components was calculated at 298.15 K. These dependencies are shown in Figure 9 in comparison with similar dependencies of two other water + oxoline and water + 1,4dioxane mixtures. As can be seen from Figure 9a, the dependence of E̅ P,1 = f(x 2 ) in the water + 1,3-dioxolane mixture, as in other aqueous Ox and 1,4-DO mixtures, is also characterized by a minimum in the region of small molar fractions x 2 .…”

“…This article is a continuation of our systematic experimental studies of the volumetric properties of binary aqueous mixtures with simple cyclic ethers. Our previous studies , present the results of studying the volumetric properties of aqueous mixtures of oxolane (Ox) and 1,4-dioxane (1.4-DO) in the temperature range from (274 to 333) K and atmospheric pressure. The discussion of the volumetric properties of the water + 1,3-DOx mixture is accompanied by their comparison with the same volumetric properties of the water + Ox and water + 1,4-DO mixtures.…”