Partial molar volumes of organic solutes in water. XXII. Cyclic ethers at temperatures (298 to 573) K and pressures up to 30 MPa

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Abstract

Density values for dilute aqueous solutions of five cyclic ethers (oxolane, 1,3-dioxolane, oxane, 1,4-dioxane, and 1,3,5-trioxane) are presented together with partial molar volumes at infinite dilution calculated from the experimental results. The measurements were performed at temperatures from (298 up to 573) K. Due to thermal decomposition, the upper temperature limit was lower for 1,3-dioxolane (448 K) and 1,3,5-trioxane (498 K). Experimental pressures were close to the saturated vapour pressure of water, and (15 and 30) MPa. The results were obtained using a high-temperature high-pressure flow vibrating-tube densimeter. Experimental standard partial molar volumes were correlated as a function of temperature and pressure using an empirical polynomial function and the semi-theoretical SOCW equation of state. Contributions of the group contribution method proposed previously were also evaluated and analyzed.

Introduction

This paper is a part of our series of the systematic experimental studies of partial molar volumes of organic solutes at infinite dilution in water (standard partial molar volumes). In the previous study [1], experimental results for standard partial molar volumes, Vm,2, of oxolane, 1,3-dioxolane, oxane, 1,4-dioxane, and 1,3,5-trioxane over the temperature range from (278 to 373) K under either atmospheric pressure or pressure 0.5 MPa were reported. New data presented here are an extension of the results obtained in the ambient and close-to-ambient range of state parameters to super ambient conditions that enable us to extend the applicability of the group contribution scheme [1] proposed previously for the estimation of standard partial molar volumes of cyclic ethers.

Section snippets

Experimental

The organic solutes were those used previously [1], i.e., oxolane (tetrahydrofuran, oxacyclopentane, Sigma Aldrich, stated mass purity greater than 0.99), 1,3-dioxolane (1,3-dioxacyclopentane, Fluka, stated mass purity greater than 0.99), oxane (tetrahydropyran, oxacyclohexane, anhydrous, stated mass purity 0.99), 1,4-dioxane (1,4-dioxacyclohexane, purriss., over molecular sieve, stated mass purity 0.995), and 1,3,5-trioxane (1,3,5-trioxacyclohexane, Sigma Aldrich, stated mass purity greater

Direct experimental results

The measured values of the density differences Δρ = ρ  ρ1 where ρ and ρ1 are the densities of the solution and water, respectively, corrected [4] for the differences between nitrogen-saturated and degassed water measured at each experimental temperature and pressure, and the molality of the organic solutes m2 at various temperatures and pressures are available in Supplementary material (tables S1 to S5; 591 data points in the range of molality from (0.05 to 0.31) mol · kg−1 for aqueous oxolane, 230

Acknowledgment

Support from the Ministry of Education, Youth and Sports of the Czech Republic (fund MSM6046137307) is acknowledged.

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