Analysis of Volumetric Properties of Liquid Mixtures. II Aqueous-Organic Solvent Systems
Abstract
An extended model of binary additive quasi-solvates (BAQS) is proposed to describe the properties of binary liquid systems. The model incorporates two additional parameters: the limiting partial molar quantities of the solution components. Notably, these parameters are determined a priori, typically from independent experimental data. Concurrently, within the model framework, the effective limiting partial molar quantities are derived from the dependence of the studied property on the mixture composition. The discrepancy between the a priori and effective values is attributed to a shift in the equilibrium between homogeneous and heterogeneous quasi-solvates, as well as a redistribution of the solvent-solute roles within heterogeneous quasi-solvates. For each component, a parameter ξ is introduced, representing the ratio of the effective excess limiting partial molar quantity to its corresponding a priori value. Based on these parameters, the excess functions of heterogeneity αE and role asymmetry βE are defined.
Using molar volume dependencies for 12 binary aqueous systems (with methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, tetrahydrofuran, 1,4-dioxane, acetonitrile, acetone, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide) at 298.15 K, along with literature data, the functions αE and βE were calculated. The study determined the compositions and function values at extrema, average function values, and quasi-solvate weighting factors for equimolar mixtures. The results demonstrate that the calculated parameters can effectively characterize structural features of aqueous-organic solutions. Despite the model's apparent simplicity, this approach is suitable for the rapid analysis of large sets of binary liquid systems.
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References
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