Abstract
The enthalpies of dilute aqueous solutions of tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1,2,5-trioxane, and an equimolal mixture of tetrahydropyran and 1,3,5-trioxane were measured at 25°C and at molalities from about 0.1 to 1.0 mol kg1. The freezing points of the same aqueous solutions (except for 1,3-dioxane) were measured over a similar molality range. The results were used to calculate the enthalpies and Gibbs free energies of the pair-wise interactions of the above solutes in dilute aqueous solutions at 25°C. From these results, the additivity principle proposed by Savage and Wood was used to get the Gibbs free energy and enthalpies of interaction for the ether-ether and ether-methylene groups. Because of the limited number of measurements, the interaction parameters were not determined with great precision. Nevertheless, the standard errors for the predicted enthalpies and Gibbs free energies are quite reasonable. The signs and magnitudes are similiar to those determined for other polar groups.
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References
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This is easily derived from the equations for φL of a mixture given by R. B. Cassel and R. H. Wood,J. Phys. Chem. 78, 2465 (1974). The equations for φC are of the same form.
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Okamoto, B.Y., Wood, R.H., Desnoyers, J.E. et al. Freezing points and enthalpies of dilute aqueous solutions of tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1,3,5-trioxane. Free energies and enthalpies of solute-solute interactions. J Solution Chem 10, 139–152 (1981). https://doi.org/10.1007/BF00644996
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DOI: https://doi.org/10.1007/BF00644996