Thermodynamics of 2-alkanol + polar organic solvent mixtures. I. Systems with ketones, ethers or organic carbonates

[Display omitted] •2-alkanol + n-alkanone, + acetophenone, + linear or cyclic ether, or organic carbonate mixtures were investigated.•Solvent-solvent interactions are determinant in systems with n-alkanones or linear carbonates.•Interactions between alcohol molecules are determinant in mixtures with...

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Veröffentlicht in:Journal of molecular liquids 2023-09, Vol.385, p.122319, Article 122319
Hauptverfasser: Antonio González, Juan, Hevia, Fernando, Felipe Sanz, Luis, Lozano-Martín, Daniel, García de la Fuente, Isaías
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Sprache:eng
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Zusammenfassung:[Display omitted] •2-alkanol + n-alkanone, + acetophenone, + linear or cyclic ether, or organic carbonate mixtures were investigated.•Solvent-solvent interactions are determinant in systems with n-alkanones or linear carbonates.•Interactions between alcohol molecules are determinant in mixtures with linear monoethers.•Flory model and Kirkwood-Buff integrals have been applied.•Orientational effects are stronger in solutions with linear monoethers. The mixtures 2-propanol or 2-butanol + n-alkanone, or + acetophenone, or + linear monoether, or + cyclic ether, or + linear organic carbonate, or + propylene carbonate have been investigated using thermodynamic data, and in terms of the Flory theory, and the Kirkwood-Buff integrals. The data considered are: excess molar enthalpies (HmE), volumes, entropies, and the temperature dependence ofHmE. The enthalpy of the 2-alkanol-solvent interactions have been determined, and the different contributions to HmE discussed. It is shown that HmE values of the 2-alkanol (fixed) + n-alkanone, or + linear carbonate mixtures change in the same manner that for n-alkanone, or linear carbonate + n-alkane (fixed) systems. In contrast, HmE values of 2-alkanol (fixed) + linear monoether or + n-alkane mixtures change similarly. This set of results suggests that solvent–solvent interactions are determinant in systems with n-alkanone or linear carbonate, while interactions between alcohol molecules are determinant in mixtures with linear monoethers. According to the Flory model, orientational effects in systems with a given 2-alkanol become weaker in the sequence: linear monoether > linear organic carbonate > n-alkanone, and are stronger in solutions with a cyclic monoether than in those with cyclic diethers, and in systems with acetophenone or propylene carbonate than in the mixtures with the corresponding linear solvents. Results obtained from the Kirkwood-Buff integrals are consistent with these findings. The application of Flory model reveals that orientational effects are similar in systems with 1- or 2-alkanols, with the exception of solutions with linear monoethers, where such effects are stronger in mixtures containing 1-alkanols. For the examined systems, the formalism of the Kirkwood-Buff integrals makes no meaningful distinction between solutions with 1-alkanols or 2-alkanols.
ISSN:0167-7322
1873-3166
DOI:10.1016/j.molliq.2023.122319