2-烷醇＋极性有机溶剂混合物的热力学。I. 含酮、醚或有机碳酸酯的体系
Thermodynamics of 2-alkanol + polar organic solvent mixtures. I. Systems with ketones, ethers or organic carbonates
AI总结：
本文结合热力学数据、Flory理论与Kirkwood-Buff积分，研究2-烷醇与酮、醚及有机碳酸酯混合物，揭示溶剂－溶剂或醇－醇相互作用及取向效应的主导规律。
摘要：
本文利用热力学数据，并依据Flory理论和Kirkwood-Buff积分，研究了2-丙醇或2-丁醇＋正烷酮、＋苯乙酮、＋线性单醚、＋环醚、＋线性有机碳酸酯或＋碳酸亚丙酯的混合物。所考察的数据包括：超额摩尔焓（$H_{\ ext{m}}^{\ ext{E}}$）、体积、熵，以及$H_{\ ext{m}}^{\ ext{E}}$的温度依赖性。测定了2-烷醇－溶剂相互作用的焓，并讨论了对$H_{\ ext{m}}^{\ ext{E}}$的不同贡献。结果表明，2-烷醇（固定）＋正烷酮或＋线性碳酸酯混合物的$H_{\ ext{m}}^{\ ext{E}}$值，其变化方式与正烷酮或线性碳酸酯＋正烷烃（固定）体系相同。相比之下，2-烷醇（固定）＋线性单醚或＋正烷烃混合物的$H_{\ ext{m}}^{\ ext{E}}$值变化相似。这组结果表明，在含正烷酮或线性碳酸酯的体系中，溶剂－溶剂相互作用起决定作用；而在含线性单醚的混合物中，醇分子之间的相互作用起决定作用。根据Flory模型，在给定2-烷醇的体系中，取向效应按线性单醚＞线性有机碳酸酯＞正烷酮的顺序减弱；含环状单醚溶液中的取向效应强于含环状二醚的溶液，含苯乙酮或碳酸亚丙酯体系中的取向效应也强于含相应线性溶剂的混合物。由Kirkwood-Buff积分得到的结果与这些发现一致。Flory模型的应用表明，在含1-烷醇或2-烷醇的体系中，取向效应相似，但含线性单醚的溶液例外：在含有1-烷醇的混合物中，此类效应更强。
英文摘要：
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 ($H_{\text{m}}^{\text{E}}$), volumes, entropies, and the temperature dependence of $H_{\text{m}}^{\text{E}}$. The enthalpy of the 2-alkanol-solvent interactions have been determined, and the different contributions to $H_{\text{m}}^{\text{E}}$ are discussed. It is shown that $H_{\text{m}}^{\text{E}}$ 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, $H_{\text{m}}^{\text{E}}$ 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.
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