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Equilibrium solubility of vanillin in some (ethanol + water) mixtures: determination, correlation, thermodynamics and preferential solvation
Journal of Molecular Liquids ( IF 6 ) Pub Date : 2021-09-13 , DOI: 10.1016/j.molliq.2021.117529
Sema Akay 1 , Berkant Kayan 1 , Abolghasem Jouyban 2, 3 , Fleming Martínez 4 , William E. Acree 5
Affiliation  

Equilibrium mole fraction solubility of vanillin in nine aqueous-ethanolic mixtures, as well as in neat water and neat ethanol, was determined at seven temperatures from T = 293.15 to T = 323.15 K. Vanillin solubility in these mixtures was adequately correlated with several well-known correlation models with the mean percentage deviations of 5.9 to 18.3%. Respective apparent thermodynamic functions, i.e. Gibbs energy, enthalpy, and entropy, for the dissolution, mixing and solvation processes, were computed using the van’t Hoff and Gibbs equations. The enthalpy–entropy relationship for vanillin was non-linear in the plot of enthalpy vs. Gibbs energy of dissolution with positive slopes from neat water to the mixture of w1 = 0.10 and the interval 0.50 < w1 < 0.90 but negative in the interval 0.10 < w1 < 0.50 and from w1 = 0.90 to neat ethanol. Accordingly, in the first cases the vanillin transfer from more polar to less polar solvent systems is enthalpy-driven but entropy-driven for the last ones. Moreover, by means of the inverse Kirkwood-Buff integrals is observed that vanillin is preferentially solvated by water molecules in water-rich mixtures but preferentially solvated by ethanol molecules in mixtures of 0.23 < x1 < 1.00.



中文翻译:

香兰素在某些(乙醇 + 水)混合物中的平衡溶解度:测定、相关性、热力学和优先溶剂化

在从T  = 293.15 到T  = 323.15 K 的七个温度下确定了香兰素在九种水-乙醇混合物以及纯水和纯乙醇中的平衡摩尔分数溶解度。已知的相关模型,平均百分比偏差为 5.9% 到 18.3%。使用van't Hoff 和Gibbs 方程计算溶解、混合和溶剂化过程的相应表观热力学函数,即吉布斯能、焓和熵。香兰素的焓-熵关系在焓与. 从纯水到w 1的混合物具有正斜率的吉布斯溶解能 = 0.10 和区间 0.50 <  w 1  < 0.90 但在区间 0.10 < w 1  < 0.50 和从w 1  = 0.90 到纯乙醇为负 。因此,在第一种情况下,香兰素从极性较大的溶剂系统转移到极性较小的溶剂系统是焓驱动的,而最后一种则是熵驱动的。此外,通过逆柯克伍德-布夫积分,观察到香兰素在富含水的混合物中优先被水分子溶剂化,但在 0.23 < x 1  < 1.00 的混合物中优先被乙醇分子溶剂化 。

更新日期:2021-09-17
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