Departamento de Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza, Spain.
Group of Applied Thermodynamics and Surfaces (GATHERS), Aragon Institute for Engineering Research (I3A), 50018 Zaragoza, Spain.
Int J Mol Sci. 2023 Jun 20;24(12):10380. doi: 10.3390/ijms241210380.
Vapor pressures and other thermodynamic properties of liquids, such as density and enthalpy of mixtures, are the key parameters in chemical engineering for designing new process units, and are also essential for understanding the physical chemistry, macroscopic and molecular behavior of fluid systems. In this work, vapor pressures between 278.15 and 323.15 K, densities and enthalpies of mixtures between 288.15 and 318.15 K for the binary mixture (2-propanol + 1,8-cineole) have been measured. From the vapor pressure data, activity coefficients and excess Gibbs energies were calculated via the Barker's method and the Wilson equation. Excess molar volumes and excess molar enthalpies were also obtained from the density and calorimetric measurements. Thermodynamic consistency test between excess molar Gibbs energies and excess molar enthalpies has been carried out using the Gibbs-Helmholtz equation. Robinson-Mathias, and Peng-Robinson-Stryjek-Vera together with volume translation of Peneloux equations of state (EoS) are considered, as well as the statistical associating fluid theory that offers a molecular vision quite suitable for systems having highly non-spherical or associated molecules. Of these three models, the first two fit the experimental vapor pressure results quite adequately; in contrast, only the last one approaches the volumetric behavior of the system. A brief comparison of the thermodynamic excess molar functions for binary mixtures of short-chain alcohol + 1,8-cineole (cyclic ether), or +di-n-propylether (lineal ether) is also included.
在化学工程中，液体的蒸气压和其他热力学性质（如混合物的密度和焓）是设计新工艺单元的关键参数，对于理解流体系统的物理化学、宏观和分子行为也是必不可少的。在这项工作中，测量了（2-丙醇+1,8-桉叶油醇）二元混合物在 278.15 至 323.15 K 之间的蒸气压、288.15 至 318.15 K 之间的混合物密度和焓。从蒸气压数据中，通过 Barker 法和 Wilson 方程计算了活度系数和过剩吉布斯自由能。还从密度和量热测量中获得了过剩摩尔体积和过剩摩尔焓。使用 Gibbs-Helmholtz 方程对过剩摩尔吉布斯自由能和过剩摩尔焓之间的热力学一致性进行了检验。考虑了 Robinson-Mathias、Peng-Robinson-Stryjek-Vera 以及 Peneloux 状态方程（EoS）的体积平移，以及统计关联流体理论，该理论为具有高度非球形或缔合分子的系统提供了非常适合的分子视角。在这三个模型中，前两个非常适当地拟合了实验蒸气压结果；相比之下，只有最后一个接近系统的体积行为。还包括了短链醇+1,8-桉叶油醇（环状醚）或+二正丙醚（直链醚）二元混合物的热力学过剩摩尔函数的简要比较。
