Abstract This work was to investigate piperonylonitrile in terms of its solid–liquid equilibrium solubility in thirteen pure solvents by employing laser monitoring technique. Solubility measurements were completed in range of temperature at (288.15–323.15) K in 1,4-dioxane and at (278.15–323.15) K in isopropanol, 2-methoxyethanol, ethanol, ethyl acetate, methanol, n-propanol, n-propyl acetate, N,N-dimethylformamide (DMF), isopropyl acetate, methyl acetate, acetone as well as acetonitrile under 0.1 MPa. The holistic solubility profile showed that piperonylonitrile solubility in all measured solvents was proportional to the increasing of test temperature. It was also found that the mole-fraction solubility values of piperonylonitrile in measured solvents at 298.15 K exhibited a sequence of: DMF (0.2636) > 1,4-dioxane (0.2212) > methyl acetate (0.1838) > acetone (0.1813) > ethyl acetate (0.1657) > n-propyl acetate (0.1486) > acetonitrile (0.1435) > isopropyl acetate (0.1295) > 2-methoxyethanol (0.1010) > methanol (0.01915) > ethanol (0.01664) > n-propanol (0.01594) > isopropanol (0.01268). The miscibility and solubility order of piperonylonitrile were further revealed by the means of Hansen solubility parameter, demonstrating that solubility behaviors could be well explained by the comprehensive action of various solubility parameters. Besides, the influence on the piperonylonitrile solubility of solute–solvent interaction and solvent–solvent interaction was illustrated via the KAT-LSER model. It was figured out that hydrogen bonding acidity and hydrogen bonding basicity exerted unfavorable influence on piperonylonitrile solubility. Moreover, the measured piperonylonitrile solubility was fitted with Wilson, NRTL, UNIQUAC, Two-Suffix Margules and NRTL-SAC model, and correlation of experimental results with the use of five activity coefficient models showed that sufficient agreement with the calculated data. Finally, the thermodynamic quantities (ΔmixH, ΔmixG and ΔmixS) of the mixing process in different solvents were computed based on measured solubility values and UNIQUAC model. The results demonstrated that the mixing process was entropy-driven and spontaneous.

中文翻译：

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胡椒腈在十三种纯溶剂中的溶解度：测定、相关性、汉森溶解度参数、溶剂效应和热力学分析

摘要 本工作采用激光监测技术研究胡椒腈在十三种纯溶剂中的固液平衡溶解度。溶解度测量在 (288.15–323.15) K 的 1,4-二恶烷和 (278.15–323.15) K 的异丙醇、2-甲氧基乙醇、乙醇、乙酸乙酯、甲醇、正丙醇、正丙基的温度范围内完成乙酸盐、N,N-二甲基甲酰胺 (DMF)、乙酸异丙酯、乙酸甲酯、丙酮以及 0.1 MPa 下的乙腈。整体溶解度曲线表明胡椒腈在所有测量溶剂中的溶解度与测试温度的增加成正比。还发现胡椒腈在 298.15 K 下在测量溶剂中的摩尔分数溶解度值表现出以下顺序：DMF (0.2636) > 1,4-二恶烷 (0.2212) > 乙酸甲酯 (0.1838) > 丙酮 (0.1813) > 乙酸乙酯 (0.1657) > 乙酸正丙酯 (0.1486) > 乙腈 (0.1435) > 乙酸异丙酯 (0.1295) > 2-甲氧基乙醇 (0.1010) > 甲醇 (0.01915) 0.01664) > 正丙醇 (0.01594) > 异丙醇 (0.01268)。通过汉森溶解度参数进一步揭示了胡椒腈的混溶性和溶解度顺序，表明各种溶解度参数的综合作用可以很好地解释溶解行为。此外，通过 KAT-LSER 模型说明了溶质 - 溶剂相互作用和溶剂 - 溶剂相互作用对胡椒腈溶解度的影响。研究表明，氢键酸度和氢键碱度对胡椒腈的溶解度产生不利影响。而且，测得的胡椒腈溶解度符合Wilson、NRTL、UNIQUAC、Two-Suffix Margules和NRTL-SAC模型，实验结果与使用五种活度系数模型的相关性表明与计算数据充分吻合。最后，基于测量的溶解度值和 UNIQUAC 模型计算了不同溶剂中混合过程的热力学量（ΔmixH、ΔmixG 和 ΔmixS）。结果表明混合过程是熵驱动的和自发的。ΔmixG 和 ΔmixS) 在不同溶剂中的混合过程是基于测量的溶解度值和 UNIQUAC 模型计算的。结果表明混合过程是熵驱动的和自发的。ΔmixG 和 ΔmixS) 在不同溶剂中的混合过程是基于测量的溶解度值和 UNIQUAC 模型计算的。结果表明混合过程是熵驱动的和自发的。