3-Nitrophthalonitrile solubility and solvation thermodynamics in aqueous solutions. (November 2022) - Liu, Ying
Graphical abstract: Highlights: Quantitative surface and HS analysis of 3-nitrophthalonitrile were studied. 3-Nitrophthalonitrile solubility in four aqueous solutions were determined and correlated. Analysis of solubility data using extended Hildebrand solubility approach. Investigation on preferential solvation via inverse Kirkwood–Buff integrals method. Abstract: This work examined the solubility, solvation behavior and computational methodologies of 3-nitrophthalonitrile in aqueous solutions of isopropanol/acetone/ethanol/NMP. The quantitative study of the molecular surface and the Hirshfeld surface analysis were utilized to explain the electrostatic characteristics of the 3-nitrophthalonitrile molecule's basicity, indicating that –CN groups are the most important electrophilic sites. All solubilities were tested using the shake-flask method at 101.2 kPa and temperatures between 278.15 and 328.15 K. The dipolarity-polarizability and solubility parameter of solutions played a crucial role in the fluctuation of solubility. The Hansen solubility parameters were employed to investigate solubility performance. The modified Wilson model, the modified van't Hoff Jouyban–Acree model, the mixture response surface model, and the Jouyban–Acree model showed satisfactory correlation values for the solubility with relative average deviation 5.20 percent. Inspection of the solvation behavior was carried out by the extended Hildebrand solubility approach subjected to the solubility at 298.15 K, achieving the RAD of no more than 2.77 %. Quantification of the preferred solvation of 3-nitrophthalonitrile was performed using the inverse Kirkwood-Buff integrals way. Positive solvation parameters in acetone/isopropanol/ethanol/NMP-rich and -middle solution compositions indicate that acetone/isopropanol/ethanol/NMP preferentially solvates 3-nitrophthalonitrile.