Journal of Chemical and Engineering Data, Vol.63, No.6, 2290-2298, 2018
Solubility and Preferential Solvation of 3-Nitrobenzonitrile in Binary Solvent Mixtures of Ethyl Acetate Plus (Methanol, Ethanol, n-Propanol, and Isopropyl Alcohol)
The solubilities of 3-nitrobenzonitrile in solvent mixtures of ethyl acetate (1) + methanol (ethanol, n-propanol or isopropyl alcohol) (2) determined over the temperature range from 278.15 to 318.15 K under atmospheric pressure (101.1 kPa) with the isothermal dissolution equilibrium method were reported. They increased with a rise of temperature and mass fraction of ethyl acetate, and the largest solubility value was observed in neat ethyl acetate for all the binary mixtures investigated. The temperature and solvent composition dependence of 3-nitrobenzonitrile solubility was analyzed through the Jouyban-Acree, van't Hoff-Jouyban-Acree, and Apelblat-Jouyban-Acree models acquiring average relative deviations lower than 1.57% and root-mean-square deviation lower than 11.52 X 10(-4) for correlative investigations. In addition, the preferential solvation parameters (delta x(1,3)) of 3-nitrobenzonitrile by ethyl acetate were determined from experimental solubility values by using the inverse Kirkwood-Buff integrals. It was found that alcohol preferentially solvated 3-nitrobenzonitrile in alcohol-rich mixtures while ethyl acetate forms local solvation shells in compositions from intermediate composition up to neat ethyl acetate. The former case was possibly due to the ordered structure of alcohol molecules around the apolar group of 3-nitrobenzonitrile, which was formed via hydrophobic hydration in alcohol-rich solutions.