Journal of Chemical Thermodynamics, Vol.102, 257-269, 2016
Solubility determination and thermodynamic modeling of 3-methyl-4-nitrobenzoic acid in twelve organic solvents from T = (283.15-318.15) K and mixing properties of solutions
Solubilities of 3-methyl-4-nitrobenzoic acid in twelve organic solvents of ethanol, isopropanol, n-propanol, n-butanol, methanol, ethyl acetate, toluene, acetone, acetonitrile, 1,4-dioxane, N-methyl-2-pyrrolidone and N, N-dimethylformamide were determined experimentally by using the isothermal saturation method over a temperature range from (283.15-318.15) K under 101.1 kPa. The solubilities of 3-methyl-4-nitrobenzoic acid in each solvent increased with the increase in temperature. In general, the solubility obeyed the following order from high to low in different solvents: (N, N-dimethylformamide, N-methyl-2-pyrrolidone) > 1,4-dioxane > acetone > toluene > ethyl acetate > isopropanol > (methanol, ethanol, n-propanol, n-butanol) > acetonitrile. The experimental solubility data of 3-methyl-4-nitrobenzoic acid in the selected solvents were correlated by the modified Apelblat equation, lambda h equation, Wilson model and NRTL model. The maximum values of root-mean-square deviation (RMSD) and relative average deviation (RAD) were 13.69 x 10 (4) and 1.18%, respectively. Generally, the four thermodynamic models were all acceptable for the systems of 3-methyl-4-nitrobenzoic acid in these solvents. In addition, the mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration (gamma(infinity)(1)) and reduced excess enthalpy (H-1(E,infinity)) were calculated. The dissolution process of 3-methyl-4-nitrobenzoic acid in the solvents was spontaneous and endothermic. The obtained solubility and thermodynamic studies would be very helpful for optimizing the purification process of 3-methyl-4-nitrobenzoic acid. (C) 2016 Elsevier Ltd.