Thermochemical investigations of associated solutions: calculation of solute--solvent equilibrium constants from solubility measurements.
A simple solution model that has lead to successful predictive equations for the partial molar excess properties of a solute in simple binary solvent mixtures containing only nonspecific interactions is extended to include association between the solute and one of the solvent components. An expression is derived and tested for its ability to describe anthracene solubilities in binary solvent mixtures containing benzene. The best description of the experimental solubilities requires the formation of a 1:1 anthracene-benzene complex, with a molarity-based equilibrium constant of KcAC approximately equal to 0.107 M-1. In comparison, a stoichiometric complexation model which attributes all solubility enhancement to the formation of anthracene-benzene complexes requires a somewhat larger equilibrium constant (KcAC approximately equal to 0.228 M-1) to describe the solubility behavior of anthracene in the benzene-n-heptane system. The results of these calculations illustrate that the determination of solute-solvent equilibrium constants from solubility data depends on the theoretical model used and the manner in which nonspecific interactions are incorporated into the model.
Thermochemical investigations of associated solutions: 5. Calculation of solute-solvent equilibrium constants from solubility in mixtures containing two complexing solvents.
Solubilities are reported for carbazole in binary dibutyl ether plus 1-chlorohexane mixtures at 25 degrees C. Results of these measurements are compared with solution models developed for solubility in systems containing specific solute-solvent interactions. A simple stoichiometric complexation model based on a 1:1 carbazole:dibutyl ether complex could describe the measured solubility to within an average absolute deviation of 1.7%. The calculated equilibrium constant, though, was about one-half of values previously determined from carbazole solubilities in several binary dibutyl ether plus alkane mixtures. A more sophisticated solution model, derived by assuming both 1:1 carbazole: dibutyl ether and carbazole:chlorohexane complexes, could describe the solubilities to within 2.4%. This latter model enables the carbazole-chlorohexane association constant to be calculated from experimental carbazole solubilities and a priori knowledge of the carbazole-dibutyl ether equilibrium constant.
SOLUBILITIES OF NITROGEN IN BINARY SOLUTIONS OF ACETONE WITH CYCLOHEXANE, BENZENE, CHLOROFORM AND 2-PROPANOL
Experimental data of nitrogen solubilities in four binary solvents with acetone and those of excess molar volumes of the solvents are presented at 25°C. Cyclohexane, benzene, chloroform, and 2-propanol are selected as the other component. The experimental excess quantities of gas solubility are represented almost quantitatively by a generalized equation of Flory-Huggins type with physical and chemical terms. It is also shown that the similarity between the excess quantity of gas solubility and the relative excess molar volume holds for the systems investigated except for the benzene-acetone system.