Influence of Inorganic Salts on Aqueous Solubilities of Polycyclic Aromatic Hydrocarbons

Setschenow constants of six alkali and alkaline earth metal-based electrolytes (i.e., NaCl, KCl, CaCl$_2$, K$_2$SO$_4$, Na$_2$SO$_4$, NaClO$_4$) for three polycyclic aromatic hydrocarbons (PAHs) (i.e., naphthalene, pyrene, and perylene) were investigated to evaluate the influence of a variety of inorganic salts on the aqueous solubility of PAHs. Inorganic salts showed a wide range of K$\_$s/ values (L/mol), ranging from 0.1108 (NaClO$_4$) to 0.6680 (Na$_2$SO$_4$) for naphthalene, 0.1071 (NaClO$_4$) to 0.7355 (Na$_2$SO$_4$) for pyrene, and 0.1526 (NaClO$_4$) to 0.8136 (Na$_2$SO$_4$) for perylene. In general, the salting out effect of metal cations decreased in the order of Ca$\^$2+/>Na$\^$+/>K$\^$+/. The effect of SO$_4$$\^$2-/>Cl$\^$-/>ClO4$\^$-/ was observed for anions of inorganic salts. The K$\_$s/ values decreased in the order of perylene>pyrene>naphthalene for K$_2$SO$_4$. However, the order of decreasing salting out effect for NaCl, KCl, CaCl$_2$, and NaClO$_4$ was perylene>naphthalene>pyrene. Hydration free energy of the 1:1 and 2:1 alkali and alkaline earth metal-based inorganic salts solution was observed to have a meaningful correlation with Setschenow constants. Thermodynamic interactions between PAH molecules and salt solution can be of importance in determining the magnitude of salting out effect for PAHs at a given salt solution.