Evaluating coal tar-water partitioning coefficient estimation methods and solute-solvent molecular interactions in tar phase

Equilibrium partitioning coefficients between an industrial coal tar sample and water (KCT/w) were determined for 41 polar and nonpolar solutes in batch systems. Together with literature values, 69 KCT/w data were analyzed using the following model approaches: Raoult's law, the single parameter linear free energy relationship (SPLFER) with octanol-water partitioning coefficients (Kow), the linear solvation energy relationships (LSERs), SPARC and COSMOtherm. Estimations by Raoult's law and the SPLFER agreed well with the experimental log KCT/w values for the investigated coal tar, with root mean square errors (RMSE) of 0.31 and 0.33, respectively. LSER resulted in as good estimations (RMSE = 0.29) as the previous two. The LSER analysis revealed significant hydrogen (H)-bond acceptor properties of the studied coal tar phase. Using naphthalene as a surrogate solvent for the coal tar phase, SPARC and COSMOtherm provided fairly good predictions (RMSE of 0.63 and 0.65, respectively) of log KCT/w, without any additional empirical parameter. Further calculations using SPARC and COSMOtherm for partitioning between water and other tar-components (e.g., benzofuran, phenol and quinoline) suggested that minor components in coal tar do not significantly influence KCT/w of nonpolar solutes, and that Raoult's law and the SPLFER thus may be generally applied to these types of solutes, e.g., polycyclic aromatic hydrocarbons and alkylbenzenes, regardless of coal tar compositions. In contrast, partitioning of H-bonding solutes (e.g., phenols) can significantly vary depending on the amount of polar tar-components such as N-heterocyclic aromatic compounds. Therefore, the presented successful applications of Raoult's law and SPLFER to the studied coal tar could be a special case, and these simple approaches may not provide reasonable estimations for partitioning of H-bonding solutes from compositionally different coal tars.