COSMO-RS solute partition ratios for solvent mixtures of unknown composition: Henry's law constants as descriptors for mixture sigma profiles

Abstract

Henry's law constants (H) for selected probe molecules have been used as descriptors to estimate the COSMO-RS sigma profiles of solvents and solvent mixtures. Henry's law constants were calculated with COSMOtherm for small sets of probe molecules in 155 organic solvents (training set), and these constants subsequently used as descriptors to model the solvent sigma profiles with 61 multiple linear regression (MLR) equations. Subsequent input into COSMOtherm of weighted basis molecule solvent mixtures whose sigma profiles closely matched those modelled for the training set solvents allowed estimation of air-solvent and water-solvent partition ratios for solutes in solvents and solvent mixtures without input of the solvent or solvent mixture identity. The best performing model had 16 descriptors and gave both a training and test set average root-mean square error (RMSE) of 0.008 and an average relative square error (RSE) of 0.07. Partition ratios (K) were then generated for a test set of 251 additional organic solute molecules in solvent/water media where solvents were test set compounds and H constants for the same probe molecules were used as descriptors. The best performing sigma profile model yielded log K RMSE values ranging from 0.17 to 0.92. Finally, this approach was applied to several mixtures ranging from simple binary mixtures to two mixtures considered to be of unknown or variable composition, complex reaction productions or biological materials (UVCBs), namely gasoline and an essential oil mixture. Mixture/water partition ratios were estimated for 251 solutes giving log K RMSE values ranging from 0.24 to 0.88.