The n-octanol and n-hexane/water partition coefficient of environmentally relevant chemicals predicted from the mobile order and disorder (MOD) thermodynamics

Abstract

The quantitative thermodynamic development of the mobile order and disorder theory in H-bonded liquids is extended in order to predict the partition coefficient. With respect to the classical predictive methods, the great advantage of the present approach resides in the possibility of predicting partition coefficient not only in the reference n-octanol/water partitioning system, but also in any mutually saturated two-phase system made up of two largely immiscible solvents. Constructed from the various free energy contributions encoded in the distribution process, the model furthermore provides a useful tool to understand both the origin and the factors, like the solute molar volume, that determine the partitioning of non-electrolytes between two immiscible liquid phases. From the comparison of the relative magnitude of the terms which contribute to the overall log P value, much information can also be gained concerning the variation of the partition coefficients of the same substances in different distribution systems. For example, the model has successfully been applied to the log P prediction of a number of environmentally important chemicals of varying structure, size and chemical nature in the n-octanol/water and n-hexane/water systems. Whatever the complexing or non-complexing substances studied, the hydrophobic effect always represent the driving force that rules distribution processes in the aqueous environments. As the dominant contribution to the partition coefficient in any organic/aqueous binary system, it is evidenced why hydrophobicity is usually considered to be a good measure of lipophilicity.