Prediction of Partition Coefficients of Fluorous and Nonfluorous Solutes in Fluorous Biphasic Solvent Systems by Mobile Order and Disorder Theory
Elwin de Wolf, Paul Ruelle, Joep van den Broeke, Berth‐Jan Deelman, Gerard van Koten · The Journal of Physical Chemistry B · 2004
The universal model for predicting lipophilicity based on the mobile order and disorder (MOD) solution thermodynamics was used for the successful prediction of the partition coefficient of 88 fluorous and nonfluorous chemicals in fluorous biphasic PFMCH/toluene and FC-72/benzene binary solvent systems at 25 °C. A general thermodynamic expression aimed to calculate the distribution of substances in any fluorous biphasic system at any temperature is presented. Interestingly, the predictive expression requires the knowledge of only the molar volume and the nonspecific cohesion parameter of the solute allowing valuable estimation of log P of nonexisting fluorous molecules. The present partition model predicts that grafting more and/or longer perfluoroalkyl tails on a given substance does not automatically result in higher partition coefficients.