Scale-Bridging Thermodynamic and Kinetic Simulation (STKS)
Ionic Liquids: Predictions of physicochemical properties with experimental and/or DFT-calculated LFER parameters to understand molecular interactions in solution
C.-W. Cho, U. Preiss, C. Jungnickel, S. Stolte, J. Arning, J. Ranke, A. Klamt, I. Krossing, J. Thöming.
The Journal of Physical Chemistry B, The American Chemical Society, 115, 6040-6050, (2011)
In this article, we present evolutionary models to predict the octanol–water partition coefficients (log P), water solubilities, and critical micelle concentrations (CMCs) of ionic liquids (ILs), as well as the anionic activity coefficients and hydrophobicities in pure water and octanol–water. They are based on a polyparameter linear free energy relationship (LFER) using measured and/or DFT-calculated LFER parameters: hydrogen-bonding acidity (A), hydrogen-bonding basicity (B), polarizability/dipolarity (S), excess molar refraction (E), and McGowan volume (V) of IL ions. With both calculated or experimental LFER descriptors of IL ions, the physicochemical parameters were predicted with an errors of 0.182–0.217 for the octanol–water partition coefficient and 0.131–0.166 logarithmic units for the water solubility. Because experimentally determined solute parameters of anions are not currently available, the CMC, anionic activity coefficient, and hydrophobicity were predicted with quantum-chemical methods with R2 values of at least 0.99, as well as errors below 0.168 logarithmic units. These new approaches will facilitate the assessment of the technical applicability and environmental fate of ionic compounds even before their synthesis.