Prediction of the Standard Gibbs Energy of Transfer of Organic Ions Across the Interface between Two Immiscible Liquids

The non-Bornian solvation model was applied for evaluation of the standard Gibbs energy (ΔGtr°,W→O) of transfer of organic ions from water (W) to organic solvent (O = nitrobenzene). The solvation energy of an ion in either W or O is basically formulated as the energy required for the formation of a nanosized ion–solvent interface around the ion; however, many organic ions with strongly charged groups (e.g., −SO3–, −CO2–, −NH3+) are preferentially hydrated in O. Here we divided the surface of an ion into “hydrated” and “non-hydrated” surfaces and then carried out regression analyses with experimental values of ΔGtr°,W→O. In the analyses, the local electric field on the surface of an organic ion was evaluated through density functional theory calculation. Good regression results were then obtained with the mean absolute error of 1.9 and 2.4 kJ mol–1 for 34 anions and 63 cations, respectively. These errors correspond to the error of ∼20 mV in the standard ion-transfer potential (ΔOWϕ°), being only two times larger than the typical experimental error (∼10 mV) in the voltammetric measurement. This non-Bornian model is promising for theoretical prediction of ΔGtr°,W→O (or ΔOWϕ°) for organic ions and possibly of the biomembrane permeability for ionic drugs.