Solubility model of metal complex in ionic liquids from first principle calculations

A predictive model based on first principles calculations has been proposed to study the solid–liquid equilibria comprising of metal complexes and ionic liquids. The model is based on first principle COSMO calculation followed by post statistical thermodynamical treatment of self-consistent properties of solute and solvent molecules. The metal complex and ionic liquid have been treated as a simple binary mixture. The ionic liquid has been treated here as a single intact molecule. The experimentally observed dual-solute relationship between the ionic liquid and redox active species in presence of a third organic solvent has been established using our model in this work. Within the model, the dual-solute relationship appeared as a simple Gibbs–Duhem relationship between these two species at ambient condition. The dual-solute relationship between the metal complex (V(acac)(3), Cr(acac)(3) and Mn(acac)(3)) and ionic liquid ([Tea][BF(4)]) has been validated by calculating the Gibbs–Duhem relationship, x(solute)vs. x(solvent(IL)) and 1/γ(solute)vs. x(solvent(IL)) plots. The present model has been applied to a set of ionic liquids, metal complexes and organic solvent (acetonitrile) for which experimental study has been done. The solvation mechanism of the metal complexes in those ionic liquids was obtained using the model. According to our findings, the ionic liquid containing imidazolium cation and [NTf(2)](−) anion is appeared as a suitable solvent for the non-aqueous redox flow cell. We have compared our results with the already reported experimental results where they were available for the non-aqueous solvents.