solITC: A rapid method to determine solubility products and heats of solution of hydrophobic ionic liquids from in situ synthesis in isothermal titration calorimeter

• Novel application of ITC to determine Ksp and ΔsolH°ΔsolH° of ILs in water is presented.
• The procedure integrates IL synthesis with thermodynamic data acquisition.
• Applicability of the method typically spans over five orders of Ksp magnitude.
• Performance was verified on three salts of diverse physical state and behavior.
• 18 Cation anion combinations potentially giving IL were examined.

This work presents a solubility isothermal titration calorimetry (solITC), a new calorimetric method that allows the determination of solubility product (KspKsp) and heat of solution (ΔsolH°ΔsolH°) of hydrophobic ionic compound in water. Based on a single titration of dilute ionic solution into its counterionic solution the method consists of observing the abrupt change of the heat flow signal due to hydrophobic phase separation and fitting the integrated heats to exact thermodynamic model. A priori analysis shows that the applicability range spans for KspKsp determination over five orders of magnitudes (typically 10-9

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