Design of Nonideal Eutectic Mixtures Based on Correlations with Molecular Properties Published as part of The Journal of Physical Chemistry virtual special issue "Deep Eutectic Solvents"

In this work, a statistical analysis was performed to reveal how the molecular properties are correlated with the nonideal behavior observed in eutectic mixtures. From this, a statistical model, combined with theory and experimental results, was developed to predict the nonideal behavior of a specific set of eutectic mixtures, consisting of quaternary ammonium bromides with dicarboxylic acids and polyols. The combination of this analysis and this model can be considered as a first step toward the a priori design of eutectic mixtures. The analysis performed is based on principal components. The descriptors used for this are molecular properties of the constituents of these mixtures. The molecular properties are a combination of experimental, theoretical, and computed properties. The analysis reveals that there are strong correlations between the nonideality of the mixtures and a measure of the acidity of the hydrogen bond donating protons, the displacement of the bromide anion, and the bulkiness of the quaternary ammonium salt. Our analysis highlights the design rules of deep eutectic systems (DES), enabling control over the extent of the liquid window. Our model enables prediction of the eutectic temperature for a range of related mixtures.