Application of Fundamental Chemical Principles for Solvation Effects: A Unified Perspective for Interaction Patterns in Solution

We demonstrate the utility of basic chemical principles like the |Delta mu| big is good (DMB) rule for the study of solvation interactions between distinct solutes such as ions and solvents. The corresponding approach allows us to define relevant criteria for maximum solvation energies of ion pairs in different solvents in terms of electronegativities and chemical hardnesses. Our findings reveal that the DMB principle culminates into the strong and weak acids and bases concept as recently derived for specific ion effects in various solvents. The further application of the DMB approach highlights a similar condition for the chemical hardnesses with a reminiscence to the hard/soft acids and bases principle. Comparable conclusions can also be drawn with regard to the change of the solvent. We show that favorable solvent interactions are mainly driven by low chemical hardnesses as well as high electronegativity differences between the ions and the solvent. Our findings highlight that solvation interactions are governed by basic chemical principles, which demonstrates the close similarity between solvation mechanisms and chemical reactions.

Automated summary

We demonstrate the utility of basic chemical principles, such as the DMB rule, for studying solvation interactions between ions and solvents. Our findings show that solvation interactions are influenced by chemical hardnesses and electronegativity differences, and are related to the concepts of strong and weak acids/bases. The change of solvents also affects the interactions. Favorable solvent interactions are mainly driven by low chemical hardnesses and high electronegativity differences.