The evolution of solvation symmetry and composition in Zn halide aqueous solutions from dilute to extreme concentrations

The emergence of cation-anion species, or contact ion pairs, is fundamental to understanding the physical properties of aqueous solutions when moving from the ideal, low-concentration limit to the manifestly non-ideal limits of very high solute concentration or constituent ion activity. We focus here on Zn halide solutions both as a model system and also as an exemplar of the applications spanning from (i) electrical energy storage via the paradigm of water in salt electrolyte (WiSE) to (ii) the physical chemistry of brines in geochemistry to (iii) the long-standing problem of nucleation. Using a combination of experimental and theoretical approaches we quantify the halide coordination number and changing coordination geometry without embedded use of theoretical equilibrium constants. These results and the associated methods, notably including the use of valence-to-core X-ray emission spectroscopy, provide new insights into the Zn halide system and new research directions in the physical chemistry of concentrated electrolytes.

Automated summary

The study focuses on the emergence of cation-anion species in aqueous solutions and their impact on the physical properties of high solute concentration systems. Zn halide solutions are used as a model system to investigate the halide coordination number and changing coordination geometry. The results provide new insights into the physical chemistry of concentrated electrolytes and open up new research directions.