Viscosity as a Smoking Gun for Complex Formation in Solution: Fe ²⁺ and Mg ²⁺ Chlorides as Examples

Electrolyte solutions at high concentration are indispensable and yet poorly understood. In particular, the extent of speciation─the formation of complexes composed of multiple species─in concentrated ionic solutions is very challenging to obtain theoretically and experimentally, but can have a strong effect on solution properties. The literature is rife with contradictory estimates of speciation from experiments. We find that speciation affects transport properties and is therefore a prerequisite to accurately model concentrated solutions. We turn this to our advantage by showing that the viscosity can be used to determine the extent of complexation in concentrated aqueous solutions. Results of simulations as well as experimental measurements are presented. The atomistic Madrid-2019 force field is extended to model FeCl₂. Solutions of FeCl₂ and MgCl₂ are compared, and the observed difference in viscosity is explained by more complexation in the former, a conclusion supported by recently reported X-ray absorption and neutron scattering experiments.