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

TL;DR

This paper demonstrates that viscosity measurements, combined with simulations, can reveal the extent of complex formation in concentrated FeCl$_2$ and MgCl$_2$ solutions, clarifying speciation effects on solution properties.

Contribution

It introduces viscosity as a practical tool to determine complexation in concentrated ionic solutions, supported by simulations and experimental data, advancing understanding of electrolyte speciation.

Findings

Viscosity correlates with complex formation in solutions.

FeCl$_2$ exhibits more complexation than MgCl$_2$.

Simulation results align with experimental measurements.

Abstract

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 FeCl$_2$. Solutions of FeCl$_2$ and MgCl$_2$ are compared and the observed difference in viscosity explained by more complexation in the former, a conclusion supported by recently reported X-ray absorption and neutron scattering experiments.