Structure and Population of Complex Ionic Species in FeCl Aqueous Solution by X-ray Absorption Spectroscopy.

Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl aqueous solution at different concentrations (1-4 molL) and temperatures (25-80 °C). We found that at low temperature and low FeCl concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl(HO)]. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single charged Fe[Cl(HO)] to the neutral Fe[Cl(HO)] causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models.