UV-Vis spectrophotometric and XAFS studies of ferric chloride complexes in hyper-saline LiCl solutions at 25-90 °C

The speciation and thermodynamic properties of ferric chloride complexes in hydrothermal solutions and hypersaline brines are still poorly understood, despite the importance of this element as a micronutrient and ore-component. Available experimental data are limited to room temperature and relatively low chloride concentrations. This paper reports results of UV-Vis spectrophotometric and synchrotron XAFS experiments of ferric chloride complexes in chloride concentrations up to 15 m and at temperatures of 25-90 °C. Qualitative interpretation of the UV-Vis spectra shows that FeCl²⁺, FeCl₂⁺, FeCl_3(aq) and FeCl₄⁻ were present in the experimental solutions. As chloride concentrations increase, higher ligand number complexes become important with FeCl₄⁻ predominating in solutions containing more than 10 m at 25 °C. The predominance fields of FeCl_3(aq) and FeCl₄⁻ expand to lower Cl concentrations with increasing T. Both XANES and UV-Vis spectra reveal a major change in the geometry of the complex between FeCl₂⁺ and FeCl_3(aq). EXAFS data confirm that the number of chloride ligands increases with increasing chloride concentration and show that Fe³⁺, FeCl²⁺ and FeCl₂⁺ share an octahedral geometry. FeCl_3(aq) could be either tetrahedral or trigonal dipyramidal, while FeCl₄⁻ is expected to be tetrahedral. EXAFS data support a tetrahedral geometry for FeCl₄⁻, especially at 90 °C, but do not allow to distinguish between a tetrahedral or trigonal dipyramidal geometry for FeCl_3(aq) because of similar Fe-Cl distances. At room temperature, EXAFS data suggest that FeCl_3(aq) may be a mixture of octahedral and tetrahedral or trigonal dipyramidal forms.The room temperature formation constants for three ferric chloride complexes (FeCl₂⁺, FeCl_3(aq) and FeCl₄⁻) determined from the UV data are generally in good agreement with previous studies. Calculations based on the properties extrapolated to 300 °C show that hematite solubility is much higher than previously estimated, and that the high orders complexes FeCl_3(aq) and FeCl₄⁻ are important at high temperatures even in solutions with low chloride concentrations. The accuracy of these properties is limited by a poor understanding of activity-composition relationships in concentrated electrolytes, and by limitations in the available experimental techniques and extrapolation algorithms; however, the inclusion of higher order complexes in numerical models of ore transport and deposition allows for a more accurate qualitative prediction of Fe behaviour in hydrothermal and hypersaline systems.