Structure and specification of iron complexes in aqueous solutions determined by X-ray absorption spectroscopy

X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques, have been used to determine the structure and speciation of complexes for Fe²⁺ and Fe³⁺ chloride solutions at a variety of pH's, ionic strengths, and chloride/iron ratios.Low intensity K-edge transition features and analysis of modified pair correlation functions, derived from Fourier transformation of EXAFS spectra, show a regular octahedral coordination of Fe(II) by water molecules with a first-shell Fe²⁺-O bond distance, closely matching octahedral Fe²⁺-O bonds obtained from solid oxide model compounds. Solution Fe²⁺-O bond distances decrease with chloride/iron ratio, pH, and total FeCl₂ concentration. A slight intensification of the $\text{1s → 3d}$ transition with increasing FeCl₂ concentration suggests that chloride may begin to mix with water as a nearest-neighbor octahedral ligand. Fe³⁺ solutions show a pronounced increase in the $\text{1s → 3d}$ transition intensities between 1.0 M FeCl₃/7.8 M Cl^? to 1.0 M FeCl₃/ 15 M Cl^?, indicating a coordination change from octahedral to tetrahedral complexes. EXAFS analyses of these solutions show an increase in first-shell Fe³⁺-ligand distances despite this apparent reduction in coordination number. This can be best explained by a change from regular octahedral complexes of ferric iron (either Fe(H₂O)₆³⁺ or trans-Fe(H₂O)₄Cl₂ or both; Fe³⁺-O bond distances of 2.10 Å) to tetra-chloro complexes Fe³⁺-Cl bond distances of 2.25 Å].