X-ray diffraction study of ferric chloride solutions and hydrated melt. Analysis of the iron (III)–chloride complexes formation

Abstract

A series of concentrated ferric chloride solutions, both neutral and acidic, as well as the hydrated melt FeCl₃⋅6H₂O have been studied by x‐ray diffraction. The changes in the radial distribution curves by varying iron concentration or Cl⁻/Fe³⁺ ratio and least squares fitting of the structure functions for various solute models lead to an unambiguous conclusion with respect to the dominant species which are present in the solutions. The existence of monochloro, dichloro, trichloro, and tetrachloro complexes, predicted by literature information in dilute solutions, has been established in the different solutions investigated. Octahedral complexes, mainly Fe(H₂O)₄Cl⁺₂ and Fe(H₂O)₃Cl₃, are the principal species occurring in neutral and acidic solutions while in the hydrated melt tetrahedral FeCl⁻₄ predominates. Species of the type FeCl₅(H₂O)²⁻ or FeCl³⁻₆ as well as polymeric network are excluded. Hydration water molecules around Cl⁻ anions has been found for both free chloride and chloride ions bonded to iron atoms. Second order interactions around Fe³⁺ ions are strongly suggested by the presence of a large peak at about 4.2 Å in the distribution curves.