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

氯化物 化学 八面体 离子 氯化铁 无机化学 分子 衍射 结晶学 三价铁 有机化学 铁质 光学 物理
作者
M. Magini,Tamás Radnai
出处
期刊:Journal of Chemical Physics [American Institute of Physics]
卷期号:71 (11): 4255-4262 被引量:76
标识
DOI:10.1063/1.438233
摘要

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.
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