The Structure of the Hydrated Gallium(III), Indium(III), and Chromium(III) Ions in Aqueous Solution. A Large Angle X-ray Scattering and EXAFS Study

Patric Lindqvist-Reis; Adela Muñoz-Páez; Sofia Díaz-Moreno; Sidhartha Pattanaik; Ingmar Persson; Magnus Sandström

doi:10.1021/ic980750y

The Structure of the Hydrated Gallium(III), Indium(III), and Chromium(III) Ions in Aqueous Solution. A Large Angle X-ray Scattering and EXAFS Study

Inorg Chem. 1998 Dec 28;37(26):6675-6683. doi: 10.1021/ic980750y.

Authors

Patric Lindqvist-Reis¹, Adela Muñoz-Páez, Sofia Díaz-Moreno, Sidhartha Pattanaik, Ingmar Persson, Magnus Sandström

Affiliation

¹ Department of Chemistry, Royal Institute of Technology, S-100 44 Stockholm, Sweden, Instituto de Ciencia de Materiales de Sevilla CSIC, University of Sevilla, C/Americo Vespucio s/n, E-41092 Sevilla, Spain, and Department of Chemistry, Swedish University of Agricultural Sciences, P.O. Box 7015, S-750 07 Uppsala, Sweden.

PMID: 11670798
DOI: 10.1021/ic980750y

Abstract

The structure of the hydrated gallium(III), indium(III), and chromium(III) ions has been determined in aqueous perchlorate and nitrate solutions by means of the large-angle X-ray scattering (LAXS) and extended X-ray absorption fine structure (EXAFS) techniques. The EXAFS studies have been performed over a wide concentration range, 0.005-1.0 mol.dm(-)(3) (2.6 mol.dm(-)(3) for chromium(III)), while the LAXS studies are restricted to concentrated solutions, ca. 1.5 mol.dm(-)(3). All three metal ions were found to coordinate six water molecules, each of which are hydrogen bonded to two water molecules in a second hydration sphere. The metal-oxygen bond distance in the first hydration sphere of the gallium(III), indium(III), and chromium(III) ions was determined by LAXS and EXAFS methods to be 1.959(6), 2.131(7), and 1.966(8) Å. The LAXS data gave mean second sphere M.O distances of 4.05(1), 4.13(1), and 4.08(2) Å for the gallium(III), indium(III), and chromium(III) ions, respectively. The perchlorate ion was found to be hydrogen bonded to 4.5(7) water molecules with the O.O distance 3.05(2) Å and Cl.O 3.68(3) Å. Analyses of the Ga, In, and Cr K-edge EXAFS data of the aqueous perchlorate and nitrate solutions showed no influence on the first shell M-O distance by a change of concentration or anion. The minor contribution from the second sphere M.O distance is obscured by multiple scattering within the tightly bonded first shell. EXAFS data for the alum salts CsM(SO(4))(2).12H(2)O, M = Ga or In, showed the M-O bond length of the hexahydrated gallium(III) and indium(III) ions to be 1.957(2) and 2.122(2) Å, respectively.