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Abstract:

A series of Cr-substituted goethites with (Cr:Fe molar ratio up to 0.12) were prepared. Thermal analysis of the solids indicates the formation of cation-deficient compounds that are more stable towards the transformation to hematite as the Cr content increases. Powder X-ray diffraction (PXRD) and extended X-ray absorption fine structure (EXAFS) techniques were used to assess the structural characteristics of the whole series of the substituted solids. XRD patterns demonstrate that the order around Fe remains typical of a goethite-like structure. Rietveld refinement of X-ray diffraction data indicates that the incorporation of Cr causes a slight decrease in the cell volume with the c -cell parameter following the Vegard's law. This decrease is accompanied by changes in opposite directions of the various Me-Me distances. EXAFS spectra at the Fe K-edge indicate that the local order around the Fe atom changes slightly upon Cr substitution: Measurements in the Cr K-edge show that the Cr environment remains unchanged in the whole series. All the observed trends in both average Rietveld and local EXAFS distances can be traced back to the differences in the coordination polyhedra around Cr and Fe. The polyhedron around Cr is more symmetric and can be described as Cr(OH0.5)6 as opposed to the polyhedron around Fe that contains two distinct sets of ligands, FeO3 (OH)3. The effects caused by substitution are governed by this difference, rather than by the smaller size of Cr(III) as compared to Fe(III). Simultaneous use of XAS and Rietveld refinement of XRD data permits tracing the trends in the average long range ordering (Me-Me distances) to local changes in distances and angles when Cr3+ substitutes Fe3+ in goethite. Complex changes in the various interatomic distances and angles may result in deceivingly simple long-range trends. These trends are therefore of limited value as probes for the atomic scale changes. On the other hand, XAS provide direct information on the fundamental, atomic-scale changes. © 2004 Elsevier Ltd.

Registro:

Documento: Artículo
Título:Long-range vs. short-range ordering in synthetic Cr-substituted goethites
Autor:Sileo, E.E.; Ramos, A.Y.; Magaz, G.E.; Blesa, M.A.
Filiación:INQUIMAE, Depto de Quim Inorg Analit/Quim Fis, Fac. de Ciencias Exactas/Naturales, Buenos Aires, Argentina
LNLS, P.O. Box 6192, Campinas, SP CEP 13084-971, Brazil
Laboratoire de Mineralogie, Cristallographie de Paris, UMR7590, Paris Cedex 05 75252, France
Unidad de Actividad Química, Centro Atómico Constituyentes, Comision Nacional de Energia Atomica, Avenida Gral, Paz 1499, San Martín 1650, Argentina
Escuela de Posgrado, Univ. Nacional de General San Martin, San Martin, Buenos Aires, Argentina
Palabras clave:chromium; geochemistry; goethite; mineral synthesis; soil chemistry
Año:2004
Volumen:68
Número:14
Página de inicio:3053
Página de fin:3063
DOI: http://dx.doi.org/10.1016/j.gca.2004.01.017
Título revista:Geochimica et Cosmochimica Acta
Título revista abreviado:Geochim. Cosmochim. Acta
ISSN:00167037
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00167037_v68_n14_p3053_Sileo

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Citas:

---------- APA ----------
Sileo, E.E., Ramos, A.Y., Magaz, G.E. & Blesa, M.A. (2004) . Long-range vs. short-range ordering in synthetic Cr-substituted goethites. Geochimica et Cosmochimica Acta, 68(14), 3053-3063.
http://dx.doi.org/10.1016/j.gca.2004.01.017
---------- CHICAGO ----------
Sileo, E.E., Ramos, A.Y., Magaz, G.E., Blesa, M.A. "Long-range vs. short-range ordering in synthetic Cr-substituted goethites" . Geochimica et Cosmochimica Acta 68, no. 14 (2004) : 3053-3063.
http://dx.doi.org/10.1016/j.gca.2004.01.017
---------- MLA ----------
Sileo, E.E., Ramos, A.Y., Magaz, G.E., Blesa, M.A. "Long-range vs. short-range ordering in synthetic Cr-substituted goethites" . Geochimica et Cosmochimica Acta, vol. 68, no. 14, 2004, pp. 3053-3063.
http://dx.doi.org/10.1016/j.gca.2004.01.017
---------- VANCOUVER ----------
Sileo, E.E., Ramos, A.Y., Magaz, G.E., Blesa, M.A. Long-range vs. short-range ordering in synthetic Cr-substituted goethites. Geochim. Cosmochim. Acta. 2004;68(14):3053-3063.
http://dx.doi.org/10.1016/j.gca.2004.01.017