Influência de Gd e de elementos de transição nas propriedades físico-químicas da goethita (x-FeOOH)

Abstract

Goethite is a common mineral, easily found in surface environments, typically forming under oxidizing conditions as a product of chemical weathering of iron-bearing minerals. Several non-ferric metals have already been found in its structure, such as, for example, Cd, Co, Ni, V, Zn and Mn. The presence of these foreign elements in the structure of goethite can lead to variations in its physicochemical properties. To study variations in the following properties: unit cell dimensions, position of infrared bands, thermal properties, mineral color, degree of crystallinity and solubility product, synthetic goethite samples were prepared under mildly acidic conditions (pH ~ 4.5 ), incorporating Mn3+, Cd2+, V3+, Zr4+, Nb5+ and Gd3+ in its structure. The systematic changes in dimensions a, b and c of the unit cell, with the increase in the concentration of foreign elements in the structure, suggest that such elements replace Fe3+ in the octahedral structure of goethite and can be related to the ionic radius of the incorporated metals. The dispersion of values for the crystallographic axis a may result from distortion of the octahedron with the incorporation of non-ferric metals or structural defects. The crystallinity of the samples decreases with the increase in the concentration of foreign elements in the structure. The vibrations of the O-H bonds, out of plane, increased from 794 to 798 cm -1, indicating a slight shortening in the length of the M-OH bond (M = metal), with the increase in the concentration of incorporated metals. M-O bond vibrations, for M = Cd, Mn, V, Nb, Zr and Gd, were obtained in the region of 50 - 500 cm -1. The appearance of new vibration frequencies, compared to the pure synthetic goethite sample, and the disappearance of others, indicate the presence of metals other than iron in the structure. Data from differential thermal analysis (DTA) demonstrate that there is greater disorder in the structure, or less crystallinity of the samples, as the content of non-ferric metal in the octahedral structure of goethite increases.