Structural vanadium in synthetic goethite

Physics

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Scientific paper

A significant correlation between Fe and V in many weathered profiles suggests a close geochemical association of the two elements. Because V 3+ is the dominant form of V in primary rocks, and because an isostructural VOOH (montroseite) exists, we suspect that goethite, FeOOH, might incorporate V 3+ in its structure. We synthesized Fe 1-x V x OOH with x up to 0.06. Because the ionic radii of V 3+ and high spin Fe 3+ are very similar (64.5 vs. 64.0 pm), even a careful measurement of the unit cell parameters did not reveal a statistically significant difference. Structural incorporation was, therefore, demonstrated by congruent dissolution in 6 M HCl. Equivalent amounts of Fe 2+ and V found in the acid digest were presumably formed by the reaction V 3+ + Fe 3+ + H 2 O = VO 2+ + Fe 2+ + 2H + . An EPR spectrum did not indicate V 4+ . For these and steric reasons, it is postulated that V is incorporated into goethite as a trivalent cation rather than as a combination of V 4+ and Fe 2+ .

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