Abstract

Aluminium substitution into goethite, α-FeOOH, has been studied systematically by infrared spectroscopy over the frequency interval 150 to 700 cm-1. A range of synthetic compositions, (Fe1-xAlx)OOH, 0 ≤ x ≤ 0.0857, plus end-member diaspore (AlOOH) were examined. The IR spectrum of FeOOH over the range of interest can be deconvoluted into 9 peaks: 670, 633, 497, 451, 409, 396, 360, 290 and 268 cm-1. With addition of Al, the spectra become broader and the frequencies of the modes shift to higher values. An effective line width parameter Δcorr was determined by autocorrelation analysis for each spectrum and there is a significant increase in the Δcorr for compositions with >5.85 mol.% Al substitution, indicating that there is very significant structural strain associated with this solid solution at compositions where a significant number of Al sites will have an additional Al atom in the first cation coordination sphere. Trends in the values of Δcorr with composition mirrored published enthalpy of mixing values indicating that Al-goethite is metastable with respect to the goethite and diaspore end-members. The role of substitutional strain and possible partial order of Al is briefly discussed.

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