Crystallization of jarosite with variable Al3+ content: The transition to alunite

Abstract

This study focused on the formation of the jarosite-alunite solid solution at relatively low temperature, 90 °C. It was found that the transition from jarosite to alunite results in significant changes in the powder X-ray diffraction pattern, the infrared spectrum and thermal behavior when the degree of substitution reached ≥50%. The initial Al/(Al + Fe) in solution, however, required to achieve these substitution levels in the solid is ≥90%. The morphology shows that the faceted jarosite form goes through an intergrown transition to a spherical morphology of pure alunite. This morphology has not been previously observed for alunite and most likely reflects the formation temperature. Rietveld analysis shows that the a lattice parameter obeys Vegard’s Rule while the c lattice parameter behavior is more complex. Empirical modelling of the incorporation of Fe into alunite supports the general trends found in the X-ray diffraction data for the behaviour of the a-axis with Al/Fe content. The dehydration of the Al3+ ion could be a significant contribution to the activation energy barrier to alunite formation as found for other minerals. Finally, dynamic light scattering showed that the nucleation behavior for jarosite and Fe-containing alunite are significantly different. Alunite appears to nucleate continuously rather than in a single nucleation event.