In situ high-temperature XRPD and FTIR study of melanterite

The thermal behavior of melanterite from the Fornovolasco mine (Tuscany, Italy) has been investigated via differential thermal analysis (DTA), thermogravimetry (TG), in situ high-temperature X-ray powder diffraction (XRPD) and Fourier-transform infrared spectroscopy (FTIR). The DTA curve showed endothermic peaks at 70, 100, 260, 500–560 and 660 °C whereas the TG curve evidenced a total mass decrease of ~68%, in keeping with the loss of all H2O and SO4 groups. Rietveld refinements were performed for all the collected patterns in the 25–775 °C range and converged at 1.57 ≤ R (%) ≤ 2.75 and 1.98 ≤ Rwp (%) ≤ 3.74. The decomposition steps FeSO4·7H2O → FeSO4·4H2O (25 ≤ T ≤ 50 °C) → FeSO4·H2O (50 < T ≤ 100 °C) → FeOHSO4 (75 < T ≤ 200 °C) → Fe2(SO4)3 (400 < T ≤ 500 °C) → Fe2O3 (500 < T ≤ 775 °C) were obtained. The high-temperature infrared analysis confirmed that melanterite undergoes a three-step dehydration in the 25–300 °C temperature range. The FeOHSO4 phase is stable over a wide range of temperature and transforms partially to Fe2(SO4)3 without the formation of Fe2O(SO4)2. The findings highlight a different behavior of the studied sample with respect to the synthetic salt.