Mössbauer spectroscopic studies of the disintegration of hexavalent iron compounds (BaFeO₄ and K₂FeO₄)

Mössbauer spectroscopic studies of BaFeO₄ and K ₂FeO₄ as prepared, then either sealed, or exposed to air, or exposed to moist air for a period up to more than one year, were performed at room temperature as a function of time. Some of the samples were studied as a function of temperature down to 4.2 K. K₂FeO₄ and BaFeO₄ after preparation, exhibit a pure Fe⁶⁺ spectrum. K₂FeO₄ shows low stability. After a period of 14 months in a sealed sample holder, the spectrum exhibits 83% noncrystalline Fe ³⁺, as Fe₂O₃ nanoparticles, and only 17% of the original Fe⁶⁺. BaFeO₄ sealed, or exposed to dry air disintegrates slowly, exhibiting a spectrum composed of three subspectra. In addition to the original Fe⁶⁺ and final Fe³⁺ subspectra, a subspectrum, of an intermediate stage of a crystalline Fe⁴⁺ system, is present. In the first month the increase of the Fe³⁺ subspectrum is 15%, and that of the Fe⁴⁺ is 8%. BaFeO₄ exposed to moist air, disintegrates at a very fast rate. The Fe³⁺ subspectrum, due to Fe₂O₃ nanoparticles, increases in the first days at the rapid rate of ∼13%/day, and there is no evidence for Fe⁴⁺ in the spectrum. The Fe⁶⁺ in BaFeO₄, Fe³⁺ and Fe⁴⁺ in the disintegrated systems are all magnetically ordered at 4.2 K. Above 90 K the Fe³⁺ subspectra exhibit a superposition of a paramagnetic doublet and a diffuse magnetic sextet, with relative intensities changing with temperature, and changing from sample to sample according to their blocking temperatures, which are determined by the distribution in size of the nanoparticles.