Abstract
The thermal behaviour in oxygen of Fe 2MoO 4 spinel prepared by the ceramic method has been investigated over the temperature range of 150–700°C on ground samples. Below 550°C, Fe 2MoO 4 is partially oxidized in the cation deficient spinel with a very large content of vacancies. The high electrical conductivity of the initial sample and its temperature dependence in oxygen can be related to a mixture of Fe 2+ and Fe 3+ valencies on both octahedral (B) and tetrahedral (A) sites, despite the observed positive value of the Seebeck coefficient. Derivative thermogravimetric studies showed that B site Fe 2+ and Mo 3+ ions will be oxidized more rapidly than A site Fe 2+ ions when the oxidation temperature is lower for Fe 2+ ions on B sites than that for Mo 3+ ions on the same sites, and this discrepancy in reactivity has been used to determine the distribution of cations between the sublattices. In addition, a significant content of Mo 4+ ions and a transfer of Mo 6+ ions from the B sites to the A sites during oxidation can be derived from XPS and IR spectrometry.
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