Abstract
The crystal structures of the high-temperature modifications of sodium and silver orthophosphates have been determined using powder neutron diffraction (PND) data. II-Na 3PO 4 adopts the space group Fm3m with a=7.512(3) A ̊ at 400°C. The PO 3− 4 group is centered around the origin, but it shows high orientational disorder. The sodium ions occupy the 1 4 1 4 1 4 and 1 2 1 2 1 2 sites. II-Ag 3PO 4, at 650°C, is similar with a=7.722(5) A ̊ . The structure of I-Ag 3PO 4 at room temperature ( P 43 n, a=6.0095 (6) A ̊ ) has been re-examined by single-crystal X-ray diffraction. The derived model, with R=0.019 for 116 independent reflections, is in agreement with the latest work reported in the literature. The structure of I-Ag 3PO 4 at 375°C, as determined by PND, has a=6.061 (1) A ̊ , and displays no gross modifications from that observed at 25°C, although the anisotropic nature of the silver sites is markedly more pronounced at this higher temperature. The cation mobility is discussed in relation to the high-temperatures structures.
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