Abstract
A new compound has been found in the system Bi 2O 3 P 2O 5. It has the composition of 6.73 mol% P 2O 5 and crystallizes in sillenite-type structure with space group I23and a = 10.1691(1)Å. A DTA trace of the compound shows a noticeable endothermic peak around 850°C and an incongruent melting peak at 890°C. Normally the sillenite-type compound has the stoichiometric composition,Bi 24 Me 2O 40 ( Me =Ge, Si, or Ti);however, the present compound results in the nonstoichiometric one. A structural model is proposed on the assumption that the24 f sites are partially occupied by Bi 3+ ions (occupancy factor 97.22%) and the tetrahedral2 asites are statistically filled by Bi 5+ and P 5+ ions. Thus the nonstoichiometric composition within the unit cell is expressed by Bi(III) 23.33[Bi(V) 0.295P 1.705]O 40. Using this model, the composition of metastable γ-Bi 2O 3 is discussed.
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