phosphorus(III) oxide

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A white or colourless waxy solid, P4O6; r.d. 2.13; m.p. 23.8°C; b.p. 173.8°C. It is soluble in ether, chloroform, and benzene but reacts with cold water to give phosphonic acid, H3PO3, and with hot water to give phosphine and phosphoric(V) acid. The compound is formed when phosphorus is burned in an oxygen-deficient atmosphere (about 50% yield). As it is difficult to separate from white phosphorus by distillation, the mixture is irradiated with ultraviolet radiation to convert excess white phosphorus into the red form, after which the oxide can be separated by dissolution in organic solvents. Although called a trioxide for historical reasons, phosphorus(III) oxide consists of P4O6 molecules of tetrahedral symmetry in which each phosphorus atom is linked to the three others by an oxygen bridge. The chemistry is very complex. Above 210°C it decomposes into red phosphorus and polymeric oxides. It reacts with chlorine and bromine to give oxo-halides and with alkalis to give phosphonates (see phosphonic acid).

Subjects: Chemistry.

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