On Solvolysis of α-Phosphorus(V) Oxide

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1. α-Phosphorus(V) oxide was allowed to react with water, with ethanol or acetone, both dry or mixed with water by adding the powder crystal directly into these liquids. The oxide was also brought in contact with water after being dispersed in diethyl ether or benzene mechanically.<BR>2. The main final hydrolysis products formed in the following cases were tetrametaphosphoric acid by direct action of a large quantity of water, pyrophosphoric acid by anhydrous ethanol, tripolyphosphoric acid by ethanol with a low water content, and highpolyphosphoric acid by anhydrous acetone. Quick contact with water after the oxide has been dispersed in ether or benzene leads to the formation of a larger amount of tetrametaphosphoric acid when these solvents were dry, while the formation of an increased amount of highpolyphosphoric acid was the result when they contained trace quantities of water initially.<BR>3. Separation, identification and estimation of various condensed phosphate species were executed by paper chromatography and colorimetric analysis.<BR>4. Reaction mechanisms were postulated to explain these results. Special attention was given to the solvolytic opening of P–O–P linkages and the accompanying condensation process of phosphate radicals.
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