Phosphorus pentoxide crystallizes in at least four forms or polymorphs. The most familiar one, a metastable form, shown in the figure, comprises molecules of P4O10. Weak van der Waals forces hold these molecules together in a hexagonal lattice. The structure of the P4O10 cage is reminiscent of adamantane with Td symmetry point group. It is closely related to the corresponding anhydride of phosphorous acid, P4O6. The latter lacks terminal oxo groups. Its density is 2.30 g/cm3. It boils at 423 °C under atmospheric pressure; if heated more rapidly it can sublimate. This form can be made by condensing the vapor of phosphorus pentoxide rapidly, the result is an extremely hygroscopic solid. The other polymorphs are polymeric, but in each case the phosphorus atoms are bound by a tetrahedron of oxygen atoms, one of which forms a terminal P=O bond involving the donation of the terminal oxygen p-orbital electrons to the antibonding phosphorus-oxygen single bonds. The macromolecular form can be made by heating the compound in a sealed tube for several hours, and maintaining the melt at a high temperature before cooling the melt to the solid. The metastable orthorhombic, "O"-form, adopts a layered structure consisting of interconnected P6O6 rings, not unlike the structure adopted by certain polysilicates. The stable form is a higher density phase, also orthorhombic, the so-called O' form. It consists of a 3-dimensional framework, density 3.5 g/cm3. The remaining polymorph is a glass or amorphous form; it can be made by fusing any of the others.
part of an o′-∞ layer
o′-∞ layers stacking
Preparation
P4O10 is prepared by burning tetraphosphorus with sufficient supply of oxygen: For most of the 20th century, phosphorus pentoxide was used to provide a supply of concentrated pure phosphoric acid. In the thermal process, the phosphorus pentoxide obtained by burning white phosphorus was dissolved in dilute phosphoric acid to produce concentrated acid. Improvements in filter technology is leading to the "wet phosphoric acid process" taking over from the thermal process, obviating the need to produce white phosphorus as a starting material. The dehydration of phosphoric acid to give phosphorus pentoxide is not possible as on heating metaphosphoric acid will boil without losing all its water.
Applications
Phosphorus pentoxide is a potent dehydrating agent as indicated by the exothermic nature of its hydrolysis: However, its utility for drying is limited somewhat by its tendency to form a protective viscous coating that inhibits further dehydration by unspent material. A granular form of P4O10 is used in desiccators. Consistent with its strong desiccating power, P4O10 is used in organic synthesis for dehydration. The most important application is for the conversion of primary amides into nitriles: The indicated coproduct P4O92 is an idealized formula for undefined products resulting from the hydration of P4O10. Alternatively, when combined with a carboxylic acid, the result is the corresponding anhydride: The "Onodera reagent", a solution of P4O10 in DMSO, is employed for the oxidation of alcohols. This reaction is reminiscent of the Swern oxidation. The desiccating power of P4O10 is strong enough to convert many mineral acids to their anhydrides. Examples: HNO3 is converted to N2O5; H2SO4 is converted to SO3; HClO4 is converted to Cl2O7; CF3SO3H is converted to 2S2O5.
Between the commercially important P4O6 and P4O10, phosphorus oxides are known with intermediate structures.
Hazards
Phosphorus pentoxide itself is not flammable. Just like sulfur trioxide, it reacts vigorously with water and water-containing substances like wood or cotton, liberates much heat and may even cause fire due to the highly exothermic nature of such reactions. It is corrosive to metal and is very irritating – it may cause severe burns to the eye, skin, mucous membrane, and respiratory tract even at concentrations as low as 1 mg/m3.
In Detective Comics #825, Batman notices that phosphorus pentoxide was at the scene of a fire, indicating that the villain Dr. Phosphorus was involved.
In Aldous Huxley's Point Counter Point, to his assistant Illidge, Lord Edward bemoans societal loss of phosphorous pentoxide.
In Aldous Huxley's Brave New World, Henry Foster tells Lenina about the recovery of phosphorus pentoxide.
In The Tunnel,, a victim was consumed by a fire started with phosphorus pentoxide.
