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Phosphorus pentoxide
Phosphorus pentoxide
Phosphorus pentoxide
Other names Phosphorus(V) oxide
Phosphoric anhydride
Identifiers
CAS number 1314-56-3 Yes check.svgY,
[16752-60-6] (P4O10)
PubChem 14812
RTECS number TH3945000
Properties
Molecular formula O10P4
Molar mass 283.89 g mol−1
Exact mass 283.889048 g/mol
Appearance white powder
very deliquescent
pungent odour
Density 2.39 g/cm3
Melting point

340 °C, 613 K, 644 °F

Boiling point

360 °C (sublimes)

Solubility in water exothermic hydrolysis
Vapor pressure 1 mmHg @ 384 °C
Hazards
EU classification not listed
NFPA 704
NFPA 704.svg
1
3
3
W
 Yes check.svgY (what is this?)  (verify)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Phosphorus pentoxide is a chemical compound with molecular formula P4O10. This white crystalline solid is the anhydride of phosphoric acid. It is a powerful desiccant.

Contents

Structure

Phosphorus pentoxide crystallizes in at least four forms or polymorphs. The most familiar one, shown in the figure, comprises molecules of P4O10. Weak van der Waals forces hold these molecules together in a hexagonal lattice (However, in spite of the high symmetry of the molecules, the crystal packing is not a close packing[1]). The structure of the P4O10 cage is reminiscent of adamantane with Td symmetry point group.[2] 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.

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. The O-form (density 3.05 g/cm³, m.p. 580 °C), adopts a layered structure consisting of interconnected P6O6 rings, not unlike the structure adopted by certain polysilicates. A lower density phase, the so-called O' form, consists of a 3-dimensional framework is also known, density 2.72 g/cm³.[3] The remaining polymorph is a glass or amorphous form; it can be made by fusing any of the others.

Phosphorus-pentoxide-sheet-from-xtal-3D-balls.png
Phosphorus-pentoxide-xtal-3D-balls.png
part of an o′-(P2O5) layer
o′-(P2O5) layers stacking

Preparation

P2O5 is prepared by burning elemental phosphorus with sufficient supply of air :

P4 + 5 O2 → 2 P2O5

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.[4] 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.[5] The dehydration of phosphoric acid to give phosphorus pentoxide is not practicable; on heating, metaphosphoric acid will decompose before it loses water.

Applications

Phosphorus pentoxide is a potent dehydrating agent as indicated by the exothermic nature of its hydrolysis:

P4O10 (am) + 6H2O (lq) → 4H3PO4 (c)   (-177 kJ)

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 amides into nitriles:[6]

P4O10 + RC(O)NH2 → P4O9(OH)2 + RCN

The indicated coproduct P4O9(OH)2 is an idealized formula for undefined products resulting from the hydration of P4O10.

Supposedly, when combined with a carboxylic acid, the result is the corresponding anhydride:

P4O10 + RCO2H → P4O9(OH)2 + [RC(O)]2O

The "Onodera reagent", a solution of P4O10 in DMSO, is employed for the oxidation of alcohols.[7] 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 N2O5H2SO4 is converted to SO3HClO4 is converted to Cl2O7.

Related phosphorus oxides

Between the commercially important P4O6 and P4O10, phosphorus oxides are known with intermediate structures.[8]

Phosphorus oxides: P4O6, P4O7, P4O8, P4O9, and P4O10.

Hazards

Non-flammable. Reacts vigorously with water and water-containing substances like wood or cotton, liberates much heat and may even cause fire. Corrosive to metal. Very irritating. May cause severe burn to the eye, skin, mucous membrane, and respiratory tract even at as low as 1mg/cm3.

Fire fighting measures: Wear full protective gear. Do NOT use water directly on fire. Use dry chemical, carbon dioxide, or alcohol-resistant foam.

First aid measures:

Inhalation: Remove from exposure to fresh air immediately. Get medical aid.

Eye: Flush eyes with plenty of water for at least 15 minutes. Get medical aid.

Skin: Flush skin with plenty of water. Get medical aid.

Fiction

In Anthony Burgess' The Wanting Seed, phosphorus pentoxide is a highly prized compound.

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, Lord Edward bemoans societal loss of phosphorous pentoxide to his assistant Illidge.

In Aldous Huxley's Brave New World, Henry Foster tells Lenina about the recovery of phosphorus pentoxide. IN [Arthur Conan Dayle]]'s The Hound of Baskervilles",coat of white phosphorus was used on the dog to make it look like a beast

References

  1. ^ Cruickshank, D.W.J. "Refinements of Structures Containing Bonds between Si, P, S or Cl and O or N: V. P4O10" Acta Cryst. 1964, volume 17, pages 677-9.
  2. ^ D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam. ISBN 0-444-89307-5.
  3. ^ D. Stachel, I. Svoboda and H. Fuess (June 1995). "Phosphorus Pentoxide at 233 K". Acta Cryst. C51 (6): 1049–1050. doi:10.1107/S0108270194012126.  
  4. ^ Threlfall, Richard E., (1951). The story of 100 years of Phosphorus Making: 1851 - 1951. Oldbury: Albright & Wilson Ltd
  5. ^ Podger, Hugh (2002). Albright & Wilson: The Last 50 Years. Studley: Brewin Books. ISBN 1-85858-223-7
  6. ^ Meier, M. S. "Phosphorus(V) Oxide" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
  7. ^ Tidwell, T. T. "Dimethyl Sulfoxide–Phosphorus Pentoxide" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.
  8. ^ Luer, B.; Jansen, M. "Crystal Structure Refinement of Tetraphosphorus Nonaoxide, P4O9" Zeitschrift fur Kristallographie 1991, volume 197, pages 247-8.

See also

External links








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