Phosphorus pentoxide
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IUPAC name
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| Systematic IUPAC name
2,4,6,8,9,10-Hexaoxa-1λ5,3λ5,5λ5,7λ5-tetraphosphatricyclo[3.3.1.13,7]decane 1,3,5,7-tetraoxide | |||
Other names
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| Identifiers | |||
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3D model (JSmol) |
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| ChEBI | |||
| ChemSpider | |||
| ECHA InfoCard | 100.013.852 | ||
PubChem CID |
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| RTECS number |
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| UNII | |||
CompTox Dashboard (EPA) |
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| Properties[1] | |||
| P2O5 | |||
| Molar mass | 141.943 g·mol−1 | ||
| Appearance |
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| Odor | Odorless | ||
| Density | 2.3 g/cm3 | ||
| Melting point | 562 °C (1,044 °F; 835 K) (sublimes) | ||
| Boiling point | 605 °C (1,121 °F; 878 K) (if heated faster than sublimation can occur) | ||
| Exothermic hydrolysis | |||
| Vapor pressure |
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| Thermochemistry[1] | |||
Enthalpy of fusion (ΔfH⦵fus) |
27.2 kJ⋅mol−1 | ||
| Hazards | |||
| Occupational safety and health (OHS/OSH): | |||
Main hazards |
Reacts with water, strong dehydrating agent, corrosive.[2] | ||
| GHS labelling:[2] | |||
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| Danger | |||
| H314 | |||
| P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340+P310, P305+P351+P338+P310, P363, P405, P501 | |||
| NFPA 704 (fire diamond) | |||
| Lethal dose or concentration (LD, LC): | |||
LC50 (median concentration) |
1217 mg/m3 (rat, 1h)[3] | ||
| Safety data sheet (SDS) | "SDS - Phosphorous pentoxide". Version 6.20. St. Louis, MO: Sigma-Aldrich. 9 July 2026. Retrieved 21 September 2026. | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Phosphorus pentoxide is a chemical compound with molecular formula P4O10 (with its common name derived from its empirical formula, P2O5). This white crystalline solid is the anhydride of phosphoric acid. It is a powerful desiccant and dehydrating agent.
Structure
[edit]Phosphorus pentoxide crystallizes in at least four forms or polymorphs. The most familiar one, a metastable form[4] (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.[5] The structure of the P4O10 cage is reminiscent of adamantane with Td symmetry point group.[6][page needed] It is closely related to the corresponding anhydride of phosphorous acid, phosphorus trioxide (P4O6, which lacks terminal oxo groups). Its density is 2.30 g/cm3. It boils at 423 °C (793 °F) under atmospheric pressure; if heated more rapidly it can sublimate. This form can be made by condensing the vapor of phosphorus pentoxide rapidly, and the result is an extremely hygroscopic solid.[7]
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.[7] The metastable orthorhombic "O"-form (density 2.72 g/cm3, melting point 562 °C (1,044 °F)) 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.[4][8] The remaining polymorph is a glass or amorphous form; it can be made by fusing any of the others.
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| Part of an o′−(P2O5)∞ layer | o′−(P2O5)∞ layers stacking |
Preparation
[edit]P4O10 is prepared by burning white phosphorus with a sufficient supply of oxygen:[9][page needed]
- P4 + 5 O2 → P4O10
The dehydration of phosphoric acid to give phosphorus pentoxide is not possible, as on heating it forms various polyphosphates but will not dehydrate sufficiently to form P4O10.
Applications
[edit]Phosphorus pentoxide is a potent dehydrating agent as indicated by the exothermic nature of its hydrolysis producing phosphoric acid:[citation needed]
- P4O10 + 6 H2O → 4 H3PO4 (−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 primary amides into nitriles:[10]
- 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.
Alternatively, when combined with a carboxylic acid, the result is the corresponding anhydride:[11]
- P4O10 + RCO2H → P4O9(OH)2 + [RC(O)]2O
The "Onodera reagent", a solution of P4O10 in Dimethyl sulfoxide (DMSO), is employed for the oxidation of alcohols.[12] 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:[citation needed]
- Nitric acid (HNO3) is converted to dinitrogen pentoxide (N2O5).
- Sulfuric acid (H2SO4 is converted to sulfur trioxide (SO3.
- Perchloric acid (HClO4) is converted to dichlorine heptoxide (Cl2O7).
- Triflic acid (CF3SO3H) is converted to Triflic anhydride ((CF3)2S2O5.
As a proxy measurement
[edit]P2O5 content is often used by industry as proxy value for all the phosphorus oxides in a material. For example, fertilizer grade phosphoric acid can also contain various related phosphorous compounds which are also of use. All these compounds are described collectively in terms of 'P2O5 content' to allow convenient comparison of the phosphorous content of different products. Despite this, phosphorus pentoxide is not actually present in most samples as it is not stable in aqueous solutions.
Hazards
[edit]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.[citation needed]
See also
[edit]- Various other phosphorus oxides
- Eaton's reagent
References
[edit]- 1 2 Haynes, William M., ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). Boca Raton, Florida: CRC Press. pp. 4–78, 6–120, 6–160. ISBN 9781498754293.
- 1 2 Sigma-Aldrich Co., Phosphorous pentoxide.
- 1 2 "Safety Data Sheet - Phosphorous pentoxide" (pdf). www.fishersci.com. Revision 10. ThermoFisher Scientific. 18 December 2025 [1 September 2010]. Retrieved 21 September 2026.
- 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.[page needed]
- ↑ Cruickshank, D. W. J. (1964). "Refinements of Structures Containing Bonds between Si, P, S or Cl and O or N: V. P4O10". Acta Crystallogr. 17 (6): 677–9. doi:10.1107/S0365110X64001669.
- ↑ Corbridge, D. E. C. Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology (5th ed.). Amsterdam: Elsevier. ISBN 0-444-89307-5.
- 1 2 Housecroft, C. E.; Sharpe, A. G. (2008). Inorganic Chemistry (3rd ed.). Prentice Hall. p. 473. ISBN 978-0-13-175553-6.
- ↑ D. Stachel, I. Svoboda and H. Fuess (June 1995). "Phosphorus Pentoxide at 233 K". Acta Crystallogr. C. 51 (6): 1049–1050. Bibcode:1995AcCrC..51.1049S. doi:10.1107/S0108270194012126.
- ↑ Threlfall, Richard E. (1951). The story of 100 years of Phosphorus Making: 1851 - 1951. Oldbury: Albright & Wilson.
- ↑ Meier, M.S. (15 April 2001). ""Phosphorous(V) Oxide". In Paquette, L. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York, NY: J. Wiley & Sons. doi:10.1002/047084289X.
- ↑ Joseph C. Salamone, ed. (1996). Polymeric materials encyclopedia: C, Volume 2. CRC Press. p. 1417. ISBN 0-8493-2470-X.
- ↑ Tidwell, T.T. (15 April 2001). "Dimethyl sulfoxide-phosphorous pentoxide". In Paquette, L. (ed.). Encyclopedia of Reagents for Organic Synthesis. New York, NY: J. Wiley & Sons. doi:10.1002/047084289X.