Phosphoryl chloride

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Phosphoryl chloride
Phosphoryl chloride
IUPAC names
Phosphoryl trichloride
Phosphorus trichloride oxide
Other names
Phosphorus oxychloride
Phosphoric trichloride
3D model (JSmol)
ECHA InfoCard 100.030.030
EC Number 233-046-7
RTECS number TH4897000
UN number 1810
Molar mass 153.33 g/mol
Appearance Clear, colourless liquid, fumes in moist air
Odor pungent and musty
Density 1.645 g/cm3, liquid
Melting point 1.25 °C (34.25 °F; 274.40 K)
Boiling point 105.8 °C (222.4 °F; 378.9 K)
Solubility highly soluble in benzene, chloroform, CS2, CCl4
Vapor pressure 40 mmHg (27 °C)[1]
2.54 D
84.35 J/mol K
-568.4 kJ/mol
Safety data sheet See: data page
ICSC 0190
Very toxic (T+)
Harmful (Xn)
Corrosive (C)
R-phrases (outdated) R14, R22, R26, R35, R48/23
S-phrases (outdated) (S1/2), S7/8, S26, S36/37/39, S45
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Lethal dose or concentration (LD, LC):
36 mg/kg (rat, oral)
US health exposure limits (NIOSH):
PEL (Permissible)
REL (Recommended)
TWA 0.1 ppm (0.6 mg/m3) ST 0.5 ppm (3 mg/m3)[1]
IDLH (Immediate danger)
Related compounds
Related compounds
Thiophosphoryl chloride
Phosphorus oxybromide
Phosphorus trichloride
Phosphorus pentachloride
Supplementary data page
Refractive index (n),
Dielectric constantr), etc.
Phase behaviour
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Phosphoryl chloride (commonly called phosphorus oxychloride) is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and choking fumes of hydrogen chloride, it is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters such as tricresyl phosphate.


Like phosphate, phosphoryl chloride is tetrahedral in shape, it features three P−Cl bonds and one strong P=O double bond, with an estimated bond dissociation energy of 533.5 kJ/mol. On the basis of bond length and electronegativity, the Schomaker-Stevenson rule suggests that the double bond form is very dominant (in contrast with POF3). The P=O bond does not utilize the d-orbitals on phosphorus as is commonly described in older textbooks as quantum chemical calculations have shown that d-orbitals are not involved in main group chemical bonding (see Hypervalent molecule). More modern texts favour a description which involves the donation of the lone pair electrons from oxygen p-orbitals to the antibonding phosphorus-chlorine bonds thus constituting π bonding.[2]

POCl3 structure.png

Physical properties[edit]

With a freezing point of 1 °C and boiling point of 106 °C, the liquid range of POCl3 is rather similar to water.

Chemical properties[edit]

POCl3 reacts with water and alcohols to give hydrogen chloride and phosphoric acid or phosphate esters, respectively:

O=PCl3 + 3 H2O → O=P(OH)3 + 3 HCl
O=PCl3 + 3 ROH → O=P(OR)3 + 3 HCl

Such reactions are often performed in the presence of an HCl acceptor such as pyridine or an amine. If POCl3 is heated with an excess of a phenol (ArOH) in the presence of a Lewis acid catalyst such as magnesium chloride, a triaryl phosphate ester such as triphenyl phosphate is formed. For example:

3  C6H5OH + O=PCl3 → O=P(OC6H5)3 + 3  HCl

POCl3 can also act as a Lewis base, forming adducts with a variety of Lewis acids such as titanium tetrachloride:

Cl3P+−O + TiCl4 → Cl3P+−O−TiCl4

The aluminium chloride adduct (POCl3·AlCl3) is quite stable, and so POCl3 can be used to remove AlCl3 completely from reaction mixtures at the end of a Friedel-Crafts reaction. POCl3 reacts with hydrogen bromide in the presence of AlCl3 to produce POBr3.


Phosphoryl chloride was first prepared in 1847 by the French chemist Adolphe Wurtz by reacting phosphorus pentachloride with water.[3]

Phosphoryl chloride can be prepared by various methods, notable examples include:

2  PCl3 + O2 → 2  POCl3
6 PCl3 + 6 Cl2 → 6 PCl5
6 PCl5 + P4O10 → 10 POCl3
3 PCl5 + 2 B(OH)3 → 3 POCl3 + B2O3 + 6 HCl
PCl5 + (COOH)2 → POCl3 + CO + CO2 + 2 HCl
3 PCl3 + KClO3 → 3 POCl3 + KCl
2 P2O5 + 3 NaCl → 3 NaPO3 + POCl3.
Ca3(PO4)2 + 6 C + 6 Cl2 → 3 CaCl2 + 6 CO + 2 POCl3


The most important use for phosphoryl chloride is in the manufacture of triarylphosphate esters (as described above) such as triphenyl phosphate and tricresyl phosphate. These esters have been used for many years as flame retardants and plasticisers for PVC. Meanwhile, trialkyl esters such as tributyl phosphate (made similarly from n-butanol) are used as liquid–liquid extraction solvents in nuclear reprocessing and elsewhere.

In the semiconductor industry, POCl3 is used as a safe liquid phosphorus source in diffusion processes. The phosphorus acts as a dopant used to create n-type layers on a silicon wafer.

In the laboratory, POCl3 is widely used as a dehydrating agent, for example the conversion of primary amides to nitriles. Similarly, certain aryl amides can be cyclised to dihydroisoquinoline derivatives using the Bischler-Napieralski reaction.

Two uses for phosphorus oxychloride in organic chemistry

Such reactions are believed to go via an imidoyl chloride; in certain cases where it is stable, the imidoyl chloride is the final product. For example, pyridones and pyrimidones can be converted to chloro- derivatives of pyridines and pyrimidines, which are important intermediates in the pharmaceutical industry.[6]

Another common laboratory use for POCl3 is in the Vilsmeier-Haack reaction, where it reacts with amides to produce a "Vilsmeier reagent", a chloro-iminium salt, which subsequently reacts with electron-rich aromatic compounds to produce aromatic aldehydes upon aqueous work-up.[7]


  1. ^ a b c d "NIOSH Pocket Guide to Chemical Hazards #0508". National Institute for Occupational Safety and Health (NIOSH). 
  2. ^ Chesnut, D. B. (1999). "The Electron Localization Function (ELF) Description of the PO Bond in Phosphine Oxide". Journal of the American Chemical Society. 121 (10): 2335–2336. doi:10.1021/ja984314m. 
  3. ^ See:
    • Wurtz, Adolphe (1847). "Sur l'acide sulfophosphorique et le chloroxyde de phosphore" [On monothiophosphoric acid and phosphoryl chloride]. Annales de Chimie et de Physique. 3rd series (in French). 20: 472–481.  ; see Chloroxyde de phosphore, pp. 477–481. (Note: Wurtz's empirical formulas are wrong because, like many chemists of his day, he used the wrong atomic mass for oxygen.)
    • Roscoe, Henry Enfield; Schorlemmer, Carl; Cannell, John, eds. (1920). A Treatise on Chemistry. vol. 1 (5th ed.). London, England: Macmillan and Co. p. 676. 
  4. ^ a b Pradyot, Patnaik (2003). Handbook of Inorganic Chemicals. New York: McGraw-Hill. p. 709. ISBN 0070494398. 
  5. ^ a b Lerner, Leonid (2011). Small-Scale Synthesis of Laboratory Reagents with Reaction Modeling. Boca Raton, Florida: CRC Press. pp. 169–177. ISBN 9781439813126. 
  6. ^ Elderfield, R. C. (ed.). Heterocyclic Compound. 6. New York, NY: John Wiley & Sons. p. 265. 
  7. ^ Hurd, Charles D.; Webb, Carl N. (1925). "p-Dimethylaminobenzophenone". Organic Syntheses. 7: 24. ; Collective Volume, 1, p. 217 

Further reading[edit]

  • Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. 
  • Handbook of Chemistry and Physics (71st ed.). Ann Arbor, MI: CRC Press. 1990. 
  • March, J. (1992). Advanced Organic Chemistry (4th ed.). New York, NY: Wiley. p. 723. 
  • The Merck Index (7th ed.). Rahway, NJ: Merck & Co. 1960. 
  • Toy, A. D. F. (1973). The Chemistry of Phosphorus. Oxford: Pergamon Press. 
  • Wade, L. G., Jr (2005). Organic Chemistry (6th ed.). Upper Saddle River, NJ: Pearson/Prentice Hall. p. 477. 
  • Walker, B. J. (1972). Organophosphorus Chemistry. Harmondsworth: Penguin. pp. 101–116. 
  • "CDC – NIOSH Pocket Guide to Chemical Hazards".