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Phosphoryl chloride

Phosphoryl chloride
Phosphoryl chloride
Phosphoryl-chloride-3D-vdW.png
Phosphoryl-chloride-3D-balls.png
POCl3.jpg
Names
IUPAC names
Phosphoryl trichloride
Phosphorus trichloride oxide
Other names
Phosphorus oxychloride
Phosphoric trichloride
Trichlorophosphate
Identifiers
10025-87-3 YesY
3D model (Jmol) Interactive image
ChEBI CHEBI:30336 YesY
ChemSpider 23198 YesY
ECHA InfoCard 100.030.030
EC Number 233-046-7
PubChem 24813
RTECS number TH4897000
UNII 9XM78OL22K YesY
UN number 1810
Properties
POCl3
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)
Reacts
Vapor pressure 40 mmHg (27°C)
Structure
tetrahedral
2.54 D
Hazards
Safety data sheet See: data page
ICSC 0190
Very toxic (T+)
Harmful (Xn)
Corrosive (C)
R-phrases R14, R22, R26, R35, R48/23
S-phrases (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
US health exposure limits (NIOSH):
PEL (Permissible)
none
REL (Recommended)
TWA 0.1 ppm (0.6 mg/m3) ST 0.5 ppm (3 mg/m3)
IDLH (Immediate danger)
N.D.
Related compounds
Related compounds
Thiophosphoryl chloride
Phosphorus oxybromide
Phosphorus trichloride
Phosphorus pentachloride
Supplementary data page
Refractive index (n),
Dielectric constantr), etc.
Thermodynamic
data
Phase behaviour
solid–liquid–gas
UV, IR, NMR, MS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY  (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.

POCl3 structure.png

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

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


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