Phosphorus Pentachloride

Phosphorus Pentachloride [phosphorus(V) chloride] is a pale yellow solid that fumes in moist air; specific gravity 1.60; melting at 148 C under pressure; boiling at 160 C (sublimes). It is soluble in benzene, ether, carbon disulphide and in carbon tetrachloride.

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Detailed Description for Phosphorus Pentachloride

Phosphorus Pentachloride [phosphorus(V) chloride] is a pale yellow solid that fumes in moist air; specific gravity 1.60; melting at 148 C under pressure; boiling at 160 C (sublimes). It is soluble in benzene, ether, carbon disulphide and in carbon tetrachloride. It is Nonflammable nor explosive. It is hydrolysed violently with water to form phosphonic acid, phosphorus oxychloride, and hydrochloric acid. It is prepared by direct union of phosphorus with excess chlorine. (excess phosphoru contaminates the product with phosphorus(III) chloride). 

Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water- and moisture-sensitive solid, although commercial samples can be yellowish and contaminated with hydrogen chloride.

The structures for the phosphorus chlorides are invariably consistent with VSEPR theory. The structure of PCl5 depends on its environment. Gaseous and molten PCl5 is a neutral molecule with trigonal bipyramidal (D3h) symmetry. The hypervalent nature of this species can be explained with the inclusion of non-bonding MOs (Molecular orbital theory) or resonance (Valence bond theory). This trigonal bipyramidal structure persists in non-polar solvents, such as CS2 and CCl4.

In solutions of polar solvents, PCl5 undergoes "autoionization". Dilute solutions dissociate according to the following equilibrium:

PCl5 is in equilibrium with [PCl+
4
]Cl

At higher concentrations, a second equilibrium becomes more prevalent:

2 PCl5 is in equilibrium with [PCl+
4
][PCl6]

The cation PCl+4 and the anion PCl−6 are tetrahedral and octahedral, respectively. At one time, PCl5 in solution was thought to form a dimeric structure, P2Cl10, but this suggestion is not supported by Raman spectroscopicmeasurements.

PHYSICAL AND CHEMICAL PROPERTIES

PHYSICAL STATE pale yellow granular powder
MELTING POINT 148 C under pressure
BOILING POINT 160 C (sublimes)
SPECIFIC GRAVITY 1.6
SOLUBILITY IN WATER Decomposes exothermically
pH  
VISCOSITY  
VAPOR DENSITY 7.2

AUTOIGNITION

 

NFPA RATINGS

Health: 3 Flammability: 0 Reactivity: 2 Other: water reactive

REFRACTIVE INDEX

 
FLASH POINT none
STABILITY Stable under ordinary conditions

 

APPEARANCE

pale yellow granular powder

ASSAY

99.0% min

PCl3

0.3% max

IRON

5ppm max

LEAD

5ppm max

 

Phosphorus(V) chloride is used to chlorinating agent and dehydrating agent for the synthesis of a variety of inorganic and organic phosphorus derivatives used as pesticides, water treatment chemicals, flame retardants, phosphite antioxidants, plasticizers and stabilizers for plastic and elastomers, lube oil and paint additives. It is also used as a catalyst in cyclization reaction. It is used to improve grain structure in metal casting.


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