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Phosphorus Pentachloride
Phosphorus pentachloride is prepared by the action of chlorine on phosphorus trichloride. To push the equilibrium over to the right, the temperature must be kept low and excess chlorine must be present. Hence the liquid phosphorus trichloride is run dropwise into a flask cooled in ice through which a steady stream of dry chlorine is passed: the solid pentachloride deposits at the bottom of the flask.
Phosphorus pentachloride sublimes and then dissociates on heating, yielding first phosphorus oxychloride, thus:
H2O + PCl5
O=PCl3 + 2HCl (1)
And then phosphoric acid:
3H2O + POCl3 H3PO4 + 3HCl (2)
The replacement of the – OH group by a chlorine atom [reaction (1)] is a very general reaction of phosphorus pentachloride. For example, if concentrated sulphuric acid is written as (HO)2SO2 then its reaction with phosphorus pentachloride may be written:
The reaction of acetic acid and phosphorus pentachloride may be written:
The oxychloride is also obtained by distillation of a mixture of the pentachloride and anhydrous oxalic acid:
(COOH)2 + PCl3 O=PCl3 + CO2
+ CO + 2HCl
This is a convenient laboratory method.
These reactions (and those of the trichloride) indicate the great tendency of (pentavalent) phosphorus to unite with oxygen (cf. silicon).
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Phosphorus pentachloride sublimes and then dissociates on heating, yielding first phosphorus oxychloride, thus:
H2O + PCl5
O=PCl3 + 2HCl (1)And then phosphoric acid:
3H2O + POCl3
H3PO4 + 3HCl (2)The replacement of the – OH group by a chlorine atom [reaction (1)] is a very general reaction of phosphorus pentachloride. For example, if concentrated sulphuric acid is written as (HO)2SO2 then its reaction with phosphorus pentachloride may be written:
The reaction of acetic acid and phosphorus pentachloride may be written:
The oxychloride is also obtained by distillation of a mixture of the pentachloride and anhydrous oxalic acid:
(COOH)2 + PCl3
O=PCl3 + CO2 + CO + 2HClThis is a convenient laboratory method.
These reactions (and those of the trichloride) indicate the great tendency of (pentavalent) phosphorus to unite with oxygen (cf. silicon).
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