Phosphorus

Allotropes of Phosphorus
The existence of phosphorus in nature in different physical form
but possessing similar chemical properties is known as
allotropes of phosphorus. The allotropes of phosphorus are:
1. Red phosphorus
2. White phosphorus

Besides these other known allotropes of phosphorus found in

nature are:
1. Black phosphorus
2. Scarlet phosphorus
3. Violet phosphorus

1. White Phosphorus
The phosphorus obtained by connecting vapours of phosphorus
under water is known as white phosphorus. It is highly reactive
as well as toxic. It is most common allotrope of phosphorus.

Physical Properties
 Colorless solid that becomes yellow in light so known as
yellow allotrope.
 Garlic smell.

 Its ignition temperature is 35 °C.

 The melting point is 44 °C.

 Highly poisonous & used as rat poison.

Chemical Properties
1. It reacts with air & gently gets oxidized to form phosphorus
pentoxide (P2O5) that glows at night.
 P4 + 5O2 ⟶ 2P2O5
It reacts with caustic soda (NaOH) producing phosphine gas on
heating & produces sodium hydrogen phosphite as the side
product.
P4 + 3NaOH + 3H2O ⟶ PH3 + 3NaH2PO2
It reacts with concentrated HNO3 to give phosphoric acid.
P4 + 20HNO3 ⟶ 4H3PO4 + 20NO2 + 4H2O

Uses:
 Used in match industry.

 Used as rat poison.

 Used to prepare phosphine gas.

2. Red Phosphorus
The phosphorus obtained by heating white phosphorus at 250 °C
at an inert atmosphere for some hour is called red phosphorus.
Properties
 Dark red powder

 Odorless, less toxic and less reactive.

 Its ignition temperature is 260 °C and m.p. is 550 °C.

 Does not react with NaOH

 Does not oxidize with air.

 With halogen, it form trihalides & pent halide.

P4 + 6Br2 ⟶ 4PBr3
P4 + 6I2 ⟶ 4PI3
P4 + 10Cl2 ⟶ 4PCl5
Uses
 Used in match industry.

 Used to prepare HBr & HI gases.

Conversion of White Phosphorus to Red Phosphorus
When white phosphorus is heated to about 250 °C in inert
atmosphere of nitrogen or carbon monoxide in presence of
iodine as catalyst, it is converted into red phosphorus.
250 °C
P4 I P4
2

White Phosphorus Red Phosphorus

Conversion of Red Phosphorus to White Phosphorus

When red phosphorus is heated strongly in an inert atmosphere
of nitrogen, vapours of phosphorus are obtained which when
condensed under water gives white phosphorus.
Inert atmosphere of N2
P4 Condensation under water P 4
Red Phosphorus White Phosphorus
Phosphine gas

Laboratory preparation
In the lab, phosphine gas is prepared by heating white
phosphorus with the solution of NaOH or KOH.
P4 + 3NaOH + 3H2O ⟶ PH3 + 3NaH2PO2

As soon as the bubbles of gas come in contact with air and

catch fire forming vortex of P2O5
2PH3 + 4O2 ⟶ P2O5 + 3H2O

This gas is combustible due to presence of phosphine

dihydride (P2H4 )
6P + 4NaOH + 4H2O ⟶4NaH2PO2 + P2H4

Fig: laboratory preparation of phosphine

Procedure
White phosphorus is taken in a flask with the concentrated
solution of caustic soda (NaOH). The flask is fitted with a
delivery tube and inlet valve to provide the inert atmosphere. Air
is removed out from the flask. Now, the flask is gently heated &
phosphine gas with a trace amount of diphosphine (P2H4) is
evolved & as each bubble escape into the air, it burns into flame
forming vortex ring of the white smoke of phosphorus pentoxide
(P2O5). The combustion of gas is due to diphosphine so the
produced phosphine gas should be passed through freezing
mixture where diphosphine condenses but phosphine does not.
Finally, pure phosphine is collected into the jar by downward
displacement of water.

Physical properties
 Colourless gas with the rotten fish smell.

 Toxic in nature.

 Slightly soluble in water & heavier than air.

Chemical properties
 Decomposition: It decomposes to give red phosphorus &
hydrogen.
4PH3 ⟶ P4 + 6H2
 Basic nature: It is weaker base than ammonia.
PH3 + H2O⟶ PH4+ + OH−
Weak basic nature of phosphine (PH3) then ammonia (NH3) is
due to the vacant orbital of phosphorus & lone pair of the
electron that cannot be donated easily.
PH3 + HX ⟶ PH4X (Phosphonium halide)
Combustion: It burns with air to form phosphorus pentoxide&
phosphoric acid.
2PH3 + 4O2 ⟶ P2O5 + 3H2O
Phosphorous pentoxide

PH3 + 2O2 ⟶ H3PO4

Phosphoric acid

Reducing agent: It reduces chlorine to chloride.

PH3 + 4Cl2 ⟶ PCl5 + 3HCl

It reduces metal ions like Cu2+, Ag+, Au3+ to respective metals.

3CuSO4 + 2PH3 ⟶ Cu3P2↓ + 3H2SO4
Cu3P2 ⟶ 6Cu + P4
3AgNO3 + PH3 ⟶ Ag3P + 3HNO3
4Ag3P ⟶ 12Ag + P4

Uses
 Used in formation of smoke during war.
 Used in production of Holme’s signal (signal in sea journey
during emergency)

Orthophosphoric acid
Preparation
 In the lab, Phosphoric acid is prepared by heating rock
phosphate with concentrated H2SO4.
Ca3(PO4)2 + 3H2SO4 ⟶ 2H3PO4 + 3CaSO4

 It can be prepared by treating phosphorus pentoxide (P2 O5)

with hot water.
P2O5 + 3H2O ⟶ 2H3PO4
  It can also be prepared by hydrolysis of PCl5
PCl5 + 4H2O ⟶ H3PO4 + 5HCl

Physical properties
 White crystalline solid.

 Weak acid & fairly soluble in water.

Chemical properties
1. Action with heat:
When phosphoric acid is heated, it produces
pyrophosphoric acid at 250-260°C & metaphosphoric acid
at 300°C by losing water molecules.
2H3PO4 ⟶ H4P2O7 ⟶ HPO3

2. Acidic properties: It is tribasic acid due to ionization of 3

hydrogen atom lean with oxygen. It forms 3-series of salt
corresponding to 3-stage of ionization.
H3PO4 ↔ H+ + H2PO4−
H2PO4− ↔ H+ + HPO4− −
HPO4− − ↔ H+ + PO4− − −
Therefore, its salt with NaOH are:
a) NaH2PO4 {sodium dihydrogen phosphate}
b) Na2HPO4 {disodium hydrogen phosphate}
c) Na3PO4 {sodium phosphate}

3. Reaction with AgNO3: A yellow ppt. of silver phosphate is

obtained.
3AgNO3 + H3PO4 ⟶ Ag3PO4 + 3HNO3
Uses
 Used to manufacture fertilizer.
 Used to make phosphate salt.
 Used to prepare medicine, detergent etc.

Different Oxyacids of phosphorus

S.N. Oxyacids Molecular Formula O.N. of P
1 Hypophosphorous acid H3PO2 +1
2 Orthophosphorous acid or H3PO3 +3
Phosphorous acid
3 Hypophosphoric acid H4P2O5 +4
4 Orthophosphoric acid or H3PO4 +5
Phosphoric acid
5 Pyrophosphoric acid H4P2O7 +5
6 Metaphosphoric acid HPO3 +5
7 Permonophosphoric acid H3PO5 +5
8 Perdiphosphoric acid H4P2O8 +5