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:
• Red phosphorus
• White phosphorus

•Besides these other known allotropes of phosphorus found in nature are:

• Black phosphorus
• Scarlet phosphorus
• Violet phosphorus
 Phosphine Preparation
• When calcium and sodium Phosphides reacts with water, phosphine gas is
obtained.
Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
• Phosphine gas is formed by the action of phosphonium iodide with
sodium hydroxide.
PH4I + NaOH → PH3 + NaI + H2O

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

Colourless gas with the rotten fish smell.

Toxic in nature.
Slightly soluble in water & heavier than air.
It changes into a liquid state at – 85°C and a solid state at – 135°C.
 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)

• Actions with halogens : It reacts with chlorine to produce phosphorous trichloride or

phosphorous pentachloride as follows –
PH3 + 3Cl2 → 3HCl + PCl3
PH3 + 4Cl2 → 3HCl + PCl5
• Combustion: It burns with air to form phosphorus pentoxide& 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 of Phosphine

Used in formation of smoke during war.

It is also used to make smoke screen in riots and wars.
Used in production of Holme’s signal (signal in sea journey during
emergency)

(Calcium phosphide (CP) is used to make the Holmes signal to signal ships in the
seas. For this purpose tin filled with calcium phosphide and calcium carbide is
thrown into the sea. They react with water to form phosphine and acetylene gases.)