Phosphorus

Position in periodic table

Phosphorus is the second member of group VA of the periodic table.
Phosphorus (Greek: Phosphorus; light bearer) was discovered by Brandt in 1669.
Although nitrogen and phosphorus have analogous electronic configuration, ns2np3. But
phosphorus differs from nitrogen in its chemical behaviour.
For example,
1. Nitrogen is a diatomic but phosphorus is tetratomic molecule.
2. Nitrogen does not form pentahalide while phosphorus does.
3. Phosphorus is more reactive unlike nitrogen.
4. Nitrogen is a diatomic molecule with multiple bonds (:N = N:) but phosphorus is is P4
tetratomic molecule with single covalent bond.

Above differences in the properties are mainly due to

i. Larger atomic size of phosphorus than nitrogen.
ii. Phosphorus is less electronegative than nitrogen.

Occurrence of phosphorus
Phosphorus being very reactive element and does not exist in free state. Important phosphate
minerals are:
(i) Phosphorite or Rock phosphate : : Ca3(PO4)2
(ii) Fluorapatite : 3Ca3(PO4)2 .CaF2
Phosphoprotein is present in eggs and milk.

Allotropes of phosphorus
Phosphorus exists as following allotropes.
a White or yellow Phosphorus
b. Red Phosphorus
c. Black Phosphorus
d. Scarlet Phosphorus
e. Violet Phosphorus
Among them, white and red allotropes are more common.

Phosphine Preparation

(i) Phosphine is prepared by the action of water or dil. HCl on calcium phosphide.
Hydrolysis
Ca3P2 + 6H2O → 3Ca (OH)2 + 2PH3;
Ca3P2 + dil.6HCI → 3CaCl2 + 2PH3
Laboratory preparation
In the laboratory, Phosphine is prepared by heating white phosphorus with concentrate alkalis in
an inert atmosphere
P4(s) + 3NaOH (aq) + 3H2O(l) → PH3 + 3NaH2PO2
Physical properties
i. Phosphorus is colorless gas with rotten fish smell.
ii. It is slightly soluble in water but heavier than air.
iii. It is toxic in nature.
IV. It boils at -85°C and solidifies -133.5°C. Due to lack of hydrogen bond among PHz molecules,
it has low b.p. than NH3.

Chemical properties
Basic nature
Phosphine is weaker base than ammonia. It is neutral towards litmus.
PH3 + H2O → PH4+ + OH
phosphonium ion
Weak basic nature of PH3, than NH3, is due to presence of d- orbital in phosphorus and greater
size of phosphorus than nitrogen, the lone pair of electrons is not easily available to donate.
Being Lewis base, it reacts with halogen acids to form quite stable phosphonium salt,
PH3 + HX → PH4X
phosphonium halide
dense white fume
Combustion
Burns will air to form phosphorus pentoxide or phosphoric acid on heating. It is non- supporter
combustion like NH3.
2PH3+402→ P205 + 3H20,
PH3 + 202 -→ H3PO4

Reducing properties
a. Reduction of chlorine Phosphine burns with chlorine to give phosphorous pentachloride.

PH3 + 4Cl2 -→ PC13 + 3HCl

Phosphine reduces solution of heavy metal like Cu++, Ag++, Au+++, Hg++, etc into corresponding
ppt, of metal phosphide, which decomposes into respective metals on standing or boiling,

3CuSO4 + 2PH3 → Cu3P2 + + 3H2SO4

copper phosphide
(black ppt)
• 3AgNO3 + PH3 -→ Ag3P+ + 6HNO3
black ppt.
Uses of phosphine
• Used in the formation of smoke screen during wars.
• Calcium phosphide is allowed to react with water to produce inflammable phosphine
which then form P2O5 and finally H3PO4 as dense fumes.
• Used in production of Holme's signals.
• Mixture of calcium carbide and calcium phosphide is taken in a container which is pierced
and thrown into sea out of the submarine. Calcium phosphide reacts with H20 and
liberates PH3 which catches fire and lights up acetylene obtained from calcium carbide.
Burning gases gives a signal in a sea-journey during emergency, called Holme's signal.