NITROGEN FAMILY (15thGroup)

General properties:-
1. Electronic configuration:-The elements of group 15 have electronic configuration ns2np3. These elements have
stable half-filled configuration and are not so reactive. Nitrogen behaves as noble element under ordinary conditions.
2. Atomic and ionic radii:- Radii increases from top to bottom. From As to Bi there is small decrease because of
presence completely filled d and f orbitals.
3. Ionisation Enthalpy:-Ionisation enthalpy decreases on moving down the group. The I.E. of Nitrogen is very high due
to its small size. The difference between N and P is comparatively high.
But the difference afterwards between two members is small. This is due to the less shielding effect of d and f
electrons in As, Sb and Bi respectively .
4.Electronegativity:- Electronegativity decreases down the group and N is the most electronegative among these.
5.Allotropy:- All the elements except N & Bi show allotropy. Phosphorus exist in a number of allotropic forms such as
white, red, scarlet, black, a-black, b-black and violet. Arsenic exist in three forms grey, yellow and black. Antimony
exist in three forms yellow, black and explosive.
6.Atomicity:- Nitrogen is diatomic molecule at room temperature. Two N atoms are bonded through a triple bond. P,
As and Sb all exist as discrete tetra-atomic molecules , viz., P4, As4,Sb4. The ppi–ppi bonding is not possible in these
elements.
Chemical properties
Oxidation states
Elements of this group can exhibit a maximum oxidation state +5.Due to inert pair effect the tendency to show +3
state increases. N and P generally exhibit -3 oxidation state due to small size and high electronegativity. The tendency
to show -3 state decreases on moving down. Nitrogen besides -3, +3 and +5 exhibits a large number of O.S.
-3 in (NH3, Li3N, Ca3N2, AlN), -2 in (NH2NH2), -1 in NH2OH, 0 in N2,
+1 in N2O, +2 in NO, +3 in N2O3, +4 in NO2 +5 in HNO3 &
N2O5.
The maximum covalency of nitrogen is 4 since it does not possess d-orbitals in the valence shell .
DINITROGEN (N2)
Commercially it is produced by the liquification and fractional distillation of air Liquid N2(B.P. 77.2K) distils out first
leaving behind O2(90K).In laboratory Nitrogen is prepared by treating aqueous NH4Cl with sodium nitrite.

Nitrogen can also be obtained by thermal decomposition of ammonium dichromate or ammonium nitrate .

Very pure nitrogen can be obtained in small amounts by thermal decomposition of sodium or barium azide.

It is a colourless, tasteless , odorless and non-toxic gas. Because of high bond enthalpy it is chemically inert at room
temperature and reactive at high temperature. Only at very high temperature(2000K ) it combines with Oxygen to
form Nitric oxide.

B. N2combines with metals at high temperature to form nitrides

AMMONIA(NH3)
In atmosphere it is formed by the decay of urea

On a small scale it is obtained by decomposition of ammonium salts

High pressure(200 ×105Pa) and high temperature(700K) and use of a catalyst like iron oxide with small Amounts of
K2O and Al2O3favoursthe formation of NH3
On a Large scale it is prepared by Haber’s Process

By the Hydrolysis of cyanamide CaCN2

Physical Properties
It is a colorless gas with characteristic pungent odor .
It is highly soluble in water. One volume of water dissolves 1300 volumes of NH3at 00C and 1 atm pressure. The
high solubility is due to hydrogen bonding.
Its aqueous solution is basic in nature.
Structure of Ammonia
N atom is in sp3hybridization state in NH3but due to presence of lone pair on N atom its structure is Pyramidal With
a bond angle of 107.80
NH3can not be dried using Conc. H2SO4, P2O5CaCl2
because it reacts with them

There for Quick lime Ca (OH)2 is used to dry it because both are bases and can’t react.
Chemical Properties
1. Combustion-
It burns in oxygen with yellow flame.

When a mixture of NH3and air is passed over platinum at 1123K NO is formed. This reaction is used in Ostwald’s
Process of HNO3formation.

2. Reaction with Chlorine-

(I) Chlorine in excess:
(II) Ammonia in excess: N2 is formed