VIDYAPEETH

FOR DROPPER JEE

Batch Code :- PJ12MB
p-Block (nitrogen family)
Extra Notes
Lecture-

Nitesh Tiwari Sir

Physical properties :
(1) Atomic radil : N < P < As < Sb < Bi

(2) Ionisation energy : N > P > As > Sb > Bi

(3) Metallic character : NP As Sb Bi

metal
non metals metalloids

Increases down the group

(4) Allotropes of phosphorus
(i) White/Yellow phosphorus

P4 (tetrahedral)
* Highly reactive due to ito strained structure
* Six P – P bonds
Properties

* Highly poisonous
* Waxy solid : garlic odour
* Show chemiluminiscence
* Insoluble in water but soluble in CS2
* Low ignition temperature catch fire easily. Kept in water
* It dissolves in boiling NaOH giving PH3
* P4 + 3 NaOH + 3H2O → PH3 + 3 NaH2PO2
* Give dense white fumes of P4O10
P4 + 5O2 → P4O10
* Red phosphorus :

* Highly polymerised structure in which P4 units are joined together.

thus it is less reactive than white phosphorus.
* Red phosphorus is obtained by heating white phosphorus at 573 K
in inert atmosphere for several days.
Properties
* Not poisonous in nature
* Ignition temperature is high, do not catch fire easily.
* Insoluble in water as well as CS2
* React with NaOH to give (H4P2O6) Hypophosphoric acid
* Do not show chemiluminiscence
Black phosphorus
 Black phosphorus

a-Black phosphorus b–Black phosphorus

* Black > Red > white (order of stability)

Nitrogen
Preparation
(A) If anionic part of ammonium salt is strongly oxidizing like Cr2O72–,
NO2–, ClO4–, IO3–, then N2 is obtained
( ) 
NH4 2 Cr2O7 ⎯⎯⎯
IMR
→ N2 + Cr2O3 + 4H2O


 NH4 NO2 ⎯⎯⎯
IMR
→ N2 + 2H2O


2NH4ClO4 ⎯⎯⎯
IMR
→ N2 + Cl2 + 4H2O + 2O2


2NH4 IO3 ⎯⎯⎯
IMR
→ N2 + I2 + 4H2O + 2O2
Comproportionation reaction
Same element from different oxidation state is converted to same
oxidation state in Comproportionation reaction
Examples

 NH4 NO2 ⎯⎯⎯
IMR
→ N2 + 2H2O

 NH4 NO3 ⎯⎯⎯
IMR
→ N2O + 2H2O

Very pure nitrogen can be obtained by the thermal decomposition

of sodium or barium azide.

Ba(N3)2 → Ba + 3N2
* Dinitrogen is a colourless, odourless, tasteless and non-toxic gas.
* Nitrogen atom has two stable isotopes: 14
N and 15
N.
* It has a very low solubility in water ൫23.2 cm3 per litre of water at
273 K and 1 bar pressure) and low freezing and boiling points.
* Dinitrogen is rather inert at room temperature because of the high
bond enthalpy of N ≡ N bond.
* Reactivity, however, increases rapidly with rise in temperature.
* At higher temperatures, it directly combines with some metals to form
predominantly ionic nitrides and with non-metals, covalent nitrides.
* A few typical reactions are:
 Heat
6Li + N2 ⟶ 2Li3 N
Heat
3Mg + N2 ⟶ Mg 3 N2
It combines with hydrogen at about 773 K in the presence of a catalyst
(Haber's Process) to form ammonia:
773k
N2 ( g) + 3H2 ( g) ⇌ 2NH3 ( g); Δ𝑓 H ⊖ = −46.1kJmol−1
Dinitrogen combines with dioxygen only at very high temperature (at
about 2000 K ) to form nitric oxide, NO.
N2 + O2 ( g) ⇌ NO(g)
Heat
 Heat
6Li + N2 ⟶ 2Li3 N
Heat
3Mg + N2 ⟶ Mg 3 N2
It combines with hydrogen at about 773 K in the presence of a catalyst
(Haber's Process) to form ammonia:

773k
N2 ( g) + 3H2 ( g) ⇌ 2NH3 ( g); Δ𝑓 H ⊖ = −46.1kJmol−1

Dinitrogen combines with dioxygen only at very high temperature (at

about 2000 K ) to form nitric oxide, NO.

N2 + O2 ( g) ⇌ NO(g)
Heat
Ammonia
Preparation

(1) Ammonia is present in small quantities in air and soil where it is

formed by the decay of nitrogenous organic matter e.g., urea.
NH2 CONH2 + 2H2 O → NH4 2 CO3 ⇌ 2NH3 + H2 O + CO2
urea
(2) By action of any base like NaOH, KOH, Ca(OH)2 on any ammonium salt :

NH4 NO3 + NaOH ⎯⎯
→ NaNO3 + NH3 + H2O

NH4 NO2 + NaOH ⎯⎯
→ NaNO2 + NH3 + H2O
Ammonia
Preparation

( NH4 )2 SO4 + Ca ( OH )2 ⎯⎯→ 2NH3 + CaSO4 + H2O



( NH4 )2 SO4 + 2NaOH ⎯⎯→ 2NH3 + 2H2O + Na 2SO4



2NH4Cl + Ca ( OH )2 ⎯⎯

→ CaCl2 + 2NH3 + 2H2O
(3) By heating of ammonium salts in which anionic part is non – oxidizing
or weakly oxidizing.

NH4Cl ⎯⎯⎯⎯
non -redox
→ NH3 + HCl

( )
NH4 2 S ⎯⎯⎯⎯ 
non -redox
→ 2NH3
+ H2S
( 4 )2 4 non-redox → 2NH3 + H2SO4
NH SO 
⎯⎯⎯⎯

( 4 )2 3 non-redox → 2NH3 + CO2 + H2O

NH CO ⎯⎯⎯⎯

( )
NH4 3 PO4 ⎯⎯⎯⎯ 
non -redox
→ 3NH3 + H3PO4
(4) Haber’s process
On a large scale, ammonia is manufactured by Haber's process.
N2 (g) + 3H2 (g) ⇌ 2NH3 (g); Δ𝑓 𝐻⊖ = −46.1 kJ mol−1
* In accordance with Le Chatelier's principle, high pressure would favour
the formation of ammonia.
* The optimum conditions for the production of ammonia are a pressure
of 200 × 105 Pa (about 200 atm), a temperature of ∼ 700 K and the use
of a catalyst such as iron oxide with small amounts of K 2 O and Al2 O3 to
increase the rate of attainment of equilibrium.
* Earlier, iron was used as a catalyst with molybdenum as a promoter.
(5) Nitrate or nitrite reduction
-
NO3 / -
NO2 + Zn / Al + NaOH ( aq.)
2- -
⎯→ NH3 +  Zn ( OH )4  or Al ( OH )4 

* Properties of NH3 :

(1) It is colourless gas with a pungent odour.

(2) It is highly soluble in water (H-bonding)

(3) It aqueous solution is basic.

NH3 + H2O NH4+ + OH-
(4) It form ammonium salts with acids

HCl + NH3 → NH4Cl

H2SO4 + 2NH3 → ( NH4 )2 SO4

(5) Form complex with d-block metal ions

2+
2+
Cu ( aq ) + 4NH3( aq ) Cu ( NH3 )4 
( aq )
( deep blue )
(6) NH3 cannot be dried by P2O5 , CaCl2 , H2SO4
P4O10 + NH3 → ( NH4 )3 PO4
2NH3 + H2SO4 → ( NH4 )2 SO4
CaCl2 + 6NH3 → CaCl2·6NH3

 dried by CaO
Phosphine

Preparation
Phosphine is prepared by the reaction of calcium phosphide with water or
dilute HCl.
Ca3 P2 + 6H2 O → 3Ca(OH)2 + 2PH3
Ca3 P2 + 6HCl → 3CaCl2 + 2PH3
In the laboratory, it is prepared by heating white phosphorus with
concentrated NaOH solution in an inert atmosphere of CO2 .
P4 + 3NaOH + 3H2 O → PH3 + 3NaH2 PO2
(sodium hypophosphite)
* When pure, it is non inflammable but becomes inflammable owing to
the presence of P2 H4 or P4 vapours.
* To purify it from the impurities, it is absorbed in HI to form
phosphonium iodide PH4 I which on treating with KOH gives off
phosphine.
PH4 I + KOH → KI + H2 O + PH3
* It is a colourless gas with rotten fish smell and is highly poisonous.
It explodes in contact with traces of oxidising agents like HNO3, Cl2
and Br2 vapours.

* It is slightly soluble in water. The solution of PH3 in water decomposes

in presence of light giving red phosphorus and H2.

* When absorbed in copper sulphate or mercuric chloride solution, the

corresponding phosphides are obtained.

* Phosphine is weakly basic and like ammonia, gives phosphonium

compounds with acids e.g.,
Phosphorus Halides

Phosphorus Trichloride
* In oxoacids phosphorus is tetrahedrally surrounded by other atoms.

* All these acids contain at least one P=O bond and one P–OH bond.

* These acids in +3 oxidation state of phosphorus tend to

disproportionate to higher and lower oxidation states. For example,
orthophophorous acid (or phosphorous acid) on heating
disproportionates to give orthophosphoric acid (or phosphoric acid)
and phosphine.

*
*
Nitric Acid

* NO thus formed is recycled and the aqueous HNO3 can be concentrated by

distillation upto ~ 68% by mass.
Oxidation of metals :
Exceptional Behaviour Of Tin

Sn + HNO3 → H2SnO3 + NO2 + H2O

( con.) metastannic acid

Sn + HNO3 → Sn ( NO3 )2 + NH4 NO3 + H2O

( dilute/very dilute )
* Fe, Co, Ni, Cr, Be, Al become passive or unreactive in con. HNO3 due to
formation of protective layer of oxide on them.

* Noble metals like Au(gold) and platinum (Pt) do not react with con.
HNO3 rather they dissolve in Aqua – Regia

* Aqua Regia
3 parts of conc. HCl + 1 part of conc. HNO3.

HNO3 + 3HCl ⎯→ NOCl + 2H2O + [Cl]

[Cl] is oxidizing agent in aqua regia.

Au + 3[Cl] ⎯→ AuCl3 ⎯⎯⎯

HCl
→ H [AuCl4]
[chloroauric acid]
* Pt + 4[Cl] ⎯→ PtCl4 ⎯⎯⎯
→
2HCl
H2[PtCl6]
chloroplatinic acid

* Reaction of non-metals/metalloids with conc. HNO3

con. HNO3 oxidises non-metals/metalloids to –ic form of oxyacids.

* Dilute/very dilute HNO3 do not react with them

 P4 + HNO3 ( con.) → H3PO4 + NO2 + H2O

 S8 + HNO3 ( con.) → H2SO4 + NO2 + H2O
 I2 + HNO3 ( con.) → HIO3 ( iodic acid )
 C + HNO3 ( con.) → CO2 + H2O + NO2
 As + HNO3 ( con.) → H3AsO4 ( arsenic acid ) + NO2 + H2O
 As + HNO3 ( con.) → H3SbO4 ( antimonic acid ) + NO2 + H2O
Oxides of Nitrogen
Q. Why does NO2 dimerise ?
NO2 contains odd number of valence electrons. It behaves as a typical
odd molecule. On dimerisation, it is converted to stable N2O4 molecule
with even number of electrons.
THANK-YOU