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p-Block Elements
 Session Objective

 Elements and there general E.C.

 Discussions on various physical properties, size, I.E.,

electronegativity, oxidation states, inert pair and
anomalous behavior of nitrogen.

 Discussion on Inert Pair Effect and anomalous behavior of

Nitrogen.

 Discussion on chemical properties on formation of there,

oxides, hydrides, halides, reaction with metals, etc.

 Preparation, physical and chemical properties of N2, NH3,

HNO3 and resonating structures.
 NCERT/practice question and answers.

Class-XII p-Block Elements 3

GROUP 15 (Nitrogen Family):
1. Electronic configuration : ns2np3
Element Symbol Property
Nitrogen N [He] 2s22p3 Non metallic
Phosphorus P [Ne] 3s23p3 Non metallic
Arsenic As [Ar] 4s24p3 Semi Metal
Antimony Sb [Kr]5s25p3 Semi Metal
Bismuth Bi [Xe] 6s26p3 Metal

2. Atomic and Ionic Radii:

Element Nitrogen Phosphorus Arsenic Antimony Bismuth

Covalent 70 110 121 141 148

radius/pm

Large difference Small difference

Class-XII p-Block Elements 4

Decrement in size:

Inner shells contains

d and f orbitals which
show poor shielding
effect

1 2 3 4 5

Decrease in the size

Class-XII p-Block Elements 5

 Both covalent and ionic radii increases. N to P it increases
but from As to Bi a small decrease is observed, due to
completely filled d & f-orbitals which show poor shielding
effect.
3. Ionization enthalpy:
I.E. decreases down the group, due to increase in size. Due
to extra stable half-filled p orbitals electronic configuration
and smaller size, I.E. is more than group -14 & 16.
4. Electronegativity :
It decreases, due to increase in size.
5. Physical Properties:
Polyatomic. N2 is diatomic gas and others are solid. Except
N, all show allotropy.

Class-XII p-Block Elements 6

6. Oxidation State:
+ 3 e-
Valence shell = ns np2 3
ns2np6

 Nitrogen show -3 oxidation state in nitrides due to small

size and high electronegativity
 Other elements show covalent nature. For e.g. phosphorus
show a formal oxidation state of -3 and form covalent
compounds even with metals.
 All the elements show +3 and +5 oxidation state.
 The tendency to show +5 oxidation state decreases down
the group due to inert pair effect.
 Due to large amount of energy needed to lose all the five
valence electrons M+5 ions can’t be formed.
Class-XII p-Block Elements 7
  Inert Pair Effect:

With E. C. ns2np3, as size increases on moving down the

group , due to poor shielding effect of d and f electrons ns 2
electrons do not participate in the bonding. This is known as
inert pair effect.

 Nitrogen shows all the oxidation state from -3 to +5.

Due to its small size , high electronegativity and strong

tendency to form pp-pp multiple bonds.

Compound NH3 NH2NH2 NH2OH N2 N 2O NO N2O3 NO2/N2O4 N2O5

Oxidation -3 -2 -1 0 +1 +2 +3 +4 +5
state

Class-XII p-Block Elements 8

  Disproportionation: The reaction in which one reactant
get oxidised as well as reduced.
Oxidation

+3 +5 +2
3HNO2  HNO3  2NO  H2O
Reduction

Oxidation
+3 +5 -3
3H3PO3  3H3PO4  PH3
Reduction

Due to inert pair effect the tendency to show disproportionation

decreases down the group.

Class-XII p-Block Elements 9

  Covalency:
Nitrogen is restricted to maximum covalency
of 4 due to the absence of d orbital. It can H
use only 4 orbitals (one s and three p).
N = 1s22s22p3 N

H
Ground state = H
H
Excited state = Tetrahedral

 That is why nitrogen does not form NF5 or NCl5.

 Heavier elements can expand their octet to show higher
covalency. For e.g. AsF5, PF6-.

Class-XII p-Block Elements 10

 Example:
1. Though nitrogen exhibits +5 oxidation state, it does not
form pentahalide. Give reason.
Solution:
Nitrogen with n = 2, has s and p orbitals only. It does not
have d orbitals to expand its covalence beyond four. That
is why it does not form pentahalide.
Exercise:
1. Discuss the general characteristics of group 15 elements
with reference to their electronic configuration,
oxidation state, atomic size , ionization enthalpy and
electronegativity.

Class-XII p-Block Elements 11

 Anomalous Properties of Nitrogen

Small size
High
Electronegativity
Phosphorus

Arsenic

pp-pp multiple bonds

Unique ability
With itself
Nitrogen

Absence of
d orbital
High Ionisation
enthalpy Antimony

Bismuth

Class-XII p-Block Elements 12

  It has tendency to form p–p multiple bonds
(N = N, N  N) with itself and with other atoms like C &
O, (C  N, N = O etc).
 Other elements do not form because of their bigger size
due to which there is no effective overlapping.
 N–N < P–P, because of high inter electronic repulsion
between non-bonding e– and small bond length.
 Due to this, catenations is weaker is N. Also due to
absence of d-orbital in N, it cannot form d-p multiple
bonding which is possible in other element like PCl6–.

 P & As can also form d-d multiple bonding i.e.

P(C2H5)3 & As(C6H5)3 which acts as ligand.

Class-XII p-Block Elements 13

 Exercise:

2. Why does the reactivity of nitrogen differ from

phosphorus?
Solution:
Nitrogen Phosphorus
1)Diatomic molecule (NN). 1) Tetra-atomic molecule (P4).
2)High bond dissociation 2) Low bond dissociation
energy due to the presence of energy due to P-P single
a triple bond. bond.
3) Inert and unreactive in 3) Highly reactive.
elemental state.

10. Why does R3PO exist but R3NO does not (R=alkyl)?
Solution:
Due to the absence of d orbitals , nitrogen cannot
extend its covalency more than 4.
Class-XII p-Block Elements 14
Chemical Properties: 1. Hydrides:

Property Trends Explanation

Bond NH3>PH3>AsH3>SbH3 Force of repulsion between the

angle adjacent bonds pairs is
maximum in NH3 .

Basic NH3>PH3>AsH3>SbH3>BiH3 As the size of the central atom

Nature increases the lone pair of
electrons occupies a larger
volume and tendency to donate
a lone pair of electrons
decreases.
Boiling PH3<AsH3<NH3<SbH3 <BiH3 NH3 has higher boiling point
point due to hydrogen bonding. But
lower than SbH3 and BiH3 as
van der Waals forces
compensates the H- bonding .

Class-XII p-Block Elements 15

Chemical Properties: 1. Hydrides:

Property Trends Explanation

Melting PH3<AsH3<SbH3 <NH3 NH3 has highest melting point

point due to hydrogen bonding.
Other hydrides do not form H –
Bonds.

Thermal NH3>PH3>AsH3>SbH3>BiH3 Decrease in bond strength of M–

stability H, due to increase in size of
central atom.

Reducing NH3<PH3<AsH3<SbH3<BiH3 Decrease in thermal stability

Character increases the tendency to
liberate hydrogen increases

Class-XII p-Block Elements 16

 Example:
2. PH3 has lower boiling point than NH3. Explain.
Solution:
Phosphine do not form intermolecular H – bonding like
ammonia. That is why it has lower boiling point.

Intext:

2. Why is BiH3 the strongest reducing agent amongst all the

hydrides of Group 15 elements?
Solution:
As we move down the group, the E–H bond can break more
easily (to evolve H2) due to weaker bond strength.

Class-XII p-Block Elements 17

 Exercise:
4. Why does NH3 form hydrogen bonds but PH3 does not?
Solution:
The electronegativity of nitrogen is much higher than
hydrogen . As a result, N-H bond is quite polar and hence NH 3
undergoes intermolecular H – bonding.
In contrast, both P and H have almost similar
electronegativity . Therefore ,P-H bond is not polar. And it
does not form H – Bonds.

Class-XII p-Block Elements 18

 Exercise:
9. The HNH angle value is higher than HPH, HAsH and HSbH
angles. Why?
Solution:
In NH3, N is sp3 hybridized and bond
N
angle is 107.8o . As we move from
ammonia to bismuthine , the H H
electronegativity of the central atom
H
decreases and hence these elements do
not undergo sp3 hybridization but
instead form s-p overlap.
The bond pairs of electrons lie away from
P
the central atom on going down the
group and therefore bond pair-bond pair
H H
is maximum in PH3 and minimum in
H
SbH3.
Class-XII p-Block Elements 19
 Exercise:
11. Explain why NH3 is basic while BiH3 is only feebly basic.
Solution:
Smaller volume
Higher density

N Bi

H H H H
H
H

The basic nature is explained on the behalf of electron

density on the central atom. The atomic size of N is much
smaller than that of Bi ,therefore, electron density on the N-
atom is much higher than that of Bi-atom.

Class-XII p-Block Elements 20

2. Halides:
They form tri and pentahalides.
(a) Penta Halides:
N can't form pentahalide due to the absence of vacant d-
orbitals.
(i) Have less thermal stability as compared to
trihalides.
(ii) Pentahalides are Lewis acids.
(b) Tri Halides:
(i) Mainly covalent except for BiF3 (ionic).
(ii) Ionic character increase down the group.
(iii) They have pyramidal shape.
(iv) Can be easily hydrolysed except for NX3.
(v) The inability of trihalide of N to hydrolyse is attributed
to the non-availability of vacant d-orbital in N. For e.g.
Class-XII p-Block Elements 21
Hydrolysis of NCl3 and PCl3

O
Cl H
H
O
H
H Cl N 3HOCl + NH3
O
Cl H
H

O Cl
H -
H Cl
Cl P
-HCl
Cl P Cl
+ O

Cl
H H

Class-XII p-Block Elements 22

 O O
H H
H Cl H
OH
-HCl
Cl P Cl P
+H2O
OH OH

OH OH

OH

Class-XII p-Block Elements 23

Intext:
1. Why are pentahalides more covalent than trihalides?
Solution:
Since elements in the +5 oxidation state have less tendency
to lose electrons than in the +3 oxidation state, therefore,
elements in the +5 oxidation state has more tendency to
share electrons than in the +3 oxidation state. Thus,
elements in the +5 oxidation state are more covalent than in
the +3 oxidation state. In other words, pentahalides are
more covalent than trihalides.
3. Rxn with metals:
They form binary compounds with metals with -3 oxidation
state E.g: Ca3N2, Ca3P2, Na3As2 (Sodium Arsenide) Zn3Sb2
(Zinc Stibide), Mg3Bi2 (Magnesium Bismuthide).

Class-XII p-Block Elements 24

4. Oxides:
All oxides of N2 (except NO & N2O) & phosphorus are
strongly acidic, oxides of arsenic are weakly acidic,
antimony are amphoteric and those of bismuth are weakly
basic.
They form oxides of type E2O3 & E2O5. Oxidation state or
electronegativity increases, acidic nature of oxide increases.
But acidic nature of oxides decreases down the group.
Nitrogen (N2):
Preparation:
1. Commercially by fractional distillation of liquid air
(b.pt.-77.2 K).
2. Laboratory Preparation:
NH4Cl(aq)+NaNO2(aq)N2(g)+2H2O(l) + NaCl(aq)
NO & HNO3 as impurities are removed by passing the gas
through H2SO4(aq) having K2Cr2O7.
Class-XII p-Block Elements 25
 3. (NH4)2 Cr2O7  N2(g) + 4H2O + Cr2O3

4. Ba(N3 )2  Ba  3 N2
Barium azide Pure

Or 2NaN3  2 Na + 3N2
This is used to inflate the air bags for safety devices in some cars.
Physical Properties: Colourless, tasteless, non-toxic gas,
isotopes are 14N & 15N, slightly soluble is water, low freezing and
boiling point. It is adsorbed by activated charcoal.
Chemical Properties: Inert at room temperature, due to high
bond enthalpy of N  N bond, but reactivity increases with
increase in temp.
1. Reaction with Metals: Form Covalent nitrides.
6Li + N2 ® 2Li3N
3Mg + N2 ® Mg3N2
Class-XII p-Block Elements 26
2. Reaction with H2 (Haber’s Process):
2 2

 2NH (g)  H  46.1kJmol
N (g)  3H (g) 
773K , Fe
 3 f
–
O –1

3. Reaction with O2:

2 2

N (g)  O (g)  2NO(g)
2000 K

Nitric oxide

Uses: Manufacture of NH3, industrial chemical. Provides inert

atmosphere in iron and steel industry. As refrigerant to
preserve food items and biological materials.
Example:
3. Write the reaction of thermal decomposition of sodium
azide.
Solution:
Thermal decomposition of sodium azide gives dinitrogen gas.
2NaN3 ® 2Na + 3N2

Class-XII p-Block Elements 27

Exercise:

12. Nitrogen exists as diatomic molecule and phosphorus

as P4?
Solution:
Because of its small size and high electronegativity
nitrogen forms pp-pp multiple bonds . Therefore, it exist
as a diatomic molecule having a triple bond between the
two N atoms. Phosphorus ,on the other hand, has larger
size and lower electronegativity and usually does not
form pp-pp multiple bonds with itself. It prefers to from
p-p single bonds and hence it exists as tetrahedral.

Class-XII p-Block Elements 28

Intext:
3. Why is N2 less reactive at room temperature?
Solution:
Due to the presence of a triple bond between the two
nitrogen atoms, the bond dissociation energy of N2 (914.4 kJ
mol–1) is very high.
Ammonia (NH3):
Preparation:
1. NH2CONH2 + 2H2O  (NH4)2CO3  2NH3 + H2O + CO2
2. 2NH4Cl + Ca(OH)2 ® 2NH3 + 2H2O + CaCl2
On small scale
(NH4)2SO4 + 2NaOH ® 2NH3 + 2H2O + Na2SO4
3. Haber's Process: N2(g) + 3 H2(g) ® 2 NH3 (g)] Large Scale

Class-XII p-Block Elements 29

 Conditions :
1) Low temperature of around 700 K because the reaction is
exothermic which favors the formation of ammonia.
Class-XII p-Block Elements 30
2) High pressure of 200 × 105 Pa. As the forward reaction
occurs with the decrease in volume, by Le Chatelier's principle.
3)Catalyst : Iron oxides with small amount of K 2O and Al2O3
and molybdenum is used as a promoter.

Physical Properties: Colourless, pungent smelling, bring tears

is eyes, lighter than air, soluble in water easily liquefies and is
basic is nature. 
NH3 (g)  H2O()  NH4 (aq)  OH (aq)

Chemical Properties:
1. Rxn with Acids:
Forms ammonium salts.
2FeCl3 (aq)  3NH4OH(aq)  Fe2 O3 .xH2 O(s) 3NH4 Cl(aq)
Brown ppt.

ZnSO4 (aq)  2NH4OH(aq)  Zn(OH)2 (s) (NH4 )2 SO4 (aq)

White ppt.

Class-XII p-Block Elements 31

2. Reaction as Lewis Base:
Due to presence of a lone pair of e– on N-atom, it can donate
its lone pair and acts as lewis base.
NH3 + BF3  H3N  BF3
2
 
Cu2 (aq)  4NH3 (aq)  Cu(NH3 )4  (aq)
Blue  Deep Blue 
Ag  (aq)  Cl  (aq)  AgCl(s)
White ppt.

 
AgCl(s)  2NH3 (aq)   Ag(NH3 )2  Cl(aq)
White point  colourless 
Uses: For nitrogenous fertilizers, for preparing HNO3 (Ostwald's
process), for sod. carbonate (Solvay's process). Refrigerant,
cleaning agent, lab. reagent.
Test for NH3:
1. Gives brown ppt with Nessler's reagent
2. With drop of HCl, it produces dense white fumes of NH4Cl.
Class-XII p-Block Elements 32
Intext:
4. Mention the conditions required to maximise the yield
of ammonia?
Solution: Ammonia is prepared by the Haber’s process.
Mo(promoter)
N2  g   3H2  g  
  2NH3  g  ;  f H0  92.4kJ mol 1

In accordance with Le Chatelier’s principle, to maximize the
yield, a high pressure of 200 × 105 Pa is used. To increase
the rate of the reaction, a temperature of around 700 K is
used and iron oxide mixed with some K2O and Al2O3 is used
as a catalyst. Mo is also used as a promoter to increase the
efficiency of the Fe catalyst.
5. How does ammonia react with a solution of Cu2+?

Solution:
2
Cu2  aq   4NH4OH  aq   Cu  NH3    4H2O
 4
Tetramminecopper (II)ion
Deep Blue

Class-XII p-Block Elements 33

Example:
4. Why does NH3 act as a Lewis base?

Solution:
Nitrogen atom in NH3 has one lone pair of electrons
which is available for donation. Therefore, it acts as a
Lewis base.

N + +
+ H N

H H H H
H H

Class-XII p-Block Elements 34

 Oxides of Nitrogen

Name Oxidation Common methods of Physical

Formula
state of preparation appearance
nitrogen and chemical
nature
Dinitrogen oxide N2O +1
NH4NO3 
Heat
 N2O  2H2O Colourless
[Nitrogen(I) oxide] gas, neutral
Nitrogen monoxide NO +2 2NaNO2  2FeSO4 
Colourless
[Nitrogen (II)oxide] 3H2SO4  Fe2 (SO4 )3  gas, neutral
2NaHSO4  2H2O  2NO
Dinitrogen trioxide N2O3 +3 Blue solid,
2NO  N2O4 
250 K
 2N2O3
[Nitrogen (III)oxide] acidic
Nitrogen dioxide NO2 +4 2Pb(NO3 )2 
673 K
 4NO2 Brown gas,
[Nitrogen(IV)oxide]  2PbO  O2 acidic

Dinitrogen tetroxide N2O4 +4 Colourless

[Nitrogen(IV)oxide] solid / liquid,
acidic
Dinitrogen pentoxide N2O5 +5 4HNO3  P4O10  Colourless solid,
[Nitrogen(V)oxide] 4HPO3  2N2O5 acidic

Class-XII p-Block Elements 35

 Formula Resonance Structures Bond Parameters
N = N = O  :N N – O : N –N –O

: :

: :

: :
N2O 113pm 119pm
L in e a r
.
NO : N = O. :  : N  O :

:
N – O

:
115pm
O 105° O
N2O3 11
4 N N
p m 130°
186pm
117° O
121 pm
P la n a r
N
120 pm
NO2 O 134° O
A n g u la r

O O m
N2O4 175 pm p 1
135° N N 12
O P la n a r O

N2O5 O O
O
N N 134°
112°
O P la n a r
O

Class-XII p-Block Elements 36

Example:
5. Why does NO2 dimerise ?
Solution:
NO2 contains odd number of valence electrons. It
behaves as a typical odd molecule. On dimerization, it
is converted to stable N2O4 molecule with even number
of electrons.
Intext:

6. What is the covalence of nitrogen in N2O5?

Solution:
In N2O5, the covalency of N is 4 as it form only 4 bonds
due to absence of d-orbitals.
O O
N O N
O O
Class-XII p-Block Elements 37
 Nitric Acid (HNO3): Nitrogen forms oxoacids
like H2N2O2 (hyponitrous acid), HNO2 (nitrous
acid) and HNO3.
Preparation:
1. NaNO3 + H2SO4  NaHSO4 + HNO3 [In Lab.]
2. Ostwald's Process: On large scale is based upon
catalytic oxidation of NH3 by atmospheric O2.
4NH3 (g)  5O2 (g) 
Pt/Rh gauge Catalyst
 4NO(g)  6H2O(g)
500K, 9bar


2NO(g)  O2 (g)  2NO2 (g)

3NO2 (g) + H2O(l)  2HNO3 (aq) + NO(g)

NO formed can be recycled and aq. HNO3 can be conc. by
distillation upto ~68% by mass. Also conc. to 98% can be
achieved by dehydration with conc. H2SO4.
Class-XII p-Block Elements 38
Properties:
1. Colourless liquid. In lab. used as 68% (by mass) and has
density 1.5 g/ml. It is a planar molecule is gaseous state.
2. Strong acid but in aq. medium.
HNO3(aq) + H2O(l)  H3O+(aq) + NO3–(aq)
3. Strong Oxidising Agent in conc. and dil. forms, as it gives [O].
2HNO3(conc.)  H2O + 2NO2 + [O]
2HNO3(dil.)  H2O + 2NO + 3 [O]
Oxidising nature depends on conc., T and nature of element.
4. Rxn with metals:
3 Cu + 8HNO3 (dil.)  3 Cu (NO3)2 + 2NO + 4H2O
Cu + 4HNO3 (conc.)  Cu (NO3)2 + 2NO2 + 2H2O
4 Zn + 10 HNO3 (dil.)  4 Zn (NO3)2 + 5 H2O + N2O
Zn + 4HNO3 (conc.)  Zn(NO3)2 + 2H2O + 2NO2
Metals like Au, Pt do not get attacked & metals like Cr, Al, Pt, do
not dissolve in conc. HNO3 as they form stable layer of its oxide.
Class-XII p-Block Elements 39
5. Rxn with Non-metals:
I2 + 10HNO3 2HIO3 + 10NO2 + 4H2O
C + 4HNO3  CO2 + 2H2O + 4NO2
S8 + 48HNO3(conc.)  8H2SO4 + 48NO2 + 16H2O
P4 + 20HNO3(conc.)  4H3PO4 + 20NO2 + 4H2O

Brown Ring Test: Add conc. H2SO4 through the wall of test
tube, slowly which has a soln of nitrate along with FeSO4(aq).
The appearance of dark brown rings at the junctions of 2
layers indicate the presence of NO3– ion.
It is because Fe2+ reduces NO3– to NO which then reacts with
Fe2+ to form a brown complex.
NO3– + 3Fe2+ + 4H+  NO + 3Fe3+ + 2 H2O
[Fe(H2O)]62  NO  [Fe(H2O)5 NO]2  H2O
Pentaaquanitrosoniumiron (I)
Brown

Class-XII p-Block Elements 40

 Uses:
1. Manufacture of NH4NO3 for fertilizers and other nitrates for
explosive and pyrotechnics.
2. For preparing nitroglycerin, TNT, organic compounds,
pickling of stainless steel, etching of metals and as oxidiser
in rocket fuel.

Class-XII p-Block Elements 41

Common Errors to be Avoided
 Inert pair effect, anomalous behavior and variable
oxidation states of this group are important.

 Haber’s (for N2) and Ostwald (for NH3) processes are

important.
 Resonating structures of oxides of nitrogen are very
important specially NO2.

 Oxidation states of N in all oxides should be

remembered.

 Balance all chemical reactions.

Class-XII p-Block Elements 42

Next Class Plan
 Various allotropes of phosphorus.
 Preparation and properties of PH3, PCl3 and PCl5 also of
O2 and O3.
 Various oxo-acids of phosphorus with structures and
oxidation states.
 General discussion on various properties of group 16
elements.
 Practice/NCERT question and answers.

Class-XII p-Block Elements 43

 Thank You

Class-XII p-Block Elements 44