P BLOCK ELEMENTS

1
Introduction to p-block Elements
P block elements are those in which the last
electron enters any of the three p-orbitals of
their respective shells. Since a p-sub-shell has
three degenerate p-orbitals each of which can
accommodate two electrons, therefore in all
there are six groups of p-block elements.

2
 Introduction to p-block Elements
• Electronic configuration
The elements of a given group differ in their
electronic configuration. The E.C. of the valence
shell is similar. This difference in the inner core
configuration influences the physical properties
of the elements. It is the reason that elements
of the same group differ in their physical and
chemical properties. The elements of different
p-block groups differ in their valence electron
configuration and also in their physical and
chemical properties.ns2, np1-6

3
 Introduction to p-block Elements
• Oxidation states
The oxidation number of any element is generally
the number of valence electrons. This is called
group oxidation state but they show other
oxidation states also. Due to increase in number
of valence electrons from left to right, the
oxidation number of elements also increase from
left to right. It is seen that oxidation number is
more stable for lighter elements.

4
 Introduction to p-block Elements
• Inert pair effect
The inert-pair effect is the tendency of the
two electrons in the outermost atomic s-
orbital to remain unshared in compounds
of post-transition metals.

5
 Reasons For Abnormal Behaviour Of
First Element
• The first element has small size, high I.P. and
high electro negativity.
• Absence of valence d-orbitals in the valence
shell.

6
Group 15 elements

7
Group 15 elements

8
Properties

9
 Trends in Properties
• Atomic and Ionic Radii
Atomic and Ionic radii keep on increasing on
moving down a group. Though radii of Group 15
is smaller than that of Group 15 since atomic radii
decreases across a group. There is an
considerable increase in atomic radii from N to P
because of strong shielding effect of s and p
orbitals. There is a small increase in the atomic
radii from As to Bi because of the poor shielding
of the d and f orbitals.

10
 Trends in Properties
• Ionization enthalpy/potential
TREND: It decreases on moving down the group.
The ionization potential of Group 15 is much
higher than that of Group 14.
REASON: On moving down the group, atomic
radius and screening effect of inner electrons
increase.
Because of the increased nuclear charge,
reduced atomic radii and half filled stable
electronic configuration of p sub-shell, the
ionization potential of Group 15 elements is
much higher than that of Group 14 elements.
11
 Trends in Properties
• Metallic and Non-metallic character.
TREND: Metallic character increases and non-
metallic character decreases while moving down
the group.
EXPLANATION: On moving down the group,
number of valence shells increases and thus
attraction from the nucleus decreases. Thus it
becomes easy to donate electrons and hence
metallic character increases, at the same time it
becomes difficult to accept electrons, so non-
metallic character decreases.
12
 Trends in Properties
• Electronegativity
TREND: It decreases on moving down the group.
Group 15 elements are more electronegative
than Group 14 elements.
REASON: The elements are smaller than Group
14 elements. Thus, these are more
electronegative than group 14 elements. As
atomic size increases on moving down the group,
so nuclear attraction decreases, hence
electronegativity decreases on moving down the
group.
13
 Trends in Properties
• OXIDATION STATES:
The Group 15 elements show variable
oxidation states. Most common ones are -3,
+3, +5.

14
 Trends in Properties
• OXIDATION STATES:
 Disproportionation Reaction:

In Disproportionation reactions, oxidation and

15
 Trends in Properties
• NATURE OF COMPOUNDS:
Compounds of nitrogen and phosphorus are
predominately covalent. But the metal nitrides
are and metal phosphides like Mg3N2 , Ca3N2 ,
Na3P , Ca3P2 etc. are ionic. The strength of single
covalent bond generally decreases on moving
down the group. Sb and Bi form ionic compounds
and give Sb3+ and Bi3+ as ions in solution because
of their low ionization potentials.

16
 Trends in Properties
• ALLOTROPY:
All elements except Bismuth show allotropy.
Allotropes of Nitrogen are α-nitrogen and ß-
nitrogen.
Allotropes of Phosphorus are white phosphorus,
red phosphorus, black phosphorus, violet
phosphorus, scarlet phosphorus, etc.
Allotropes of Arsenic and Antimony are also
found.

17
 Trends in Properties
• Catenation:
The property of self linkage of similar atoms is called
catenation. Since N-N bond is weak, Nitrogen shows
little tendency for catenation. Phosphorus has
comparatively more tendency to catenation. This is
mainly due to the unexpectedly high P-P bond
strength.
The N-N bond is weaker than P-P bond. It is
because of lone pair of electrons on N atom, that repel
the bond pair electrons due to it’s small size. It does
not happen in case of P atom because of it’s
comparatively larger size.

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 Trends in Properties
• Tendency to form multiple bonds:
Nitrogen has tendency to form multiple single,
double and triple bonds with itself or with
other elements. Several compounds of N,P,As
such as P4O6, P4O10, As4O10, P(C2H5)3 ,
As(C6H5)3 are known that have multiple single
and double bonds.

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Examples of some group 15 compounds.

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 Trends in Properties
• Anomalous Behaviour of Nitrogen
Nitrogen shows anomalous behavior as
compared to other Group 15 elements due to:
1. It’s small size.
2. Its high I.P. and high electronegativity.
3. Absence of d-orbitals.
4. Tendency to form multiple bonds.

21
 Reactivity
Under normal condition Nitrogen is chemically
inert. It neither burns nor it supports
combustion. The main reason behind this is
the high bond dissociation energy of N-N
triple bond.
They form hydrides such as NH3 , PH3 ,
AsH3 , SbH3 , BiH3.

22
 Reactivity
It is observed that Ammonia is more basic than
phosphine and so on.
This is mainly because of the small size of
small size of nitrogen atom. Due to the small size
of the Nitrogen atom, the electron pair of
nitrogen is concentrated over a small region. As
the size of the central atom decreases, so the
ability to donate electrons decreases hence the
basic character of the hydride also decreases.

23
 Reactivity
The stability and H-M-H bond angle decreases
with the increase in the molecular weight of the
hydride (i.e., on moving down the group).
This could be explained using the VSEPR
theory. In all the three hydrides, the central atom
is sp3 hybridized. Three sp3 hybrid orbitals overlap
on each other while one line pair lies on the
opposite side. Due to greater lone pair-bond pair
repulsion the tetrahedral shape of the molecule is
disturbed and it assumes a pyramidal shape.
Their bond angle mainly differs due to the
increase in electronegativity on going down the
group. 24
Reactivity

25
 Reactivity
• Reducing Power
Since stability of hydrides increases on moving
down a group, their reducing power also
increases. Thus, except NH3 all are good
reducing agents.

26
 Boiling Point
• The Boiling point decreases in the following
order: BiH3 > SbH3 > NH3 > AsH3 > PH3
Reason: The boiling of NH3 is found to be
higher because it forms hydrogen bonds in
water which require higher energy to break.
The Boiling points of BiH3 & SbH3 are also
higher than expected because of their strong
van der waal’s forces chiefly because of their
higher atomic mass.

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 Boiling Point
300

290

280

270

260

250

240
Boiling Point
230

220

210

200

190

180
NH3 PH3 AsH3 SbH3 BiH3

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 Solubility
• Only Ammonia is soluble in water because it
has the ability to form hydrogen bond, while
the other group-15 elements are not capable
of forming any hydrogen bond when dissolved
in water.

29
 Oxides of Elements
• These elements form two kinds of oxides, E2O3
and E2O5. N2O5 is more acidic than N2O3. Thus,
oxide in their higher oxidation state of the
element is more acidic than that of lower
acidic state. Their acidic character decreases
down the group and for the same oxidation
state the acidic character decreases down the
group. This order is as follows: N2O5 > P4O10
> As4O10 > Sb4O10.
30
 Reactivity Towards Halogens
• The Group 15 elements form two types of
halides, trihalides (EX3) and pentahalides
(EX5). Nitrogen does not form any
pentahalides because of the absence of vacant
d-orbitals.
• Except NF3 all other halides are hydrolyzed in
water. It is because Neither of Nitrogen and
Fluorine have any vacant d-orbitals to accept
the lone pair electrons from water.

31
Reactivity Towards Halogens

32
Reactivity Towards Halogens

33
Reactivity Towards Halogens

34
 Reactivity Towards Metals
• Elements of group 15 react with the metals
and generally show oxidation number -3 in
this process. Some of the notable compounds
are: Ca3N2 , Ca3P2 , Na3As , Zn3Sb2 , Mg3Bi2

35
 Dinitrogen (N2)
• Commercial Preparation:
Dinitrogen is prepared by the fractional
distillation of liquid air. The liquid air should
be free from dust and CO2. Liquid dinitrogen
has the lowest boiling point and hence distills
first, leaving behind O2.

36
 Dinitrogen (N2)
• Laboratory Preparation:
 By treating aqueous solution of Ammonium chloride
with Sodium nitrite.
NaNO2+NH4Cl→NaCl+N2+2H2O
 By the thermal decomposition of Ammonium
chromate.
(NH4​)2​Cr2​O7 −Δ→ ​N2​+Cr2​O3​+4H2​O
 By Thermal decomposition of Sodium and Barium
azide.
Ba(N3)2 −Δ→Ba + 3N2
 By reaction of NH3 and red hot CuO
2NH3​+3CuO→N2​+3Cu+3H2​O
37
 Dinitrogen (N2)
• Physical Properties:
It is colorless, odorless, tasteless and non-toxic
gas. The two stable isotopes are 14N and 15N.
Nitrogen has low boiling point, low freezing
point and low solubility in water. It gets
absorbed by activated charcoal.

38
 Dinitrogen (N2)
• Chemical Properties:
Reaction with Metals:
6Li + N2 –Δ→ 2Li3N
3Mg + N2 –Δ→ Mg3N2
2Al + N2 –Δ→ 2AlN
Reaction With Non-metals:
N2 + 3H2 –Δ→ 2NH3
N2 + O2 –Δ→ 2NO

39
 Dinitrogen (N2)
• Chemical Properties:
Reaction with Alumina:
Al2O3 + 3C + N2 –Δ→ 2 AlN + 3CO

Reaction With Calcium Carbides:

40
 Dinitrogen (N2)
• Uses of Dinitrogen
1. It is used in the manufacture of Ammonia and
other nitrogen containing chemicals such as
HNO3, Calcium cyanide, etc.
2. It is used to provide inert atmosphere in iron
and steel industry. It also acts as inert diluent in
reactive chemicals.
3. Liquid dinitrogen is used as refrigerant to
preserve biological materials, food items and in
cryosurgery.
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 Ammonia(NH3)
• Preparation of Ammonia:
2NH4Cl + Ca(OH)2 -heat→ CaCl2 + 2H2O + 2NH3(g)
N2 (g) + 3H2 (g) ↔ 2NH3 (g)

42
 Ammonia(NH3)
• Preparation of Ammonia:
N2 (g) + 3H2 (g) ↔ 2NH3 (g)

43
 Ammonia(NH3)
• Properties:
Ammonia is colorless gas with pungent odor. It
is dissociated through intermolecular
hydrogen bonds. Therefore, m.p. and b.p. of
nitrogen are higher than expected. It is highly
soluble in water. Its aqueous solution is basic
due to the formation of OH- ions.

44
Structure of Ammonia(NH3)

45
 Ammonia(NH3)
• Chemical Properties of Ammonia.
1. Basic Nature

46
 Ammonia(NH3)
• Chemical Properties of Ammonia.
2. Reaction with Metal Salt Solutions:
FeCl3 + 3NH4OH –→ Fe(OH)3 + 3NH4Cl
ZnSO4 + 2NH4OH –→ Zn(OH)2 + (NH4)2SO4
Ag+ + 2NH3 –→ [Ag(NH3)2]+
AgCl + 2NH4OH –→ [Ag(NH3)2]Cl + 2H2O

47
 Ammonia(NH3)
• Chemical Properties of Ammonia.
3. Reaction with Metals:
2Na + 2NH3 –200⁰C→ 2NaNH2 + H2
4. Oxidation:
4HN3 + 5O2 –Pt,800⁰C→ 4NO + 6H2O
5. Reaction with Sodium Hypochlorite (Raschig
Process):
2NH3 + NaOCl → NH2.NH2 + NaCl + H2O

48
 Ammonia(NH3)
• Chemical Properties of Ammonia.
6. Reaction with Halogens:
3Cl2 + 8NH3→N2 + 6NH4Cl
3Br2 + 8NH3→N2 + 6NH4Br
3Cl2 + NH3→NCl3 + 3HCl

49
 Ammonia(NH3)
• Chemical Properties of Ammonia.
7. Liquid Ammonia as a solvent:
2NH3 ⇋ NH4+ + NH2-
8. Reaction with hot copper oxide and ferrous
oxide(Ammonia acts as reducing agent):
2NH3​+3CuO–Δ→N2​+3Cu+3H2​O
2NH3​+3FeO–Δ→N2​+3Fe+3H2​O

50
 Ammonia(NH3)
• Uses of Ammonia.
(1) In the preparation of nitrogenous fertilizers such
as urea, ammonium nitrate, ammonium
phosphate, calcium ammonium nitrate (CAN)etc.
(2) In the manufacture of nitric acid.
(3) As a laboratory reagent.
(4) Liquid ammonia is used as a refrigerant in ice
factories and cold storages.
(5) In the manufacture of sodium carbonate by
Solvay ammonia process.

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Nitrogen Oxides

52
Nitrogen Oxides

53
Nitrogen Oxides

54
Nitrogen Oxides

55
 Nitrogen Oxides
• Both NO and NO2 form dimers. The main
reason behind this is that they have odd
number of valence electrons. So they contain
one unpaired electron that takes part in
dimerization. Both the dimers N2O2 and N2O4
are colorless and diamagnetic.

56
 Nitric Acid
• The reactions and the rest properties as well
as uses are same as class X.

59
 Phosphorus
• Occurrence:
Phosphorus is a very reactive element. Hence,
it does not occur in native state(free state). It
occurs in combined state. Phosphorus is an
essential constituent of animal and plant
matter.

60
 Phosphorus
• Allotropy:
Important allotropic forms of Phosphorus are
as follows:
1. White Phosphorus.
2. Red Phosphorus.
3. Black Phosphorus.

61
 White Phosphorus
• It can be obtained by following the given
chemical reaction:
2Ca3(PO4)2 + 6SiO2 + 10C → P4 + 6 CaSiO3 + 10CO
• Structure:

62
 White Phosphorus
• Chemical reactions of White Phosphorus:
P4 → 2P2
P4 + 5O2 → P4O10
When white phosphorus is kept in open air in
dark, it begins to glow due to aerial oxidation.
This is the reason for the glow of fire fly.
P4 + 6Cl2 → 4PCl3
P4 + 10Cl2 → 4PCl5
63
 White Phosphorus
• Chemical reactions of White Phosphorus:
8P4 + 3S8 → 8P4S3
P4 + 12Na → 4Na3P
P4 + 6Ca → 2Ca3P2
*P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2(V.V.I)

64
 Red Phosphorus
• It can be obtained by keeping white
phosphorus in an inert atmosphere at 570 K
for several days. Inert atmosphere is
necessary because white phosphorus ignites
readily.
• Structure:

65
 Red Phosphorus
• Reactions of Red Phosphorus:
P4 + 5O2 → P4O10
P4 + 6Cl2 → 4PCl3
P4 + 10Cl2 → 4PCl5
P4 + 12Na → 4Na3P

66
 Black Phosphorus
• α-White Phosphorus is obtained by heating
red phosphorus inn a scaled tube at 803 K.
ß-White Phosphorus is obtained by heating
white phosphorus at 473 K under high
pressure in an inert atmosphere.
• Structure:

67
 Phosphine
• Preparation
4H3PO4 → PH3 + 3H3PO4
Ca3P2 + 6 H2O → 2PH3 + Ca(OH)2
Ca3P2 + 6HCl →2PH3 + CaCl2
Na3P + 3H2O → PH3 + 3NaOH
Na3P + 3HCl → PH3 + 3NaCl
AlP + 3HCl → PH3 + AlCl3

68
 Phosphine
• Laboratory Preparation:
P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2
If Phosphorus is allowed to come in contact
with the atmosphere, then P2H4 burns in air to
form white rings(called vortex rings) of meta
phosphoric acid.
2P2H4 + 7O2 → 4HPO3 + 2H2O

69
 Phosphine
• Laboratory Preparation:

70
 Phosphine
• Reactions of Phosphine:
PH3 + HBr → PH4Br
PH3 + HI → PH4I
4PH3 → P4 + PH4I
4PH3 (aq) → P4 + 6H2
PH3 + 3Cl2 → PCl3 + 3HCl
PH3 + 4Cl2 → PCl5 + 3HCl
3CuSO4 + 2PH3 → Cu3P2 + 3H2SO4
3HgCl2 + 2PH3 → Hg3P2 + 6HCl

71
 Phosphine
• Structure:

72
 Phosphorus Halides
• Preparation of PCl3
P4 + 8SOCl2 → 4PCl3 + 4SO2 + 2S2Cl2
P4 + 6Cl2 → 4PCl3 (Lab. Prep.)
• Reactions of PCl3
PCl3 + 3H2O → H3PO3 + 3HCl
3CH3COOH + PCl3 → 3CH3COCl + H3PO3
3C2H5OH + PCl3 → 3C2H5Cl + H3PO3

73
 Phosphorus Halides
• PCl3 Structure:

74
 Phosphorus Halides
• Preparation of PCl5
P4 + 10Cl2 → 4PCl5
PCl3 + Cl2 → PCl5
P4 + 10SO2Cl2 → 4PCl5 + 10SO2

75
 Phosphorus Halides
• Reactions of PCl5
PCl5 –Δ→ PCl3 + Cl2
PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO4 + 3HCl
CH3COOH + PCL5 → CH3COCl + POCl3 + HCl
2Ag + PCl5 → 2AgCl + PCl3
PCl5 + H2 → PCl3 + 2HCl

76
 Phosphorus Halides
• Explain why PCl5 is solid
Ans: PCl5 has the tendency to exhibit in ionic
form as [PCl4]+ and [PCl6]-. So it exhibits solid
state.

77
 Phosphorus Halides
• PCl5 Structure:

78
Oxo-acids of Phosphorus

79
Oxo-acids of Phosphorus

80
Oxo-acids of Phosphorus

81