P-Block Elements

SYNOPSIS
P-BLOCK ELEMENTS & THEIR COMPOUNDS
TRENDS IN PROPERTIES OF p-BLOCK ELEMENTS

A. GROUP 13 ELEMENTS: THE BORON FAMILY

Oxidation state and trends in chemical reactivity:
General oxidation state = +3
Reactivity towards acids and alkalies:
2Al(s) + 6HCl(aq) → 2Al3+(aq) + 6Cl-(aq) + 3H2(g)
2Al(s) + 2NaOH(aq) + 6H2O(1) → 2Na+[Al(OH)4]-(aq) + 3H2(g)
Sodium tetrahydroxoaluminate (III)

Reactivity towards halogens:

2E(s) + 3X2(g) → 2EX3(s) (X = F, Cl, Br, I)

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 BORON (B):
Some important reactions of boron and its compounds:

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 o Small amines such as NH3, CH3NH2 and (CH3)2NH give unsymmetrical cleavage of
diborane.
B2H6 + 2NH3 → [H2B(NH3)2]+ + [BH4]-
o Large amines such as (CH3)3N and pyridine give symmetrical cleavage of diborane.

2(CH3)3N + B2H6 → 2H3B ← N(CH3)3

200C,20 atm
B2H6  2CO  2BH3 CO(borane carbonyl)

B. GROUP OF 14 ELEMENTS: THE CARBON FAMILY

Carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb) are members of Group 14.
Electronic Configuration: ns2np2
Oxidation states and trends in chemical reactivity:
Common oxidation states = +4 and +2. Carbon also exhibits the negative oxidation state.
Oxidation state increases in the sequence: Ge < Sn < Pb.

i. Reactivity towards oxygen:

All members when heated in oxygen form oxides. There are mainly two types of
oxides, i.e. monoxide and dioxide of the formulas MO and MO2, respectively.

ii. Reactivity towards water:

Tin decomposes steam to form dioxide and dihydrogen gas.

iii. Reactivity towards halogen:

These elements can form halides of formula MX2 and MX4 (where X = F, Cl, Br, I).
Stability of dihalides increases down the group.

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 SOME IMPORTANT REACTIONS OF CO, CO2 AND METAL CARBIDES:

 CLASSIFICATION OF SILICATES:

A. Orthosilicates:

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 B. Pyrosilicates:

C. Cyclic silicates:

D. Chain silicates:

E. Two-dimensional sheet silicates:

In such silicates, the oxygen atoms of each tetrahedral are shared with adjacent SiO44-
tetrahedrals. Such sharing forms a two-dimension sheet structure with the general
formula (Si2O5)n2n.

F. Three-dimensional sheet silicates:

These silicates involve all four oxygen atoms in sharing with adjacent SiO44- tetrahedral
units.

 SILICONES:
 Silicones can be prepared from the following types of compounds only.
i. R3SiCl
ii. R2SiCl2
iii. RSiCl3

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  Silicones from the hydrolysis of (CH3)3SiCl:
2(CH3 )3 SiCl 
2(CH3 )Si(OH) 
H2 O

 Silicones from the hydrolysis of a mixture of (CH3)3SiCl and (CH2)2SiCl2:

 When a compound like CH3SiCl3 undergoes hydrolysis, a complex cross-linked

polymer is obtained.
 The hydrocarbon layer along the silicon-oxygen chain makes silicones water-
repellent.

COMPOUNDS OF LEAD:

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 COMPOUNDS OF TIN:

C. GROUP 15 ELEMENTS: THE NITROGEN FAMILY

Electronic Configuration: ns2np3

Atomic and Ionic Radii: Covalent and ionic (in a particular state) radii increase in size
down the group.
Physical Properties:
All the elements of this group are polyatomic. Metallic character increases down the
group. The boiling points, in general, increase from top to bottom in the group, but the
melting point increases up to arsenic and then decreases up to bismuth. Except nitrogen,
all the elements show allotropy.

Chemical Properties:
Oxidation states and trends in chemical reactivity:
The common oxidation states of these elements are +3, +3 and +5. The stability of +5
oxidation state decreases and that of +3 state increases (due to inert pair effect) down the
group; Bi3+ > Sb3+ >As3+; Bi5+ <Sb5+ < As5+. Nitrogen exhibits +1, +2, +4 oxidation states
also when it reacts with oxygen.

Anomalous properties of nitrogen:

i. Stability of hydrides decreases from NH3 to BiH3 which can be observed from their bond
dissociation enthalpy. Consequently, the reducing character of the hydrides increases.
Basicity also decreases in the order: NH3 > PH3 > AsH3 > SbH3 ≥ BiH3.

Properties of hydrides of Group 15 elements

Property NH3 PH3 AsH3 SbH3 BiH3

Melting point (K) 195.2 139.5 156.7 185 -
Boiling point (K) 238.5 185.5 210.6 254.6 290
(E-H) Distance/pm 101.7 141.5 151.9 170.7 -
HEH angle(°) 107.8 93.6 91.8 91.3 -
∆fH-/kJ mol-1 -46.1 13.4 66.4 145.1 278
∆dissH-(E-H)/KJ mol- 389 322 297 255 -

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 ii. The oxide in the higher oxidation state of the element is more acidic than that of the
lower oxidation state. Their acidic character decreases down the group. The oxides of the
type E2O3 of nitrogen and phosphorus are purely acidic, those of arsenic and antimony
are amphoteric, and those of bismuth are predominantly basic.

iii. Nitrogen does not form pentahalide due to non-availability of d-orbitals in its valence
shell. Pentahalides are more covalent than trihalides. Halides are hydrolysed in water
forming oxyacids or oxychlorides.
PCl3 + H2O→H3PO3 + HCl;
SbCl3 + H2O→SbOCl↓ (orange) + 2HCl;
BiCl3 + H2O→BiOCl↓ (white) + 2HCl

iv. These elements react with metals to form their binary compounds exhibiting the +3
oxidation state, such as Ca3N2 (calcium nitride), Ca3P2 (calcium phosphide) and Na3As2
(sodium arsenide).

NITROGEN (N) AND ITS COMPOUNDS:

Oxides of Nitrogen

Name Formula Oxidation Common methods of Physical

methods preparation appearan
of ce and
preparati chemical
on nature

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 Dinitrogen N2O +1 NH4NO3 
Heat
N2O  2H2 O Colourless
oxides[Nitrogen(I) gas,
oxide] neutral
Nitrogen NO +2 2NaNo2 + 2FeSO4 + Colourless
monoxide[Nitrogen(II 3H2SO4→ Fe2(SO4)2 + gas,
) oxide](Nitric acid) 2NaHSO4 + 2H2O + 2NO neutral
Dinitrogen trioxide N2O2 +3 2NO  N2 O2 
250k
2N2 O3 Blue solid,
[Nitrogen(III)oxide(Ni acidic
trogen sesquioxide)
Nitrogen NO2 +4 2Pb(NO3 )2 
637K
 4NO2  2PbO brown
O2
dioxide[Nitrogen gas, acidic
(IV)oxide]
Dinitrogen tetroxide N2O4 +4 2NO2
coat
N2O 4 Colourless
Heat
[Nitrogen(IV)oxide] solid/
liquid,
acidic
Dinitrogen N2O5 +5 4HNO3 P4O10 4HPO3 2N2Colourless
O3
pentoxide[Nitrogen solid,
(IV)oxide] acidic

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 HNO3
a) dilute
NH4NO3 + 4Sn + 10HNO3 → 4Sn(NO3)2 + NH4NO3 + 3H2O
b) concentrated
Sn + 4HNO3 → H2SnO3 + 4NO2 + H2O
Meta stannic acid antimonic acid
b) concentrated

PHOSPHORUS (P) AND ITS COMPOUNDS:

When white phosphorus is heated in the atmosphere of CO2 or coal gas at 573 K, red
phosphorus is produced.
α-Black phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K. β-
Black phosphorus is prepared by heating white phosphorus at 473 K under high pressure.
Order of thermodynamic stability of various allotropes of phosphorus: black > red > white.

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 Oxoacids of Phosphorus

Name Formula Oxidation Characteristic Preparation

state of bonds and
phosphorus their number
Hypophosphorus H2PO2 +1 One P–OH White P4 + alkali
Two P–H
One P=O
Orthophosphorus H3PO3 +3 Two P–OH P2O3 + H2O
One P–H
One P=O
Pyrophosphorus H4P2O5 +3 Two P–OH PCl3 + H3PO3
Two P–H
Two P–H
Hypophosphoric H4P2O6 +4 Four P–OH Red P4 + alkali
Two P=O
One P–P
Orthophosphoric H3PO4 +5 Three P–OH P4O10 + H2O
One P=O
Pyrophosphoric H4P2 O7 +5 Four P–OH Heat
One P=O phosphorus
One P–O–P acid
Metaphosphoric (HPO3)3 +5 Three P–OH Phosphorus
Three P=O acid + Br2, heat
Three P–O–P in a sealed tube

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 D. GROUP 16 ELEMENTS: THE OXYGEN FAMILY
Electronic Configuration: ns2 np4

Atomic and Ionic Radii:

Due to an increase in the number of shells, atomic and ionic radii increase from top to
bottom in the group. The size of oxygen atoms is however exceptionally small.

Physical Properties:
Oxygen and sulphur are non-metals, selenium and tellurium are metalloids, whereas
polonium is a metal. Polonium is radioactive and is short lived (Half-life is 13.8 days). The
melting and boiling points increase with increase in the atomic number down the group.

Catenation:
Tendency for catenation decreases down the group. This property is prominently
displayed by sulphur (S8). The S-S bond is important in the biological system and is found
in some proteins and enzymes such as cysteine.

Chemical Properties:
Oxidation states and trends in chemical reactivity:
Elements of the group exhibit +2, +4, +6 oxidation states, but +4 and +6 are more
common.
Anomalous behaviour of oxygen:
The anomalous behaviour of oxygen is due to its small size and high electronegativity.
The absence of d orbitals in oxygen limits its covalency to four.

i. Their acidic character increases from H2O to H2Te. The increase in acidic character can be
understood in terms of decrease in bond (H-E) dissociation enthalpy down the group.
Owing to the decrease in bond (H-E) dissociation enthalpy down the group, the thermal
stability of hydrides also decreases from H2O to H2Po. All the hydrides except water
possess reducing property and this property increases from H2S to H2Te.

Property H2O H2S H2Se H2Te

m.p./K 273 188 208 222

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 b.p./K 373 213 232 269
H-E distance/pm 96 134 146 169
HEH angle(°) 104 92 91 90
∆fH/kJ mol-1 -286 -20 73 100
∆dissH(H-E)/KJ mol- 463 347 276 238
Dissociation 1.8×10-16 1.3×10-7 1.3×10-4 23×10-3
constant1

ii. Reducing property of dioxide decreases from SO2 to TeO2; SO2 is reducing, while TeO2 is
an oxidising agent. Oxides are generally acidic.

iii. Stabilities of the halides decrease in the order: F > Cl > Br > I. Sulphur hexafluoride SF6 is
exceptionally stable for steric reasons.
The well-known monohalides are dimeric. Examples: S2F2, S2Cl2, S2Br2, Se2Cl2, Se2Br2.
These dimeric halides undergo disproportionation as given below:
2Se2Cl2 → SeCl4 + 3Se

OXYGEN (O2) AND ITS COMPOUNDS:

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 Oxo-acids of Sulphur
1. Sulphurous Acid series
a) H2SO3 S(IV) Sulphuric acid

2. Sulphuric Acid series

a) H2SO4 S(V) Sulphuric acid

3. Peroxo acid series

a) H2SO4 S(VI) Peroxomonosulphuric acid

Caro , acid)

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 E. GROUP 17 ELEMENTS: THE HALOGEN FAMILY
Fluorine, chlorine, bromine, iodine and astatine are members of Group 17.
Electronic Configuration: ns2np5
Atomic and Ionic Radii:
The halogens have the smallest atomic radii in their respective periods due to maximum
effective nuclear charge.
Physical Properties:
Fluorine and chlorine are gases, bromine is a liquid, whereas iodine is a solid. Their
melting and boiling points steadily increase with atomic number. The X–X bond
disassociation enthalpies from chlorine onwards show the expected trend: Cl–Cl > Br–Br
> F–F > I–I.

Chemical Properties:
Oxidation states and trends in chemical reactivity:
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 All the halogens exhibit −1 oxidation state. However, chlorine, bromine and iodine exhibit
+ 1, +3, +5 and +7 oxidation states also.
2F2(g) + 2H2O(𝓁) → 4H+(aq) + 4F-(aq) + O2(g)
X2(g) + H2O(𝓁) → HX(aq) + HOX(aq); (where X = Cl or Br)

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 F. GROUP 18 ELEMENTS: (THE ZERO GROUP FAMILY)
helium, neon, argon, krypton, xenon and radon.
o The most abundant element in air is Ar. The order of abundance in the air is Ar>Ne
>Kr >He > Xe.

Electronic Configuration: ns2np6

Atomic Radii:
Atomic radii increase down the group with increase in the atomic number.

Physical Properties:
All the noble gases are monatomic. They are colourless and tasteless. They are sparingly
soluble in water. They have very low melting and boiling points because the only type of
interatomic interaction in these elements is weak dispersion forces.

Chemical Properties:
In general, noble gases are the least reactive. Their inertness to chemical reactivity is
attributed to the following reasons:
i. The noble gases except helium (1s2) have completely filled ns2 np6 electronic
configuration in their valence shell.
ii. They have high ionisation enthalpy and more positive electron gain enthalpy. The
reactivity of noble gases has been investigated occasionally ever since their
discovery, but all attempts to force them to react to form compounds were
unsuccessful for quite a few years. In March 1962, Neil Bartlett, then at the
University of British Columbia, observed the reaction of a noble gas. First, he
prepared a red compound which is formulated as O2+ PtF6-. Then he realised that the
first ionisation enthalpy of molecular oxygen (1175 kJ mol -1) was almost identical
with that xenon (1170 kJ mol-1). He made efforts to prepare the same type of
compound with Xe+ PtF6- by mixing Pt F6 and xenon. After this discovery, a number
of xenon compounds mainly with the most electronegative elements like fluorine
and oxygen have been synthesised.
If helium is compressed and liquefied, it forms He(I) liquid at 4.2 K. This liquid is a
normal liquid like any other liquid. But if it is further cooled, then He(II) is obtained
at 2.2 K, which is known as super fluid, because it is a liquid with properties of

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 gases. It climbs through the walls of the container and comes out. It has a very high
thermal conductivity and very low viscosity.

Clathrate Compounds:
During the formation of ice, Xe atoms will be trapped in the cavities (or cages) formed by
the water molecules in the crystal structure of ice. Compounds thus obtained are called
clathrate compounds.
Clathrate provides a convenient means of storing radioactive isotopes of Kr and Xe
produced in nuclear reactors.

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