Chem i str y | 16.

13

3. GROUP 15 ELEMENTS (NITROGEN FAMILY)

3.1 Introduction

N 7

P  15

As  33 ns2np3
Sb  51

Bi  83

(a) Electronic Configuration: ns2np3 .

(i) Atomic and Ionic Radii Covalent and ionic (in a particular state) radii increase in size, down the group.

(b) Ionisation Enthalpy: Ionisation enthalpy decreases down the group due to the gradual increase in atomic
size. This is due to the extra stability of half-filled p-orbitals leading to a smaller size. The order of successive
ionization enthalpies, as expected is ∆iH1 < ∆iH2 < ∆iH3

(c) Electronegativity: Decreases down the group with increasing atomic size.

(d) Physical Properties: All the elements of this group are polyatomic. Dinitrogen is a diatomic gas. Nitrogen
and phosphorus are non-metals, arsenic and antimony are metalloids and bismuth is a metal. This is due to
the decrease in ionization enthalpy and increase in atomic size. 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.

(e) Chemical Properties:

(i) Oxidation State: The common oxidation states of these elements are -3, +3 and +5. The tendency to
exhibit -3 oxidation state decreases down the group due to increase in size and metallic character. The
stability of +5 oxidation state decreases down the group. The stability of +5 oxidation state decreases
and that of +3 state increases (due to inert pair effect) down the group. Nitrogen exhibits +1, +2, +4
oxidation states also when it reacts with oxygen.
(ii) Reactivity towards hydrogen: All the elements of Group 15 from hydrides of the type EH3 where E=N,
P, As, Sb or Bi. Basicity also decreases in the order NH3 > PH3 > AsH3 > SbH3 > BiH3
(iii) Reactivity towards oxygen: All these elements form two types of oxides: and E2O5 . The oxide in the
higher oxidation state of the element is more acidic than that of lower oxidation state. Their acidic
character decreases down the group.
(iv) Reactivity towards halogens: These elements react to form two series of halides: EX3 and EX5
(v) Reactivity towards metals: All these elements react with metals to form their binary compounds
exhibiting -3 oxidation state.
Exp. Ca3N2 (calcium nitride) Ca3P2 (calcium phosphide), Na3As2 (sodium arsenide), Zn3Sb2 (zinc antimonide)
and Mg3Bi2 (magnesium bismuthide).

3.1.1 Anomalous Behaviour of Nitrogen

Nitrogen differs from the rest of the members of this group due to its small size, high electronegativity, high
ionization enthalpy and non-availability of d orbitals. Nitrogen has the unique ability to form pπ − pπ multiple
bonds with itself and with other elements having a small size and high electronegativity (e.g., C,O). Another factor
which affects the chemistry of nitrogen is the absence of d orbitals in its valence shell. Besides restricting its
covalency to four, nitrogen cannot form dπ − pπ bond as the heavier elements can, for e.g., R3P = O or R3P = CH2
(R=alkyl group). Phosphorus and arsenic can form dπ − dπ bond also with transition metals, when their compounds
like P(C2H5 )3 and As(C6H5 )3 act as ligands.
1 6 . 1 4 | p - Block Elements

3.2 Important Compounds of Nitrogen

3.2.1 Dinitrogen
Preparation:
(a) In the laboratory, dinitrogen is prepared by treating an aqueous solution of ammonium chloride with sodium
nitrite.
NH4 Cl(aq) + NaNO2 (aq) → N2 (g) + 2H2O(l) + NaCl(aq)

(b) It can also be prepared by the thermal decomposition of ammonium dichromate.
Heat
(NH4 )2 Cr2O7  → N2 + 4H2O + Cr2O3

Properties: Dinitrogen is a colourless, odourless, tasteless and non-toxic gas.

Chemical properties:
(a) 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);

(b) Dinitrogen combines with dioxygen only at a very high temperature (at about 2000 K) to form nitric oxide, NO.
Heat
N2 + O2 (g)  → 2NO(g)

The main use of dinitrogen is in the manufacture of ammonia and other industrial chemicals containing
nitrogen (e.g., calcium cyanamide). It also finds use where an inert atmosphere is required (for e.g., in the iron
and steel industry, inert diluent for reactive chemicals). Liquid dinitrogen is used as a refrigerant to preserve
biological materials, food items and in cryosurgery.

3.2.2 Ammonia
By urea: NH2CONH2 + 2H2O →(NH4 )2 CO3
Decomposition of (NH4 )2 CO3 gives 2NH3 + H2O + CO2
By Haber’s process.
−46.1kJmol−1
N2 (g) + 3H2 (g) → 2NH3 (g); ∆ƒH0 =

According to Le Chatelier’s principle, high pressure would favour the formation of ammonia.

Properties: Ammonia is a colourless gas with a pungent odour.

Chemical Properties: Due to hydrogen bonding, it exists in both solid and liquid states and has higher melting
and boiling points than expected on the basis of its molecular mass.

Basic nature of ammonia

NH3 (g) + H2O(I) → NH4 + (aq) + OH−
Cu2+ (aq) + 4NH3 (aq) → [Cu(NH3 )4 ]2+ (aq)
(blue) (deepblue)
 Chem i str y | 16.15

Ag+ (aq) + Cl− (aq) → AgCl(s)

(colourless) (whiteppt)
AgCl(s) + 2NH3aq → [Ag(NH3 )2 ]Cl(aq)
(whiteppt) (colourless)

Uses: Ammonia is used to produce various nitrogenous fertilisers (ammonium nitrate, urea, ammonium phosphate
and ammonium sulphate) and in the manufacture of some inorganic nitrogen compounds, the most important one
being nitric acid. Liquid ammonia is also used as a refrigerant.

3.2.3 Oxides of Nitrogen

Table 16.3: Oxides of nitrogen

Name Formula Oxidation state of Common preparation methods Physical appearance

nitrogen and chemical nature

Dinitrogen oxide N 2O +1 Heat Colourless gas,

NH4NO3  → N2O + 2H2O
neutral
[Nitrogen(I) oxide]

Nitrogen monoxide NO +2 2NaNO2 + 2FeSO 4 + 3H2SO 4 Colourless gas,

→ Fe2 (SO 4 )3 + 2NaHSO 4 neutral
[Nitrogen(II) oxide]
+2H2O + 2NO

Dinitrogen trioxide N2O3 +3 Blue solid, acidic

250K
2NO + N2 O 4  → 2N2 O3
[Nitrogen(III) oxide]

Nitrogen dioxide NO2 +4 673K Brown gas, acidic

2Pb(NO3 )2  →
[Nitrogen(IV) oxide] 4NO2 + 2PbO + O2

Dinitrogen tetroxide N2O4 +4 cool Colourless solid/

2NO2  → N2O 4
Heat
liquid, acidic
[Nitrogen(IV) oxide]

Dinitrogen pentoxide N2O5 +5 2HNO3 + P4 O10 Colourless solid,

cool acidic
[Nitrogen(V) oxide] 
Heat
→ 4HPO3 + 2N2O5

Table 16.4: Resonance structure and bond parameters of some oxides

Formula Resonance Structures Bond Parameters

N2O
:

: :
N=N=O  NN O
: : N N O
113pm 119pm
:

Linear

NO
:

: :
N=O  N=O
: : N O
115pm
:

N2O3 O
:

O O O O 105o O
:
:

11
:

:
:

4p o

N N N N m N N 130
186pm
O 117 o
O
:

O
:
:

121pm
:

Planar
1 6 . 1 6 | p - Block Elements

NO2 N
N N 120pm
O

:
O
O O

:
O 134o O

:
:

:
:

:
Angular

N2O4 O O O O O O
:

:
:

:
:

:
:

:
175 pm m
1p
:

:
:

:
N N N N 135
o
N N 12
O O O O

:
:

: :
O Planar O
:

:
:

:
N2O5 O m

: :
O O
:O
:
:

: pm 9p

:
:

:
O
: :

: :
O O 15
1 O 11
:

:
N N N N
N N 134
o
: :

: :
O o
:O O :O 112

:
:
:

:
Planar

MASTERJEE CONCEPTS

•• NO is paramagnetic in its gaseous state but diamagnetic in its liquid or solid state, The NO molecule
has eleven valence electrons and is thus paramagnetic in nature due to unpaired electron. In solution
or solid state, it forms a loose dimer in such a way that magnetic field of unpaired electrons of two
molecules cancel out it behaves as diamagnetic in nature
•• NF3 is stable but NCl3 and NI3 are readily hydrolysed and are explosives NF3 is not hydrolysed because
neither N nor F can expand their octet by using d-orbitals. On the other hand NCl3 and Nl3 hydrolyse
violently because Cl and I can expand their octet by using d-orbitals.
NCl3 + 3H2O → NH3 + 3HOCl
Vaibhav Gupta (JEE 2009, AIR 54)

3.2.4 Nitric Acid

Preparation: By Ostwald’s process:

4NH3 (g) + 5O2 Pt/Rh gauge catalyst

→
500K,9 bar
4NO(g) + 6H2O(g)
(from air)

2NO(g) + O2 (g) =
2NO2 (g)
3NO2 (g) + H2O(1) → 2HNO3 (aq) + NO(g)

NO thus formed is recycled and the aqueous HNO3 can be concentrated by distillation upto ~68% by mass. Further
concentration to 98% can be achieved by dehydration with concentrated H2SO 4

Properties: It is a colourless liquid (f.p. 231.4 K and b.p. 355.6 K). Laboratory grade nitric acid contains ~68% of the
HNO3 by mass and has a specific gravity of 1.504.

Chemical reaction of HNO3 with metal and non-metals:

HNO3 (aq) + H2O(l) → H3O + (aq) + NO3− (aq)
3Cu + 8HNO3 (dil) → 3Cu(NO3 )2 + 2NO + 4H2O
Cu + 4HNO3 (conc.) → Cu(NO3 )2 + 2NO2 + 2H2O
4Zn + 10HNO3 (dil) → 4Zn(NO3 )2 + 5H2O + N2O
 Chem i str y | 16.17

Zn + 4HNO3 (conc.) → Zn(NO3 )2 + 2H2O + 2NO2

I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O
C + 4HNO3 → CO2 + 2H2O + 4NO2
S8 + 48HNO3 → 8H2SO 4 + 48NO2 + 16H2O
P4 + 20HNO3 → 4H3PO 4 + 20NO2 + 4H2O

Brown Ring Test: The familiar brown ring test for nitrates depends on the ability of Fe2+ to reduce nitrates to nitric
oxide, which reacts with Fe2+ to form a brown coloured complex. The test is usually carried out by adding a dilute
ferrous sulphate solution to an aqueous solution containing nitrate iron, and then carefully adding concentrated
sulphuric acid along the sides of the test tube. A brown ring at the interface between the solution and sulphuric
acid layers indicates the presence of nitrate ion in solution.

3.3 Phosphorus

3.3.1 Types of Phosphorous

(a) Yellow or white phosphorous (b) Red Phosphorous (c) Black Phosphorous
White P: (a) White P exists as discrete P, molecules. It has tetrahedral geometry. Bond angle is 60° instead of 109°.
With this bond angle, white P is associated with the strain accounting for its less stability and greater reactivity.
(b) Ignition temp of white P is 30°C i.e. it is highly reactive and when it undergoes ignition, it releases a large
amount of energy which is emitted in the form of light, termed as Fluorescence.
P
Red P: (a) Formed from white P by breakage of one P – P bond and so chain of P4 P P
P
molecules is formed. Figure 16.3: a Red

(b) Long Chain of P4 , molecules are formed and when compared with white P, red P has P
P
P
more density, less reactivity with breakage of P – P bond, strain of P4 decreases P P

(c) Ignition temp of red P is above 230°C P P P

P P
Black P: (a) Exists in a hexagonal form like graphite.
P P
(b) It is least reactive and has maximum density. P
Figure 16.4: b Black
(c) Black P exists as a solid of high density.
(d) It is a good conductor of electricity.

Uses:
(a) Phosphorous is largely used in the matches industry.
(b) White phosphorous is used as a rat poison.

3.3.2 Some Important Compounds of Phosphorous

(a) Phosphorus Trichloride: P4 + 8SOCl2 → 4PCl3 + 4SO 4 + 2S2Cl2

Properties: It is a colourless oily liquid and hydrolyses in the presence of moisture. P

PCl3 + 3H2O → H3PO3 + 3HCl

Cl Cl Cl Pyramidal

Figure 16.5: Structure of PCl3

1 6 . 1 8 | p - Block Elements

(b) Phosphorus Pentachloride

P4 + 10Cl2 → 4PCl5
Preparation:
P4 + 10SO2Cl2 → 4PCl5 + 10SO2

Note: In gaseous and liquid phases, it has a trigonal bipyramidal structure Structure of PCl5
as shown. The three equatorial P-Cl bonds are equivalent, while the two axial Cl
bonds are longer than equatorial bonds. This is due to the fact that the axial Cl
bond pairs suffer more repulsion as compared to equatorial bond pairs.

240pm
Properties: PCl5 is a yellowish white powder and in moist air, it hydrolyses to 202
P
POCl3 and finally gets converted to phosphoric acid. pm
Cl Cl
PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO 4 + 3HCl
Cl
heat
PCl5 → PCl3 + Cl2 Figure 16.6: Structure of PCl5

Note: In the solid state it exists as an ionic solid, [PCl4 ]+ [PCl6 ]− in which the cation, [PCl4 ]+ is tetrahedral and the
anion, [PCl6 ]− octahedral.

3.3.3 Oxoacids of Phosphorus

Table 16.5: Oxoacids of Phosphorus

Name Formula Oxidation state of Characteristic bonds and their Preparation

Phosphorous number
Hypophosphorous H3PO2 +1 One P-OH white P4 + alkali

(phosphinic) Two P-H

One P=O
Orthophosphorous H3PO3 +3 Two P-OH P2O3 + H2O

(Phosphonic) One P-H P-O-P

One P=O
Pyrophosphorous H4P2O5 +3 Two P-OH PCl3 + H3PO3
Two P-H
Two P=O
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 H4P2O7 +5 Four P-OH heat phosphoric
acid
Two P=O
One P-O-P
Metaphosphoric (HPO3)n +5 Three P-OH Phosphorus acid
+Br2, heat in a
Three P=O
sealed tube
Three P-O-P
 Chem i str y | 16.19

O
O O O O
P
P P P P
HO OH
HO O O OH
OH OH H OH
OH OH OH H
H3PO4 H4P2O7 H3PO3 H3PO2
Orthophosphoric acid Orthophosphoric acid Orthophosphorous acid Hypophophosphorous acid

O O
O O
P OH O
P
HO
OH P P P
O O O O O O
P
OH O OH
O O
Cyclotrimetaphosphoric acid, (HPO3)3 Polymetaphosphoric acid, (HPO4)4

Figure 16.7: Halogen acids of Phosphorous

Illustration 19: Concentrated HNO3 turns yellow in sun light. Explain.  (JEE MAIN)

Sol: HNO3 is partially decomposed in sun light to produce NO2 . The NO2 formed dissolves in HNO3 to produce
yellow colour.
Sunlight
4HNO3  → 4NO2 + 2H2O + O2

Illustration 20: Nitric oxide becomes brown when released into air. Explain.  (JEE MAIN)

Sol: Nitric oxide reacts with air to get oxidized to NO2 which has brown yellow vapours.
2NO + O2 → 2NO2

Illustration 21: Aluminium containers can be used for storing conc. HNO3 . Why?  (JEE MAIN)

Sol: Al becomes passive when in contact with HNO3 due to a fine coating of its oxide on its surface and thus, Al
containers can be used to store conc. HNO3 .

Illustration 22: Copper dissolves in HNO3 , but not in HCl. Why?  (JEE MAIN)

Sol: Copper is placed below H in electrochemical series and does not liberate H2 from acid. However, HNO3
oxidises Cu due to its strong oxidant nature.

3Cu + 8HNO3(Dil.) → 3Cu(NO3 )2 + 4H2O + 2NO

Cu + 4HNO3(Conc .) → Cu(NO3 )2 + 2H2O + 2NO2

Illustration 23: NO is paramagnetic in gaseous state but diamagnetic in liquid or solid state, why?  (JEE MAIN)

Sol: The NO molecule has eleven valence electrons and thus, paramagnetic in nature due to the unpaired electron.
In solution or solid state, it forms a loose dimer in such a way that the magnetic field of unpaired electrons of two
molecules cancel out and it behaves as diamagnetic in nature.
1 6 . 2 0 | p - Block Elements

Illustration 24: Which among P4 O10 ,Cl2O7 ,I2O5 has the greatest affinity for water?  (JEE ADVANCED)

Sol: P4 O10 , one of the most powerful dehydrating agents known. Cl2O7 is the product of dehydration of HClO 4 by
P4 O10 . 12HClO 4 + P4 O10 → 6Cl2O7 + 4H3PO 4
Also, I2O5 is obtained by heating HIO3 and thus, it cannot have too great affinity for water.

Illustration 25: Describe the action of heat on the following compounds:  (JEE ADVANCED)
(i) Ammonium nitrate (ii) Ammonium nitrite
(iii) Ammonium Chloride (iv) A mixture of NaNO2 and NH4 Cl
(v) Ammonium dichromate (vi) Orthophosphoric acid
(vii) Phosphorous acid (viii) Hypophosphorous acid
(ix) Copper nitrate (x) Silver Nitrate

Sol: (i) NH4NO3 → N2O + 2H2O

(ii) NH4NO2 → N2 + 2H2O


(iii) NH4 Cl ←→ NH + HCl
 3

(iv) NaNO2 + NH4 Cl → N2 + NaCl + 2H2O

(v) (NH4 )2 Cr2O7 → N2 + Cr2O3 + 4H2O


205 C
(vi) 2H3PO 4  → H4P2O7 + H2O

600 C
H3PO 4  → HPO3 + H2O
Red heat
4H3PO 4 
→ P4 O10 + 6H2O

(vii) 4H3PO3 → 3H3PO 4 + PH3

(viii) 2H3PO2 → H3PO 4 + PH3

(ix) 2Cu(NO3 )2 → 2CuO + 4NO2 + O2

(x) 2AgNO3 → 2Ag + 2NO2 + O2

Illustration 26: What happens when an aqueous solution of hydrazine reacts with:
(i) An aqueous solution I2 .
(ii) An alkaline solution of copper sulphate.
(iii) An aqueous alkaline solution of potassium ferricyanide.
(iv) An ammoniacal solution of silver nitrate. (JEE ADVANCED)

Sol: (i) N2H4 + 2I2 → N2 + 4HI

(ii) N2H4 + 2CuSO 4 + 4KOH → N2 + 2Cu + 2K 2SO 4 + 4H2O

(iii) 4K 3 [Fe(CN)6 ] + 4KOH + N2H4 → 4K 4 [Fe(CN)6 ] + 4H2O + N2

(iv) N2H4 + 2NH4 OH + 2AgNO3 → N2 + 2Ag + 2NH4NO3 + 2H2O

 Chem i str y | 16.21

Illustration 27: An inorganic compound (A) when heated decomposes completely to give only two gases (B) and
(C). (B) is a neutral gas, fairly soluble in water and itself decomposes on heating to two different gases (D) and (E).
(A) When warmed with NaOH gives another gas (F) which turns mercurous nitrate paper black. After sometime,
the gas (F) ceases to evolve, however its supply is restored by treating residual solution with aluminium powder.
Identify (A) to (F) and give necessary equations. (JEE ADVANCED)

Sol: NH4NO3 

Heat
→ N2O + 2H2O
(A) (B) (C)

Heat
2N2O  → N2 + O2
(B) (D) (E)

NH4NO3 +NaOH → NaNO3 + NH3 +H2O

(A) (F)
Al + NaOH + H2O → NaAlO2 + 3H

NaNO3 + 8H → NaOH + NH3 + 2H2O

2NH3 +Hg2 (NO3 )2 + 2H2O → Hg2 (OH)2 +2NH4NO3

(F) Black

Illustration 28: NF3 is stable but NCl3 and NI3 are readily hydrolysed and are explosives. Explain.  (JEE ADVANCED)

Sol: NF3 is not hydrolysed because neither N nor F can expand their octet by using d-orbitals. On the other
hand, NCl3 and NI3 hydrolyse violently because Cl and I can expand their octet by using their d-orbitals.
NCl3 + 3H2O → NH3 + 3HOCl

4. GROUP 16 ELEMENTS (OXYGEN FAMILY)

4.1 Introduction
These are called chalcogen. Because these are ore forming elements {Chalco=ore}
O

S 

Se  ns2np 4 (electronic configuration table)
Te 

Po 

(a) Electronic Configuration: ns2np 4

(b) Atomic and Ionic Radii: Due to the increase in the number of shells, atomic and ionic radii increase from top
to bottom in the group. The size of oxygen atom is, however, exceptionally small.
(c) Electron Gain Enthalpy: Because of the compact nature of oxygen atom, it has less negative electron gain
enthalpy than sulphur. However, from sulphur onwards the value again becomes less negative up to polonium.
(d) Physical Properties: Oxygen and sulphur are non-metals, selenium and tellurium metalloids, whereas
polonium is a metal. Polonium is radioactive and is short lived (Half-life= 13.8 days).
The melting and boiling points increase with an increase in atomic number down the group.
1 6 . 2 2 | p - Block Elements

4.1.1 Anomalous Behaviour of Oxygen

Due to its small size and high electronegativity, strong hydrogen bonding is observed in H2O and not in H2S .
(a) Reactivity with hydrogen: All the elements of Group 16 form hydrides of the type H2E (E=O, S, Se, Te, Po).
Their acidic character increases from H2O to H2 Te . The increase in acidic character can be explained in terms
of a decrease in bond enthalpy for the dissociation of H-E bond down the group. Owing to the decrease in
enthalpy for the dissociation of H-E bond, down the group, the thermal stability of hydrides also decreases
from H2O to H2Po . All the hydrides except water possess reducing property and this character increases from
H2S to H2 Te .

(b) Reactivity with oxygen: All these elements from oxides of the EO2 and EO3 types where E=S, Se, Te or Po.

(c) Reactivity towards the halogens: Elements of group 16 form a large number of halides of the type, EX 6 ,EX 4
and EX 2 where E is an element of the group and X is a halogen. The stability of the halides decreases in the
order F− > Cl− > Br − > I − .

4.2 Dioxygen
Preparation: Dioxygen can be obtained in the laboratory by the following ways:
(a) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
Heat
2KCIO3  → 2KCl + 3O2
MnO 2

(b) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely divided metals
and manganese dioxide. 2H2O2 (aq) → 2H2O(l) + O2 (g)
(c) On a large scale, it can be prepared from water or air. Electrolysis of water leads to the release of hydrogen at
the cathode and oxygen at the anode.

Properties: Dioxygen is a colourless and odourless gas. Its solubility in water is to the extent of 3.08 cm3 in 100 cm3
water at 293 K which is just sufficient for the vital support of marine and aquatic life.
Some of the reactions of dioxygen with metals, non-metals and other compounds are given below:
2Ca + O2 → 2CaO
4Al + 3O2 → 2Al2O3
P4 + 5O2 → P4 O10
C + O2 → CO2
2ZnS + 3O2 → 2ZnO + 2SO2
CH4 + 2O2 → CO2 + 2H2O

Some compounds are catalytically oxidized. For e.g.

2 5V O
2SO2 + O2 → 2SO3
CuCl
2
2HCl + O2  → 2Cl2 + 2H2O

4.3 Sulphur
(a) Rhombic sulphur ( α -sulphur): This allotrope is yellow in colour, m.p. 385.8 K and specific gravity 2.06.
Rhombic sulphur crystals are formed on evaporating the solution of roll sulphur in CS2 . It is insoluble in water
but dissolves to some extent in benzene, alcohol and ether. It is readily soluble in CS2 .
(b) Monoclinic sulphur ( β -sulphur): This form of sulphur is prepared by melting rhombic sulphur in a dish
and cooling. Till a crust is formed. Two holes are made in the crust and the remaining liquid poured out. On
removing the crust, colourless needle shaped crystals of β -sulphur are formed. It is stable above 369 K and
 Chem i str y | 16.23

transforms into α -sulphur below it. Its m.p. is 393 K and specific gravity 1.98. It is soluble in CS2 . Conversely,
α -sulphur is stable below 369 K and transforms into β -sulphur above this temperature. At 369 K both the
forms are stable. This temperature is called transition temperature. Both rhombic and monoclinic sulphur
have S8 molecules. These S8 molecules are packed to give different crystal structures.

S S
S 204p S
m
107
S S
S 205.7 pm
S S
S S +
102.2
(a) S
S
(b)

Figure 16.8: Forms of Sulphur S

4.3.1 Sulphur Dioxide

Preparation: When sulphur is burnt in air or oxygen to form SO2 S(s) + O2 (g) → SO2 (g)

Properties: Sulphur dioxide is a colourless gas with pungent smell and is highly soluble in water.

Structure of SO2 molecules

:

S S
:
:

:
O: O: O O
:

: :
:

The molecule of SO2 in angular. It is a resonance hybrid of the two canonical forms.
Uses: Sulphur dioxide is used (i) in refining petroleum and sugar (ii) in bleaching wool and silk and (iii) as an
anti-chlor, disinfectant and preservative. Sulphuric acid, sodium hydrogen sulphite and calcium hydrogen sulphite
(industrial chemicals) are manufactured from sulphur dioxide.

4.3.2 Oxoacids of Sulphur

Sulphur forms a number of oxoacids such as
H2SO3 ,H2S2O3 ,H2S2O 4 ,H2S2O5 ,H2S x O6 (x = 2 to5), H2SO 4 ,H2S2O7 ,H2SO5 ,H2S2O8

O O O O O

S S S S S S
O O O O O O O O O
HO HO
HO HO HO HO HO HO

Sulphurous acid Sulphuric acid Peroxidisuphuric acid Pyrosulphic acid (Oleum)

(H2SO3) (H2SO4) (H2S2O8) (H2S2O7)

Figure 16.9: Oxoacids of Sulphur

1 6 . 2 4 | p - Block Elements

4.3.3 Sulphuric Acid

Manufacture: Sulphuric acid is one of the most important industrial chemicals worldwide. Sulphuric acid is
manufactured by the Contact Process which involves three steps:

(a) Burning of sulphur or sulphide ores in air to generate SO2

(b) Conversion of SO2 to SO3 by the reaction with oxygen in the presence of a catalyst (V2O5 ) , and

(c) Absorption of SO3 in H2SO 4 to give Oleum (H2S2O7 ) . The SO2 produced is purified by removing dust and
other impurities such as arsenic compounds.
The key step in the manufacture of H2SO 4 is the catalytic oxidation of SO2 with O2 to give SO3 in the presence of
V2O5 (catalyst).
V O
2 5
2SO2 (g) + O2 (g) → 2SO3 (g); ∆rH = 196.6 kJ mol−1

Manufacture of Sulphuric Acid: The reaction is exothermic, reversible and the forward reaction leads to a
decrease in volume. The SO3 gas from the catalytic converter is absorbed in concentrated H2SO 4 to produce
oleum. Dilution of oleum with water gives H2SO 4 of the desired concentration. In the industry, two steps are
carried out simultaneously to make the process a continuous one and also to reduce the cost.
SO3 + H2SO 4 → H2S2O7 (Oleum). The sulphuric acid obtained by Contact process is 96-98% pure.

Properties: Sulphuric acid is a colourless, dense, oily liquid with a specific gravity of 1.84 at 298 K. It dissolves in
water with the evolution of a large quantity of heat. While preparing sulphuric acid solution from concentrated
sulphuric acid. The concentrated acid must be added slowly into water with constant stirring. The chemical reaction
of sulphuric acid is as a result of the following characteristics: (a) low volatility (b) strong acidic character (c) strong
affinity for water and (d) ability to act as an oxidizing agent.
H2SO 4 (aq) + H2O(l) → H3O + (aq) + HSO 4 − (aq)
= ; K a1 very large(K a1 > 10)

1.2 x10−2
HSO 4 − (aq) + H2O(l) → H3O + (aq); K a =
2

Chemical Reactions:
2MX + H2SO 4 → 2HX + M2SO 4 (X =
F, Cl, NO3 )
(M = Metal)
H2SO 4
C12H22O11  → 12C + 11H2O
Cu + 2H2SO 4 (conc.) → CuSO 4 + SO2 + 2H2O

3S + 2H2SO 4 (conc.) → 3SO2 + 2H2O

C + 2H2SO 4 (conc.) → CO2 + 2SO2 + 2H2O

MASTERJEE CONCEPTS

•• Among H2O, HCland NH3 ,H2O has the highest boiling point and HCl the lowest. H2O is capable
of showing more stronger H-bonding than NH3 , while HCl has no H-bonding. The b.p. order is
H2O > NH3 > HCl.

•• H2S acts only as a reducing agent while SO2 can act both as a reducing agent and oxidizing agent. S
in SO2 has a oxidation state of +4. It lies between the minimum oxidation state (-2) and maximum
oxidation (+6) of S. Thus, S in SO2 can show an increase in its oxidation number (i.e., act as a
reductant) or can show a decrease in its oxidation number (i.e., it acts as an oxidant). On the other
hand, in H2S, S is in -2 oxidation state and can only increase its oxidation state to act as a reductant.
GV Abhinav (JEE 2012, AIR 329)
 Chem i str y | 16.25

Illustration 29: What are the oxidation states of S in the following compounds: (JEE MAIN)
(a) PbS (b) SO2 (c) SF6 (d) Na2S2O3 (e) H2SO3

Sol: (a) -2, (b) +4, (c) +4, (d) +2, (e) +4

Illustration 30: H2S acts only as reducing agent while SO2 can act both as reducing agent and oxidising agent.
Explain.  (JEE MAIN)

Sol: S in SO2 has oxidation state +4. It lies between the minimum oxidation state (-2) and maximum oxidation
state (+6) of S. Thus S in SO2 can show an increase in its ox. no. (i.e., act as reductant) or can show a decrease in its
ox. no. (i.e., act as oxidant). On the other hand, in H2S, S is in -2 oxidation state and can only increase its oxidation
state to act as reductant.

Illustration 31: Nitric acid cannot be used to prepare H2S . Explain. (JEE MAIN)

Sol: Nitric acid is an oxidizing agent. It will oxidise H2S .

H2S + 2HNO3 → 2NO2 + S + 2H2O

Illustration 32: Among H2O , HCl and NH3 , H2O has the highest boiling point and HCl the lowest. (JEE MAIN)

Sol: H2O is capable of showing more stronger H-bonding than NH3 , while HCl has no H-bonding. The b.p. order
is H2O > NH3 > HCl

Illustration 33: Conc. H2SO 4 cannot be used for drying up H2S . Explain  (JEE MAIN)

Sol: Conc. H2SO 4 oxidises H2S to S and thus cannot be used as for drying up H2S .
H2SO 4 + H2S → 2H2O + SO2 + S

Illustration 34: Ozone destroys a mercury meniscus. Why?  (JEE ADVANCED)

Sol: Ozone oxidises Hg to mercury suboxide which starts sticking to glass and loses its mobility. Hence, Hg loses
its meniscus in contact with ozone. However, it can be regained by the action of H2O2 .
2Hg + O3 → Hg2O + O2

Illustration 35: KMnO 4 should not be dissolved in conc. H2SO 4 . Explain.  (JEE ADVANCED)

Sol: KMnO 4 forms explosive covalent compound, Mn2O7 with conc. H2SO 4
2KMnO 4 + H2SO 4(conc) → K 2SO 4 + Mn2O7 + H2O
However it can be dissolved in dil. H2SO 4 to give nascent oxygen, if it is to be used as an oxidant

Illustration 36: SO2 acts as bleaching agent. Explain. (JEE ADVANCED)

Sol: SO2 in presence of water is oxidized to H2SO 4 liberating nascent hydrogen, which reduces/bleaches the
colouring matter.
SO2 + 2H2O → H2SO 4 + 2[H]
Colouring matter + 2[H] → Colourless compound
1 6 . 2 6 | p - Block Elements

Illustration 37: An acidified K 2Cr2O7 paper turns green when exposed to SO2 . Explain.  (JEE ADVANCED)

Sol: SO2 reduces K 2Cr2O7 to green chromium sulphate.

3SO2 + K 2Cr2O7 + H2SO 4 → K 2SO 4 + Cr2 (SO 4 )3 + H2O Green

Illustration 38: A white turbidity is obtained by passing H2S in aqueous solution of SO2 Why? (JEE ADVANCED)

Sol: Aqueous solution of SO2 and H2S undergoes redox changes to produce colloidal sulphur as white turbidity.
2H2S + H2SO3 → 3H2O + 3S (Colloidal sulphur)

5. GROUP 17 ELEMENTS (HALOGEN FAMILY )

5.1 Introduction
Named because they are sea - salts forming elements.
F 

Cl 
 2 5
Br  ns np
I 

At 

General Properties:
(a) State and Nature
(i) F and Cl are Gas
(ii) Br: Liquid
(iii) I, At is solid
(iv) All are non metallic. But non metallic character decreases down the group.
(v) I has metallic lustre on heating and undergoes sublimation.

(b) Atomic Radii, Ionic Radii, B.P. and M.P., Density: All these characters increase down the group

(c) Ionization Potential and Electronegativity: Decreases down the group

(d) Electron Affinity (E.A)

From F to Cl → E.A increases.
Due to the availability of a vacant d-orbital in Cl and then E.A. decreases
So, order is Cl > F > Br > I.

(e) Valency and Oxidation State:

(i) ns2 np5
(ii) Valency = 1
If halogens combines with more E.N. elements, then O.S. =+1.
(iii) For Cl, Ground State:
Valency = 1
 Chem i str y | 16.27

2 5
3s 3p 3d
st
1 E.S.

2 4 1
3s 3p 3d
3
sp d Trigonal bipyramidal

(f) Bond Energy: F – F bond dissociation energy is less than that of Cl-Cl and Br-Br. It is due to larger inter
electronic (electron-electron) repulsion between the non-bonding electrons in the 2p orbitals of fluorine
atom than in the 3p orbitals of chlorine atoms.
F-F Cl-Cl Br-Br I-I
38 kcal/mol 57 kcal/mol 45.5 kcal/mol 35.6 kcal/mol Cl2 > Br2 > F2 > l2

5.1.1 Oxidising Power

The electron affinity, or tendency to gain electrons reaches a maximum at chlorine. Oxidation may be regarded as
the removal of electrons so that an oxidizing agent gains electrons.
Thus halogens act as oxidizing agents.
The strength of an oxidizing agent (i.e. oxidation potential) depends upon several energy terms and is represented
by following diagram.
1 1 1
1 2
Heat 1 2
heat 1 heat
X 2 (s) 
Fusim
→ X 2 (1) 
Evaporation
→ X 2 (g) 2
 Electron
→ X(g) 
h eat of
→ X − (g)  → X − (hydrated)
2 2 2 Dissociation affinity hydration

The heat of fusion, evaporation and dissociation are positive and electron affinity and heat of hydration are negative.
The net energy (E) required for oxidizing reaction is given by-

1 1 1
E(net) = H + H + H − E.A. − H(hyd)
2 f 2 v 2 d

Element Enet (kcal)

F2 −186.5
Cl2 −147.4
Br2 −136.4
I2 −122.4

Thus oxidizing powers decrease on descending in group VII. Fluorine is a strong oxidising agent as seen in the
reaction given below where oxygen in water has been oxidised. The oxidation of H2O by Cl2 is thermodynamically
possible but since the energy of activation is high, this reaction does not occur.
1
F2 + H2O → 2H+ + 2F− + O2
2
Cl2 + H2O → HCl + HOCl

Iodine is even weaker where the free energy change indicates that for oxidation of water, it needs a supply of
energy.
1 6 . 2 8 | p - Block Elements

Chemical Properties
(a) Reaction with H2
(i) All halogens reacts with H2 to form hydrogen halides.
H2 + X 2 → 2HX
(ii) Reactivity of Halogens F > Cl > Br > I
(iii) HCl, HBr, HI acts as reducing agent.

(b) Reaction with H2O

(i) H2O acts as reducing agent only with fluorine.
2F2 + 2H2O → 4HF + O2

(ii) H2O + I2 → No Reaction.

(c) Displacement reaction

(i) F2 + 2NaX → 2NaF + X 2 {X = Cl,Br,I}

Cl2 + 2NaX → 2NaCl + X 2 {X =Br2 , I2 }

So order of displacement [F2 > Cl2 > Br2 > I 2 ]

(ii) If Halogen is in –ve O.S., then it is replaced by more E.N. element.
(iii) If Halogen is +ve O.S., then it is replaced by less E.N. element.

(d) Reaction with metals: Metal halides are formed F > Cl > Br > I

(e) Reaction with non-metals: Non-metallic halides are formed.

Eg. NF3 , PCl3 etc.

(f) Reaction with NH3
(i) 3F2 + NH3 → NF3 + 3HF
(ii) 3Cl2 + NH3 → NCl3 + 3HCl

(g) Reaction with NaOH

(i) F2 + NaOH (dil.) → 2NaF + OF2 + H2O
(ii) 2F + 4NaOH (conc.) → 4NaF + 2H O + O
2 2 2

(h) Formation of oxides

(i) No oxides of F because of its maximum E.N. character.
(ii) Rest form

X 2O X 2O3 X 2O5 X 2 O7
Eg. +1 +3 +5 +7
Cl2O Cl2O3 Cl2O5 Cl2O7

(iii) All these oxides are acidic

(iv) Acidity decreases down the group and maximum active oxide is Cl2O7

(i) Formation of oxyacids

(i) F does not form any oxyacid due to High E.N.
 Chem i str y | 16.29

(ii) Rest oxyacids are

HXO HXO2 HXO3 HXO 4
+1 +3 +5 +7
Hypohalous Halous Halic acid  Perhalic acid 
acid    acid
          
(j) Interhalogens
Products are obtained by uniting two halogen compounds:
AB AB3 AB5 AB7

Where A = less E.N. Halogen
B = More E.N. Halogen
ClF ClF3 BrF5 IF7
Eg.
BrCl BrCl3 ICl5
IBr IBr3

These interhalogens have polarity because of different E.N.

Note: Abnormal behaviour of Fluorine as compared to Other Members:
Fluorine differs considerably from other halogens due to its-
•• Small size
•• High electronegativity.
•• Non availability of d – orbitals in its valence shell.
•• Low bond dissociation energy of F – F bond.
•• Boiling point of HF is the highest and then it increases down the group.
•• Due to hydrogen bonding, HF is a liquid while HCl, HBr and HI are gases.
•• Solubility of salts
AgF is soluble in water while AgCl, AgBr and AgI are insoluble.
It combines with hydrogen explosively at a low temperature and even in the dark.
None of the other halogens combine so readily.
H2 + F2 → 2HF
(i) It liberates oxygen as well as ozone with water.
2H2O + 2F2 → 4HF + O2
3H2O + 3F2 → 6HF + O2

Family Members of Halogen

(a) Fluorine (F2)
(i) Uses: It is used in the preparation of fluorine compounds such as.
Freon: Freon – 12 i.e. CF2Cl2 as used in refrigeration and air conditioning in place of NH3 and SO2
Teflon: ( −F2C − CF2 )n It is a new plastic.
1 6 . 3 0 | p - Block Elements

Chlorine (Cl2)
(a) Preparation: By the electrolysis of brine (Aq. Solution of NaCl) in nelson cell. This is the cheapest method


NaCl ←→ Na+ + Cl−



H2O ←→ H+ + OH−


H+ + e− → H
At Cathode:
H + H → H2

Cl− → Cl + e−
At anode:
Cl + Cl → Cl2 ↑

(b) Deacon’s process:

4HCl + O2  → 2H2O + 2Cl2
CuCl 2
4     :    1
 

Chlorine gas thus obtained contains N2 and O2 and is used for the manufacture of bleaching powder by
Hasenclever’s process
(c) Uses:
(i) As a germicide and disinfectant.
(ii) Domestic antiseptic solution (NaOCl)

Bromine (Br2)
(a) Preparation: (a) Bittern: Mother liquor contains about 0.25% of bromine or MgBr2 and is known as bittern.
Bittern is treated wih Chlorine gas.
MgBr2 + Cl2 → MgCl2 + Br2

(b) Uses: (a) It is used in preparation of ethyl bromide which is used in the manufacturing of tetraethyl lead (TEL)
as an important anti – knock compound in the petroleum industry.
C2H6 + Br2 → C2H5Br + HBr

4C2H5Br + 4Na − Pb → (C2H5 )4 Pb + 4NaBr + 2Pb

Iodine (I2)
(a) I2 is the rarest of all the halogens. Its main source is kelp (varee).

(b) Properties: (a) It is only sparingly soluble in water but readily in NaOK iodide due to formation of triiodide.
KI + I2 → KI3
However, this solution behaves as a simple mixture of KI and free I2 .
1 1
Note: Tincture of iodine contains ounce I2 , ounce KI and 1 pinch of rectified spirit.
2 4
 Chem i str y | 16.31

Table 16.6: Oxy acids of Halogens

Oxidation Chlorine Bromine Iodine Name of acid Name of salt of

state halogens
+1 HClO HBrO HIO Hypohalous Hypohalite Stability and acidity
+3 HClO2 - - Halous Halite Increases but
+5 HClO3 HBrO3 HIO3 Halic Halate Oxidizing power
+7 HClO4 HBrO4 HIO4 Perhalic Perhalate decreases

Oxy Acids of Halogens:

(a) Fluorine does not form any oxy-acids because it is more electronegative than oxygen.
(b) Other halogens form four series of oxy acids with formulae

HXO → Hypohalous
HXO2 → Halous

HXO3 → Halic

HXO 4 → Perhalic acids or Halic (I), Halic (III), Halic (V) and Halic (VII)

(c) Thermal stability – Stability increases and oxidizing power decreases
(d) Oxidising power-
ClO −
↓
ClO 4 −

Hypochlorites are the strongest oxidizing agents.

(e) Relative acidity ∝ oxidation no.

HClO 4 > HClO3 > HClO2 > HClO

Note: (i) In all these acids and salts halogen is in sp3 hybridised state.
(ii) Stronger the acid, the weaker will be its conjugate base and vice-versa.
ClO 4 − < ClO3− < ClO2− < ClO − (relative basic character)
Thus, ClO 4 − is the weakest base and HClO 4 (conjugate acid of ClO 4 − ) is the strongest acid.
ClO 4 − > ClO3− > ClO2− > ClO −

←
Relative stability of Cl − O bonds
1 6 . 3 2 | p - Block Elements

MASTERJEE CONCEPTS

•• Fluorine exhibits a covalence of one only whereas other halogens show a covalence ranging from
1 to 7. Because in fluorine vacant d-orbitals are not present and so the electron can’t be unpaired
by electronic excitation. On the other hand, rest all halogens show covalence from 1 to 7 by the
excitation of their p-electrons to d-subshells.
•• KHF2 is well known, whereas KHCl2 or KHBr2 does not exist. H2F2 exists as dimeric molecule
due to H-bonding and thus, shows dibasic nature. Hence, it gives two series of salts KHF2
[K + and F− ..........H − −F− ] and KF [K + and F− ] whereas HCl and HBr do not show hydrogen bonding
and thus formation of KHCl2 or KHBr2 is not possible.
Chinmay S Purandare (JEE 2012, AIR 698)

Illustration 39: Pure Hl kept in a bottle acquires a brown colour after some time. Explain.  (JEE MAIN)

Sol: Hl is strong reducing agent and is oxidized by oxygen to I2 . The liberated iodine is dissolved there and imparts
a brown colour to the solution. 4HI + O2 → 2H2O + 2I2

Illustration 40: Iodine dissolves more in Kl solution, than in pure water. Explain (JEE MAIN)

Sol: I2 is non-polar in nature and thus its solubility in water (a polar solvent) is less which however becomes more
if Kl is present due to a complex formation. I2 + KI → KI3 (soluble complex)

Illustration 41: Chlorine is a gas while iodine is a solid under ordinary conditions. Explain.  (JEE MAIN)

Sol: Due to high mol. wt., Van der Waals’ forces of attraction one stronger in I2 .

Illustration 42: Fluorine exhibits a covalence of one only whereas other halogens show a covalence ranging from
1 to 7.  (JEE MAIN)

Sol: Because in fluorine, vacant d-orbitals are not present and so electrons can’t be unpaired by electronic
excitation. On the other hand, rest all halogens show covalence from 1 to 7 by excitation of their s and p-electrons
to d-subshells.

Halogens (Cl, Br, I) ns np nd

Ground state

Covalence = 1
I excited state

Covalence = 3

II excited state

Covalence = 5

III excited state

Covalence = 7

Fluorine is the most electronegative element and thus shows only negative oxidation state. Furthermore, it has
2s22p5 configuration and thus shows only -1 oxidation state in order to complete its octet. Also like other halogens,
it does not have vacant d-orbitals in its valence shell.
 Chem i str y | 16.33

Illustration 43: Fluorine is a non-metal whereas iodine shows some metallic properties as well. Explain.
 (JEE MAIN)
Sol: Owing to small size and high I.E., F has no tendency to lose electron. I is large and has lower I.E. So, it may lose
an electron.

Illustration 44: Why are halogens coloured and on moving from F2 to I2 , the colour of halogens becomes dark,
why?  (JEE ADVANCED)

Sol: Because energy required in electronic excitation and de-excitation lies in visible region. On moving from
F2 to I2 , the size of atom increases and so energy levels become closer and so promotion energy becomes less.
So, colour deepens.

Illustration 45: Dry chlorine does not act as bleaching agent. (JEE ADVANCED)

Sol: The bleaching action of Cl2 is due to its reaction with H2O to liberate nascent oxygen.

Illustration 46: Iodine stains on cloths can be removed by hypo.  (JEE ADVANCED)

Sol: Hypo reacts with iodine to form water soluble sodium tetrathionate and sodium iodide.
I2 + 2Na2S2O3 → 2NaI + Na2S 4 O6

Illustration 47: Colour of KI solution containing starch turns blue when chlorine water is added to it. Explain.
 (JEE ADVANCED)
Sol: Cl2 replaces I2 from its aqueous solution due to its higher standard reduction potential than iodine.
Cl + 2KI → 2KCl + I
2 2

Illustration 48: KHF2 is well known, whereas KHBr2 does not exist. Explain.  (JEE ADVANCED)

Sol: H2F2 exists as dimeric molecule due to H—bonding and thus shows dibasic nature. Hence it gives two series of
salts KHF2 as [ K + and F− ........H − F− ] and KF [ K + and F− ] whereas HCl and HBr do not show hydrogen bonding and
thus formation of KHCl2 or KHBr2 is not possible.

6. NOBLE GASES OR RARE GASES

6.1 Introduction
They occur in the atmosphere infrequently and are hence also referred to as the rare gases.
He 2 1s2

Ne 10 

Ar 18 

Kr 36  ns2np6
Xe 54 

Rn 86 

All have octet configuration except He having duplet configuration.

(a) They exist in gaseous state.
(b) Rn is produced by the disintegration of radium and is radioactive itself.
1 6 . 3 4 | p - Block Elements

(c) Ramsay discovered these gases.

(d) The first inert gas to be discovered by Ramsay was argon.

Occurance: Group 18 of the periodic table consists of six elements – helium, neon, argon, krypton, xenon and
radon which are collectively known as the Noble Gases.
All the noble gases except radon occur in the atmosphere. Their total abundance in dry air is 1% by volume of
which argon is the major component. Neon, argon, krypton and xenon are obtained as by-products of liquefication
of air and separation of its constitution by fractional distillation. The main commercial source of helium is natural
gas. Helium is the second most abundant element in the universe (23% compared to 76% hydrogen) although its
terrestrial abundance is very low. Radon is obtained as the decay product of 226Ra.
226 222 4
88 Ra → 86 Rn + 2 He

Isolation: Except He, non-radioactive noble gases are commercially isolated from air by two methods.

(a) Fractional distillation of liquid air (claude’s method): Due to the difference in b.p. the various constituents
of air are separated from each other.
(b) Dewar’s coconut charcoal adsorption method:
(i) O2 and N2 are removed by means of compound formation.
(ii) The principle of this method is that the adsorption capacity of these gases at low temperature by coconut
charcoal increase with the increase in their atomic weights.
(iii) Thus He has the lowest and Xe has the maximum adsorption capacity.

General Properties
(a) Atomic radii, melting point and boiling point, density:
(i) All increases down the group.
(ii) He is the only element having two boiling point i.e. 4.1 K and 2.5 K.
(iii) It is the only element which exists in two liquid phases i.e. He and He2 .

(b) Ionisation energy:

(i) They possess very high ionisation energy.
(ii) Ionisation energy of Xe is nearly equal to that of molecular oxygen.

(c) Electron affinity: Due to complete octet, noble gas atoms are unable to take extra electrons.

(d) Monatomicity: Due to very high I.E. and nearly zero E.A. noble gas atoms are not capable of combining and
Cp
their value of γ = is close to 1.66.
Cv

(e) Force of attraction between atoms of noble Gases:

Vander Waal’s force between the atoms increases from He to Xe.

(f) Solubility in water: Slightly soluble in water and solubility in water increases with the increase in atomic
number.
(g) Chemical nature:
(i) Noble gases are almost chemically inert.
(ii) But Kr, Xe and Rn are slightly reactive because of the radioactive nature of these gases.
 Chem i str y | 16.35

(h) Adsorption of inert gases:

(i) Done on coconut. Gas particles are adsorbed at the surface of coconut charcoal
(ii) Larger the size, more will be the adsorption. So, maximum adsorption of Xe at highest temp.
(iii) First gas discovered was Argon. (Ar Lazy gas)
(iv) The other inert gas isolated was Neon.
(v) The other inert gas which remained a hidden gas krypton (Kryptos = Hidden)
(vi) Then Xenon (Xenon = danger) was discovered
(vii) Rn emits α , β, γ radiations.
(viii) Discovery of the by Lockeyer on sun’s atmosphere.

Family members of noble gases:

Noble gas compounds proved elusive for many years. The real chemistry of noble gases began in 1962 with the
isolation of an orange yellow solid by Neil Bartlett from the reaction of xenon with PtF6. Bartlett had noticed that
PtF6 reacts with oxygen to form O2 +[PtF6]‒ and since the ionization enthalpies of O2 and Xe are close to each other
=[X e 1170;
= O2 1175 kJ mol−1 ] , he reasoned that PtF6 would react with xenon to form Xe+ [PtF6 ]−* . Since this
exciting discovery, several other xenon compounds, mainly with the most electronegative elements-fluorine and
oxygen, have been synthesised. The compounds of krypton are fewer, only the difluoride (KrF2) has been studied
in detail. Compounds of radon have not been isolated but only identified by radiotracer techniques. No true
compounds of Ar, Ne or He are known.

Xenon (Xe): It is the only element that forms true compounds and that too with highly reactive elements F2. Xenon
forms three binary fluorides, XeF2 , XeF4 and XeF6 by the direct union of elements under appropriate sunlight or
light from a high pressure mercury arc lamp:

6 73 K, 1 bar
Xe(g) + F2 (g) 
→ XeF2 (s)

(xenon in excess)
8 73 K, 7 bar
Xe(g) + 2F2 (g) 
→ XeF2 (s)
(1:5 ratio)
5 73 K, −70 bar
Xe(g) + 3F2 (g) 
→ XeF6 (s)
(1:20 ratio)

XeF2 , XeF4 and XeF6 are colourless solids subliming readily at 298 K. They are powerful fluorinating agents. They
are readily hydrolysed by even traces of water. The hydrolysis of XeF2 can be represented by the equation:
2XeF2 (s) + 2H2O(l) → 2Xe(g) + 4HF(aq) + O 2 (g)
The structures of the three xenon fluorides can be deduced from VSEPR theory (Valence shell electron pair theory).
XeF2 and XeF4 have linear and square planar structures, respectively. XeF6 has seven electron pairs (6 bonding
pairs and one lone pair) and would thus have a distorted octahedral structure as found experimentally in the gas
phase. In the solid state, XeF6 contains tetrameric and hexameric units in which acceptors form cationic species and
fluoride ion donors form fluoroanions.
XeF2 + PF5 →[XeF]+ [PF6 ]− XeF4+
SbF5 →[xeF3 ]+ [SbF6 ]− XeF6 + MF → M+ [XeF7 ]−
[M = Na,K,Rb or Cs]
 1 6 . 3 6 | p - Block Elements

(a) XeF2:

1:2
Xe XeF2
+ 1:5
(i) XeF2 :
F

1:
XeF4

20
5s 5p 5d
3
sp d
(b) XeF4: XeF4
Linear geometry

(ii) XeF4 :

5s 5p 5d
3 2
sp d
(c) XeF6: Square planar

(iii) XeF6 :
3 3
sp d
Distorted octahedral

(d) Reaction with H2O:

XeF6 + H2O → H2F2 + XeOF4

sp3d2 (Square Pyramidal)

XeOF4 + H2O → XeO2F2 + H2F2

Xenon dioxy difluoride (sp3d) i.e. Trigonal bipyramid
XeO2F2 + H2O → XeO3 + H2F2

Explosive Xenon trioxide (sp3 )

Neon and Argon:

(a) Gets trapped in the interstitial spaces of H2O or alcohols and this type of mixture resulted in what is called as
a clatharate compound.
(b) These compounds are not formed by He.

Uses:
(a) Noble gases are widely used to provide inert atmospheres in metallurgical process
(b) 
He is used as a cooling medium in gas cooled atomic reactions because of its high thermal conductivity, low
viscosity and low density.
(c) Liquid He is used in gas thermometers required for low temperature measurement.
(d) Neon in neon lamps.
(e) Neon is used in neon tubes for rectifiers, voltage regulators etc.
(f) Argon is used in filling incandescent lamps.
(g) Xe is used in the discharge tube for quick photography.
(h) Rn is used in the treatment of cancer (Radiotherapy)
 Chem i str y | 16.37

MASTERJEE CONCEPTS

•• Noble gases have zero electron affinity. Noble gases have stable electronic configuration. Hence, it
is difficult to add the electron
•• Atomic size of noble gases is maximum in their period. For noble gases only, Van der Waals’ radii can
be obtained. For rest of the elements, covalent or Ionic radii are obtained. Van der Waals’ radii are
always larger than covalent radii.
•• Decreasing order of Xe-F bond length in XeF2, XeF4, XeF6
XeF2 > XeF4 > XeF6
2.00Å 1.95Å 1.89Å
Bond shortening may be accounted in terms of an increase in the charge on a xenon atom.
Vaibhav Gupta (JEE 2009, AIR 54)

Illustration 49: Helium and neon do not form compounds with fluorine. Explain.  (JEE MAIN)

Sol: They are chemically unreactive, owing to small size and high I.E.

Illustration 50: Why do noble gases have zero electron affinity?  (JEE MAIN)

Sol: Noble gases have stable electronic configuration. Hence, it is difficult to add the electron resulting in zero
electron affinity.

Illustration 51: Why are noble gases less reactive?  (JEE MAIN)

Sol: Due to completely filled outermost shell.

Illustration 52: Atomic size of noble gases is maximum in their period. Explain.  (JEE MAIN)

Sol: For noble gases only Van der Waals’ radii can be obtained. For rest all elements, covalent or ionic radii are
obtained. Van der Waals’ radii are always larger than covalent radii.

Illustration 53: Noble gases have maximum ionization energy in their period.  (JEE MAIN)

Sol: Due to a more effective nuclear charge which increases along the period.

Illustration 54: The b.p. of noble gases increases with the increase in at. no. Explain.  (JEE ADVANCED)

Sol: As at. wt. increases, Van der Waals’ forces of attraction becomes strong.
Illustration 55: Why is helium molecule, ( He2 ) not formed?  (JEE ADVANCED)

Sol: For He2 , bond order is zero.

Illustration 56: Xenon has a closed shell configuration but forms compounds with fluorine. Explain. 
 (JEE ADVANCED)
Sol: Gases and thus the outermost shell electrons of Xe are excited to d-subshell.

Illustration 57: Complete the following reactions. (JEE ADVANCED)

1 6 . 3 8 | p - Block Elements

(i) XeF6 + H2O →

(ii) XeF2 + H2 →

(iii) XeF6 + SiO2 →

(iv) XeF6 + NH3 →

(v) XeF6 + SbF5 →

(vi) XeF4 + KI →

−78 C o
(vii) XeF4 + BCl3  →

(viii) XeF2 + HClO 4 →

Sol:
(i) XeF6 + 3H2O → XeO3 + 6HF
(ii) XeF2 + H2 → Xe + 2HF

(iii) 2XeF6 + SiO2 → 2XeOF4 + SiF4

2XeOF4 + SiO2 → 2XeO2F2 + SiF4

2XeO2F2 + SiO2 → 2XeO3 + SiF4
Explosive

(iv) XeF6 + 8NH3 → Xe + 6NH4F + N2

(v) XeF6 + SbF5 → [XeF5 ]+ [SbF6 ]−

 Addition ionic product is formed

(vi) XeF4 + 4KI → Xe + 4KF + 2I2

−78 C o
(vii) 3XeF4 + 4BCl3  → 4BF3 + 3Xe + 6Cl2

(viii) XeF2 + 2HClO 4 → Xe(O − ClO3 )2 + 2HF]

Illustration 58: Arrange the XeF2 , XeF4 , XeF6 in decreasing order of Xe-F bond length give reason also. 
 (JEE ADVANCED)
Sol: XeF2 > XeF4 > XeF6 , bond shortening may be accounted for in terms of increase in the charge on a xenon atom.
2.00 A 1.95Α 1.89 Α