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CHAPTER:- GROUP 16 ELEMENTS [By : Nagendra Kumar]

❖ The following elements are found in the group 16:-

ELEMENTS Symbol At. No. At. Wt.
Oxygens O 08 16
Sulphur S 16 32
Selenium Se 34 79
Tellurium Te 52 127
Pollonium Po 84 210

❖ The elements of group 16 are also called as Chalcogens because they form ore.
❖ General electronic configuration: ns2 np4
❖ GENERAL TRENDS IN PHYSICAL PROPERTIES:-
➢ Atomic and ionic radii: Increases down the group due to increase in no. of orbits
down the group.

➢ DENSITY:- The density of the elements increases down the group.

➢ MELTING AND BOILING POINT:-

The m.p. and b.p. increases down the group upto Te and then decreases for Po.
The large difference in m.p. and b.p. point of oxygen and sulphur is due to the
fact that oxygen is diatomic while sulphur is polyatomic.

➢ IONISATION ENERGY:-
The ionization energy decreases down the group due to increase in the size of
atom down the group.

➢ OXIDATION STATE:-
• Most of the elements of this show the oxidation state of -2, +2, +4, +6.
• Oxygen can show -1/2, -1, -2, and +2.

➢ ELECTRON AFFINITY:-
• The elements of group has high electronegetivity whose value decreases
down the group.
• Oxygen has lower electron affinity due higher electronic repulsion due to
smaller size.

➢ ELECTRONEGATIVITY:-
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• The electronegativity decreases down the group due to increase in the size
of atom down the group and decrease in effective nuclear charge down the
group.
➢ Metallic character:
Increases down the group.
Oxygen & sulphur are non metals, Se and Te are semi – metals and Po is metal.
➢ ALLOTROPY:- All the elements of the group show allotropy.
ELEMENTS ALLOTROPIC FORMS
Oxygen 1. Dioxygen.
2. Ozone.
Sulphur 1. Rhombic Sulphur.
2. Monoclinic Sulphr.
3. Plastic Sulphur.
Selenium 1. Rhombic Selenium.
2. Monoclinic Selenium

❖ CHEMICAL PROPERTIES:-
1. REACTIVITY WITH HYDROGEN:-
▪ The elements of group 16 forms volatile hydrides with hydrogen of H 2M
type, where M = O / S / Se / Te.
▪ The hydrides are weakly acidic in nature & the acidic nature of the hydrides
increases down the group as follows: H2O < H2S < H2Se < H2Te.

2. REACTIVITY TOWARDS THE HALOGENS:-

▪ The elements of group 16 forms different types of halides of type MX6, MX4 &
MX2.
▪ The stability of the halides decreases in the order F > Cl > Br > I.
▪ Amongst the hexahalides, hexafluorides are only the stable halides.
▪ All hexaflourides aregaseous in nature and have octahedral structure.
▪ Sulphur hexafluorides are exceptionally stable for stearic reason.

3. REACTIVITY TOWARDS OXYGEN:-

▪ All the elements of the group form the compounds of type MO2 type and MO3
type.
▪ The reducing properties of the oxides decrease down the group.
▪ SO2 is a reducing agent while TeO2 is an oxidizing agent.
▪ Both types of oxides are acidic in nature.

❖ ANOMALOUS BEHAVIOUR OF OXYGEN:-

➢ The important anomalous behavior of oxygen are :-
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1. Oxygen is diatomic linear molecule while the others are octa – atomic solids
with eight membered puckered structure.
2. Oxygen shows -1/2, -1, -2 and +2 oxidation state but the other can show -2, +2,
+4, +6 oxidation state.
3. Oxygen can show H – bonding in their compounds while the other elements
can’t show H – bonding in their compounds.
4. Oxygen can show maximum covalancy of 2 but the other can show the
maximum covalancy of 6.
5. Oxygen forms mainly ionic and polar compounds.
6. Oxygen is paramagnetic in nature.
➢ The cause of the anomalous behavior of oxygen are:-
1. It’s small size.
2. It’s high electronegativity.
3. It’s high ionization energy.
4. Absence of d – orbital.

❖ DIOXYGEN
➢ Molecular formula:- O2.
➢ Preperation:-
1. By heating oxygen containing compounds:- Dioxygen can be obtained by
heating the oxygen containg compounds like permagnets, chlorates, and
nitrates.
3KClO3 Heat / MnO2 2KCl + 3O2
2. By thermal decomposition of higher oxides of metals:- Dioxygen can be
prepared by heating the oxides of that metals which lie low in the
electrochemical series and the higher oxides of some metals.
2Ag2O 4Ag + O2
2HgO 2Hg + O2
2Pb3O4 6PbO + O2
2PbO2 2PbO + O2
3. From hydrogen peroxide:- Hydrogen peroxide can be readily decomposed into
water and dioxygen.
2H2O2(aq.) 2H2O(l) + O2(g)
4. Commercial manufacture:- Commercially, dioxygen can be manufactured by
fractional distillation of air at 90 K.

➢ PHYSICAL PROPERTIES:-
1. It is colourless and odour less gas.
2. It is slightly soluble in water.
3. It is paramagnetic in liquid state.
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4. It freezes at 55K and boils at 90K.

➢ CHEMICAL PROPERTIES:-
1. Reaction with metals:- Active metals like Na, Ca, etc. react at room temperature
forming the respective oxides.
For example:-
2Ca + O2 2CaO
4Al + 3O2 2Al2O3
2. Reaction with non – metals:- Oxygen reacts with several non – metals and form
several types of oxides.
For example:-
P4 + 5O2 P4O10
C + O2 CO2

3. Reaction with compounds:- Some of the compounds react with oxygen and
form their oxide or higher oxides.
For example:-
2ZnS + 3O2 2ZnO + 2SO2
CH4 + 2O2 CO2 + 2H2O
SO2 + O2 V2O5 2SO3
4HCl + O2 CuCl2 2H2O + 2Cl2
➢ USES:-
1. It is used in oxyacetylene welding.
2. It is used in manufacture of steel.
3. It is used for artificial respiration in hospitals.
4. Liquid oxygen is used as fuel in rocket.

❖ SIMPLE OXIDES:-
• The binary compounds of oxygen with various elements are called as
oxides.
➢ Types of oxides:-
1. Acidic oxides:-
▪ These are generally formed by the combination of non – metals and oxygen.
▪ The acidic oxides are generally covalent compounds, which are volatile in
nature & dissolve in water to give acidic solution.

Ex.:- P4O10, CO2, SO3 etc.

P4O10 + 6H2O 4H3PO4

SO3 + H2O H2SO4

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2. Basic oxides:- When oxygen reacts with metals, forms mostly basic oxides.
These are the oxides which forms base when dissolved in water.
For example:- Na2O, CaO, MgO etc.

3. Amphoteric oxides:- The oxides which behaves as both acids as well as a base
are called as amphoteric oxides. For ex.:- Al2O3, PbO, ZnO etc.
Al2O3 + 6 HCl 2AlCl3 + 3Cl2
Base
Al2O3 + 6NaOH + 3H2O 2Na3[Al(OH)6]
Acid

4. Neutral oxides:- The oxides which neither act as acid nor as base are called as
Neutral oxides. Ex.:- CO, N2O, NO etc.

5. Mixed oxides:- The oxides of same metal in which the metal has different
oxidation state in the two oxides, are mixed with each other.
Ex.:- Fe3O4 = [FeO + Fe2O3]
Pb3O4 = [2PbO + PbO2]

❖ OZONE
▪ Molecular formula:- O3.
▪ Preperation:-
1. Laboratory method:- In the laboratory, ozone is prepared by the passing
silent electric discharge through the dry and pure oxygen in Simen’s
ozonizer
▪ Physical properties:-
1. It is a pale blue gas with pungent smell.
2. In liquid state, it is deep blue, & in solid state, it is violet black solid.
3. It’s m.p. is 80.6K & b.p. is 161.2K.
4. It is slightly soluble in water & readily soluble in organic solvents like CCl 4.
5. It is diamagnetic in nature.
6. It is neutral to litmus.

▪ Chemical properties:-
1. It is a good oxidizing agent because it can release nescent oxygen.
O3 O2 + O
2. Reaction with PbS:- Ozone oxidizes PbS to PbSO4.
PbS + 4O3 PbSO4 + 4O2
3. Reaction with iodides:- Ozone reacts with metal iodides and converts the
iodide ion into iodine.
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2 I¯ + O3 + H2O 2OH¯ + O2 + I2.

4. Reaction with nitric oxide:- Ozone reacts with nitric oxide and gives
nitrogen dioxide.
NO + O3 NO2 + O2
▪ Uses:-
1. It is used as germicide, disinfectant, & for sterilizing water.
2. It is also used for beaching oils, flour, starch etc.
3. It is used as oxidizing agent in the manufacture of Potassium permagnate.
4. It is in the industries to manufacture silk & and Synthetic camphor.
5. It is used as oxidizing agent in laboratory.
▪ Structure:-
❖ SULPHUR
▪ Atomic number:- 16
▪ Atomic weight:- 32
▪ Electronic configuration:- 1s2 2s2 2p6 3s2 3p4.
▪ Valance electron:- 6
▪ Maximum covalancy:- 6
▪ Oxidation state:- -2, +2, +4, +6.
▪ Valancy:- 2
➢ Occurance:-
▪ Sulphur occurs in the earth’s crust to the extent of 0.05%.
▪ It is found in free state as well as combined state in ores.
▪ It is found also in the volcanic region.
➢ Allotropic forms of Sulphur:-
1. Rhombic sulphur:-
• It is most stable form of sulphur.
• It is bright yellow in colour.
• It is also called as α sulphur.
• It is insoluble in water but soluble in CS2.
• It’s density is 2.07 gm/cc.
• It’s m.p. is 285.8K.
• It occurs as S8 molecule.
2. Monoclinic sulphur:-
• It is formed by melting monoclinic sulphur in a dish followed by cooling at
96˚C.
• It has colourless needle shaped crystals.
• It’s m.p. is 120˚C.
• It’s density is 1.98 gm/cc.
• It is soluble in CS2.
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• It has S8 molecule.
• It is also called beta sulphur.
• It slowly changes to rhombic sulphur.
3. Plastic sulphur:-
• It is formed by pouring molten sulphur in cold water.
• It is amourphus form of sulphur.
• It is called as gamma sulphur.
• It has not sharp m.p.
• It’s density is 1.95 gm/cc.
• It is insoluble in water as well as CS2.

❖ SULPHUR DIOXIDE
➢ Molecular formula:- SO2.
➢ Preperation:-
1. By burning sulphur in air:-
S + O2 SO2.
2. Laboratory method:- In laboratory, it is prepared by treating a sulphite with dil.
Sulphuric acid.
Na2SO3 + Dil. H2SO4 NaSO4 + H2O + SO2.
3. Industrial preparation:- In industries, it can be obtained during roasting of the
sulphide ores,
4FeS2 + 11O2 2Fe2O3 + 8SO2
The gas after drying, is liquefied and stored in steel cylinders.

➢ Physical properties:-
1. It is colourless gas with pungent suffocating odour.
2. It is heavier than air.
3. It is highly soluble in water.
H2O + SO2 H2SO3
4. It’s b.p. is -10˚C and m.p. is -76˚C.

➢ Chemical properties:-
1. Reaction with NaOH:- It reacts with NaOH and forms sodum sulphite. If SO2 be
in excess, finally sodium hydrogen sulphite is formed.
2NaOH + SO2 Na2SO3 + H2O
Na2SO3 + H2O + SO2 2NaHSO3
2. Reaction with chlorine:- SO2 reacts with chlorine in presence of carbon to give
sulphuryl chloride.
SO2 + Cl2 SO2Cl2
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3. Reaction with O2:- SO2 reacts with oxygen in presence of V2O5, & gives SO3.
2SO2 + O2 2SO3.
4. As reducing agent:- It converts Fe3+ ion to Fe2+ ion and also decolourises
acidified potassium permagnet solution.
2Fe3+ + SO2 + 2H2O 2Fe2+ + SO42- + 4H+
5SO2 + 2MnO4- + 2H2O 5SO42- + 4H+ + 2Mn2+

❖ MANUFACTURE OF SULPHURIC ACID (By Contact process)

The following steps are involved in the manufacture of sulphuric acid by Contact
process:
Step 1: Production of SO2:
It is obtained by burning of powdered sulphur.

S8 + 8O2 8SO2

Step 2: Oxidation of SO2:

It is the key step in the manufacture of sulphuric acid. SO2 is oxodised
in catalytically by using air.
2SO2 + O2 2SO3
➢ Suitable conditions for good production of SO3 are as follows:
1. Temperature: 400 – 500°C
2. Pressure : 1.5 – 2 atm.
3. Catalyst: V2O5
4. The gas should be dry and free from As2O3.
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5. Excess of oxygen should be used.

Step 3: conversion of SO3 into sulphuric acid:

SO3 is absorbed into Conc. H2SO4 to get oleum.
SO3 + H2SO4 H 2 S 2 O7

Oleum may be diluted to get sulphuric acid of required concentration.

➢ Physical propeerties:
1. Pure sulphuric acid is colourless but impure sulphuric acid is yellow.
2. Density : 1.84 g/cc.
3. Boiling point: 621K.
4. Solubility: Soluble in water and highly exothermic exothermic.
5. Corrosive to skin.

➢ Chemical properties:
Chemical reactions of sulphuric acid is due to
a) Low volatility.
b) Strong acidic character.
c) Strong affinity for water.
d) Ability to act as an oxidizing agent.
1. Reaction with metal halides:
On treatment with metal salts it forms hydrogen halides or other
corresponding acids.
2MX + H2SO4 2HX + M2SO4 (Where X = F / Cl / NO3)

2. It is good dehydrating agent. It dehydrates many acids and removes water from
many organic compounds.
C12H22O11 H SO
2 4 12C + 11 H2O
3. It is a good oxidizing agent too. Concentrated sulphuric acid oxidizes both
metals ans non – metals & itself get reduced to SO2.

Cu + 2 H2SO4 (Conc.) CuSO4 + SO2 + 2H2O

3S + 2 H2SO4 (Conc.) 3SO2 + 2H2O

C + H2SO4 (Conc.) 2SO2 + 2H2O

4. It is a dibasic acid, in aqueous solution it ionizes into ions in two steps.
H2SO4 (aq.) + H2O (l) H3O+(aq) + HSO4¯(aq)
HSO4¯(aq) + H2O(l) H3O+(aq) + SO42¯(aq)
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5. Due to low volatility it is used in manufacture of more volatile acids like HF,
HCl, HNO3 etc.
2MX + H2SO4 2HX + M2SO4
[where X = F / Cl / NO3 & M = Metal]

➢ USES:
1. It is used in as acid in laboratories and industries.
2. It is used in lead storage cell.
3. It is used in manufacture of HCl, HNO3, fertilizers etc.
4. It is used as drying agent.
5. It is used in the refining of metals.