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16
TH
COLUMN ELEMENTS

GUPTA CLASSES
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Chalcogens Ore formers
Group 16 elements include oxygen, sulphur, selenium, tellurium and polonium. Oxygen and
sulphur are non-metals, selenium and tellurium are metalloids and polonium is a radio-active
metal.
Occurrence: Oxygen is the most abundant element in earth crust. In Free State it exists as O
2
gas.
Which is 23% by volume of atmosphere? It also occurs as O
3
in upper atmosphere. In the earth
crust it appears as silicates, aluminates and carbonates etc.
It makes up 89% by mass of water.
Sulphur occurs in the form of sulphides and sulphates. In Free State it occurs in volcanic areas.
In the form of H
2
S gas it occurs natural gas and crude oil.
Selenium occurs as selenides and tellurium as telluride along with sulphide ores.
1. Electronic configuration
O 8 [He] 2s
2
2p
4

S 16 [Ne] 3s
2
3p
4

Se 34 [Ar] 3d
10
4s
2
4p
4

Te 52 [Kr] 4d
10
5s
2
5p
4

Po 84 [Xe] 4f
14
5d
10
6s
2
6p
4


2. Atomic radii and ionic radii
Atomic and ionic radii of 16
th
column elements are smaller than those of 15
th
column elements of
the same period due to increase in nuclear charge. Atomic radii and ionic radii increase from top
to bottom due to addition of one shell in each period.

3. Ionisation enthalpy
Fisrt I.E. of 16
th
column elements are lower than 15
th
column elements of the same period as 15
th

column elements have extrastable half-full p-subshell. I.E. decreases from top to bottom in the
group due to increase in size.

4. Electron gain enthalpy
16
th
column elements have higher negative value of electron gain enthalpy than elements of 15
th

column of same period. Negative electron gain enthalpy decreases from S to Po. Oxygen has
lower value of negative electron gain enthalpy due to abnormally small size. Order of negative
value of electron gain enthalpy is
S > Se > Te > Po > O
Second electron gain enthalpy has a positive value.

5. Electronegativity
They have high value of electronegativity which decreases from top to bottom.

6. Oxidation states
(a) Negative O.S. : Elements of this group show negative O.S. of 2. Tendency to show ve
O.S. decreases from top to bottom.
Oxygen shows an O.S. of 2 except in OF
2
, where O.S. of oxygen is +2.
(b) Positive O.S.: Other members of the group also show +ve O.S. of +2, +4 and +6, but +4 and
+6 O.S. are more common. S, Se, Te show +4 O.S. with oxygen and +6 O.S. with fluorine.
16
th
COLUMN ELEMENTS
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Stability of +6 O.S. decreases from top to bottom and stability of +4 O.S. increases from top to
bottom.

7. Elemental state
Oxygen exists as a diatomic gas at room temperature. Due to small size oxygen atom has a
tendency to form multiple bonds (p p), so forms discrete O
2
molecules. So weaker Vander
Walls forces, so O
2
is a gas.
S, Se and Te due to large atomic size do not form multiple bonds; they form only single bonds
and form S
8
, Se
8
, Te
8
molecules with large surface area, stronger Vander Waals forces, so they
are solids at room temperature.

8. Multiple bonding
Oxygen forms pp bonds due to small size. Other members of the group from pd bonds
for effective pd overlap, size of d orbital should be similar to p orbital. So tendency to form
pd bond decreases from sulphur to selenium. CS
2
is moderately stable, CSe
2
decomposes
readily and CTe
2
is unstable.

9. Catination
Sulphur has highest tendency of catination in the group due to relatively stronger SS bonds.

10. Allotropy
All the members of the group show allotropy.
(a) Oxygen shows two allotropes O
2
and O
3
.
(b) Allotropes of sulphur
(i) Rhombic sulphur or octahedral sulphur or -suphur: it is the most stable form of sulphur, it is
yellow in colour, insoluble in water, dissolves to some extent in benzene, alcohol and ether,
readily soluble in CS
2
. Little thermal and electrical conductance. It has octahedral crystals in
which S
8
molecules exists.
(ii) Monoclinic sulphur or -sulphur: It is dull yellow in colour, soluble in CS
2
, insoluble in
water, stable only above 369K. It also has S
8
molecules.
(iii) Engels sulphur : Cyclo S
6
. Chair like structure.
(iv) Plastic sulphur: It contains spiral chains. It is regared as super cooled liquid.
(v) Above 1000 K sulphur exists as S
2
molecules with two unpaired electrons, so it is
paramagnetic in nature. It has blue colour.

Reactivity towards hydrogen (Hydrides)
Elements of 16
th
column form hydrides of type H
2
E i.e. H
2
O, H
2
S, H
2
Se, H
2
Te and H
2
Po.
Structure of hydrides: All hydrides have angular shape involving sp
3
-hybridisation of the central
atom with two lone pairs of electrons and two bond pairs of electrons.

Order of bond angle is H
2
O > H
2
S > H
2
Se > H
2
Te
Boiling points of hydrides H
2
O > H
2
Te > H
2
Se > H
2
S
Abnormally high boiling point of water is due to intermolecular
hydrogen bonding and increase in boiling point from H
2
S to H
2
Te is
due to increase in size and Vander Waals forces.
Acidic character: As atomic size increases from O to Te, so EH
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bond length increases from OH to TeH and bond dissociation energy decreases from OH to
TeH. So
Thermal stability decreases from H
2
S to H
2
Te and acidic and reducing nature nature increases
from H
2
S to H
2
Te.

Reactivity with oxygen (Oxides)
All the elements of the group form oxides of the type EO
2
and EO
3
. SO
2
is a gas, SeO
2
is a solid.
Reducing properties decrease from SO
2
to TeO
2
. SO
2
is a reducing agent whereas TeO
2
is an
oxidizing agent. S, Se and Te also form EO
3
. Both types of oxides are acidic in nature.

Reaction with halogens
The members of this group form halides of the type EX
2
, EX
4
and EX
6
. Stability of the halides is
in the order F

> Cl

> Br

> I

All hexafluorides are gases, have octahedral structure. SF
6
is exceptionally stable.
SF
4
is a gas, SeF
4
is a liquid and TeF
4
is a solid.
All elements except Se form di chlorides and di bromides. Di halides are formed by sp
3
-
hybridesation of central atom and have distorted tetrahedral structure.
Monohalides are dimeric. S
2
F
2
, S
2
Cl
2
, S
2
Br
2
, Se
2
Cl
2
, Se
2
Br
2
. Dimeric halides undergo
disproportionation.
2SeCl
2
SeCl
4
+ 3Se

DIOXYGEN (O
2
)
Preparation
1. By heating oxygen containing salts like chlorates, nitrates, permanganates,
2KClO
3

2
MnO /
2KCl + 3O
2

2. By thermal decomposition of oxides of metals low in electrochemical series.
2Ag
2
O (s) 4Ag (s) + O
2
(g)
2HgO (s) 2Hg (l) + O
2
(g)
2Pb
3
O
4
(s) 6PbO (s) + O
2
(g)
2PbO
2
(s) 2PbO (s) + O
2
(g)
3. Decomposition of H
2
O
2
in presence of finely divided metals or MnO
2

2H
2
O
2
2H
2
O + O
2

4. On large scale oxygen is prepared by liquefaction of air.

Properties
It is a colourless, odourless gas. Paramagnetic in nature exists in three stable isotopes O
16
, O
17

and O
18
.
(i) Oxidizes some elements (metals and non-metals) to their oxides
2Ca + O
2
2CaO
4Al + 3O
2
2Al
2
O
3

P
4
+ 5O
2
P
4
O
10

C + O
2
CO
2

(ii) Some compounds are oxidized by oxygen
2ZnS + 3O
2
2ZnO + 2SO
2

CH
4
+ 2O
2
CO
2
+ 2H
2
O
2SO
2
+ O
2

5
O
2
V
2SO
3

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4HCl + O
2

2
CuCl
2Cl
2
+ 2H
2
O

Oxides:
Binary compounds of oxygen with other elements are known as oxides.
Simple oxides: MgO, Al
2
O
3

Mixed oxides: Pb
3
O
4
, Fe
3
O
4

Acidic oxides: SO
2
, Cl
2
O
7
, CO
2
, N
2
O
5
, Mn
2
O
7
, CrO
3
, V
2
O
5
.
Basic oxides: Na
2
O, CaO, BaO
In general oxides of metals are basic and those of non-metals are acidic.
Some metallic oxides are amphoteric (Al
2
O
3
).
Neutral oxides are CO, NO, N
2
O.

OZONE
It is an allotropic modification of oxygen. It is short lived at sea level due to high reactivity. At
the height of about 20 km it is formed from atmospheric oxygen by the action of ultraviolet
radiation. This ozone layer protects the earths surface from ultraviolet radiations.
3O
2

. v . u
2O
3

Preparation
By passing silent electric discharge through pure, cold and dry dioxygen. Conversion of O
2
to O
3

is 10%.
3O
2
2O
3
(g); H
o
= +142 kJ
Pure ozone can be condensed in a vessel surround by liquid oxygen.
Structure of ozone
Central O atom in ozone is sp
2
-hybridised. It has one lone pair and two bond pairs of electrons
with bond angle 117
o
.


O
3
is a resonance hybrid of following structures.

Due to resonance of both OO bonds have partial double bond character and both bonds are
equal (128pm).
Physical properties
Pale blue gas having a strong characteristic smell.
It condenses to a deep blue liquid and then to a violet black solid. Slightly soluble in water but
readily dissolves in turpentine oil.
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Cinnamon oil, CCl
4
, Glacial acetic acid.
O
3
is a diamagnetic, neutral to litmus.
Decomposition
O
3
is thermodynamically unstable. In decomposition of O
3
H is ve and S is +ve. So G will
have a ve value. At ordinary temperature it decomposes slowly to give O
2
but at 473 K in
presence of MnO
2
, Pt or Cu
2
O, the decomposition takes place rapidly.
Oxidizing agent
O
3
has higher energy content, so it decomposes as follows
O
3
O
2
+ O
So it is a powerful oxidizing agent
1. Black lead sulphide is oxidized to white lead sulphate
O
3
(g) O
2
(g) + O (g) ] 4
PbS (s) + 4O (g) PbSO
4
(s)
PbS (s) + 4O
3
(g) PbSO
4
(s) + 4O
2
(g)
2. CuS, ZnS and CdS are oxidized to respective sulphates
CuS + 4O
3
CuSO
4
+ 4O
2

ZnS + 4O
3
ZnSO
4
+ 4O
2

CdS + 4O
3
CdS
4
+ 4O
2

3. Halogen acids are oxidized to halogens
O
3
O
2
+ O
2HCl + O H
2
O + Cl
2

2HCl + O
3
H
2
O + Cl
2

4. Oxidises nitrites to nitrates
KNO
2
+ O
3
KNO
3
+ O
2

5. Liberates I
2
with moist KI
O
3
O
2
+ O
2KI + H
2
O + O 2KOH + I
2

6. Oxidises acidified ferrous sulphate to ferric sulphate
O
3
O
2
+ O
2FeSO
4
+ H
2
SO
4
+ O Fe
2
(SO
4
)
3
+ H
2
O
7. Potassium ferrocyanide to ferricyanide
O
3
O
2
+ O
2K
4
Fe(CN)
6
+ H
2
O + O 2K
3
Fe(CN)
6
+ 2KOH
8. Potassium manganate to potassium permanganate
O
3
O
2
+ O
2K
2
MnO
4
+ H
2
O + O 2KMnO
4
+ 2KOH
9. I
2
to HIO
3

O
3
O
2
+ O
I
2
+ 5O I
2
O
5

I
2
O
5
+ H
2
O 2HIO
3

10. Sulphur to H
2
SO
4

O
3
O
2
+ O
S + 3O SO
3

SO
3
+ H
2
O H
2
SO
4

11. Moist phosphorus to phosphoric acid
O
3
O
2
+ O
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P
4
+ 10O P
4
O
10

P
4
O
10
+ 6H
2
O 4H
3
PO
4

12. As to H
3
AsO
4

O
3
O
2
+ O
2As + 5O As
2
O
5

As
2
O
5
+ 3H
2
O 2H
3
AsO
4

13. Silver oxidized to Ag
2
O
2Ag (s) + O
3
(g) Ag
2
O (s) + O
2
(g)
14. Mercury is oxidized to Hg
2
O
2Hg + O
3
Hg
2
O + O
2

Hg
2
O dissolves in Hg which loses its meniscus and starts sticking to glass (tailing of
mercury)
15. Oxidizes SO
2
to SO
3
and acidified SnCl
2
to SnCl
4
.
3SO
2
+ O
3
3SO
3

3SnCl
2
+ 6HCl + O
3
3SnCl
4
+ 3H
2
O
16. Bleaching action: Bleaches vegetable colouring material. Bleaching action is due to
oxidation.
17. Reducing agent: Reduces H2O2, BaO2 etc.
H
2
O
2
+ O
3
H
2
O + 2O
2

BaO
2
+ O
3
BaO + 2O
2

Uses of ozone
1. Bleaching agent, disinfectant and germicide.
2. Purifying air.
3. As a reagent.

SULPHUR DIOXIDE (SO
2
)
Preparation
1. By burning sulphur in air
S (s) + O
2
(g) SO
2
(g)
2. Lab-preparation : By treating sulphite with dilute H
2
SO
4

Na
2
SO
3
(s) + H
2
SO
4
(aq) Na
2
SO
4
+ SO
2
+ 2H
2
O
3. By heating copper turning with conc. H
2
O (l)
Cu (s) + 2H
2
SO
4

CuSO
4
+ SO
2
+ 2H
2
O
4. By roasting of iron pyrites
4FeS
2
(s) + 11O
2
(g) 2Fe
2
O
3
(s) + 8SO
2
(g)
Physical properties
It has colourless gas with a pungent smell, highly soluble in water.
Acidic nature
It is acidic in nature dissolves in water to give sulphurous acid.
SO
2
(g) + H
2
O (l) H
2
SO
3
(aq)
Reacts with sodium hydroxide
Reacts readily with NaOH to give sodium sulphite which reacts with excess of SO
2
to give
sodium hydrogen sulphite.
2NaOH + SO
2
Na
2
SO
3
+ H
2
O
Na
2
SO
3
+ H
2
O + SO
2
2NaHSO
3

Reacts with Cl
2
in presence of charcoal to give sulphuryl chloride (SO
2
Cl
2
)
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SO
2
(g) + Cl
2
(g)
Charcoal
SO
2
Cl
2

Reacts with oxygen in presence of V
2
O
5

2SO
2
(g) + O
2
(g)
5
O
2
V
2SO
3
(g)
Reducing agent
When moist, SO
2
behaves as a reducing agent. Converts Fe
3+
to Fe
2+
ions. And decolourises
acidified KMnO
4
solution.
2Fe
3+
+ SO
2
+ 2H
2
O 2Fe
2+
+ SO
4
2
+ 4H
+

5SO
2
+ 2MnO
4

+ 2H
2
O 5SO
4
2
+ 4H
+
+ 2Mn
2+

Uses
1. In refining of petroleum and sugar.
2. In bleaching wool and silk.
3. As antichlor disinfectant and perseverant.
4. Liquid SO
2
is used as a refrigerant. As solvent to dissolve number of organic and
inorganic chemicals.
Structure
S is sp
2
-hybridised with one lone pair and two bond pairs of electrons. So SO
2
molecule is
angular. It is a resonance hybrid of following structures

OXO-ACIDS OF SULPHUR
Sulphur form number of oxo acids which are classified as follows
1. Sulphurous acid series: when O.S. of sulphur is +4.
(a) sulphurous acid: H
2
SO
3

(b) thyiosulphurous acid: H
2
S
2
O
2

(c) Hyposulphurous acid : H
2
S
2
O
4

2. Sulphuric acid series: O.S. of sulphur is +6.
(a) Sulphuric acid: H
2
SO
4

(b) Thiosulphuric acid: H
2
S
2
O
3

(c) Pyrosulphuric acid: H
2
S
2
O
7

3. Thionic acid series:
(a) Polythionic acid: H
2
S
n
O
6
(n = 3, 4, 5, 6)
4. Peroxy acid series:
(a) Caros acid: H
2
SO
5

(b) Marshalls acid: H
2
S
2
O
8

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SULPHURIC ACID (H
2
SO
4
)
Manufacture
Contact process: It involves three steps.
I. Preparation of SO
2
by burning of S or iron pyrites.
S (s) + O
2
(g) SO
2
(g)
4FeS
2
(s) + 11O
2
(g) 2Fe
2
O
3
(s) + 8SO
2
(g)

II. Conversion of SO
2
to SO
3
. SO
2
is heated with oxygen in presence of V
2
O
5
(catalyst) under a
pressure of 2bar at 720 K.
2SO
2
(g) + O
2
(g)
720K , bar 2
5
O
2
V

2SO
3
(g); H = 196.6 kJ/mol.
Before passing through catalytic converter SO
2
is passed through arsenic purifier containing
gelatinous hydrated ferric oxide.
III. SO
3
is absorbed in conc. H
2
SO
4
to give oleum.
SO
3
+ H
2
SO
4
H
2
S
2
O
7
(oleum)
Oleum is diluted with water to give H
2
SO
4
of desired conc.
Properties
Colourless, dense, oily liquid with a specific gravity 1.84 at 298 K. Dissolves in water with
evolution of large quantities of heat, so conc. acid must be added to water slowly with constant
stirring. H
2
SO
4
has
(i) Low volatility
(ii) Strong acidic character.
(iii) Strong affinity for water.
(iv) Oxidising agent.
(v) Acid forms two series salts. Normal salts and acid salts.
(vi) H
2
SO
4
is used to prepare more volatile acids due to its low volatility.
(vii) As a strong dehydrating agent
C
12
H
22
O
11

4
SO
2
H
12C + 11H
2
O
(viii) As an oxidizing agent
(a) Cu + 2H
2
SO
4
CuSO
4
+ SO
2
+ 2H
2
O
(b) 3S + 2H
2
SO
4
3SO
2
+ 2H
2
O
(c) C + 2H
2
SO
4
CO
2
+ 2SO
2
+ 2H
2
O
Uses
1. in manufacture of fertilizers and explosives
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2. In petroleum refining
3. In manufacture of pigments
4. In manufacture of nitrocellulose
5. In lead storage batteries

CONCEPTUAL QUESTIONS
1. H
2
S is less acidic then H
2
Te, Why?
Ans- As atomic size of S is smaller than atomic size of Te, so SH bond length is smaller
than Te H bond length. So bond dissociation energy of SH bond is greater than TeH
bond. So H
2
S is less acidic than H
2
Te.
2. Write order of thermal stability of hydrides of 16
th
column elements.
Ans- Order of thermal stability of hydrides of 16
th
column element is
H
2
O > H
2
S > H
2
Se > H
2
Te > H
2
Po
3. Why is H
2
O a liquid whereas H
2
S is a gas?
4. Which of the following does not react with oxygen directly? Zn, Ti, Pt & Fe.
Ans- Pt.
5. Why does O
3
acts as a powerful oxidizing agent?
Ans- As decomposition of O
3
to O
2
and O has a negative value of G, so O
3
is an unstable
molecule. Atomic oxygen so obtained for oxidation of other substances, so O
3
is a powerful
oxidizing agent.
6. How is O
3
estimated quantitatively?
Ans- O
3
reacts with excess of KI solution to liberate I
2
, which is titrated against a standard
solution of sodium thiosulphate.
7. Which form of sulphur is paramagnetic?
Ans- In vapour state sulphur exists as S
2
having two unpaired electrons, so it is
paramagnetic.
8. What happens when
(i) H
2
SO
4
is added to calcium fluoride
Ans- Hydrogen fluoride is produced.
CaF
2
+ H
2
SO
4
CaSO
4
+ 2HF
Cal. Fluoride Hydrogen fluoride
(ii) SO
3
is passed through water
Ans- Sulphuric acid is produced
SO
3
+ H
2
O H
2
SO
4

9. Why is Ka
1
>> Ka
2
for H
2
SO
4
?
Ans- H
2
SO
4
is a strong acid due to its first ionization of H
2
SO
4
to H
3
O
+
and HSO
4

. The
ionization of HSO
4

to SO
4
2
and H
3
O
+
is very small. So Ka
1
>> Ka
2
.
10. SF
6
is known whereas SH
6
is not known?
Ans- Fluorine is a very strong oxidizing agent and it oxidizes S to its highest O.S. i.e. +6. So
SF
6
is formed. Hydrogen can not oxidize sulphur to +6 O.S., so SH
6
is not formed.
11. Why OF
2
should be called oxygen difluoride and not fluorine oxide?
Ans- As electronegativity F > O.
12. SCl
6
is not known whereas SF
6
is known.
Ans- Fluorine is a strong oxidizing agent and it oxidizes sulphur to its highest O.S. i.e. +6.
So SF
6
is formed. Chlorine being a weaker oxidizing agent oxidizes sulphur to only +4 O.S.,
so SCl
4
can be formed, but not SCl
6
.
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13. SF
6
is used as gaseous electrical insulator, why?
Ans- SF
6
is a colourless, odourless, non-toxic gas. It is thermally stable, chemically inert and
has high tendency to suppress internal discharges, so SF
6
is used as electrical insulator.
14. Why SF
6
is inert towards hydrolysis?
Ans- In SF
6
sulphur atom is sterically protected by 6 Fluorine atoms, hence water molecule
do not attack sulphur atom. So SF
6
is inert towards hydrolysis.
15. Why is oxygen a gas whereas sulphur a solid at room temperature?
Ans- Oxygen has small atomic size, so it has tendency to form multiple bonds (p p). So
oxygen forms diatomic molecules (O
2
) with low surface area, weaker Vander Waals forces,
so it a gas at room temperature. S atom as large size, so it does not form p p bonds. It
forms only S S bonds and forms S
8
molecules with large surface area, stronger Vander
Waals forces. So it is a solid at room temperature.
16. Which aerosol deplete ozone layer?
Ans- Aerosol spray of freons deplete ozone layer.
17. How is SO
2
and air pollutant?
Ans- SO
2
dissolves in water to give sulphuric acid which is part of acid rain.
18. Why sulphur disappears when boiled with an aqueous solution sodium sulphite?
Ans- Sulphur reacts with sodium sulphite to give water soluble sodium thiosulphate.
Na
2
SO
3
+ S Na
2
S
2
O
3

Sod. Sulphite Sod. Thiosulphate
19. Knowing the electron gain enthalpy value of O O

, H
o
= 141 kJ and O

O
2
, H
o
=
+702 kJ
How can you account for the formation of large number of oxides.
Ans- Due large charge on O
2
ion the lattice enthalpy of oxides is high resulting in higher
decrease in energy. So large number of oxides is formed.