P block Elements-

Group 16
Shireen, Vrinda, Sanskriti, Anushka,
Anam, Shweta
Group 16
Elements
Oxygen, sulphur, selenium, tellurium and polonium constitute Group 16 of
the periodic table.
This is sometimes known as group of chalcogens. The name is derived from
the Greek word for brass and points to the association of sulphur and its
congeners with copper.
Most copper minerals contain either oxygen or sulphur and frequently the
other members of the group.
Occurrence
Oxygen is the most abundant of all the elements on earth. Oxygen forms about 46.6% by
mass of earths crust.
Dry air contains 20.946% oxygen by volume.
The abundance of sulphur in the earths crust is only 0.03-0.1%.
Combined sulphur exists primarily as sulphates such as gypsum CaSO4.2H2O, epsom salt
MgSO4.7H2O, baryte BaSO4 and sulphides such as galena PbS, zinc blende ZnS, copper pyrites
CuFeS2.
Traces of sulphur occur as hydrogen sulphide in volcanoes. Organic materials such as eggs,
proteins, garlic, onion, mustard, hair and wool contain sulphur.
Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores.
Polonium occurs in nature as a decay product of thorium and uranium minerals.


Configuration Atomic Ionic Radii Ionisation Enthalpy
The elements of
Group16 have six
electrons in the
outermost shell and
have ns
2
np
4
general
electronic
configuration.

atomic and ionic
radii increase from
top to bottom in the
group due to
increase in the
number of shells,
The size of oxygen
atom is
exceptionally small.
Ionisation enthalpy decreases
down the group. It is due to
increase in size.
The elements of this group have
lower ionisation enthalpy
values compared to those of
Group15
This is due to the fact that Group
15 elements have extra stable half
filled p orbitals electronic
configurations.
Electronic
Group 16 Properties
Electron Gain Enthalpy Electronegativity
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 upto
polonium.
Next to fluorine, oxygen has the
highest electronegativity value amongst
the elements.
The electronegativity decreases with an
increase in atomic number.
This implies that the metallic character
increases from oxygen to polonium.
Group 16 Properties
Physical Properties
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.
The large difference between the melting and boiling points of oxygen and
sulphur may be explained on the basis of their atomicity; oxygen exists as
diatomic molecule (O
2
) whereas sulphur exists as polyatomic molecule (S
8
).
Oxygen and sulphur are non-metals, selenium and tellurium metalloids,
whereas polonium is a metal. All these elements exhibit allotropy.
Chemical Properties
Oxidation states and trends in chemical reactivity
The stability of -2 oxidation state decreases down the group.
Polonium hardly shows 2 oxidation state.
Since electronegativity of oxygen is very high, it shows only negative oxidation state
as 2 except in the case of OF2 where its oxidation state is + 2.
Sulphur, selenium and tellurium usually show + 4 oxidation state in their
compounds with oxygen and + 6 with fluorine.
The stability of + 6 oxidation state decreases down the group and stability of + 4
oxidation state increase (inert pair effect).
Bonding in +4 and +6 oxidation states are primarily covalent.
Chemical Properties
Anomalous behaviour of oxygen
One typical example of effects of small size and
high electronegativity is the presence of strong
hydrogen bonding in H
2
O which is not found in
H
2
S.
The absence of d orbitals in oxygen limits its
covalency to four and rarely exceeds two.
In case of other elements of the group, the valence
shells can be expanded and covalence exceeds four.
The anomalous behaviour of oxygen, like other members of p-block present in
second period is due to its small size and high electronegativity.
Hydrogen bonding in H
2
O
Chemical Properties
Reactivity with hydrogen
Their acidic character increases from H
2
O to H
2
Te. The increase in acidic
character can be explained in terms of decrease in bond (HE) dissociation
enthalpy down the group.
Owing to the decrease in bond (HE) dissociation enthalpy down the group, the
thermal stability of hydrides also decreases from H
2
O to H
2
Po.
All the hydrides except water possess reducing property and this character increases
from H
2
S to H
2
Te.
All the elements of Group 16 form hydrides of the type H
2
E (E = S, Se, Te, Po)
Reactivity with oxygen
Elements form oxides of the EO2 and EO3 types where
E = S, Se, Te or Po.
Ozone (O3) and sulphur dioxide (SO2) are gases while selenium dioxide
(SeO2) is solid.
Reducing property of dioxide decreases from SO2 to TeO2; SO2 is reducing
while TeO2 is an oxidising agent.
Besides EO2 type, sulphur, selenium and tellurium also form EO3 type
oxides (SO3, SeO3, TeO3). Both types of oxides are acidic in nature.
Reactivity towards the halogens
Elements of Group 16 form a large number of halides of the type, EX6, EX4 and EX2 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.
Amongst hexahalides, hexafluorides
are the only stable halides.
Nature of hexafluorides 1. gaseous
2. octahedral
structure
Amongst tetrafluorides, SF4 is a gas,
SeF4 a liquid
TeF4 a solid.
SF6 is exceptionally
stable for steric
reasons.
These fluorides have:
sp3d hybridisation
trigonal bipyramidal
structures
in which one of the
equatorial positions is
occupied by a lone
pair of electrons
This geometry is also
regarded as see-saw
geometry.
All elements except selenium form
dichlorides and dibromides.
These dihalides are formed by

sp3 hybridisation tetrahedral structure.
The well known monohalides are dimeric
in nature.
Eg: S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
These dimeric halides undergo disproportionation as
given below:
2Se2Cl2 SeCl4 + 3Se
Dioxygen Preparation
(i) By heating oxygen containing salts such as chlorates, nitrates and permanganates.
2KClO heat & MnO22KCl + 3O2
(ii) By the thermal decomposition of the oxides of metals low in the electrochemical
series and higher oxides of some metals.
2Ag2O(s) 4Ag(s) + O2(g); 2Pb3O4(s) 6PbO(s) + O2(g)
2HgO(s) 2Hg(l) + O2(g) ; 2PbO2(s) 2PbO(s) + O2(g)
(iii) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such
as finely divided metals and manganese dioxide.
2H2O2(aq) 2H2O(1) + O2(g)
(iv) On 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.

Industrially, dioxygen is obtained from air by first removing carbon dioxide and water
vapour and then, the remaining gases are liquefied and fractionally distilled to give
dinitrogen and dioxygen.
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.
It liquefies at 90 K and freezes at 55 K.
It has three stable isotopes: 16O, 17O and 18O. Molecular oxygen, O2 is unique in being
paramagnetic inspite of having even number of electrons.
Dioxygen directly reacts with nearly all metals and non-metals except some metals ( e.g:
Au, Pt) and some noble gases.
Its combination with other elements is often strongly exothermic which helps in
sustaining the reaction.
To initiate the reaction, some external heating is required as bond dissociation
enthalpy oxygen-oxygen double bond is high(493.4 kJ mol1).
Some of the reactions of dioxygen with metals, non-
metals and other compounds are given below:
2Ca + O2 2CaO
4Al + 3O 2Al2O3
P4 + 5O2 P4O10
C2 + O2 CO
2ZnS + 3O2 2ZnO + 2SO2
CH4 + 2O2CO2 + 2H2O
Some compounds are catalytically oxidised. For e.g.,
2SO + O
2
V2O52SO
3

4HCl + O
2
CuCl2 2Cl + 2H
2
O
S
i
m
p
l
e

O
x
i
d
e
s

Acidic oxides
Basic oxides
Amphoteric
oxides
Simple Oxides
Oxides can be simple (e.g., MgO, Al2O3 ) or mixed (Pb3O4, Fe3O4).

1. Acidic oxide: An oxide that combines with water to give an acid is termed Acidic
oxide (e.g., SO2, Cl2O7, CO2, N2O5 ).
For example, SO2 combines with water to give H2SO3, an acid. SO
2
+ H
2
O H
2
SO
3.
General rule: Only non-metal oxides are acidic but oxides of some metals in high oxidation state
also have acidic character (e.g., Mn
2
O
7
, CrO
3
, V
2
O
5
).

2. Basic oxides: The oxides which give a base with water are known as basic oxides
(e.g., Na
2
O, CaO, BaO).
For example, CaO combines with water to give Ca(OH)
2
, a base.

3. Amphoteric oxides
Some metallic oxides exhibit a dual behaviour.
They show characteristics of both acidic as well as basic oxides. Such oxides are
known as Amphoteric oxides.
They react with acids as well as alkalies.
There are some oxides which are neither acidic nor basic.
Such oxides are known as neutral oxides.
Examples of neutral oxides are CO, NO and N
2
O.
For example, Al
2
O
3
reacts with acids as well as alkalies.
Ozone
Ozone is an allotropic form of oxygen.
It is too reactive to remain for long in
the atmosphere at sea level.
At a height of about 20 kilometres, it is
formed from atmospheric oxygen in the
presence of sunlight.
This ozone layer protects the earths
surface from an excessive concentration
of ultraviolet (UV) radiations.
Preparation
When a slow dry stream of oxygen is
passed through a silent electrical discharge,
conversion of O2 to O3 (10%) occurs.
The product is known as ozonised oxygen.
3O2 2O3 H
o
(298 K) = +142 kJ mol1
Since the formation of ozone from oxygen
is an endothermic process, it is necessary to
use a silent electrical discharge in its
preparation to prevent its decomposition.
If concentrations of ozone greater than 10
per cent are required, a battery of ozonisers
can be used, and pure ozone (b.p. 385 K)
can be condensed in a vessel surrounded by
liquid oxygen.
1. Pure O3 Colour: pale blue gas, dark blue liquid & violet-black
solid.
2. Smell: Ozone has a characteristic smell
3. Harm: small concentrations it is harmless. if the concentration
rises to 100 PPM, causes uncomfortable breathing with
headache, nausea.
4. Stability: Ozone is thermodynamically unstable
5. Therefore high concentrations of ozone can be dangerously explosive.
6. Due to the ease with which it liberates atoms of nascent
oxygen(O3 O2 + O), it acts as a powerful oxidising agent.
Eg: it oxidises lead sulphide to lead sulphate and iodide ions to
iodine.
PbS(s) + 4O3(g) PbSO4(s) + 4O2(g)
2I(aq) + H2O(l) + O3(g) 2OH(aq) + I2(s) + O2(g)
Ozone
decomposing
into oxygen
heat liberated
H is negative
& S is
positive

large negative
Gibbs energy
change (G)
Properties
1. Nitrogen oxides combine very rapidly with ozone and
the possibility that nitrogen oxides emitted from the
exhaust systems of supersonic jet aeroplanes might be
slowly depleting the concentration of the ozone layer
in the upper atmosphere.
NO g + O3 g NO2 g + O2 g

2. Threat to the ozone layer is probably posed by the use
of freons which are used in aerosol sprays and as
refrigerants.


Upper Atmosphere OZONE LAYER
NO
O3
NO3
O2
aerosol sprays

Structure of OZONE
The two oxygen-oxygen bond lengths in the ozone
molecule are identical (128 pm) and the molecule is
angular
as expected with a bond angle of about 117o. It is a
resonance hybrid of two main forms.
Uses:
It is used as a germicide, disinfectant and for
sterilising water.
It is also used for bleaching oils, ivory, flour, starch,
etc.
It acts as an oxidising agent in the manufacture of
potassium permanganate.
Sulphur forms numerous allotropes of which the yellow rhombic and
monoclinic forms are the most important.

1. Rhombic sulphur (-sulphur): The stable form at room temperature
Colour: yellow
M.P: 385.8 K and
Specific gravity: 2.06.
Preparation: Rhombic sulphur crystals are formed on evaporating the solution of roll
sulphur in CS2.
Solublity: - Insoluble in water but
- Dissolves in benzene, alcohol and ether.
- It is readily soluble in CS2.
Transforms to monoclinic sulphur when heated above 369 K.


Monoclinic sulphur (-sulphur)
M.P. is 393 K
Specific gravity 1.98.
Solublity: It is soluble in CS2.
Preparation: Prepared by melting -sulphur in a dish and cooling,
till 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 -sulphur.
It is stable above 369 K and transforms into -sulphur below it.
Transition Temperature.
The temperature ie: 369 K at which both the allotropic forms
rhombic and monoclinic are stable is called Transition Temperature.
Both rhombic and monoclinic sulphur have S8 molecules.
The S8 ring in both the forms is puckered and has a crown
shape.
Several other modifications of sulphur containing 6-20 sulphur
atoms per ring have been synthesised in the last two decades.
In cyclo-S6, the ring
adopts the chair form.
At elevated
temperatures(~1000 K),
S2 is the dominant
species and is
paramagnetic like O2.
Sulphur Dioxide Preparation
Sulphur dioxide is formed together with a little (6-8%) sulphur
trioxide when sulphur is burnt in air or oxygen:
S(s) + O2(g) SO2 (g)
In the laboratory it is readily generated by treating a sulphite with
dilute sulphuric acid.
SO3
2-
(aq) + 2H
+
(aq) H2O(l) + SO2 (g)
Industrially, it is produced as a by-product of the roasting of sulphide
ores.
4FeS2 (s) +11O2 (g) 2Fe2O3 (s) + 8SO (g)
The gas after drying is liquefied under pressure and stored in steel
cylinders.
Sulphur dioxide Properties
Colour: colourless gas
Smell: pungent smell
Solublity: highly soluble in water.
Liquefaction: at room temperature under a pressure of
two atmospheres and boils at 263 K.
1. Reaction with water:
Sulphur dioxide, when passed through water, forms a
solution of sulphurous acid.
2. Reaction with NaOH:
It reacts readily with sodium hydroxide solution, forming
sodium sulphite, which then reacts with more sulphur
dioxide to form sodium hydrogen sulphite.

2NaOH + SO2 Na2SO3 + H2O
Na2SO3 + H2O + SO2 2NaHSO3
Sulphur dioxide reacts with chlorine in the presence of
charcoal (which acts as a catalyst) to give sulphuryl
chloride, SO2Cl2.
It is oxidised to sulphur trioxide by oxygen in the presence
of vanadium(V) oxide catalyst.

When moist, sulphur dioxide behaves as a reducing agent.
For
example, it converts iron(III) ions to iron(II) ions and
decolourises acidified potassium permanganate(VII)
solution; the latter reaction is a convenient test for the gas.
The molecule of SO2 is angular.
It is a resonance hybrid of the two
canonical forms.
Uses of Sulphur dioxide
1. in refining petroleum and sugar
2. in bleaching wool and silk and
3. as an anti-chlor, disinfectant and preservative.
4. Sulphuric acid, sodium hydrogen sulphite and calcium hydrogen sulphite
(industrial chemicals) are manufactured from sulphur dioxide.
5. Liquid SO2 is used as a solvent to dissolve a number of organic and
inorganic chemicals.
Oxoacids of Sulphur
Sulphur forms a number of oxoacids such as H2SO3, H2S2O3, H2S2O4,
H2S2O5, H2SxO6 (x = 2 to 5), H2SO4, H2S2O7, H2SO5, H2S2O8 .
Some of these acids are unstable and cannot be isolated.
They are known in aqueous solution or in the form of their salts.

Contact Process

Sulphuric acid is manufactured by the Contact Process
which involves three steps:
(i) burning of sulphur or sulphide ores in air to generate
SO2.
(ii) conversion of SO2 to SO3 by the reaction with oxygen
& catalyst (V2O5),
(iii) absorption of SO3 in H2SO4 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 H2SO4 is the catalytic
oxidation of SO2 with O2 to give SO3 in the presence of
V2O5 (catalyst).
Reaction
The reaction is exothermic, reversible and the forward reaction leads to a decrease
in volume.
Therefore, low temperature and high pressure are the favourable conditions for
maximum yield.
But the temperature should not be very low otherwise rate of reaction will become
slow.
In practice, the plant is operated at a pressure of 2 bar and a temperature of 720 K.
The SO3 gas from the catalytic converter is absorbed in concentrated H2SO4 to
produce oleum.
SO3 + H2SO4 H2S2O7
(Oleum)
The sulphuric acid obtained by Contact process is 96-98% pure.


Properties of Sulphuric acid
Sulfuric acid is a highly corrosive strong mineral
acid with the molecular formula HSO.

It is a colorless to slightly yellow viscous liquid
which is soluble in water at all concentrations.
Specific gravity of 1.84 at 298 K.
The acid freezes at 283 K and boils at 611 K.
It dissolves in water with the evolution of a large
quantity of heat.
The chemical reactions of sulphuric acid are 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 oxidising agent.
In aqueous solution, sulphuric acid ionises in two steps.
H2SO4(aq) + H2O(l) H3O+(aq) + HSO4 (aq); Ka1 = very large (Ka1 >10)
HSO4(aq) + H2O(l) H3O+(aq) + SO4(aq) ; Ka2 = 1.2 102
The larger value of Ka1 (Ka1 >10) means that H2SO4 is largely dissociated
into H+ and HSO4.
Greater the value of dissociation constant(Ka), the stronger is the acid.
The acid forms two series of salts: normal sulphates
(such as sodium sulphate and copper sulphate) and
acid sulphates (e.g., sodium hydrogen sulphate).
Sulphuric acid, because of its low volatility can be
used to manufacture more volatile acids from their
corresponding salts. 2 MX + H2SO4 2 HX +
M2SO4 (X = F, Cl, NO3) (M = Metal)
Concentrated sulphuric acid is a strong dehydrating
agent.
Many wet gases can be dried by passing them
through sulphuric acid, provided the gases do not
react with the acid.
Drops of
concentrated sulfuric
acid rapidly dehydrate
a piece of cotton
towel.
Sulphuric acid removes water from organic
compounds; it is evident by its charring action on
carbohydrates.
C12H22O11 H2SO412C + 11H2O
Hot concentrated sulphuric acid is a moderately
strong oxidizing agent.

Both metals and non-metals are oxidised by
concentrated sulphuric acid, which is reduced to SO2.
1. Cu + 2 H2SO4(conc.) CuSO4 + SO2 + 2H2O
2. 3S + 2H2SO4(conc.) 3SO2 + 2H2O
3. C + 2H2SO4(conc.) CO2 + 2 SO2 + 2 H2O
Concentrated
sulfuric acid when
stirred into sugar
produces a steaming
black carbon foam.

It is needed for the manufacture of hundreds of other compounds
and also in many industrial processes.
The bulk of sulphuric acid produced is used in the manufacture of
fertilisers e.g., ammonium sulphate, superphosphate).
Other uses are in:
(a) petroleum refining
(b) manufacture of pigments, paints and dyestuff intermediates
(c) detergent industry
(d) metallurgical applications (e.g., cleansing metals before enameling,
electroplating and galvanizing)
(e) storage batteries
(f) in the manufacture of nitrocellulose products.
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