GROUP 16 (VIA) ELEMENTS

the oxygen sulphur family

(Oxygen O, Sulphur S, Selenium Se, Tellurium Te,

Plolonium Po. )

the electronic structure s2p4. The elements are called the

chalcogens or ore-forming elements, because many metal
ores are oxides or sulphides.
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Elements

O
Oxygen

S
Sulphur

Se
Selenium

Te
Tellurium

simple electron
config.

2,6

2,8,6

2,8,8,6

2,8,18,18,6

2,8,18,32,18,6

electron config.

[He]
2s22p4

[Ne]
3s23p4

[Ar]3d10
4s24p4

[Kr]4d10
5s25p4

[Xe]4f145d106s2
6p4

Atomic unit

15. 99

32. 06

78. 96

127. 60

210

melting pt./oC

-218

117

217

450

254

boiling pt./oC

-183

445

685

990

962

density/gcm-3

<0.1

2.1

4.8

6.2

9.3

1st IE/ kJmol-1

1314

1000

941

869

812

Oxidation States

-2,(-1)

-2, +2, +4, +6

-2, +2, +4,

+6

-2, +2, +4,

+6

-2, +2, +4, +6

Covalent radius/

0.66

1.04

1.17

1.43

1.67

Electronegativity

3.44

2.58

2.55

2.10

2.00

colourless
gas

yellow solid
(monoclinic
/rhombic
allotropes)

Silver
metalloid or
red powder
allotropes

silver white
metalloid

radioactive
silvery solid

Appearance (RTP)

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16

34

52

Po Polonium
(radioactive)

84

Chemistry of Group 16 elements in relation to Electronic

Structure:
1-Each element in this group has the electronic configuration
S2p4 with six electrons in its outermost energy level. The
elements tend to attain the inert gas configuration either by:
a-Accepting two electrons forming M2- ions, or
b-Sharing two electrons and forming two covalent bonds,
only oxygen is highly electronegative (3. 5), and easily forms
ionic metal oxides which contain the O2- ions thus giving an
oxidation state of 2. On the other hand, S2-, Se2- and Te2ions are less probable.
The elements also form covalent compounds containing two
electron pair bonds such as H2O, Cl2O, H2S, SCl2.
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3-Except for oxygen, all the elements show oxidation states

ranging from 2 to 6. Oxygen is never more than divalent
because its second shell is limited to eight electrons and to
excite an electron to a higher shell would require a very high
energy. The elements S, Se , Te and Po, however, have empty
d orbitals and can have a coordination number of four or six
by using the orbitals for bonding

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Compounds of S, Se, and Te with oxygen are typically tetravalent.

The maximum oxidation states of +6 are seen with their
compounds with fluorine, the stability of the higher oxidation,
states decreasing down the group. The +6 state shows only
oxidizing properties while the compounds in the +4 oxidation state
have both oxidizing and reducing properties.
3-Because sulphur, Se, Te and Po has lower electronegativities than
oxygen, their compounds have less ionic character. The changes in
properties of compounds on going form S to Po can be associated
with increasing size of the atoms and decreasing electronegativity.
Some examples are:
a-The decreasing thermal stability of H2X (X=S, Se, Te or Po)
b-The increasing tendency to form anionic complexes like Se Br62-,
TeBr62- and PoI62- .
c-The appearance of some metal-like properties in Te and Po. Thus
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5
the oxides MO are ionic and react with HCl to give the chlorides.

4-Metallic and Non metallic character

The metallic character increases down the group. Oxygen and Sulphur
are non-metals; Selenium and tellurium have weaker nonmetallic
character while polonium, which is radioactive and short lived, is
markedly metallic. The increase in metallic character is shown in
a-The electronic structures of the elements
b-Increasing tendency to from M2+ ions.
d - p overlap
c-Decrease in stability of M2- ions.
5-Type of Bonding
The bonds between S and O or Se and O are much shorter than might be
expected for a single bond and therefore may be regarded as double
bonds. Usually when double or triple bonds occur, some orbitals overlap
laterally giving () bonds. For sulphur particularly, as in other second
row elements, there is multiple d - P bonding . bond is formed by
the sideways overlap of a p-orbital on the oxygen with a d orbital on the
sulphur, giving the p-d bonding
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S O

Differences between Oxygen and the other elements of Gp 16

1-Oxygen differs from the rest of the group because of its higher
electro negativity of p orbitals.
2-Because of the limitation of the second shell to eight electrons,
oxygen is never more than divalent and has a minimum
coordination number of four (because there are no d-orbitals in the
second shell) the other elements, however, can have a coordination
number of six by using d orbitals.
3-Because it is more electronegative, oxygen forms compounds
which are more ionic than those of the other elements in the Gp.
4-Hydrogen bonding is formed in many oxygen compounds while
only weak hydrogen bonds involving sulphur exist.
5-Oxygen is stable as a diatomic molecule, which accounts for its
being a gas. S, Se, Te and Po are solids at normal temperature and
have more complex structure.
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6-Oxygen occurs as two nonmetallic forms, O2 and ozone O3, the

other elements exist in more than one allotropic forms (i. e.
polymorphic) in which the structures change for simple diatomic
molecules, to rings and chains, to a simple metallic lattice.
7-Oxygen and sulphur are insulators (non metallic character), Se
and Te are semiconductors and Po shows metallic conduction.
8-Oxygen, and to a greater extent sulphur, differ from the rest of
the elements in their ability to catenate and form polyoxides and
polysulphides. (H2O2, H2S2, H2S3, H2S4)

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Chemical Reactivity:
all the elements except the inert gases react with oxygen, the reactions
being strongly exothermic. S, Se and Te are moderately reactive and
burn in air to form dioxides. They combine with many metals and non
metals, but are not attacked by acids, except those which are oxidizing
agents (non metallic character). Polonium dissolves in H2SO4, HF, HCl
and HNO3 (metallic character). S and Se dehydrogenate saturated
hydrocarbons. With olefins, sulphur forms cross-links, which is
important in the vulcanizing of rubber.

Oxides and oxyacids of S, Se and Te

Dioxides MO2
The dioxides of S, Se and Te are obtained by burning the elements
in air. Sulphur dioxide, SO2 is also produced by heating many
sulphides in air :
H2S + O2 SO2 + H2O
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SeO2 and TeO2 are obtained by treating the metals with hot nitric
acid to form H2SeO3 and 2TeO2.HNO3, respectively, then
evaporating the water or nitric acid by heating. SO2 is a gas and
forms discrete molecule even in the solid state. Its structure, is seen
below, SeO2 is solid at room temperature. The gas has some
structure as SO2 but the solid forms infinite chains, which are not
planar.
The dioxides are acidic in nature and acidic character decreases as
we move down the group.
TeO2 and PoO2 both crystallize in two ionic forms

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Oxides of Gp. 15
Element

MO2

MO3

SO2

SO3

Se

SeO2

SeO3

Te

TeO2

TeO3

Po

PoO2

Other Oxides
S2O

S2O3
TeO
PoO

SO2 is readily soluble in water forming sulphurous acid, H2SO3

solution. SeO2 forms selenious acid H2SeO3, while TeO2 is almost
insoluble in water but dissolves in alkali to form tellurites and in
acids to form basic salts. This indicates its amphoteric character.
SO2 is important in the manufacture of sulphuric acid and for
bleaching. Solution of SO2 and of sulphites has reducing properties.
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Sulphur Dioxide , SO2

The SO2 molecule has the following resonance structure. The two
bonds have the same bond length.
..

..

..

:O

:O
..

..

:O
..

O
S:

S:

..
..

:O
..

..
:

..

..

The resultant sp2 hybridization results in a planar triangular structure for

the SO2 molecule with one corner occupied by a lone pair and the other
two corners by oxygen atoms.
The bonds do not alter the shape of the molecule, but only shorten the
bond lengths. The bond angle is reduced to 119. 5 (the ideal value of
120 is predicted from Sp2 hybridization) due to the repulsion by the lone
pair of electrons.
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Trioxides MO3
Sulphur trioxide SO3 is obtained by reaction of SO2 with O2. The
reaction is slow and a catalyst such as Pt or V2O5 is used.
SO3 reacts violently with water to form sulphuric acid. Industrially, SO 3
is dissolved in 98% H2SO4 to give oleum or fuming sulphuric acid. This
is mainly pyrosulphuric acid H2S2O7 which is then diluted. SO3 is used as
such for preparing sulphonated oils and alkyl are suphonate detergents. It
is also a powerful oxidizing agent; it oxidizes HBr to Br and P to P 4O10.
The SO3 molecule, in the gas phase, has a planar, triangular structure (sp2
hybridzation) involving three resonance structures. It forms polymers in
the solid state.

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..

..

:O
..

..

..

..

:O :

..

:O
O

..

:S

S:

..

..

:S

:O :

..

:O

..

:O :

..

..

O..

:O

..

:S

..

..

O:

..

The bond angles of 120 accord with sp2 hybridization, all bonds are
similar in bond length.

Selenium Trioxide SeO3 and tellurium Trioxide TeO3

SeO3 is formed by a silent electric discharge on Se and O2 gases, and
TeO3 is formed from telluric acid H6TeO6 by strong heating. Both
trioxides are acid anhydrides
SeO3 + H2O11/24/16
H2 SeO4
selenic acid
14

Sulphuric Acid H2SO4

This acid is of enormous industrial importance and is manufactured in
larger quantities than other acids. The most important industrial process
for its manufacture is the contact process, which involves oxidation of
SO2 by air to SO3 in presence of V2O5 as a catalyst and the lead chamber
process, where homogeneous catalysts used for SO2 oxidation are oxides
of nitrogen. Sulphuric acid is usually sold as a 98% mixture with water
(18M). When SO3 is further passed into 98% H2SO4, fuming sulphuric
acid or oleum which contains pyrosulphuric acid H2S2O7 is obtained.

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Sulphuric Acid H2SO4

This acid is of enormous industrial importance and is manufactured in
larger quantities than other acids. The most important industrial process
for its manufacture is the contact process, which involves oxidation of
SO2 by air to SO3 in presence of V2O5 as a catalyst and the lead
chamber process, where homogeneous catalysts used for SO2 oxidation
are oxides of nitrogen. Sulphuric acid is usually sold as a 98% mixture
with water (18M). When SO3 is further passed into 98% H2SO4, fuming
sulphuric acid or oleum which contains pyrosulphuric acid H2S2O7 is
obtained.

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16