GROUP 6

th
A
Oxygen , sulphur , selenium , tellurium and polonium belong to VIA group of
periodic table . O, S, Se and Te are also known as chalcogens (ore forming elements).
Polonium is the only radioactive element in the group. It was discovered by Curie.
Most abundant element in earth crust is oxygen , Oxygen occurs freely in the
atmosphere of which it comprises 20.8% by volume . With carbon , nitrogen and
hydrogen , it is essential to living matter. Water contains 89% by weight of combined
oxygen . Oxygen is perhaps , the most abundant element on the surface of moon also .
The approximate abundance of oxygen in the crystal rocks of the earth is about 45%
by weight .

Sulphur occurs uncombined in many parts of the world. Selenium and tellurium are
comparatively rare elements. Polonium, the radioactive element, has 27 isotopes,
which are all radioactive. Of these
210
Po occurs naturally.

Oxygen is the second most electronegative element after fluorine, but in the VIA
group oxygen is the most electronegative element. Oxygen was discovered by
Priestley. In laboratory it is prepared by heating KClO
3
in presence of MnO
2
as
catalyst. Oxygen is a principal component of water and of the rocks and minerals in
the earth's crust. About 21% of the components of dry air consist of O
2
molecules.
The second form of the element oxygen, called ozone is present in very small
amounts in the upper atmosphere and protects us from harmful effects of ultraviolet
rays from the sun. Oxygen is obtained as a result of thermal decomposition of salts
containing anions (e.g. KNO
3
, KClO
3
, KMnO
4
etc. Certain higher oxides, such as
PbO
2
, Pb
3
O
4
etc also liberate oxygen on thermal on thermal decomposition. On large
scale, oxygen is prepared by fractional distillation of liquid air. Oxygen is collected
by downward displacement of water. Any drying agent can be used for absorption of
O
2
. But alkaline pyrogallol is most suitable. Oxygen molecule is paramagnetic and
best explained by MO theory. The normal Oxidation State of oxygen is -2. Oxygen
can not form more than two bonds because of non availability of d-orbitals in its outer
shell . The density, melting point (K) and boiling point (K) of oxygen are 1.14 g/ cc,
54.20 and 90.0 respectively. The ionisation energy of oxygen is 314-k. cals/ mole.

The molecules O
2
and O
3
called allotropes, because these are different forms of the
same element oxygen. On absorbing UV radiation, ozone decomposes to diatomic O
2

molecules. Among the elements in the periodic table, only the noble gases, halogens
of elements with oxygen are exothermic and hence release heat. Many of such
reactions are slow at room temperatures but the rate of reaction increases as the
temperature is increased. With metallic elements, oxygen forms ionic compounds
containing either O
2-
(oxide ion), the O
2
2-
(peroxide ion) or the O
2-
(supper oxide ion).
Oxygen reacts with metals to form oxides, many of which are not soluble in water.
For example, CuO and Ag2O are insoluble in water. Oxygen reacts with non-metals
to form a large number of molecular compounds, such as CO, CO
2
, NO, NO
2
, SO
2
,
SO
3
, H
2
O, P
2
O
5
(P
4
O
10
) etc. Oxygen always exists as diatomic (O
2
) molecule.
Oxygen is an essential component of many organic compounds, such as fats,
carbohydrates, proteins etc. The outer electronic configuration of the elements of VIA
group is ns
2
np
4
.

The metallic character increases from oxygen to polonium. The group VI a
elements show almost purely non-metallic chemistry with feeble metallic
properties becoming just precipitable as the atomic number increases. Oxygen is
highly electronegative, sulphur is less electronegative than oxygen, and Both O
and S are non-metals. Se and Te are metalloids and Po is weakly electropositive
metal which is rare as well as radioactive . The general increase in metallic
character on descending the group is demonstrated by (a) Increasing basic and
ionic character of the oxides (b) Increasing tendency to form complexes such as
SeBr
6
2-
TeBr
6
2-
and PoI
6
2-
(c) Decreasing stability of hydrides (d) Increase in
density (e) The decrease in ionisation energy , electronegativity and electron
affinity from O to Po, an (f) A more negative reduction potential for the
conversion of the elements to the -2 oxidation state. The metallic properties
therefore begin to appear in Te in a less stable hydride, Te H
2
and in amphoteric
character in the oxide, TeO
2
. I.P. and electronegativity decreases form O to Po.

Oxygen shows -2 oxidation state in most of its compounds, but +2 in OF
2
, + 1 in
O
2
F
2
and -1 in peroxides . All the other elements show oxidation states of -2, +2, +4
and +6. It is due to the presence of d-orbitals in them.

Since atom of these elements are two electrons short of the noble gas configuration,
they are expected to have tendencies to achieve noble gas configuration by gaining or
sharing of two electrons. The electronegativity of oxygen is very high. So its
compounds with most metallic elements can be more but for other elements, only
those compounds with the most electropositive elements can be more than 50% ionic.
Essentially covalent bonding resulting results with a variety of less electronegative
metals and non-metals and in these the VIA group elements may be considered to
have a formal charge of -2

Tendency to form chain is less evident with Oxygen. It forms O-O links in peroxides
and in O
2
F
2
; in Ozone and O
4
F
2
the chain contains three O atoms and in O
4
F
2
there
are 4 oxygen atoms. All species with O
3
and O
4
chain are stable.Sulphur exhibits
strong tendency to catenation. The enhanced tendency of catenation in S is due to
fairly large bond energy of the S-S bond .

Due to its high electronegativity, oxygen shows an oxidation state of 2- in all of its
compounds except (a) In OF
2
, where it has +2 oxidation state (b) In peroxides, where
it has -1 oxidation state (c) In super oxides (e.g.) KO
2
), where it exhibits -1/2
oxidation state.

The positive oxidation states of +2, +4 and +6 become increasingly more common as
we move from S to Po. The +4 and +6 states are more common and stable. The +4
State is most stable for Te and the VI or II state is most stable for Po. In +4 oxidation
state, these elements show oxidising and reducing properties , but in +6 state, they are
predominantly oxidising ( such as H
2
SO
4
) .

Compounds of S to Po in +2 state are few and comparatively unstable. For example,
SO , SeO , TeO , are unstable . Odd positive oxidation states, such as +3 or +5 are
rare. Bonding in positive oxidation states is covalent.

Due to fairly large bond energy of the S - S bond, sulphur exhibits a strong tendency
to catenation. Although bond energies of Se-Se and Te -Te bonds are smaller, the
tendency to form chains persists in the crystallised form of these compounds.

The catenation property of sulphur is maximum in the group. Tendency to form
chains is less evident with oxygen. It forms O-O links in peroxides and in O
2
F
2
;
in ozone and O
3
F
2
the chain contains three O atoms and in O
4
F
2
there are 4
oxygen atoms . All species with O3 and O
4
chains are stable. Sulphur exhibits
tendency to catenation. The enhanced tendency of catenation in S is due to fairly
large bond energy of the S-S bond.

Density, melting point and boiling point increase from O to Po. Oxygen is diatomic
molecule, sulphur, selenium and tellurium are octa atomic. For example, sulphur
molecule is octa atomic (S
8
) and it has a puckered ring structure. All the elements in
oxygen family exist in allotropic forms. Two allotropic forms of oxygen are O
2
and
O
3
. Sulphur exist in forms like rhombic monoclinic, plastic etc. Rhombic sulphur is
stable upto 95.6C. Monoclinic sulphur is stable above 95.6C. At 95.6C both forms
exist in equilibrium. This temperature is called transition temperature. Most
abundant and common form of sulphur is rhombic sulphur. Oxygen and sulphur are
non-conductors, selenium and tellurium are semi conductors and polonium is
conductor .

All the elements of VIA group form hydrides of the type H
2
M, (H
2
O, H
2
S, H
2
Se,
H
2
T
2
and H
2
Po). The stability of hydrides decreases from H
2
O to H
2
Po.The acidic
nature of hydrides decreases from H
2
O to H
2
Po , ( H
2
O< H
2
S < H
2
Te < H
2
Po). The
reducing power of the hydrides increases from H
2
O to H
2
Po , (H
2
O < H
2
S < H
2
Se <
H
2
Te 0C ).The volatility of these hydrides decreases from H
2
S to H
2
Te .Decreasing
order of bond angles is H
2
O ( 104) > H
2
S ( 92.5 ) > H
2
Se (90) > H
2
Te ( 89)
.Increasing order of H-A bond length is : H
2
O ( 0.95A) < H
2
S ( 1.45A ) < H
2
Te (
1.72 A) .All the hydrides , except water are gases at room temperature .All hydrides ,
except water are volatile , poisonous and bad smelling .In acid solution , the acidity of
hydrides increase from H
2
S to H
2
Te. All the hydrides have bent structure. The bond
angle decrease from H
2
O to H
2
Te .Due to intermolecular hydrogen bonding, water is
liquid and has high melting and boiling point compared to other hydrides of the group
elements.

In the formation of water molecule, oxygen atom undergoes sp
3
Hybridisation.
Because of the repulsion of non-bonding electron pairs, the tetrahedral bond angle is
decreased from 109 28 ' to 104 5'. In the case of other hydrides the bond angle is
nearly 90. This indicates that in these hydrides only pure valence p-orbitals re
involved in covalent bonding.

Thermal stability, bond angle , bond strength and basic character decreases
from oxygen to polonium .

All the elements of this form halides of the type M
2
X
2
, MX
2
, MX
2
, MX
4
and MX
6

( M = S, Se, Te and X = halogens ) in which oxidation states of chalcogens are +1, +2
, +4 an +6 respectively .

Oxygen combine with chlorine to form a number of oxides such as Cl
2
O (chlorine
monoxide), ClO
2
(chlorine dioxide), Cl
2
O
6
(chlorine hexoxide) and Cl
2
O
7
(chlorine
heptoxide) in which the oxidation states of chlorine are +1, +4, +6, and +7
respectively.

Elements other than oxygen generally form tetrachlorides of the type SCl
4
, SeCl
4
,
TeCl
4
and PoCl
4
, SCl
4
is unstable liquid while other are stable solids.

The tetrahalides have distorted trigonal bipyramid structure. S, Se and Te form
fluorides of the type SF
6
, SeF
6
and TeF
6
. These can be prepared by direct combination
of these elements (S, Se and Te) with fluorine. All these fluorides undergo hydrolysis
and degree of hydrolysis increases with increase in atomic number. (TeF
6
, SeF
6
and
SF
6
). These fluorides have octahedron structure due to sp
3
d
2
Hybridisation of the
central atom.

All these elements form oxides of the type of MO
2
and MO
3
(M=S, Se, Te and Po).
Sulphur Forms SO
2
and So
3
.

Due to its high electronegativity oxygen shows an oxidation state of -2 in all of its
compounds expect (a) In OF
2
, where it has +2 oxidation state (b) In peroxides, where
it has -1 oxidation state (c) In super oxides (e.g KO
2
) where it exhibits -1/ 2 oxidation
state.

The Positive oxidation states of +2, +4 and +6 become increasingly more common as
we move from S to Po. The +4 and +6 states are more common and stable. The +4
state is most stable for Te and the VI or II stage is mo0st stable for Po. In +4
oxidation state, these elements show oxidation and reducing properties, but in +6 state
they are predominantly oxidising (such as H
2
SO
4
).

Compounds of S to Po in +2, states are few and comparatively unstable. For example
So, SeO, TeO are unstable. Odd positive oxidation states such as +3 or +5 are rare.
Bonding in positive oxidation states is covalent.

Due to fairly large bond energy of the S S bond sulphur exhibits a strong tendency
to catenation. Although bond energies of Se Se and Te Te bond are smaller the
tendency to form chains persists in the crystallised form of these compounds.

As the metallic character increases, the acidic nature of oxides gradually increases.
Reducing power gradually decreases and oxidising power increases.

S. Se and Te produce trioxides of the type SO
3
, SeO
3
and TeO
3
. The acidic nature of
these oxides is in the order SO
3
> SeO
3
> TeO
3
. Te and Po also form monoxides of
the type TeO, PoO.

The ionic character of dioxide increases and acidic character decreases will an
increase in atomic number. The solubility of dioxides in water decreases from SO
2
to
TeO
2
.


The strength of resulting oxyacids decreases in the order H
2
SO
3
> H
2
SeO
3
> H
2
TeO
3
.

Thermal stabilities of trioxides is in the order TeO
3
> SeO
3
> SO
3
. The trioxides are
acidic in nature. They dissolve in water to form ic acids. The strength of ic acids
decreases in the order H
2
SO
4
> H
2
SeO
4
> H
2
TeO
4
.

Sulphur forms a number of oxyacids. These are sulphoxylic acid (H
2
SO
2
),
sulphurous acid (H
2
SO
3
) sulphuric acid (H
2
SO
4
), pyrosulphurous acid (H
2
S
2
O
5
),
thiosulphuric acid (H
2
S
2
O
3
), pyrosulphuric acid (H
2
S
2
O
7
) dithionic acid (H
2
S
2
O
6
)
, peroxymonosulphuric acid or Caro's acid (H
2
SO
5
) and peroxydisulphuric acid
or Marshall's acid (H
2
S
2
O
8
).

Peroxymonosulphuric acid (H
2
SO
5
) and peroxydisulphuric acid (H
2
S
2
O
8
) are the
peroxy acids with O O linkage.

The dioxides of VIA group elements dissolve lin water to give ous acids of the type
(H
2
MO
3
). PoO
2
in insoluble in water but soluble in acids.In the 'ous acids the
oxidation state of elements is +4.

The trioxides of VIA group elements form ic acids of the type H
2
MO
4
. The strength
of ic acids follows the order H
2
SO
4
> H
2
SrO
4
> H
2
TeO
4
. In these acids the oxidation
number of elements is +6.

Sulphurous acid is unstable and acts as oxidising and reducing agent. Sulphuric
acid acts as oxidising dehydrating and pickling agent. King of chemicals is
H
2
SO
4
. It is hygroscopic.

Ozone an allotrope of oxygen is largely present in the upper layer of atmospher
(stratosphere) and prevents the powerful UV radiation from the sun. Ozone is bluish
(Pale blue) gas with fishy odour. In liquid state it is blue in colour. It is more soluble
in water than oxygen. It is soluble in turpentine oil. It acts as oxidising reducing and
bleaching agent. It tails mercury by oxidation. Its bleaching action is due to oxidation.
It turns benzidine paper brown, starch iodine paper blue and tetraethyl base paper
violet. A mixture of ozone and cyanogen, (CN
2
) is used ar rocket fuel. Ozone is
diamagnetic and has angular structure. The O O bond length is 1.27 A. O
3

reduces H
2
O
2
to water. J Ozone was first noticed by Van Marum. J Schenbien
named it ozone because of its peculiar smell. Soret (1866) consider it as an
allotrope of oxygen and he also studied its triatomic nature . Ozone is largely
present in the upper layer of the atmosphere, where it is formed by the action of U.V
rays on O
2
. Ozone can be prepared byn subjecting pure dry O
2
to electric discharge
in an apparatus known as ozonizer. There are two important types of ozonizers -
Siemen ozonizer and Brodie's ozonizer. When F
2
is passed into water a mixture of
O
2
and O
3
is formed . Ozone is pale blue gas at room temperature with a
characteristic fishy odour. In liquid state ozone is blue in colour. Ozone is slightly
more soluble in water than oxygen. Ozone is soluble in terpentine oil and aborbed
by it . Solubility of O
3
in water is more than that of O
2
because of its polarity. J
Formation of ozone from O
2
is an endothermic reaction and is accompanied by
decrease in volume . O
3
readily decomposes to O
2
at room temperature.
Ozone acts as a powerful oxidising agent, reducing agent and bleaching agent.
Ozone bleaches vegetable colours by oxidation. Ozone tails mercury by oxidation
In some cases all the three atoms of ozone molecule are
used up for oxidation. For example,


In general in the oxidation of SO
2
, SeO
2
, TeO
2
etc to their higher oxides, all the three
O atoms of O
3
are used up. Ozone is known as dry bleach as it bleaches in the
absence of moisture. Ozone forms addition compounds with organic compounds
containing carbon- carbon multiple bonds and these addition compounds are known
as ozonides. Thus ozone is used to located the position of carbon-carbon multiple
bond in the organic compounds.. It is used as a germicide and disinfectant for
purification of air and sterilisation of water. It is used to purify air in underground
railways, zoos, mines etc. Ozone is diamagnetic and has angular structure. O O
bond length in O
3
is 1.27 A which lies between single (1.48A) and double bond
lengths (1.10 A) due to resonance. The bond angle is 11649'.O
3
bleaches coloured
matter by oxidation.

H
2
SO
4
removes water from oxalic and formic acids. H
2
SO
4
is manufactured by lead
chamber process and contact process. In lead chamber process oxides of nitrogen
act as catalyst and act as carriers of oxygen from air SO
2
. In contact process V
2
O
5
is
used as a catalyst. H
2
SO
4
forms hydrates with explosive violence. Its affinity for
water is very high. Metals like Zn, Mg, Na, K, Al Sn etc. Which lie above hydrogen
in electrochemical series react with dilute H
2
SO
4
to liberate H
2
. Metals like Pb Au, Pt
do not react with H
2
SO
4
. Charring of sugar in presence of H
2
SO
4
is due to
dehydration. The dehydrating action of H
2
SO
4
can be explained by the formation of
monohydrate (H
2
SO
4
.H
2
O) and dihydrate (H
2
SO
4
. 2H
2
O).

Compounds consisting of oxygen and a second element are called oxides. Example
are : K
2
O,CaO,Fe
2
O
3
,CO
2
,P
2
O
5
,SO
3
,Cl
2
O
7
,OsO
4
etc. All chemical elements except
He, Ne and Ar form oxides. The chemical bond between oxygen and the second
element in oxides may be ionic or covalent. According to chemical properties, oxides
are classified as salt forming and non salt forming. N
2
O , NO and SiO
2
are non-
salt forming oxides. The salt forming oxides are subdivided into basic acid and
amphoteric oxides. Basic oxides are those whosw hydrates are bases. For example,
Na
2
O and CuO are basic oxides because their corresponding hydrates, NaOH and
Cu(OH)
2
are bases. Mono and divalent metal oxides belong generally to basic oxides.
The chemical bonding in this case is ionic. Oxides of alkali metals (Li, Na, K, Rb, Cs,
Fr) and those of alkaline earth metals (Ca, Sr, Ba, Ra) react with water to form bases.
The remaining basic oxides do not practically react with water. All basic oxides react
with acids to from salts and water. Basic oxides also react with oxides to give salts.


Acid oxides are those whose hydrates are acidic. Non metal and mental oxides belong
to his class oxides. Examples are N
2
O
3
, P
2
O
5
, CrO
3
, Mn
2
O
7
, CO
2
, V
2
O
5
, SO
3
, Cl
2
O
7
.
These are acid oxides because their corresponding hydrates HNO
2
, H
3
PO
4
, H
2
CrO
4
,
HMnO
4
, H
2
CO
3
, H
3
VO
4
, HClO
4
are acid. The chemical bonding in the acid oxides
may be ionic and covalent. Most acid oxides react with water to yield acids. SiO2
does not react with water. Acid oxides with bases or alkalies to form salts and water


The metal oxides while depending upon the medium, exhibit either basic or acidic
properties, that is , react with both acids and bases are called aqmphoteric oxides.
Hydrates of amphoteric oxides can exist both in acidic and basic forms.


Amphoteric oxides react with both acids and bases


The Amphoteric oxides do not directly add to water. Generally oxides of metals are
basic and those of non- metals are acidic. The basic nature of oxides in a group
increases from top to bottom and acidic nature of oxides decreases. The basic
nature of oxides decreases in a period from left to right and acidic nature of
oxides increases.

The most acidic oxide in second period is N
2
O
5
, formed by nitrogen. The
increasing order of acidic nature of oxides in third period is Na
2
O < MgO <
Al
2
O
3
< SiO
2
< P
2
O
5
< SO
3
< Cl
2
O
7
.

Gun powder is a mixture of sulphur, charcoal and KNO
3
.

H
2
S is weak dibasic acid. It is dried over P
2
O
5
or CaCl
2
. So
2
bleached due to
reducation. SO
2
act as an oxidising and reducing agent. In SO
2
, S is sp
2

hybridised. Thus bgond angle in SO
2
is 120. SO
2
molecule has an angular shape.
Shape of SO
3
molecule is planar triangular. The Hybridisation of S is sp
2
and bond
angle is 120. SO
4
2-
ion is tetrahedral because of sp
3
hybridization. O
3
, NO, NO
2
,
KO
2
etc. have three electron bonds. O
2
molecule is paramagnetic due to unpaired
electrons.

Sulphur and iodine do not combine to form any compound. However some solid
solution of sulphur and iodine are known.