Group 16- Oxygen family (chalcogens)

Element Electronic configuration Types Physical state

Oxygen (O) 2s2 2p4 non-metal Gas
Sulfur (S) 3s2 3p4 (3d) non-metal Solid
Selenium (Se) 3d10 4s2 4p4 metalloid Solid
Telluerium (Te) 4d10 5s2 5p4 metalloid Solid
Polonium (Po) 4f14 5d10 6s2 6p4 metal (HL:13.8 days) Solid
Livermorium (Lv) 5f14 6d10 7s2 7p4 Radioactive metal Solid

Element Occurance
Oxygen (O) Oxygen is the most abundant of all the elements on earth, 46.6% by mass
of earth’s crust. Dry air contains 20.946% oxygen by volume.
Sulfur (S) Abundance of sulphur in the earth’s crust is only 0.03-0.1% and present in
gypsum CaSO4 .2H2O, epsom salt MgSO4 .7H2O, baryte BaSO4 and
sulphides such as galena PbS, zinc blende ZnS, copper pyrites CuFeS2.
Selenium (Se) Selenium and tellurium are also found as metal selenides and tellurides in
Telluerium (Te) sulphide ores. Polonium occurs in nature as a decay product of thorium and
Polonium (Po) uranium minerals
Livermorium (Lv) Synthetic radioactive element

Atomic Size: O < S < Se < Te < Po

Ionization Energy: O > S > Se > Te > Po

Electron Affinity: S > Se > Te > Po > O

Mp/Bp : O << S < Se < Po < Te

All these elements exhibit allotropy. 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

1 Poovarasan Ramasamy
oxygen and sulphur may be explained on the basis of their atomicity; oxygen exists as diatomic
molecule (O2 ) whereas sulphur exists as polyatomic molecule (S8).

Anomalous behaviour of oxygen: This due to its small size and high electronegativity. One typical
example of effects of small size and high electronegativity is the presence of strong hydrogen
bonding in H2O which is not found in H2S. The absence of d orbitals in oxygen limits its covalency
to four and in practice, rarely exceeds two.

Chemical Properties:

1. Oxidation number:
*Oxidation State Stability of +2 O.S.  as we move down the group.
*Oxygen show -2 to +2 oxidation state. S, Se and Te show +4 and +6 generally.
*Stability of +4 O.S.  while that of +6  down the group.
*Grp-16 elements show +6 O.S. show with Oxygen and Fluorine.
*Compounds in +4 and +6 O.S. are covalent in nature.

2.Reactivity with Hydrogen:

3. Reactivity with Oxygen:

*All these elements form oxides of the EO2 and EO3
*O3 and SO2 are gases, while SeO2 is solid.
*Reducing property of dioxides decreases from SO2 and TeO2.
*SO2 is reducing while TeO2 is an oxidizing agent.

4. Reactivity with Halogen:

*Stability of halides decreases in order F – > Cl– > Br– > I – .

*They form dichlorides and dibromides. SF4 is gas, SeF4 is liquid and TeF4 is solid.
*Amongst heaxahalides, hexafluorides are the only stable halides.(Reason: Steric)
*All hexafluorides are gaseous in nature.
*Monohalides exist as dimer : S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2.
*These dimeric forms undergo disproportionation.

Dioxygen

Preperation: a) By heating oxygen containing salts such as chlorates, nitrates and permanganates

2 Poovarasan Ramasamy
b) By the thermal decomposition of the oxides of metals low in the electrochemical series and
higher oxides of some metals

c) Hydrogen peroxide is readily decomposed into water and dioxygen by catalysts such as finely
divided metals and manganese dioxide.

e) 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.

Properties: Dioxygen is a colourless and odourless gas. It liquefies at 90 K and freezes at 55 K.

Molecular oxygen, O2 is unique in being paramagnetic inspite of having even number of electrons
(MOT). Dioxygen directly reacts with nearly all metals and non-metals except some metals ( e.g.,
Au, Pt) and some noble gases.

General properties of oxides

Practically all of the elements react with dioxygen to form oxides. There are several ways in which
oxides may be classified, depending on their structure or their chemical properties.

Classification based on structure:

Normal oxides: In these, the oxidation number of M can be deduced from the empirical formula
Mx Oy , taking the oxida tion number of oxygen as (–II). These oxides, for example H2O, MgO and
Al2O3 , contain only M–O bonds.

Peroxides: These contain more oxygen than would be expected from the oxidation number of M.
Some are ionic and contain the peroxide ion O22−, for example those of Group 1 and 2 metals
(Na2O2 and BaO2 ). Others are covalently bound and contain —O—O—in the structure, for example
H2 O2 (H—O—O—H), peroxomono sulphuric acid and peroxodisulphuric acid.

3 Poovarasan Ramasamy
Superoxides: KO2 , contain more oxygen than would be expected

Suboxides: Here the formula contains less oxygen than would be expected from the oxidation
number of M. They involve M—M bonds in addition to M—O bonds, for example O=C=C=C=O

Classification based on chemical properties:

Basic oxides: Metallic oxides are generally basic. Most metal oxides are ionic and contain the O2−
ion. When they react with water the O2− ion is converted into OH−.

However, many metal oxides with formulae M2O3 and MO2 , though ionic, do not react with water.
Examples include Tl2O3 , Bi2O3 and ThO2 . These react with acids to form salts, and so are basic.
lowest oxidation state is the most ionic and the most basic. Thus CrO is basic, Cr2O3 amphoteric
and CrO3 acidic.

Amphoteric oxides: Many metals yield oxides which are amphoteric, and react with both strong
acids and strong bases. Examples include BeO, Al2O3 , Ga2O3 , SnO, PbO and ZnO.

Acidic oxides: Non-metallic oxides are usually covalent. Many occur as discrete molecules (CO2 ,
NO2 , SO2 , Cl2O) and have low melting and boiling points, though some, such as B2O3 and SiO2 ,
form infinite ‘giant molecules’ and have high melting points. They are all acidic. There are many are
the anhydrides of acids. In cases where the element exists in more than one oxidation state, e.g.
N2O3 and N2O5 , SO2 and SO3 , the higher oxidation state is the most acidic.

Neutral oxides: A few covalent oxides have no acidic or basic properties (N2O, NO, CO)

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

4 Poovarasan Ramasamy
presence of sunlight. This ozone layer protects the earth’s 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 oxygen to ozone (10%) occurs. The product is known as ozonised oxygen.

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.

Properties:
i) Pure ozone is a pale blue gas, dark blue liquid and violet-black solid.
ii) Diamangnetic in nature
iii) Ozone is thermodynamically unstable with respect to oxygen since its decomposition into
oxygen results in the liberation of heat (∆H is negative) and an increase in entropy (∆S is
positive). These two effects reinforce each other, resulting in large negative Gibbs energy change
(∆G) for its conversion into oxygen. It is not really surprising, therefore, high concentrations of
ozone can be dangerously explosive.

Chemical properties: Due to the ease with which it liberates atoms of nascent oxygen (O3 → O2 +
O), it acts as a powerful oxidising agent. (Eo= +2.07 V)

Tailing of mercury: Pure Hg is a mobile liquid. Its

mobility decreases when brought in contact with O3.
It is starts sticking with glass surface due to
formation of Hg2O in the surface of Hg.

Depletion of ozone layer: Experiments have shown

that nitrogen oxides (particularly nitrogen
monoxide) combine very rapidly with ozone and
there is, thus, 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. Another threat to this ozone layer is
probably posed by the use of freons which are used
in aerosol sprays and as refrigerants.

Estimation of ozone: When ozone reacts with an excess of potassium iodide solution buffered with
a borate buffer (pH 9.2), iodine is liberated which can be titrated against a standard solution of
sodium thiosulphate.

5 Poovarasan Ramasamy
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

Allotropes of Sulfur

Sulphur forms numerous allotropes of which the yellow rhombic (α-sulphur) and monoclinic (β -
sulphur) forms are the most important. The stable form at room temperature is rhombic sulphur,
which transforms to monoclinic sulphur when heated above 369 K

Rhombic sulphur (-sulphur)

(i) This allotrope is yellow in colour, m.p. 385.8 K and specific gravity 2.06. It is insoluble in
water but dissolves to some extent in benzene, alcohol and ether. It is readily soluble in CS 2.

Monoclinic sulphur (-sulphur)

(i) Its m.p. is 393 K and specific gravity 1.98. (ii) It is soluble in CS2

Both rhombic and monoclinic sulphur have S8 molecules.

These S8 molecules are packed to give different crystal structures.

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 (SO2)

Preparation : 1) By combustion of Sulphur in presence of Oxygen.

2) By reaction of metal sulphites with dilute HCl (Laboratory method)

Similarly, bisulphites also give SO2 with dilute HCl

6 Poovarasan Ramasamy
Properties : Colourless gas with pungent smell. It is heavier than air and is highly soluble in water.
Acidic oxide and thus dissolve in water forming sulphurous acid. It can act as reducing as well as
oxidising agent.

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.

Sulphur dioxide is used (i) in refining petroleum and sugar (ii) in bleaching wool and silk and (iii) as
an anti-chlor, disinfectant and preservative. Sulphuric acid, sodium hydrogen sulphite and calcium
hydrogen sulphite (industrial chemicals) are manufactured from sulphur dioxide. Liquid SO2 is used
as a solvent to dissolve a number of organic and inorganic chemicals.

Oxoacids of sulfur

7 Poovarasan Ramasamy
 Sulphuric Acid (H2SO4)

It is also known as Oil of Vitriol and King of Chemicals.

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 with 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. In
contact process, impurity of As2O3 is absorbed by Fe2O3. xH2O. 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).

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.

Properties (i) Sulphuric acid is a colourless, dense, oily liquid with a specific gravity of 1.84 at 298
K. (ii) The acid freezes at 283 K and boils at 611 K. (iii) It dissolves in water.

Chemical properties:

Acidity:

Sulphuric acid, because of its low volatility can be used to manufacture more volatile acids from
their corresponding salts

8 Poovarasan Ramasamy
Dehydrating Property : Concentrated sulphuric acid is a strong dehydrating agent.

Oxidizing nature:

1. Conc. H2SO4 acts as mild O.A. and reduces to SO2

M + conc. H2SO4 ⎯→ Metal sulphate + SO2 + H2O

2. dil. H2SO4 doesn't act as O.A. only as acid.

M + dil. H2SO4 ⎯→ Metal sulphate + H2

3. Only conc. H2SO4 reacts with non-metals.

NM + conc. H2SO4 ⎯→ Anhydride of Parent ‘ic’ acid of NM + SO2

Hypo/Sodium Thiosulphate [Na2S2O3.5H2O]

The structure of thiosulphate ion, S2O32- ion is similar to the sulphate ion, SO42- is except that one
of the positions of the tetrahedron is occupied by sulphur atom.

Preparation

Properties It reduces halogens so acting as reducing agent. due to this reaction hypo is used as an
antichlor. (remove chlorine)

It can dissolve silver halides and hence used in photography for removing unaffected silver
bromide during fixing of negatives. So, act as a complexing agent.

Volumetric analysis of I2 (decolourisation of I2)

This reaction is used for the iodometric estimation of oxidising agents like CuSO4, CaOCl2, MnO2,
K2Cr2O7, KMnO4 etc., which on reaction with KI liberates I2 which in turns determined by titration
using Na2S2O3.

9 Poovarasan Ramasamy