ELEMENTS OF GROUP VIA

• Elements in this group include: oxygen

(O), sulphur (S), selenium (Se), tellurium
(Te) and polonium (Po).
• They are collectively called chalcogen.
• They belong to the p-block of the periodic
table.
• Oxygen and sulphur are non-metals,
selenium and tellurium are metalloids,
while polonium is a metal.
 Abundance and Occurrence
• Oxygen is the most abundant element in the earth’s
crust. It is second to nitrogen as the most abundant in
the atmosphere.
• Sulphur is the sixteenth most abundant element in
earth's crust. It occurs in combined form as sulphide
ores, as H2S in natural gas and petroleum and as
organosulphur compounds in coal.
• Selenium and tellurium are relatively rare. Selenium
occurs in only a few minerals, while Te is usually
combined with other metals, e.g. in sylvanite
(AgAuTe4).
• Polonium are mainly radioactive.
 Extraction
• Oxygen is obtained industrially by fractional
distillation of liquid air.
• Sulphur is usually extracted from underground
deposits by using the Frasch process.
 Extraction
• For areas that have no deposit of sulphur, it is
now recovered on large scale from natural
gases and crude petroleum oil.
• Selenium and tellurium are obtained from
electrolytic refining of copper.
• Most isotopes of polonium are produced by
bombarding bismuth with neutrons in a
nuclear reactor.
 Uses
• Oxygen is essential for respiration by both plants and
animals. It is largely used in iron and steel industry. O 2
is used for oxy-acetylene welding and metal cutting.
Liquid oxygen is used as oxidizer for the fuels in
rocket.
• Sulphur is largely used for making H2SO4 which is
used for making fertilizers. Other uses of sulphur
include vulcanization of rubber, production of
gunpowder, manufacture of CS2 for use in making
rayon, insecticides, fungicides etc.
 Uses
• Selenium is used in glass making for
decolourization of glass. Se is used in Xerox-
type photocopiers to make the photoreceptor to
capture images. It acts as a semiconductor and
therefore is often used in the manufacture of
rectifiers.
• Tellurium is mostly used in making steel and
other non-ferrous alloys.
 O S Se Te Po

Atomic number 8 16 34 52 84

Ground state [He]2s22p4 [Ne]3s23p4 [Ar]3d104s24p4 [Kr]4d105s25p4 [Xe]4f145d106s66p4

electronic
configuration

M.P(K) 54 388 494 725 527

B.P (K) 90 718 958 1263 1235

1st ionization 1314 999 941 869 813

energy(KJ/mol)

Atomic radius 73 104 119 142 168

(pm)

Ionic radius (pm) 140 185 198 221 -

Electronegativity 3.6 2.6 2.4 2.1 2.0

Some Physical Properties of Group

6A Elements
 Physical Properties
• Oxygen is a gas at room temperature and exists as a diatomic
molecule
• It is colourless, odourless and tasteless. When in its liquid form, it
has a blue-ish colour.
• Oxygen occurs in two allotropic forms – dioxygen (O2) and ozone
(O3). In general, O2 (or dioxygen) is the form referred to when
talking about the elemental or molecular form because it is the most
common form of the element.
• Ozone, is a pale-blue poisonous gas with a strong odour. It is a very
good oxidizing agent, stronger than dioxygen, and can be used as a
substitute for chlorine in purifying drinking water.
• Ozone at very high altitudes in the atmosphere is responsible for
protecting the Earth's surface from ultraviolet radiation.
 Physical Properties
• Sulphur is a solid at room temperature and is very unique in
its ability to form a wide range of allotropes.
• The two common crystalline forms of elemental sulphur are
rhombic which is stable at room temperature and
monoclinic sulphur which is stable at 95.5◦C.
• Selenium and tellurium also exhibit allotropy of which grey
selenium and silvery white tellurium are the only important
allotropes of these elements. Polonium, a radioactive
element, exists in two metallic allotropes .
 Properties and Periodic Trends
• They all have 6 electrons in their outermost shell,
which accounts for the similar chemical properties
among the elements.
• The metallic properties increase with increase in
atomic number.
• Melting points and boiling point increases from
oxygen to tellurium while melting point and boiling
point of polonium is less than tellurium but greater
than selenium.
 Properties and Periodic Trends
• The large difference in the melting points and
boiling points of oxygen (54 K and 90 K) to
those of sulphur (388 K and 718 K) is because
oxygen exists as a diatomic molecule (O2) while
sulphur exists as polyatomic molecule (S8).
• Electronegativity and ionization energy decrease
down the group as atomic weight increases.
• Atomic radius and ionic radius all increase
down the group.
 Anomalous Properties of Oxygen
• Oxygen is a diatomic gas while other members are
solids.
• Its small size and high electronegativity allows it to
form strong hydrogen bonding.
• Non-availability of d-orbitals in the valency shell.
• It forms p-pπ bonds to itself, carbon and nitrogen.
• Oxygen molecule is paramagnetic in nature in
gaseous, liquid and solid states and has two unpaired
electrons while the rest are diamagnetic.
 Chemical Properties
• All the elements of Group VIA react with hydrogen to form
hydrides of the type H2E (E =O, S, Se, Te or Po). Except H2O,
all other hydrides are poisonous foul smelling gases. Their
acidic character and reducing nature increases down the group.
• All these 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. Both types of oxides are acidic in
nature.
• Elements of this group react with halogens to form halides. The
main types of halides formed are: Monohalides of the type
M2X2, Dihalides of the type MX2, Tetrahalides of the type MX4,
Hexahalides of the type MX6.
 Hydrides
• The hydrides (MH2) may be formed by direct
combination of the elements (M = O – Te) with
hydrogen.
• These are water (H2O), hydrogen sulphide (H2S),
hydrogen selenide (H2Se), hydrogen telluride (H2Te)
and hydrogen polonide (H2Po).
• Water is a liquid at room temperature while others are
colourless volatile foul smelling gases.
• Water is the most abundant chemical compound and
the ocean covers almost 71% of the earth’s surface.
 Hydrides
H2O H2S H2Se H2Te

M.P(◦C) 0 -86 -65.7 -51

B.P (◦C) 100 -60 41.3 -4

Enthalpy of formation -286 20.1 73 99.6

(KJ/mol)

Bond angle(◦) 104.5 92 91 90

Bond distance (pm) 96 134 146 169

Some Physical Properties of MH2 Compounds

 Properties and Trends
• The hydrides decrease in stability from H2O to H2Te due to
increase in bond distance (H2O > H2S > H2Se > H2Te).
• They become less stable because the bonding orbitals become
larger and more diffused: hence overlap with the hydrogen 1s
orbital is less effective. The acidic character increase from H 2O
to H2Te.
• The enthalpies of formation increase from top to bottom.
• Boiling points decreases from H2O to H2S and then increases
(H2S < H2Se < H2Te < H2O) while volatility increases from H2O
to H2S and then decreases to H2Te (H2S > H2Se > H2Te > H2O).
• Low volatility and high boiling point of water is due to
hydrogen bonds.
 Oxides
• Group VIA elements form two types of oxides:
dioxides of the type MO2 and trioxides of the type
MO3.
• Dioxides can be prepared directly by burning the
elements in air. The oxides are soluble in water in
which SO2 and SeO2 forms acidic oxides while TeO2
forms amphoteric oxide and much less soluble.
 SO2
• SO2 is a colourless heavy gas with a choking smell.
• It is readily soluble in water forming hydrated SO 2.
• It can be condensed to liquid which is used as a solvent.
• SO2 acts as a Lewis base due to presence of lone pairs
of electrons.
• It acts as a reducing agent in both in acid and in
alkaline medium. For example, SO2 reduces K2Cr2O7 in
to chromium sulphate
K2Cr2O7 + H2SO4 + 3SO2 → K2SO4 + Cr2(SO4)3 + H2O
• SO2 acts as a bleaching agent in the presence of
moisture in which its bleaching action is due to
reduction.
 SO3
• Sulphur trioxide is the only important trioxide.
• It is manufactured on a large scale by reacting
SO2 with O2 in the presence of catalyst like Pt
or V2O5.
2SO2 + O2 ⎯→ 2SO3 ΔH = –196 kJ/mol
• SO3 is the anhydride of H2SO4 and it is called
sulphuric anhydride.
SO3 + H2O → H2SO4
 Oxoacids
• The oxoacids of sulphur are more numerous
and more important than those of Se and Te. To
emphasize similarities, the acids are listed in
four series:
• Sulphurous acid series
• Sulphuric acid series
• Thionic acid series
• Peroxoacid series
 Oxoacids
Formula Name Oxidation number

H2SO3 Sulphurous acid +4

H2S2O5 Pyrosulphurous acid (+ 5, + 3)

H2S2O4 Dithionous acid (+ 5, + 3)

H2SO4 Sulphuric acid +6

H2S2O3 Thiosulphuric acid – 2, + 6

H2S2O7 Pyrosulphuric acid (+ 6, + 6)

H2S2O6 Dithionic acid (+ 5, + 5)

H2Sn+2O6 Polythionic acid (+ 5, + 5)

H2SO5 Peroxomonosulphuric acid +6

H2S2O8 Peroxodisulphuric acid (+ 6, + 6)

The Oxoacids of Sulphur

 Sulphuric acid
• H2SO4 is the most important acid used in the chemical industry.
• It is manufactured by the Contact process which involves three
steps:
(i) Burning of sulphur or sulphide ores in air to generate SO2.
S + O2 →SO2
(ii) Conversion of SO2 to SO3 by the reaction with oxygen in the
presence of a catalyst (V2O5)
2SO2 + O2 →2SO3
(iii) Absorption of SO3 in H2SO4 to give Oleum (H2S2O7).
SO3 + H2SO4 → H2S2O7
• Oleum is diluted with water to get sulphuric acid of desired
concentration
H2S2O7 + H2O → 2H2SO4
• The favourable conditions for maximum yield are a pressure of 2
bar and a temperature of 720 K.
 Sulphuric acid
• Sulphuric acid is a colourless, heavy, viscous liquid.
• It dissolves in water with the evolution of a large
quantity of heat. Hence, care must be taken while
preparing sulphuric acid solution from concentrated
sulphuric acid. The concentrated acid must be added
slowly into water with constant stirring because the
reverse addition may cause explosive spurting of the
acid mixture by the steam formed.
• The aqueous solution of H2SO4 is a strong dibasic acid.
• Concentrated sulphuric acid is a strong dehydrating
agent.
 Sulphuric acid
• The largest use of sulphuric acid is in the
manufacture of fertilizers (e.g., ammonium
sulphate, superphosphate).
• It also used in petroleum refining, manufacture
of pigments, paints and dyestuff intermediates,
detergent, metallurgical applications (e.g.
Cleansing metals before enamelling),
electroplating and galvanising, storage
batteries and as a laboratory reagent.