Group 16

16 August 2022 22:56

THE GROUP 16 ELEMENTS – CHALCOGENS

The first four elements are non-metals.

Collectively they are called ‘the chalcogens’ or ore–forming elements, because a large number of metal ores are
oxides or sulphides.

O and S are totally non-metallic. Non-metallic character is weaker in Se and Te. Po is markedly metallic, and
is also radioactive and short-lived.

Oxygen is a very important element in inorganic chemistry, since it reacts with almost all the other elements.

Most of its compounds are covered under the other elements. S, Se and Te are moderately reactive and burn in air
to form dioxides.

They combine directly with most elements, both metals and non-metals, though less readily than with O.

As expected for non-metals, S, Se and Te are not attacked by acids except those which are oxidizing agents.

Oxygen shows several differences from the rest of the group.

These are associated with its smaller size, higher electronegativity, and the lack of suitable d orbitals.

Oxygen can use p orbitals to form strong double bonds.

The other elements can also form double bonds, but these become weaker as the atomic number increases.

Thus CO2 (O=C=O) is stable, CS2 less stable, CSe2 polymerizes rather than form double bonds and CTe2 is
unknown.

Sulphur shows a much greater tendency to form chains and rings than the other elements .

The filling of the 3d shell affects the properties of Ge, As, Se and Br.

The atoms are smaller, and the electrons are held more tightly.

This is the reason why Se is reluctant to attain the highest oxidation state of (+VI) shown by S.

Thus HNO3 oxidizes S to H2SO4 but only oxidizes Se to H2SeO3 .

All compounds of Se, Te and Po are potentially toxic, and should be handled with care.

Organo derivatives, and volatile compounds such as H2Se and H2Te, are 100 times more toxic than HCN.

The atmospheric chemistry of acid rain is not fully understood. SO2 is oxidized by ozone or hydrogen peroxide
to SO3. This reacts with water or hydroxyl radicals to give H2SO4.
Acid rain causes damage to trees, plants and buildings, and causes respiratory ailments in man and animals.
About 60% of atmospheric SO2 comes from coal fired power stations. Most of the rest comes from oil refineries,
oil fired power stations and smelters.

Dioxygen is paramagnetic and therefore contains two unpaired electrons.

Liquid dioxygen is pale blue in colour, and the solid is also blue.

Low concentrations of O3 can be made by UV irradiation of O2.

O3 is an unstable, blue, diamagnetic gas, b.p. – 112°C.

It is dark blue in liquid state and violet-black in solid state. It also absorbs strongly in the UV region.

The gas is toxic, and continuous exposure to concentrations of 0.1 ppm must be avoided.

The decomposition is exothermic.

Ionization energies are less than those of nitrogen family.

M.pt and B.pt increases with the increase in atomic number as we move down the group because of the increase
in magnitude of the van der Waals forces.

They are less metallic due to high ionisation energy.

O<S <Se<Te <Po

Non metal Metalloid Metal

They have high electron affinity

S>Se>Te>Po>O

Density increase down the group

All the elements exhibit allotropy

O2,Te and Po have 2 allotropic forms

Sulphur has most allotropes than any other elements

Se has six allotropes

Tendency to form P𝝅-d𝝅 multiple bonds decreases from S to Te

Dioxygen:

It occurs in three isotopic forms

Preparation

2Pb3O4 → 6PbO + O2

3MnO2 → Mn3O4 + O2
3KClO3 → 2KCl + 3O2

Properties

It is colourless, Odourless and tasteless diatomic gas

It is paramagnetic in nature and liquifies to give pale blue liquid

It is neutral oxide and supporter of combustion

All most all metals form oxides

USES

In steel manufacturing

In oxy-hydrogen and oxy-acetylene welding torches.

Liquid oxygen is used in rocket propellants

Used as an oxidising agent

Classification of oxides

Classification based on structure

First consider the classification according to their geometric structure. In this way oxides are classified as normal
oxides, peroxides or suboxides.

Normal oxides
In these, the oxidation number of M can be deduced from the empirical formula MxOy, taking the oxidation
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 H2O2 (H—O—O—H),

peroxomonosulphuric acid and peroxodisulphuric acid

Suboxides
They contain less oxygen then would be expected from the oxidation number of M.

They involve M-M bonds in addition to M-O bonds

O=C=C=C=O

Superoxides contains O2- ions, mixed oxides contain Pb3O4, Fe3O4 etc..

Classification based on reaction with water

Acidic oxides

Mostly non metallic, covalent, discrete molecules

Some like B2O3 and SiO2 form infinite giant molecules

CO2, SO2, Cl2O, SO3 etc..

Basic oxides

Metallic oxides are generally basic. Most metal oxides are ionic and contain the O2− ion.

The oxides of the more electropositive metals, Groups 1 and 2, and the lanthanides are typical.

A large amount of energy is required to form an ionic oxide.

This is because the O2 molecule must first be broken into atoms, and then the energy (the electron affinity)
required to add two electrons to form O2− is also large.

Thus ionic oxides are formed by compounds with high lattice energy.

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.

Where a metal can exist in more than one oxidation state, and thus form more than one oxide, e.g. CrO, Cr2O3,
CrO3, PbO, PbO2, and Sb4O6, Sb4O10, the 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

Al2O3 + 6HCl → 2Al3+ + 6Cl- + 3H2O

Al2O3 + 2OH- + 3H2O → 2[Al(OH)4]-

Neutral oxides

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

OXIDES OF SULPHUR

Dioxide

SO2 is produced commercially on a vast scale:

1. By burning S in air. S+O2 → SO2

2. By burning H2S in air. 2H2S + 3O2 → 2SO2 + 2H2O

By roasting various metal sulphide ores with air

SO2 is a colourless gas , which has a choking smell, and is very soluble in water .

The SO2 in solution is almost completely present as various hydrated species such as SO2∙ 6H2O and the solution
contains only a minute amount of sulphurous acid H2SO3.

SO2 levels above 5 ppm are poisonous to man.

SO2 gas forms discrete V-shaped molecules, and this structure is retained in the solid state.

The bond angle is 119°30′.

SO2 can act as an oxidizing agent.

SO2 may be detected in the laboratory:

1. By its smell.

2. Because it turns a filter paper moistened with acidified potassium dichromate solution green, due to the
formation of Cr3+ .

K2Cr2O7 + 3SO2 + H2SO4 → Cr2(SO4)3 + K2SO4 + H2O

It turns starch iodate paper blue

2KIO3 + 5SO2 + 4H2O → 2KHSO4 + 3H2SO4 + I2

SeO2 : Solid, polymeric-infinite non planar chain

TeO2, PoO2………..Ionic crystals

Basic character of oxide increases down the group

SO2 has also been used as a non-aqueous solvent.

Trioxide

SO3 is the only important trioxide.

It is manufactured on a huge scale by the Contact process in which SO2 reacts with O2 in the presence of a
catalyst (Pt or V2O5).

Most of the SO2 produced is oxidized to SO3 by the Contact process, and used to manufacture H2SO4.

2SO2(g) + O2(g) ⇌2SO3(g)

SO3 reacts vigorously with water, evolving a large amount of heat and forming H2SO4.

The SO3 reacts with water vapour and causes the formation of a dense mist of H2SO4 droplets, which are difficult
to condense and pass out of the absorber into the atmosphere.
To avoid this, it has been found best to dissolve SO3 in 98–99% H2SO4 in ceramic packed towers, to give oleum
or fuming sulphuric acid.

This is mainly pyro sulphuric acid H2S2O7.

Water is continuously added to keep the concentration of H2SO4 constant.

H2S2O7 + H2O → 2H2SO4

In the gas phase SO3 has a plane triangular structure

SO3 is a powerful oxidizing agent, especially when hot. It oxidizes HBr to Br2 and P to P4O10. Commercially SO3

is important in the manufacture of H2SO4.

OZONE

It is an allotropic form of oxygen

It is formed due to the action of ultraviolet rays on the oxygen of the air

3O2 ⇌ 2O3 (Electric discharge)

Oxygen is never completely converted into ozone and always obtain a mixture of oxygen and ozone. It is called
ozonized oxygen.

Ozone absorbs radiation strongly in the ultraviolet region

Pure ozone is a blue gas, with a strong irritating smell.

It is slightly soluble in H2O, but highly soluble in turpentine oil, acetic acid and CCl4.

It is diamagnetic and toxic in high concentration

It is powerful oxidizing agent.

4O3 + PbS → 4O2 + PbSO4

It acts as a good bleaching agent due to its oxidizing nature.

Ozone bleaches in absence of moisture so it is also known as dry bleach.

It is used to sterilize drinking water

It is useful as bleaching agent for bleaching of different fabrics

ALLOTROPIC FORMS OF SULPHUR

Rhombic Sulphur

It is more stable

It is also called ∝ Sulphur

It is insoluble in H2O but soluble in CS2

It has puckered ring structure

Monoclinic Sulphur

It is stable only above 95.6oC, below this it changes into Rhombic form.

It is also called 𝛽 Sulphur

It is insoluble in H2O but soluble in CS2

It has long needle shaped crystals

It is in form of S8

Plastic Sulphur

It is obtained by pouring boiling Sulphur in cold water

It is amorphous form of Sulphur and does not have sharp m.p.

It is also called 𝛾 Sulphur

It is insoluble in H2O and CS2

It contains long S8 rings and chains of a large number of Sulphur atoms

It is also regarded as super cooled liquid

Density : ∝ Sulphur > 𝜷 Sulphur > 𝜸 Sulphur

Oxoacids of sulphur

Sulphurous acid (H2SO3)

Oxidation state is +4, dibasic

Two series of salts, sulphites and bisulphites
Act as reducing agent as well as oxidizing agents
Free acid does not exist

Dithionous acid (H2S2O4)

Oxidation state is +3, dibasic

Sulphuric acid (oil of vitriol) (H2SO4)

Oxidation state is +6, dibasic

Two series of salts, sulphates and bisulphates
Act as oxidising agent and dehydrating agent

Preparation

H2O + SO3 → H2SO4

SO3 + HNO3 → H2SO4 + NO2

Contact process
/
2SO2 + O2 ⎯⎯⎯⎯⎯⎯⎯ 2V2O5

SO3 + H2SO4 → H2S2O7 (oleum)

Oleum may then be diluted with calculated quantity of H2O to get H2SO4 of required concentration

H 2S 2 O 7 + H 2O → H2SO4

Lead chamber process

2SO2 + O2 + H2O + [NO] → H2SO4 + [NO]

Pure H2SO4 is colourless but commercial acid is yellow in colour due to presence of impurities

FeS + H2SO4 → FeSO4 + H2S

Sucrose + Conc. H2SO4 → 12C + 11H2O

Oxalic acid + Conc H2SO4 → CO2 + CO + H2O

Thiosulphuric acid (H2S2O3)

Oxidation state are -2 and +6

Free acid does not exist but salts are stable
Acts as reducing agents
It can form thiosulphates

Peroxomonosulphuric acid (Caro's acid) (H2SO5)

Oxidation state is +6

Monobasic and forms peroxydisulphates

Stable crystalline and hygroscopic acid

Powerful oxidising agent

Disulphuric acid / pyrosulphuric acid / oleum / fuming sulphuric acid (H2S2O7)

Oxidation state is +6

Dibasic and forms pyrosulphates

Strong oxidising

Powerful dehydrating agent

Peroxodisulphuric acid (H2S2O8) (Marshall's acid)

Oxidation state is +6

Forms peroxydisulphates

Stable crystalline and hygroscopic solid

Strong oxidising agent

Dithionic acid (H2S2O6)

Oxidation state is +5

Dibasic and forms dithionates

Free acid is not known

∆
H2S2O6 → H2SO4 + SO2

Polythionic acid (H2SnO6) (n= 3 to 6)

Oxidation state +5 and 0

Dibasic and forms polythionates

Stable

Oxoacids of Se and Te

Se ….. H2SeO3 Selenious acid

….. H2SeO4 Selenic acid

Te H2TeO6 [Te(OH)6] Telluric acid

OXOHALIDES

Thionyl compounds

The following thionyl compounds are known SOF2, SOCl2, SOBr2

The structure of these oxohalides is tetrahedral with one position occupied by a lone pair.

Most thionyl compounds are readily hydrolysed by water, though SOF2 only reacts slowly.

SOCl2 + H2O → SO2 + 2HCl

Sulphuryl compounds

The following sulphuryl halides are known SO2F2, SO2Cl2, SO2FCl, SO2FBr

Sulphuryl chloride SO2Cl2 is a colourless fuming liquid and is made by direct reaction of SO2 and Cl2 in the
presence of a catalyst.
It is used as a chlorinating agent.

Sulphuryl fluoride is a gas and is not hydrolysed by water, but the chloride fumes in moist air and is hydrolysed
by water.

The sulphuryl halides have a distorted tetrahedral structure.

They may be regarded as derivatives of H2SO4, where both OH groups have been replaced by halogens.

If only one group is replaced, halosulphuric acids are obtained.

FSO3H, ClSO3H, BrSO3H

Fluorosulphuric acid forms many salts, but chlorosulphuric acid forms none and is used as a chlorinating agent in
organic chemistry.

HYDRIDES

The elements all form covalent hydrides. These are water H2O, hydrogen sulphide H2S, hydrogen selenide H2Se,
hydrogen telluride H2Te and hydrogen polonide H2Po. Water is liquid at room temperature, but the others are all
colourless, foul smelling toxic gases.

H2O > H2S > H2Se > H2Te

Stability, Volatile character (except H2O), Bond angle, Ionic character

H2O < H2S < H2Se < H2Te

Poisonous nature, acidic nature, reducing character, weakening of M-H bond with increase in size,

More acidic hydride is more stable salts it forms.

Halides
Hexahalides are formed by F

Covalent in nature

Hybridization SP3d2

Tetrahalide are lewis acid

Hybridization is SP3d

Hybridization of dihalide is SP3

ANOMALOUS BEHAVIOUR OF OXYGEN

It is due to

Smaller size, High value of ionization energy & electronegativity

• Absence of d-orbitals in the valence shell

• Oxygen is a diatomic gas while the other elements exist as octa-atomic orbitals at room temperature

• Molecular O2 is paramagnetic whereas the molecules of other members are diamagnetic in nature

• Oxygen shows only +2 positive oxidation state, others can show +2, +4, +6 oxidation state

• H2O is liquid, while other hydrides are gas at room temperature

• Oxygen forms P𝜋-P𝜋 double bonds with the elements having similar size such as C, N etc.

• Oxygen shows a maximum covalency of two while other members can show a maximum covalency of six.