S.

3 chemistry work
SULPHUR AND ITS COMPOUNDS
Compiled by
LUGOBE ISAAC,0771805005/0700701902

Introduction
Sulphur is in period 3 and group VI of the periodic table. It has atomic number
number 16 and electronic configuration 2.8.6.

Occurrence
It occurs in both Free State and combined state. In free state, it occurs in
underground deposits and it is widely distributed in volcanic regions. In combined
states it occurs as sulphates, sulphides (mainly hydrogen sulphide) and sulphite. It
also occurs in crude oil.

Extraction of sulpur
1. By frasch process
Sulphur is found deep below the ground (160-200) metres, this makes mining it
impossible. It is extracted by a method invented by a man called Frasch and the
method is Frasch process. Sulphur is extracted from the underground deposits by
this method basing on its low melting point.

The Frasch process

Procedure
1. Drill the Frasch pump consisting of three concentric pipes down the sulphur
deposit.
2. Super heated water (steam) at about 170˚C is then forced down the outer most
tube to melt the sulphur.
3. A jet of hot compressed air is then pumped down through the inner most tube.
This hot compressed air pumps the molten sulphur out through the middle tube to
the surface where the sulphur is cooled and solidified. The sulphur obtained is
about 99.5% pure and can be used directly.

2. From natural gas and petroleum

Natural gas obtained during the distillation of petroleum contains hydrogen sulphide.
The hydrogen sulphide can be removed by dissolving it in a suitable solvent. The gas
is removed from the solvent and one third (1/3) of the hydrogen sulphide obtained is
burnt in oxygen to form sulphurdioxide.

2H2S(g) + 3O2(g) 2H2O(l) +2SO2(g)

The sulphurdioxide reacts with the two third (2/3) of the hydrogen sulphide left to
form sulphur.
SO2(g) + H2S(g) S(s) + H 2O(l)
The water is evaporated to leave sulphur solids.

Physical properties of sulphur

1. It is a yellow solid at room temperature
2. It is a typical non metal
3. It is insoluble in water but soluble in some organic solvents e.g. methyl benzene
and carbon disulphide

Allotropes of sulphur
Sulphur has two major crystalline forms .i.e. allotropes namely

1. Rhombic sulphur (alpha sulphur, α-sulphur)

Rhombic is an octahedral crystal; its bright yellow in color; its melting point is 114˚C;
it has a density of 2.8g/cm3 and it is stable at a temperature below 96˚C.
Structure
Formation of rhombic sulphur
Shake some powdered sulphur with carbon disulphide for some time
in a test tube. (Take care to extinguish all flames from the vicinity).

Filter the content of the test tube into a dry beaker through a dry filter
paper and funnel over the mouth of the beaker; fasten a filter paper over
the mouth of the beaker and pierce a few pin holes in it, and set the
beaker aside.

The carbon disulphide will slowly evaporate depositing crystals of

rhombic sulphur which because of the slow evaporation will be large
enough for their shape to be seen.

NB The formation of the crystal takes place at room temperature.

2. Monoclinic sulphur (Beta sulphur,β-sulphur)

It is a needle shaped crystal (prismatic); it is pale yellow in color (almost
transparent); it has a melting point of 119˚C; it has a density of 1.98 g/cm 3; it is stable
above 96˚C, below 96˚C it reverts to rhombic sulphur.
Formation of monoclinic sulphur Structure
Place powdered sulphur in a very large crucible. Heat it and stir gradually while
adding some sulphur until the crucible is full of molten sulphur. Use a small flame for
heating otherwise the sulphur will burn.

Allow the sulphur to cool. After some time, a solid crust begins to form on the surface.

When the crust has formed make two holes (at wide separation) using a glass rod on it
and pour out the molten sulphur from inside which has not crystallized.

Remove the crust and observe needle shaped crystals of monoclinic sulphur formed
beneath the crust and through out the inner surface of the crucible.
Transition temperature is a temperature at which rhombic sulphur changes to
monoclinic sulphur and vice versa. At a temperature below 96˚C, rhombic sulphur
exists and as the temperature goes above 96˚C, the rhombic sulphur changes to
monoclinic form. The transition temperature is there fore 96˚C.

To show that both rhombic and monoclinic sulphur are allotropes of sulphur When the
same mass of either rhombic or monoclinic sulphur is burnt in oxygen, the same
mass of sulphur dioxide is obtained in each case and nothing else.

Question
What are the differences between monoclinic and rhombic sulphur

Other forms of sulphur

 Amorphous sulphur
This is a non crystalline form of sulphur which is insoluble in carbon disulphide(CS 2).
It is formed as an almost insoluble powder if a saturated solution of hydrogen sulphide
is oxidized by leaving it to stand in open air for some times i.e.

2H2S(aq) + O2(g) 2S(s) +2H2O(l)

(From air) (Amorhous sulphur)

 Plastic sulphur
If sulphur at its boiling point is poured into cold water, a dark-sticky (elastic) solid
called plastic sulphur is formed. Plastic sulphur is elastic because it contains zig-zag
(entangled) chains of S8 molecules.

N.B Plastic sulphur is unstable and slowly hardens to form yellow rhombic sulphur.
Plastic sulphur is not a separate allotrope of sulphur since it is not crystalline in
nature.

Action of heat on sulphur

Sulpur under goes a series of changes when it is heated. Both rhombic and monoclinic
sulphur consist of S8 molecules with different arrangements. It is this differences in
arrangement of sulphur atoms that is responsible for the different observations made
when sulphur is heated.
1. If yellow powdered sulphur is heated in the absence of air just above the melting
point (about 115˚C), it melts into a clear amber (pale yellow) mobile liquid. This
liquid is mobile because the sulphur-8 (S8) molecule rings can flow over one
another with ease.
2. On further heating (to about 160˚C), the yellow liquid becomes darker and very
viscous. This is because the S8 rings are broken and form long chains of sulphur 8
(S8) atoms. The liquid is viscous because the long chains entangle with one another
and thus do not flow readily over each other. Above 160˚C the darker viscous
sulphur liquid becomes mobile and reddish brown in color.
3. Near its boiling point (444˚C), the liquid now becomes lighter in color, thin and
more mobile (less viscous). This is because the long entangled chains break down
forming chains of S1 and S2 atoms which can flow more readily.
4. The sulphur eventually boils at 444˚C and forms a light brown sulphur vapor.

Other properties of sulphur

1. It is a reactive element and it combines directly with other elements (metals and
non metals)
a) If a piece of burning sulphur is lowered into a gas jar of oxygen, it continues to
burn even more brightly with a blue flame forming whites fumes with a choking
 smell. The white fumes with a choking smell are a mixture of white sulphur
trioxide and colorless sulphur dioxide gases.

S(s) + O2(g) SO2(g)

2S(s) + 3O2(g) 2SO3(g)
b) If mixture of iron dust (iron fillings) and powdered sulphur is heated in a hard
glass test tube, the two elements combine vigorously and a spontaneous red glow
spreads through the mixture since the reaction is exothermic. A dark grey (black)
hard mass of iron(II)sulphide is formed.

Fe(s) + S(s) FeS(s) +heat

Almost all sulphides are black.

c) Zinc reacts more vigorously with sulphur if the mixture is heated forming zinc
sulphide.

Zn(s) + S(s) ZnS(s)

d) Hot copper foil (wire) also glows in sulphur vapor forming copper(I) sulphide.

2Cu(s) + S(g) Cu2S(s)

e) Carbon combines directly with sulphur to form a liquid, carbon disulphide. Very
high temperatures are required for this reaction to occur.
C(s) + 2S(s) CS2(l)

f) Reaction with acids

Dilute acids have no effects on sulphur. However,
a) Hot concentrated sulphuric acid oxidizes sulphur to sulphur dioxide and the
sulphuric acid its self is also reduced to sulphur dioxide.

S(s) + 2H2SO4(aq) 3SO2(g) + 2H2O(l)

b) Hot concentrated nitric acid oxidises sulphur to sulphuric acid and brown
fumes of nitrogen dioxide is given off.

6HNO3(aq) + S(s) 6NO2(s) + H2SO4(aq) +2H2O(l)

Uses of sulphur
1. It is used in the making of matches, gun powder and fire works.
2. Used in the vulcanization (hardening) of rubber
3. Used in the manufacture of sulphuric acid in the contact process.
4. Used as a fungicide and in medicine, ointments and drugs used for the treatment
of skin diseases. e.g. Sulphonamide.
5. Used in the production of calcium hydrogen sulphite,Ca(HSO 3)2 that acts as a
bleaching agent in the wood pulp in manufacture of paper.
6. Sulphur is used in the manufacture of various compounds like carbon disulphide
(CS2) and sodium thiosulphide Na2S2O3 used in photography.
7. Fruit trees are sprayed with sulphur products like carbon disulphide (CS 2) to kill
insects and fungi which cause diseases.

COMPOUNDS OF SULPHUR

Hydrogen sulphide (H2S)

Laboratory preparation
It can be prepared in a laboratory by the action of dilute hydrochloric acid or dilute
sulphuric acid on iron(II) suphide. The preparation must be done in a fume cupboard
as hydrogen sulphide gas is very poisonous.
Set up of apparatus

As the acid reaches the iron (II)sulphide, effervescence begins and the hydrogen
sulphide is collected over warm water since in is soluble in cold water. If it is required
dry, the gas is passed over anhydrous calcium chloride and then collected by
downward delivery method.
Equation
FeS(s) + 2HCl(aq) H2S(g) + FeCl2(aq)

Dilute sulphuric acid may also be used

FeS(s) + H2SO4(aq) H2S(g) + FeSO4(aq)

NB
1. Concentrated sulphuric acid is never used to dry the hydrogen sulphide as it reacts
with the gas.
(3H2S(g) + H2SO4(aq) 4S(s) +4H2O(l))
2. The hydrogen sulphide prepared in this case contains some impurities especially
hydrogen chloride gas and hydrogen.

Physical properties
i) It has a strong repulsive characteristic of a rotten egg smell
ii) It is a colorless gas
iii) It is very poisonous but not as dangerous as carbon monoxide
iv) It is slightly denser than air that is why it is collected by downward delivery
v) It can be liquefied under high pressure
vi) It dissolves in cold water forming a fairly weak acidic solution

H2S(s) + (aq) H2S(aq)

The weak acid formed dissociates forming ions
H2S(aq) 2H+ (aq) + S2-(aq)

Test for hydrogen sulphide

 a) Hydrogen sulphide can easily be detected by its strong repulsive smell of rotten
eggs.
b) When hydrogen sulphide is passed through a solution of Lead(II)nitrate or
Lead(II)ethanoate, a black precipitate of lead(II)sulphide is observed.

i.e. Pb2+(aq) + S2-(aq) PbS(s)

With Lead(II)nitrate
Pb(NO3)2(aq) + H2S(g) PbS(s) + 2HNO3(aq)

With Lead(II)ethanoate
(CH3COO)2Pb(aq) + H2S(g) PbS(s) + 2CH3COOH(aq)

Chemical properties of hydrogen sulphide

1. Hydrogen sulphide burns in excess air (oxygen) with a pale blue flame forming
suphur dioxide and water vapor.
2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(g)

However, in limited supply of air, a yellow deposit of sulphur is formed.

2H2S(g) + O2(g) 2S(s) + 2H2O(g)

2. Hydrogen sulphide is a powerful reducing agent and it gives up its hydrogen to

many compounds which are therefore reduced and hydrogen sulphide itself is
oxidized to sulphur. For example

a) When sulphur dioxide is bubbled through a solution of hydrogen sulphide, a yellow

deposit of sulphur appears and water is formed.
2H2S(aq) + SO2(g) 3S(s) + 2H2O(l)

b) Hydrogen sulphide reacts with halogens to form hydrogen halides and yellow
deposits of sulphur e.g. when hydrogen sulphide is mixed with chlorine gas, a pale
yellow deposit of sulphur and white fumes of hydrogen chloride gas are produced.
H2S(g) + Cl2(g) S(s) + 2HCl(g)

When hydrogen sulphide is bubbled through bromine water, the reddish brown
bromine water is decolorized and pale yellow precipitate of sulphur appears.
H2S(g) + Br2(l) S(s) + 2HBr(aq)

c) When hydrogen sulphide is bubbled through a solution of iron(III)chloride, the

solution changes from pale yellow to pale green. This is because hydrogen sulphide
reduces iron(III)chloride (the pale yellow solution) to iron(II)chloride (a pale green
solution). The hydrogen sulphide itself is oxidized to sulphur which appears as a
yellow deposit. Hydrogen chloride gas is also formed which dissolves to form
hydrochloric acid.

2FeCl3(aq) + H2S(aq) 2FeCl2(aq) + S(s) + 2HCl(aq)

d) When hydrogen sulphide is bubbled through a solution of acidified potassium

manganate(VII), the solution changes color from purple to colorless and a yellow
deposit of sulphur is also formed. This is because, hydrogen sulphide reduces
manganate(VII) ions (purple in color) to manganese(II) ions(colorless) and the
hydrogen sulphide itself is oxidized to sulphur.

2KMnO4(aq) + 6H2SO4(aq) + 5H2S(g) K2SO4(aq) + 2MnSO4(aq) +5S(s) +8H2O(l)

e) When hydrogen sulphide is bubbled through a solution of acidified potassium

dichromate(VI) the solution changes from orange to green as a result of reduction
of the the dichromate(VI) ions to chromium(III) ions.

2K2Cr2O7(aq)+ 8H2SO4(aq)+ 3H2S(g) 2Cr2(SO4)3(aq) + 2K2SO4(aq) +5S(s) + 7H2O(l)

f) Hydrogen sulphide reduces concentrated sulphuric acid according to the following

 reaction
3H2S(g) + H2SO4(aq) 3S(s) +4H2O(l)

g) When hydrogen sulphide is bubbled through concentrated nitric acid, brown fumes
of nitrogen dioxide together with a pale yellow precipitate of sulphur are observed.

H2S(g) + 2HNO3(aq) 2NO2(g) + S(s) + 2H2O(l)

3. Hydrogen sulphide gas precipitates insoluble sulphides e.g. it precipitates black

copper(II)sulphide from blue copper(II)sulphate solution.

CuSO4(aq) + H2S(g) CuS(s) + H2SO4(aq)

OXIDES OF SULPHUR
There are two principle oxides of sulphur namely sulphur dioxide and sulphur
trioxide.

Sulphur dioxide (Sulphur (IV) Oxide), SO2

Laboratory preparation
Sulphur dioxide in the laboratory can be prepared in two ways
a) Action of concentrated sulphuric acid on copper metal
b) By action of dilute sulphuric acid or hydrochloric acid on any sulphite salt e.g
sodium sulphite(Na2SO3).

Preparation by the action of concentrated H2SO4 on copper metal

Setup

Place copper metal in the flask and arrange the apparatus as shown above.
Gently heat the mixture until when it is hot. Effervescence occurs as sulphur dioxide
is evolved.
Equation
Cu(s) + H2SO4(aq) CuSO4(aq) + SO2(g) + H2O(l)

The gas is passed through a wash bottle containing concentrated sulphuric acid to dry
the gas and it is the collected by downward delivery since it is denser than air. The gas
is not collected over water as it is very soluble in water.

Laboratory preparation of sulphur dioxide from sodium sulphite and dilute

sulphuric or hydrochloric acid
The procedure and the arrangement of apparatus remains as shown above but no
heating is required for the reaction. However, if the reaction slows down, the flask may
be heated gently.
Set up

Equation
Na2SO3(s) + 2HCl(aq) SO2(g) + 2NaCl(aq) +H2O(l)

Sodium hydrogen sulphite can also be used under the same conditions.
NaHSO3(s) + HCl(aq) SO2(g) + 2NaCl(aq) +H2O(l)

Physical properties of sulphur dioxide

1. It is a poisonous gas
2. It is a colorless gas with a characteristic pungent smell
3. It is denser than air
4. It can easily be liquefied under pressure
5. It is an acidic gas i.e. it turns moist blue litmus paper red
6. It is very soluble in water forming sulphurous acid

Chemical properties of sulphurdioxide

1. Reaction with alkalis
Sulphur dioxide is neutralized by alkalis
i) When the alkali is in excess sulphites are formed.
2NaOH(aq) + SO2(g) Na2SO3(aq) + H2O(l)

ii) When the sulphur dioxide is in excess, hydrogen sulphites are formed and water is
not a product in this case.
Na2SO3(aq)+H2O(l)+ SO2(g) 2 NaHSO3(aq)

2. As a reducing agent
In the presence of water, sulphur dioxide behaves as a reducing agent
a) When sulphur dioxide is bubbled through acidified potassium dichromate(VI)
solution, the solution changes from orange to green. This is because, sulphur
dioxide reduces chromium (VI) ions to chromium (III) ions.

K2Cr2O7(aq) + H2SO4(aq) + 3SO2(g) Cr2(SO4)3(aq) + K2SO4(aq) + H2O(l)

NB This is a characteristic test for sulphurdioxide

b) Sulphur dioxide also reduces acidified potassium Manganate(VII) to manganese (II)

sulphate. The color changes from purple to colorless and the sulphur dioxide is
itself oxidized to sulphuric acid.
 2KMnO4(aq)+ 2H2O(l)+5SO2(g) 2MnSO4(aq)+2H2SO4(aq)+K2S04(s)

This is also used as a test for sulphur dioxide.

c) When sulphur dioxide is bubbled through a solution of iron(III)suphate, the color

changes from yellow to pale green. This is because the sulphur dioxide reduces
iron (III) sulphate to iron (II) sulphate and the sulphur dioxide is oxidized to
sulphuric acid.

Fe2(SO4)3(aq) + 5SO2(g) +2H2O(l) 2FeSO4(aq) + 2H2S04(aq)

d) Sulphur dioxide reduces concentrated nitric acid to form brown fumes of nitrogen
dioxide and itself is oxidized to sulphuric acid.

SO2(g) + 2HNO3(aq) 2NO2(g) + H2SO4(aq)

e) Colored solutions of halogen are made colorless when sulphur dioxide is bubbled
through them. This is because sulphur dioxide reduces the halogens to hydrogen
halides. For example
When sulphur dioxide is bubbled through chlorine water (yellowish green liquid), a
mixture of hydrochloric acid and sulphuric acid are obtained which appear colorless.

H2O(l) + SO2(g) + Cl2(g) 2HCl(aq) +H2SO4(aq)

Bromine water (a reddish brown liquid) is turned colorless as bromine is reduced to

hydrobromic acid by sulphur dioxide.
H2O(l) + SO2(g) + Br2(g) 2HBr(aq) +H2SO4(aq)

3. As an oxidizing agent
Sulphur dioxide acts as an oxidizing agent when it reacts with reducing agents more
powerful than itself. Consider the reactions below
a) When sulphurdioxide is bubbled through a solution of hydrogen sulphide, a yellow
precipitate is observed. This is because sulphur dioxide oxidizes hydrogen sulphide
to yellow sulphur and sulphur dioxide is itself reduced to sulphur.

SO2(g) + 2H2S(aq) 3S(s) + 2H2O(l)

b) When a piece of magnesium ribbon is lowered into a gas jar of sulphur dioxide, it
continuous to burn with a bright flame to form white solids (magnesium oxide) and
a yellow solid(sulphur). This is because sulphur dioxide oxidizes magnesium to
magnesium oxide and itself is reduced to sulphur.

2Mg(s) + SO2(g) 2MgO(s) + S(s)

4. As a bleaching agent
Sulphur dioxide bleaches wet flowers like roses and hibiscus and any other wet
material by reduction. It does this by removing oxygen from the colored material.

Dye + SO2(g) +2H2O(l) Dye + H2 + H2SO4(aq)

Complex which
appears colourless

The original color of the bleached material may be restored after prolong exposure to
air due to aerial oxidation. This explains why old news papers appear yellow after some
times.

5. Reaction with oxygen

 Under normal conditions, sulphur dioxide does not react with oxygen. However when a
mixture of dry and pure sulphur dioxide and oxygen is passed over heated platinum
catalyst (or vanadium(V)oxide), sulphur trioxide gas is formed.

2SO2(g) O2(g) 2SO3(g)

6. As an acid anhydride
Sulphur dioxide is an acid anhydride, reacting with water to form sulphurous acid.

SO2(g) + H2O(l) H2SO3(aq)

Sulphurous acid is a dibasic acid and reacts with sodium hydroxide solution to form
two salts of sodium, the acid salt;sodium hydrogen sulphite (NaHSO3)and the normal
salt;sodium sulphite (Na2SO3)

NaOH(aq) + H2SO3(aq) NaHSO3(aq) + H2O(l)

2NaOH(aq) + H2SO3(aq) Na2SO3(aq) + 2H2O(l)

Uses of sulphur dioxide

1. It is used in the manufacture of sulphuric acid by contact process.
2. It is a poisonous gas and it is used in fumigation to kill germs in clothes and
houses.
3. It is used for preservation of food staff and fruits during transportation and
storage, as it prevents fermentation.
4. It is used as a bleaching agent e.g it is used to make calcium hydrogen sulphite
(Ca(HSO3)2) that makes wood pulp white in paper manufacture, used to bleach silk,
straw e.t.c.

Sulphites (SO32-)
These are salts derived from sulphurous acid.

Test for sulphite

Procedure
To a solution of substance containing sulphite, add 3 drops of barium nitrate solution
followed by excess nitric acid. (or add barium chloride solution followed by excess
hydrochloric acid)
Observation
White precipitates immediately appear which dissolve with effervescence on adding
dilute nitric acid.

Ba2+(aq) + SO42-aq) BaSO3(s)

On addition of nitric acid

BaSO3(s) + HNO3(aq) Ba(NO3)2(aq) + SO2(g) + H2O(l)

Sulphur trioxide (SO3)

Laboratory preparation
It can be prepared in the laboratory by passing a dry mixture of oxygen and sulphur
dioxide over a heated platinum catalyst or (Platinized asbestos) at a temperature of
450-500˚C.
Set up of apparatus

Equation for the reaction

2SO2(g) + O2(g) 2SO3(g)

The sulphur trioxide is seen as dense white fumes and may be solidified in a freezing
mixture of ice and a little sodium chloride. The sulphur trioxide container is protected
from atmospheric moisture by calcium chloride tube.

Properties of sulphur trioxide

1. It has very high affinity for water and combines with it violently forming sulphuric
acid.

SO3(g) + H2O(l) H2SO4(aq)

This reaction is highly exothermic i.e. it gives out a lot of heat and it is because of this
that sulphur trioxide is kept in air tight containers.

2. Sulphur trioxide combines with concentrated sulphuric acid to form fuming

sulphuric acid called oleum.
SO3(g) + H2SO4(aq) H2S2O7(l)

Sulphuric acid (H2SO4)

Large scale (Industrial) manufactureof sulphuric acid by contact process

In the manufacture of sulphuric acid by contact process, sulphur dioxide and oxygen
are the starting materials.

The sulphur dioxide is oxidized to sulphur trioxide which is then absorbed by

concentrated sulphuric acid forming oleum (fuming sulphuric acid) to which water is
added to form the sulphuric acid.

This process can be divided into the following essential stages;

a) Preparation of sulpur dioxide
Sulpur dioxide can be obtained from the following source;
i) Burning sulpur in air. This is cheap and produces sulphur dioxide in large
quantities
S(s) + O2(g) SO2(g)
ii) Roasting sulphide ores in air
4FeS2(s) + 11O2(g) 8SO2(g) + 2Fe2O3(s)
(Iron pyrite)

2ZnS(s) + 3O2(g) 2SO2(g) + 2ZnO(s)

(Zinc blende)
Other sources of sulphur dioxide include; burning of hydrogen sulphide from crude oil
in air; flue gas desulphurization in power stations e.t.c.

Oxygen is obtained from fractional distillation of liquid air.

b) Purification of the gases

The sulphur dioxide and the oxygen are purified and dried (i.e. cleared off any dust
particles and other impurities which can poison the catalyst especially if it is
platinum.
c) Preparation of sulphur trioxide
The purified gases are passed over a finely divided vanadium (V) oxide,(V2O5) catalyst
at a temperature of 450-500 C and a pressure of 2-3 atmospheres, sulphur trioxide is
formed. Vanadium (V) oxide is commonly used because it is cheaper and not easily
poisoned by impurities.
Catalyst (V2O5)
2SO2 (g) + O2 (g) 2SO3 (g)
Temp 450-500 0C
Pressure, 2-3 atm
The catalyst Vanadium (V) oxide is so effective that 95% conversion of sulphur dioxide
to sulphur trioxide is achieved at 450-500 C and 2 atmospheres. The reaction is
exothermic and there fore produces heat enough to maintain the temperature of the
catalyst.

d) Conversion of sulphur trioxide to sulphuric acid

Sulphur trioxide,SO3 must not be allowed to come in contact with water as the
reaction is intensely exothermic that it vaporizes the sulphuric acid formed (i.e.
produces a lot of mist consisting of dry droplets of H2SO4 ).

To prevent this happening, the sulphur trioxide, SO3 is absorbed in concentrated

sulphuric acid, H2SO4 to form an oily liquid called an Oleum
 H2SO4(aq) + SO3(aq) H2S2O7(l)
The oleum produced is carefully diluted to give 95-98% pure concentrated sulphuric
acid.

H2S2O7(l) + H2O(l) 2H2SO4(aq)

Summary of the contact process

Precipitato
SO
2 r- removes Drier-
removes Converter: V2O5, 450-500˚C, 2 atm.
dust and
moisture Sulphur trioxide is SO3
impurities
from the
O2 gases

Absorption
chamber- Conc.
H2SO4 absorbs SO3
forming oleum

Dilution chamber- the

oleum is diluted with
Sulphuric acid water to form
concentrated sulphuric
acid

In the above process, the following conditions favor high yield of sulphur trioxide:
 Presence of a catalyst. The catalyst must be finely divided to increase the
surface area for the reaction.
 Low temperature as the reaction is exothermic (releases heat),
 Slightly high pressure above the atmospheric pressure as the reaction is
 Accompanied by a decrease in volume.
 High concentration of oxygen or sulphur dioxide.

Properties of sulphuric acid

a) Physical properties
1. Concentrated Sulphuric acid is a dense, colorless and oily liquid.
2. Concentrated sulphuric acid has very high affinity for water and a lot of heat is
produced when the acid is diluted.
3. Concentrated sulphuric acid is hygroscopic. I.e. gradually absorbs moisture from
the air and therefore when left exposed to air, in a beaker, the total volume
gradually increases due to absorption of water. This is why it is used as a drying
agent for many of the gases.

b) Chemical properties
1. Sulphuric acid as an acid
It is the dilute sulphuric acid that reacts as a typical acid.
i. Dilute sulphuric acid ionizes to form hydrogen ions
H2SO4(aq) 2H+(aq) + SO42- (aq)
ii. Sulphuric acid liberates hydrogen gas from reactive metals e.g. Na, Mg.
 Na(s) + H2SO4(aq) Na2SO4(aq) + H2(g)

iii. It reacts with bases to form salt and water only. Since it is a dibasic acid, it
produces two types of salts, the normal salt (sulphate) when alkali is in excess
and the acidic salt (hydrogen sulphate) when the acid is in excess.
H2SO4(aq) + NaOH(aq) NaHSO 4(aq) + 2H2O(l)
H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)

iv. It reacts with carbonates and hydrogen carbonates to liberate carbondioxide gas
Na2CO3(aq) + H2SO4(aq) Na2SO4(aq) + H2O(l) + CO2(g)
Ca(HCO3)2(aq) + H2SO4(aq) CaSO4(aq) + H2O(l) CO2(g)

NB. With calcium carbonate and lead (II) carbonate, there is little effervescence and the
reaction stops soon because the sulphates formed are insoluble and form a coating
around the carbonate preventing any further attack by sulphuric acid on the
carbonate.

2. As an oxidizing agent
Hot concentrated sulphuric acid is a powerful oxidizing agent and in all reactions, it is
itself reduced to sulphur dioxide. Metals are oxidized to sulphates and non metals to
their oxides. Example include:
a) Hot concentrated sulphuric acid oxidizes copper to copper (II) sulphate and the
sulphuric acid itself is reduced to sulphur dioxide.

2H2SO4(l) + Cu(s) CuSO4(aq) +SO2(g) +2H2O(l)

b) When charcoal is heated with concentrated sulphuric acid, the charcoal is oxidized
to carbon dioxide and the sulphuric acid is reduced to sulphur dioxide.

2H2SO4(l) + C(s) CO2(aq) +2SO2(g) +2H2O(l)

c) Hot concentrated sulphuric acid oxidizes sulphur to sulphur dioxide and the
sulphuric acid itself is reduced to sulphur dioxide also.

2H2SO4(l) + S(s) 3SO2(g) +2H2O(l)

d) When a sample of hydrogen sulphide gas is bubbled through concentrated
sulphuric acid, the hydrogen sulphide is oxidized to sulphur and the sulphuric
acid is reduced to sulphur dioxide.

H2S + H2SO4(l) S(s) + SO2(g) +2H2O(l)

3. As a dehydrating agent
Concentrated sulphuric acid is a very strong dehydrating agent i.e. it removes the
elements of water from many compounds. Examples
a) When concentrated sulphuric acid is added to blue copper (II) sulphate crystals,
the copper(II)sulphate crystals gradually become white as their water of
crystallization is lost.
Concentrated H2SO4
CuSO4.5H2O(s) CuSO 4(s) + 5H2O(g)
b) When cold concentrated sulphuric acid is added to sugar crystals in an
evaporating dish, the sugar crystals turn progressively from white, to yellow then to
brown and finally to black. A spongy black mass of charcoal rises almost filling up
the dish , water vapor is given off and the dish becomes very hot as the reaction is
exothermic (generates energy).
Concentrated H2SO4
C12H22O11(s) 12C(s) + 11H2O(g) + Heat
In this reaction ,the concentrated acid removes the elements of water from sugar
leaving a black mass of carbon.
A similar action is the explanation of a very marked corrosive action of the acid on
flesh and cloth made of cotton. Cotton is largely cellulose whose simplest formula is
(C6H10O5)n.

c) Concentrated sulphuric acid dehydrates oxalic acid on heating to form a mixture of

carbon monoxide, carbon dioxide and water.
Concentrated H2SO4
H2C2O4(s) CO(g) + CO 2(g) + H2O(l)

d) Excess concentrated sulphuric acid dehydrates ethanol at a temperature of 170 C

forming ethene.
Concentrated H2SO4,170˚C
C2H5OH(l) C 2H4(g) + H2O(l)

When concentrated sulphuric acid removes elements of water from a compound with
the formation of a new compound, it is described as a dehydrating agent.

4. As a drying agent
When concentrated sulphuric acid removes water from a mixture, it acts as a drying
agent.
Concentrated sulphuric acid reacts exothermically with water. When a solution is
made, it is essential to pour the acid into water, stirring to disperse the heat evolved. It
is dangerous to add water to concentrated sulphuric acid as small pockets of water are
likely to boil.

Gases are dried by bubbling them through concentrated sulphuric acid. For basic
gases like ammonia, another drying agent is used.

Uses of sulphuric acid

1. Used in the manufacture of fertilizers like ammonium sulphate.
2. Making of paints and pigments
3. Manufacture of detergents and soap
4. Production of other chemicals such as metallic sulphates, hydrochloric acid,
hydrofluoric acid and plastics.
5. Extraction of metals and metal manufacturing including pickling to clean metallic
surfaces.
6. Extraction of alkenes in petroleum refinery.
7. With nitric acid, it is used to make dyes and explosives.

Sulphates
 These salts are derived from sulphuric acid.
All sulphates are soluble in water except barium sulphate, lead(II)sulphate and
calcium sulphate is slightly soluble in water.

Action of heat on sulphates

Most of the sulphates are resistant to heat, but if they are hydrated, they lose
their water of crystallization and become powdery upon slight heating. E.g.

Na2SO4.10H2O(s) Na2SO4(s) + 10H2O(l)

However, iron (II) sulphate, copper (II) sulphate, ammonium sulphate and
sulphates of other metals lower than copper in the reactivity series are
decomposed upon strong heating. For example
i. When a green hydrated solid of iron (II) sulphate is heated gently, it loses its
water
of crystallization which condenses on the cooler part of the test tube forming
dirty yellow anhydrous solids of iron (II) sulphate.

FeSO4.7H2O(s) FeSO4(s) + 7H2O(l)

On further heating, the anhydrous dirty yellow solids decompose giving off sulphur
dioxide (which turn orange potassium dichromate green) in addition to white
fumes of sulphur trioxide and leave a brown solid of iron (III) oxide.
2FeSO4(s) Fe 2O3(s) + SO3(g) + SO2(g)

Overall equation: 2FeSO4.7H2O(s) Fe2O3(s) + 14H2O (l) + SO3(g) +SO2(g)

ii. When a blue copper(II)sulphate crystal is heated, it loses its

water of crystallization forming white anhydrous powder of
copper(II)sulphate.

CuSO4.5H2O(s) CuSO4(s) + 5H2O(l)

On strong heating, the white anhydrous white solid decomposes into white fumes of
sulphur trioxide and a black solid residue
(copper(II)oxide).

CuSO4(s) CuO(s) + SO3(g)

Chemical test for sulphates

To the solution of the suspected sulphate in water, add barium chloride and
dilute hydrochloric acid (barium nitrate solution and dilute nitric acid can also
be used.) a white precipitate which is insoluble in excess acid indicates the
presence of a sulphate.

BaCl2 (aq) + Na2SO4 (aq) BaSO4(s) + 2NaCl (aq)

White
precipitate
(Insoluble
barium