SULPHUR AND ITS COMPOUNDS

Sulphur
Occurrence
 Sulphur occurs as free sulphur and as hydrogen sulphide in petroleum
gases

Extraction of sulphur by the Frasch sulphur pump (Frasch process)

 A hole about 30cm in diameter is dug into the soil and the hole is lined
with an iron pipe.
 A sulphur pump is sunk into the iron pipe.
 It consists of three concentric tubes; in the outermost tube, superheated
water at 1700C and at a pressure of 10 atmospheres, to keep it in a liquid
form, is sent down to the beds of sulphur.
 The sulphur melts and flows into the reservoir at the base of the pump.
 Hot compressed air under a pressure or about 15 atmospheres is sent
down through the innermost tube.

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  It pushes the molten sulphur and water up through the middle tube and it’s
collected in containers.
 Water is evaporated off and almost 99% pure sulphur is obtained.

Extraction of sulphur from natural gas

 Natural gases obtained during the refining of petroleum contain hydrogen
sulphide which is absorbed by special solvents.
 The gas is removed from the solvent and a small portion of the gas is
burnt in air to form sulphur dioxide.
2H2S(g) + 3O2(g) → 2H2O(1) + 2SO2(g)

The remaining portion of the gas is left to react with the sulphur dioxide to
formsulphur and water. The water is evaporate off.
2H2S(g) + SO2(g) → 3S(s) + 2H2O(l)

Uses of sulphur
1. Used in manufacture of sulphuric acid
2. Used to dust vines to prevent the growth of fungi.
3. Used in making calcium hydrogensulphite which is used as a bleaching agent
of wood pulp in manufacture of paper.
4. It si adde to rubber to make it hard (vulcanisation of rubber)
5. Used in manufacture of carbon disulphide which is used to ill weevils
6. Used in making ointments for treatment of skin diseases such as ringworm.

Properties of sulphur
Physical properties
It is a yellow non-metal. It is insoluble in water. It is a poor conductor of heat and
electricity.

Chemical properties
1. Action of heat on sulphur (In absence of air)
When a yellow solid of sulphur is heated, it melts at about 113 0C to a clear
amber liquid which flows easily like water. Sulphur contains small rings of
atoms, [Link] liquid flows with ease because the rings have been seperated.
On further heating at about 1600C, the sulphur becomes brown and viscous. It
flows slowly because the small rings of 8 atoms break and longer chains are
formed. These chains twist together and do not flow readily colour and mobile
again (less viscous). The chains break and become shorter which can flow
more readily. Sulphur boils at 4440C and forms a brown vapour. On cold
surfaces, the vapour condenses directly into a yellow sublimate.

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2. Combustion of sulphur (in plantiful supply of air)
When burning sulphur is plunged into a gas-jar of air, the sulphur burns with a
blue flame leaving a misty gas. The mist is due to traces of sulphur trioxide
formed smultaneously with sulphur dioxide.
S(s) + O2(g) → SO2(g)

3. Reaction with metals and non-metals

The mixture of iron filings and sulphur when heated glows red giving a black
solid of iron(II) sulphide.
Fe(s) + S(s) → Cu2S(s)
A hot copper foil glows in sulphur vapour forming a black solid, copper(I)
sulphide.
2Cu(s) + S(s) → Cu2S(s)
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)

4. Action of acids on sulphur

Dilute acids do not act upon sulphur. It is oxidised by hot concentrated
sulphuric acid with formation of sulphur dioxide.
S(s) + 2H2SO4(1) → 3SO2(g) + 2H2O(l)
Sulphur is oxidised by hot concentrated nitric acid to sulphuric acid. bromine
is added to speed up the rate of reaction.
S(s) + 6HNO3(l) → H2SO4(aq) + 6NO2(g) + 2H2O(l)

Allotropes of sulphur
Sulphur has five allotropes; monoclinic sulphur, rhombic sulphur, amorphous
sulphur, plastic sulphur and colloidal sulphur.

Experiment: Preparation of rhombic sulphur (alpha-sulphur)

Dissolve some powdered sulphur in carbon disulphide in a boiling tube. Place
it in a beaker after extinguishing all flames in the area around. Filter the
solution into another dry beaker and lace a piece of clean filter paper on top
of the beaker. Pierce some small holes in the filter paper and place the set up
near a window for a day to allow the carbon disulphide to evaporate. Large
rhombic cryastals o sulphur will form having a shape shown in the figure
below.
(Diagram)

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Experiment: Preparation of monoclinic sulphur (Beta-sulphur)
Place some powdered sulphur in an evaporating dish. Carefully heat it until it
melts. Stir and gradully add more sulphr until the crucible is full of molten
sulphur. Stop heating and allow it to cool. A crust will form on the surface of
sulphur. Carefully pierce through the crust and immediately pour off the liquid
sulphur inside. Cut away the crust by cutting around the edge of the crucible
with a knife. Small needle shaped crystals will be seen inside the evaporating
dish as shwon in the figure below.
(Diagram)

Transition temperature
This is the temperature at which a change from one form of sulphur to
another form takes place. It is 960C. rhombic sulphur is stable below 960C.
above this temperature, it slowly chnages to the monoclinic form.

Differences between rhombic and monoclinic sulphur

Rhombic sulphur consists of relatively large yellow, transulcent, octahedral
cryatals with a meting point of 1140C and density of 2.08g/cm3. Monoclinic
sulphur consists of needle shaped, pale-yellow transparent crystals with a
melting point of 1190C and density of 1.98g/cm3. Crystals of rhombic sulphur
are stable below 960C while monoclinic sulphur is stable above this
temperature.

Amorphus sulphur
Amorphous sulphur is formed by oxidation of hydrogen sulphide by air. When
a saturated solution of hydrogen sulphide is left exposed to air for about two
days. An almost white powder of amorphous sulphur is formed.
2H2S(aq) + O2(g) → 2S(s) + 2H2O(l)

Plastic sulphur
When boiling sulphur is quickly cooled by pouring into cold water, a
yellow/brown elastic solid called plastic sulphur is formed.

Colloidal sulphur
When dilute hydrochloric acid is added to dilute sodium thiosulphate, a yellow
suspension of colloidal sulphur if formed.
Na2S2O3(aq) + 2HCl(aq) → 2NaCl(aq) + H2O(l) + S(s) + SO2(g)

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Sulphur dioxide
Experiment: Laboratory preparation of sulphur dioxide
Hot concentrated sulphuric acid reacts with copper turnings giving off sulphur
dioxide. The gas is dried by passing it through a bottle containing
concentrated sulphuric acid and collected in a gas-jar by upward
displacement of air since it is denser than air, as shown in figure below.

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

Instead of using copper turnings, it is also ossible to prepare the gas by using
sodium sulphiric and dilute sulphuric acid.
Na2SO2(aq) + H2SO4(aq) → Na2SO4(aq) + H2O(l) + SO2(g)
Sulphur dioxide is very soluble in water and therefore heating reduces its
solubility in the water formed in the flask. Since sulphur dioxide is very soluble
in water, it cannot be collected over water.

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 Properties of sulphur dioxide
1. It is a colourless gas with an irritating smell.
2. It turns damp blue litmus paper red because it is acidic gas.
SO2(g) + H2O(1) → H2SO3(aq)
3. It is very soluble in water and its solubility in water can be shown by the
fountain experiment.
4. It is more dense than air.
5. It is a powerful reducing agent.
(a) When sulphur dioxide is bubbled through a solution of iron(III) salt for
sometime, iron(III) ions are reduced to iron(II) ions where the colour of the
solution changes from brown to pale green.
(b) When sulphur dioxide is dissolved in water, it forms sulphurous acid which
is a bleaching agent. Sulphurous acid takes up oxygen from the dye to
form sulphuric acid. The removal of oxygen from a dye converts the dye to
a colourless compound. This is essentailly a different reaction from that of
most bleaching agents, which oxidise the dye to a colourless compound.
(c) Sulphur dioxide reduces concentrated nitric acid to nitrogen dioxide, the
sulphur dioxide being oxidised to sulphuric acid.
SO2(g)+2HNO3(1) → H2SO4(1)+2NO2(g)
(d) Sulphuric dioxide reduces yellow acidified potassium dichromate solution
to green chronium(III) sulphate and itself oxidised to sulphuric acid. this is
a characteristic test for sulphur dioxide.
3SO2(g)+Cr2O72-(aq) +2H+(aq) → 3SO42-(aq) +2Cr3+(aq) + H2O(1)

6. Sulphur dioxide acts as an oxidising agent when it reacts with a more

powerful reducing agent than itself.
(a) Sulphur dioxide reacts with hydrogen sulphide to form a yellow deposit of
sulphur.
Sulphue dioxide oxidises hydrogen sulphide to water by supplying oxygen
and itself reduced to sulphur.
2H2S(g) + SO2(g) → 2H2O(1) + 3S(s)
(b) Burning magnesium continues to burn in sulphur dioxide for sometime
forming a white powder of magnesium oxide and sulphur.
2Mg(s) + SO2(g) → 2MgO(s) + S(s)

Uses of sulphur dioxide

1. It is used for the manufacture of sulphuric acid
2. It is used as a bleaching agent in paper industry
3. It is used as a preservative of some liquids such as orange juice where it
reacts with oxygen and prevents oxidation of the liquid.
4. It is used for fumigation of houses since it is poisonous and kills micro
organisms.

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Sulphur trioxide
Experiment: Preparation of sulphur trioxide
It is prepared by pasing a mixture of dry sulphur dioxide and dry air over heated
vanadium(V) oxide (or latinised asbestos) at a temperature of 450-500 0C as
shown in figure 4.4.. sulphur trioxide is seen as dense white fumes which are
solidified in a freezing mixture of ice and dsodium chloride.
2SO2(g) + O2(g) → 2SO3(g)

SULPHURIC ACID
Sulphuric acid is dilbastic mineral acid.

Industrial manaufacture of sulphuric acid by the contact process

Sulphur is burnt in air to produce sulphur dioxide
S(s) + O2(g) → SO2(g)

Sulphur dioxide may contain some impurities such as arsenic compounds which
may ‘poison the catalyst’, that is, make the catalyst ineffective. Therefore sulphur
dioxide is cleaned to remove the impurities then it is dried. Then sulphur dioxide
is mixed with air and passed along heated pipes containin pellets of vanadium
pentoxide (V2O5) at a temperature of 450 0C-5000C under a pressure of 200
atmospheres. Sulphur trioxide is formed.
2SO2(g) + O2(g) → 2SO3(g)
It is the close contact of the reacting gases with vanadium pentoxide which gives
the contact process its name. sulphur trioxide formed is dissolved in
concentrated sulphuric acid to produce a fuming liquid called oleum.
SO3(g) + H2SO4(l) → H2S2O7(l)
The oleum is diluted with a known amount of water to give concentrated
sulphuric acid.
H2S2O7(l) + H2O(l) → 2H2SO4(aq)
The whole process is summarised in the figure below
Sulphur
Sulphur SO2 Cleaners
Air burner and driers
Air
Catalyst
Oleum SO3 chamber
Sulphuric Dilution Absorption
acid chamber chamber

Sulphur trioxide is not dissolved in water directly because the reaction is too
exothermic leading to the boiling of the sulphuric acid produced and therefore
produces a spray of sulphuric acid which would affect the workers in the factory.

Properties of sulphuric acid

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Concentrated sulphuric acid is a colourless liquid, which does not show any
acidic properties unless water is present. A great deal of heat is produced when
concentrated sulphuric acid is diluted with water. It is therefore advisable to add
the acid to water rather than water to acid because the first droplets of water
vaporize quickly to steam and spit out droplets of concentrated acid.
Chemical properties
1. Sulphuric acid behaves as a strong acid in dilute concentration.
(a) Metals displace hydrogen from sulphuric acid.
Mg(s)+H2SO4(aq) → MgSO4(aq) + H2(g)

(b) It reacts with bases to form salt and water only.

ZnO(s)+H2SO4(aq) → ZnSO4(aq)+H2O(l)
2NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l)

(c) It reacts with carbonates and hydrogencarbonates liberating carbon dioxide.

Na2CO3(s) + H2SO4(aq) → Na2SO4(aq) + H2O(l) + CO2(g)
2NaHCO3(s) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l) + 2CO2(g)

2. When concentrated and hot, it acts as an oxidizing agent to both metals and
non-metals and it is reduced to sulphur dioxide. It accepts electrons or
supplies oxygen in its reaction.
(a) It oxidizes copper to Copper(II) sulphate. Reaction with zinc and iron
produces similar results.
Cu(s)+2H2SO4(l) → CuSO4(aq) + 2H2O(l) + SO2(g)

(b) It oxidizes sulphur and carbon to their oxides.

2S(s) + 2H2SO4(l) → 2H2O(l) +3SO2(g)
C(s) + 2H2SO4(l) → CO2(g) + 2SO2(g) + 2H2O(l)
(c) It oxidizes hydrogen sulphide to sulphur forming a yellow deposit.
H2S(g) + H2SO4(l) → S(s) 2H2O(l) + SO2(g)

3. It is a dehydrating agent. Sulphuric acid has a very affinity for water and can
remove it from substances including air, that is, it is hygroscopic. It can be
used as a drying agent for most gases.
(a) When concentrated sulhuric acid is poured onto sugar (sucrose) in a
beaker, the sugar turns yellow then brown and finally a black spongy mass
of charcoal rises filling the beaker. Steam is given off and the whole mass
becomes very hot. The acid takes out the elements of water from sugar
leaving a black mass of carbon.
C12H22O11(s) → 12C(s) +11H2O(l)
Similar reactions take place when other carbohydrates are used.
C6H12O6(s) → 6C(s) +6H2O(l)
(glucose)

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 (b) When concentrated sulphuric acid is added to blue crystals of copper(II)
sulphate (hydrated) and warmed, they change to a white solid of
anhydrous copper(II) sulphate as water of crystallization is removed by
concentrated sulphuric acid.
CuSO4.5H2O(s) → CuSO4(s) + 5H2O(l)
(c) Other substances which are dehydrated by concentrated sulphuric acid
include ethanol, methanoic acid and oxalic acid.
C2H5OH(l) → C2H4(g) + H2O(l)
Ethanol Ethane

HCOOH(1) → CO(g) + H2O(l)

Methanoic acid

H2C2O4(s) → CO(g) + CO2(g) + H2O(l)

Oxalic acid

Uses of sulphuric acid

1. It is used in car batteries and accumulators as an electrolyte
2. It is used in manufacture of fertilizers such as ammonium sulphate
3. Used in extraction of metals and also cleaning them prior to plating
4. Used in manufacture of paints

SULPHATES
Sulphate Colour Effect of heat Solubility

Lead(II) sulphate White Decomposes Insoluble

Copper(II) sulphate Anhydrous-white Decomposes Soluble

Hydrated-blue

Iron (II) sulphate Hydrated-green Decomposes Soluble

Anhydrous-white

Iron (III) sulphate Brown No effect soluble

Zinc sulphate White White Soluble

Calcium sulphate White White Insoluble

Sodium sulphate White No effect Soluble

Potassium sulphate White No effect Soluble

Aluminium sulphate White No effect Soluble

Barium sulphate White No effect Insoluble

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Ammonium sulphate White No effect soluble

Action of heat on sulphates

When a blue solid of hydrated Copper(II) sulphate is heated, water vapor is given
off as water of crystalisation, giving a white solid. On further heating, it
decomposes to form white fumes of sulphur trioxide and a black residue of
Copper(II) oxide.
CuSO45H2O(s) → CuSO4(s) +5H2O(1)
CuSO4(s) → CuO(s) + SO3(g)
Overall equation: CuSO4.5H2O(s) → CuO(s) + 5H2O(1) + SO3(g)

Hydrated iorn(II) sulphate (green) loses its water of crystallisation when heated to
form a white solid. On further heating, it decomposes to give white fumes of
sulphur trioxide together with sulphur dioxide and a reddish brown solid of
iron(III) oxide.
FeSO4.7H2O(s) → FeSO4(s) +7H2O(l)
2FeSO4(s) → Fe2O3(s) + SO3(g) + SO2(g)
Overall equation: 2FeSO4.7H2O(s) → Fe2O3(s) + 14H2O(l) + SO3(g) + SO2(g)

Testing for soluble sulphate (SO42-)

To the solution of the suspected suplhate in water, add dilute hydrocholoric
acid followed by barium chloride solution (barium nitrate solution and
dilute nitric acid can be used). A white precipiate of barium sulphate which is
insoluble in the acid indicates the presnece of a sulphate ion.
BaCl2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaCl(aq)
Ba(NO3)2(aq) + Na2SO4(aq) → BaSO4(s) + 2NaNO3(aq)
Or Ba2+(aq) + SO42-(aq) → BaSO4(s)

Carbonate ions (CO32-) and sulphite ions (SO32-) are precipitated as barium
arbonate and barium sulhite respectively, if carbonate and sulphite ions are
present in solution.
Ba2+(aq) + CO32- + CO32-(aq) → BaCO3(s)
Ba2+(aq) + SO32-(aq) → BaSO3(s)

The purpose of adding dilute nitric acid hydrochloric acid is to remove the
carbonate ions and the sulphite ions if they are present in solution.
2H+(aq) SO32-(aq) → H2O(l) + SO2(g)
2H+(aq) + CO32-(aq) → H2O(l) + CO2(g)

The sulphate ions (SO42-) remain in solution because they do not react with
dilute hydrochloric acid or nitric acid. also lead(II) nitrate solution forms a white
precipitate of lead(II) sulphate with a sulphate.
Pb2+(aq) + SO42-(aq) → PbSO4(s)

HYRDOGEN SULPHIDE
Experiment: Laboatory preparation of hydrogen sulphide

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As the acid reaches the iron(II) sulphide, effervescence begins and hydrogen
sulhide is collected over warm water because it is quite solule in cold water
(Diagram)

FeS(s) + 2HCl(aq) → FeCl2(aq) + H2S(g)

Dilute sulphuric acid may be used
FeS(s) + H2SO4(aq) → FeSO4(aq) + H2S(g)
To prepare hydrogen sulphide from sulphur, iron(II) sulphide is first prepared by
heating a mixture of iron and sulphur.
Fe(s) + S(s) → FeS(s)
Hydrogen sulphide can be dried by using anhydrous calcium chloride.
Concentrated sulphuric acid is not used to dry the gas because it reacts with
hydrogen sulphide forming a yellow precipitate of sulphur.
H2SO4(1) 3H2S(g) → 4H2O(1) + 4S(s)

Testing for hydrogen sulphide

A strip of filter paper is soaked in Lead(II) ethanoate solution and dropped into a
gas-jar of hydrogen sulphide. The paper turns black. This colour change is
caused by precipitation of black Lead(II) sulphide.
(CH3COO)2Pb(aq) +H2S(g) → 2CH3COOH(aq) + PbS(s)

PROPERTIES OF HYDROGEN SULPHIDE

Physical properties
1. The gas is colorless and has a repulsive smell similar to that of a rotten egg. It
is in fact given off from rotting eggs and also from decaying cabbages both of
which contain sulphur.
2. It is also fairly soluble in water forming a weak acidic solution.
3. It is denser than air.
4. The gas is extremely poisonous.

Chemical properties
1. Hydrogen sulphide is a powerful reducing agent
It reduces oxidizing agents and itself oxidized to sulphur which appears as a pale
yellow precipitate.
a) Hydrogen sulphide reduces iron (III) chloride to iron (II) chloride. When
hydrogen sulphide is passed through iron (III) chloride solution (yellow), a

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 yellow precipitate of sulphur appears. On filtering, a green solution of iron (II)
chloride appears as the filtrate.
2FeCI3 (aq) +H2S (g → 2FeCI2 (aq) + 2HCI (aq) +S(s)
b) Hydrogen sulphide reacts with concentrated nitric acid to form brown fumes of
nitrogen dioxide and a yellow deposit of sulphur. Also the mixture becomes
hot. The hydrogen sulphide reduces the nitric acid to nitrogen dioxide.
2HNO3 (I) + H2S (g) → 2H2O (1) + 2NO2 (g) + S(s)

2. Combustion of Hydrogen sulphide

a) With a plentiful supply of air
Hydrogen sulhide burns with a blue flame forming water and sulphur dioxide.
2HsS (g) +3O2 → 2H2O (1) + 2SO2 (g)

b) With a limited supply of air

When hydrogen sulphide is burnt in a limited supply of air, a yellow deposit of
sulphur is formed. The oxygen supply cannot oxidize the gas completely and
therefore free sulphur is deposited.
2HsS(g) + O2(g) → 2S(S) + 2H2O(1)

3. Reaction with salts of metals

Hydrogen sulphide can precipitate insoluble sulphide of copper and lead only
by reacting with solutions o their salts. A dark brown precipitate of copper (II)
sulphide and a black precipitate of lead (II) sulphide are formed.
CuSO4(aq) + H2S(g) → CuS(S) + H2SO4(aq)
Pb(NO3)2(aq) + H2S(g) → PbS(s) + 2HNO3(aq)

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