Page 1 of 20 SULPHUR AND ITS COMPOUNDS

SULPHUR AND ITS COMPOUNDS

Sulphur is a non-metal found in group VI of the periodic table just below oxygen. Its atomic number is 16
and its electronic configuration is 2:8:6.

OCCURRENCE

Sulphur occurs in the free or uncombined state as underground deposits in some places such as Sicily,
Japan, Louisiana and Texas.

In the combined state, it occurs in:

 Some metal ores such as: Galena (PbS), Zinc blende (ZnS), Iron pyrites (FeS), Copper pyrites (CuFeS2 ).
 Natural gas mainly as hydrogen sulphide.
 Sulphates such as barite (BaSO4 ) and gypsum (CaSO4 · 2H2O)

EXTRACTION OF SULPHUR (THE FRASCH PROCESS)

Sulphur is extracted from underground deposits by the Frasch process, invented in 1891 by the American
chemist Herman Frasch.

In the process, a hole, about 30cm in diameter, is drilled through the soil layers to the sulphur bed. A
sulphur pump made up of three concentric pipes is sunk down the hole to the sulphur bed. Super-heated
water at about 170℃ and under a high pressure of about 10atm is forced through the outermost pipe to
the sulphur bed. This melts the sulphur (the low melting point of sulphur; 115℃, is of advantage here).

Hot compressed air at a pressure of about 15atm is blown down through the innermost pipe to force the
molten sulphur out through the middle pipe. This molten sulphur is prevented from solidifying by the high
temperature maintained in the middle pipe by heat from the super-heated water in the outermost pipe and
from the hot compressed air in the innermost pipe.

The molten sulphur is pumped continually to the surface, where it is allowed to cool in large tanks. The
molten sulphur solidifies and is separated from the sulphur-water emulsion by decantation. The sulphur
obtained is about 99% pure.

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Sulphur is not usually mined from the underground deposits because:

 The top soils on the underground deposits are usually made up of quick sand which is loose; hence the
mines can easily collapse and kill the miners.
 Poisonous gases like H2 S, HCl and SO2 can be encountered endangering the lives of the miners.
 Sulphur obtained from mining is of lower purity.
 The mining process is tedious and more costly
THE USES OF SULPHUR

1. Sulphur is used in the manufacture of sulphuric acid.

2. It is used in the vulcanization of rubber, a process which converts the soft, pliable natural rubber into
the hard, tough rubber of which car tyres and similar products are made.
3. It is used in the manufacture of gunpowder and matches.
4. It is used to make skin ointments, drugs and dyes.
5. It is used to make calcium hydrogensulphite,Ca(HSO3 )2 which is a bleaching agent for wood pulp that is
used to manufacture paper.
6. It is used to make fungicides and insecticides for spraying crops.

ALLOTROPES OF SULPHUR

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Sulphur exhibits allotropy, which is the existence of an element in two or more different forms but in the
same physical state. The various forms are known as allotropes.

ALLOTROPES OF SULPHUR

Some allotropes of sulphur are crystalline while others are amorphous (non-crystalline).

CRYSTALLINE ALLOTROPES OF SULPHUR

These are:
 Rhombic sulphur (𝛼-sulphur)
 Monoclinic sulphur (𝛽-sulphur)

RHOMBIC SULPHUR (𝜶-SULPHUR)

Its crystals are octahedral in shape and bright yellow in colour. It is stable at temperatures below 96℃. Its
density is 2.06g/cm3 and melting point is 113℃. Sulphur exists naturally in this form.

MONOCLINIC SULPHUR (𝜷-SULPHUR OR PRISMATIC SULPHUR)

Its crystals are thin, needle-shaped and amber-coloured. It is stable at temperatures above 96℃ and below
119℃. Its density is 1.96g/cm3 and melting point is 119℃.

Rhombic sulphur changes into monoclinic sulphur when heated above 96℃, while monoclinic sulphur
changes into rhombic when cooled below 96℃

96℃ is called the transition temperature for rhombic and monoclinic sulphur.

Definition: This is the temperature above which rhombic sulphur changes into monoclinic and below which
monoclinic sulphur changes into rhombic sulphur.

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Rhombic and monoclinic sulphur are both made up of puckered rings of the S8 molecules which are
arranged differently giving rise to different crystal structures.

Remark: Both rhombic and monoclinic sulphur burn in oxygen to produce sulphur dioxide. This reaction can
be used as a chemical test to show that rhombic and monoclinic allotropes are forms of the same element.

AMORPHOUS ALLOTROPES OF SULPHUR

There are two main types:

 Plastic sulphur
 Flowers of sulphur

PLASTIC SULPHUR

It is made by heating powdered sulphur until it boils, and then pouring the hot liquid into cold water. The
resulting substance is plastic sulphur. It is a yellow or brown solid somewhat elastic like rubber.

FLOWERS OF SULPHUR

When sulphur vapour is rapidly cooled, a fine yellow powder called flowers of sulphur is produced.

PROPERTIES OF SULPHUR

a) PHYSICAL PROPERTIES
1. Sulphur is a yellow solid.
2. Its melting point is 115℃ and boiling point is 444℃
3. It is insoluble in water but soluble in non-polar solvents such as carbon disulphide.
4. It does not conduct electricity.

b) CHEMICAL PROPERTIES
1. Reaction with metals: Sulphur combines directly with most metals to form sulphides when heated in
the absence of air. Examples:
Zn(s) + S(s) → ZnS(s)
⏟
𝐙𝐢𝐧𝐜 𝐬𝐮𝐥𝐩𝐡𝐢𝐝𝐞

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Fe(s) + S(s) → FeS(s)
⏟
𝐈𝐫𝐨𝐧 (𝐈𝐈) 𝐬𝐮𝐥𝐩𝐡𝐢𝐝𝐞

Cu(s) + S(s) → Cu2 S(s)

⏟
𝐂𝐨𝐩𝐩𝐞𝐫 (𝐈) 𝐬𝐮𝐥𝐩𝐡𝐢𝐝𝐞

2. Reaction with non-metals:

a) With oxygen: Sulphur burns in a plentiful supply of oxygen with a bright blue flame and sulphur dioxide

is produced.

S(s) + O2 (g) → SO2 (g)

b) With hydrogen: Sulphur reacts with hydrogen at high temperatures and hydrogen sulphide is formed.

H2 (g) + S(s) → H2 S(g)

c) With carbon: Sulphur combines with red-hot coke and a colourless liquid called carbon disulphide is

formed.

C(s) + S(s) → CS2 (l)

3. Reaction with concentrated nitric acid: Hot concentrated nitric acid oxides sulphur to sulphuric acid

and is reduced to nitrogen dioxide.

S(s) + 6HNO3 (aq) → H2 SO4 (aq) + 6NO2 (g) + 2H2 O(l)

4. Reaction with concentrated sulphuric acid: Sulphur is oxidized to sulphur dioxide by hot concentrated

sulphuric acid.

S(s) + 2H2 SO4 (aq) → 3SO2 + 2H2 O(l)

COMPOUNDS OF SULPHUR

A. HYDROGEN SULPHIDE (𝐇𝟐 𝐒)

It is a hydride of sulphur which is usually present in volcanic gases, sulphur springs and in gases from the
decay of organic matter containing sulphur.

LABORATORY PREPARATION OF HYDROGEN SULPHIDE

In the laboratory, hydrogen sulphide is prepared by the action of dilute hydrochloric acid on iron (II)
sulphide.

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Apparatus:
Some iron (II) sulphide is put in a flat-bottomed flask and the apparatus is set up as shown below in a fume
cupboard because hydrogen sulphide is a poisonous gas.

Procedure:
 Dilute hydrochloric acid is added through the thistle funnel to the iron (II) sulphide in the flask.
 As the acid reaches the iron (II) sulphide, effervescence occurs and hydrogen sulphide gas in evolved.
2HCl(aq) + FeS(s) → FeCl2 (aq) + H2 S(g)
 The gas produced is collected over warm water because hydrogen sulphide is less soluble in warm
water than in cold water.
 If the gas is required dry, it is passed through a U-tube containing fused anhydrous calcium chloride to
dry it.
 The dry gas is then collected by downward delivery since it is denser than air.

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Hydrogen sulphide can also be prepared using the Kipp’s apparatus. This apparatus is also to
obtain gases like H2, CO2, etc and its made up of 3 chambers A, B and C. the solid reactant is
placed in B while dilute HCl is poured through A into C. when the tap T is opened, the
pressure inside B drops enabling the acid in C to rise into B reacting with FeS to form H2S
which is collected through the tap T.
 When the tap T is closed, the pressure in B increases thereby pushing back the acid
into C and out of contact with FeS. The production of H2S therefore stops until the tap T is
reopened.

PROPERTIES OF HYDROGEN SULPHIDE

a) Physical properties
 It is a colourless gas with repulsive smell like that of a rotten egg.
 It is extremely poisonous and so should always be prepared in a fume cupboard.
 It denser than air.
 It moderately soluble in water.

b) Chemical properties
1. Reaction with air: Hydrogen sulphide burns in a plentiful supply of air with a blue flame to give sulphur
dioxide and water.
2H2 S(g) + 3O2 (g) → 2SO2 (g) + 2H2 O(l)
In a limited supply of air, sulphur is deposited.
2H2 S(g) + O2 (g) → 2S(s) + 2H2 O(l)

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2. Acidic properties: Hydrogen sulphide is an acidic gas and ionizes slightly in warm water to form a weak
dibasic acid. This acid neutralizes alkalis to give salts and water e.g. it neutralizes sodium hydroxide to
give sodium sulphide, Na2 S.
2NaOH (aq) + H2 S(g) → Na2 S(aq) + 2H2 O(l)
With excess hydrogen sulphide, sodium hydrogensulphide is formed.
NaOH (aq) + H2 S(g) → NaHS(aq) + H2 O(l)

3. As reducing agent: It is a strong reducing agent and when it reduces, it is oxidized to sulphur which is
deposited as a yellow solid.
 It reduces concentrated sulphuric acid to sulphur dioxide and water.
H2 S(g) + H2 SO4 (aq) → SO2 (g) + 2H2 O(l) + S(s)
As a consequence, concentrated sulphuric acid cannot be used to dry hydrogen sulphide.
 It reduces halogens in aqueous solution to the corresponding hydrogen halides, e.g.
Cl2 (aq) + H2 S(g) → 2HCl(aq) + S(s)
 It reduces the brownish-yellow iron (III) chloride solution to greenish iron (II) chloride solution.
2FeCl3 (aq) + H2 S(g) → 2FeCl2 (aq) + 2HCl(aq) + S(s)
 It reduces moist sulphur dioxide to sulphur.
2H2 S(g) + SO2 (g) → 3S(s) + 2H2 O(l)
 It decolourises the purple colour of acidified potassium permanganate and sulphur is deposited as a
yellow solid. The change in colour is due to the reduction of the purple manganate (VII) ions (MnO−
4 ) to

the very pale pink manganese (II) ions (Mn2+ ).

2KMnO4 (aq) + 3H2 SO4 (aq) + 5H2 S(g) → K 2 SO4 (aq) + 2MnSO4 (aq) + 8H2 O(l) + 5S(s)
 It changes the colour of acidified potassium dichromate from orange to green with a yellow deposit of
sulphur. The colour change is due to the reduction of orange dichromate ions (Cr2 O2−
7 ) to the green

chromium (III) ions (Cr 3+ )

K 2 Cr2 O7 (aq) + 4H2 SO4 (aq) + 3H2 S(g) → K 2 SO4 (aq) + Cr2 (SO4 )3 (aq) + 7H2 O(l) + 3S(s)
 Hydrogen sulphide reduces concentrated nitric acid to nitrogen dioxide.
2HNO3 (aq) + H2 S(g) → 2H2 O(l) + 2NO2 (g) + S(s)

4. As a precipitating agent: It precipitates metal sulphides from solutions of their salts, e.g.
FeSO4 (aq) + H2 S(g) → FeS(s)
⏟ + H2 SO4 (aq)
Black precipitate

ZnSO4 (aq) + H2 S(g) → ZnS(s)

⏟ + H2 SO4 (aq)
White precipitate

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Pb(NO3 )2 (aq) + H2 S(g) → PbS(s)
⏟ + 2HNO3 (aq)
Black precipitate

TESTS FOR HYDROGEN SULPHIDE

1. Hydrogen sulphide smells like a rotten egg and turns a filter paper moistened with lead (II) nitrate
solution black due to the deposition of a black precipitate of lead (II) sulphide.
2. Hydrogen sulphide changes the colour of acidified potassium dichromate from orange to green leaving
a yellow deposit of sulphur.
3. Hydrogen sulphide decolourizes the purple colour of potassium permanganate with yellow deposit of
sulphur.

USES OF H2S

It is used for the analysis of metals and their ores

SULPHIDES

These are the salts of the weak dibasic acid, hydrogen sulphide. This acid forms normal salts called
sulphides and acid salts called hydrogensulphides.

All sulphides with the exception of sodium, potassium and ammonium sulphides are insoluble in water.

PREPARATION OF SULPHIDES

Sulphides are prepared by the following methods:

1. By neutralization: The sulphides of sodium, potassium and ammonium are prepared by neutralization
reactions between hydrogen sulphide and their corresponding alkalis.
2NaOH(aq) + H2 S(g) → Na2 S(aq) + 2H2 O(l)
2KOH(aq) + H2 S(g) → K 2 S(aq) + 2H2 O(l)
2NH4 OH(aq) + H2 S(g) → (NH4 )2 S(aq) + 2H2 O(l)
2. By direct combination: A mixture of a metal and sulphur is heated and they combine directly to form
the sulphide of the metal. Examples of sulphides prepared by this method are zinc sulphide and iron (II)
sulphide.
Zn(s) + H2 S(g) → ZnS(s)
Fe(s) + H2 S(g) → FeS(s)
3. By precipitation: Some insoluble sulphides are prepared by bubbling hydrogen sulphide through
solutions of their corresponding salts. e.g.

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CuSO4 (aq) + H2 S(g) → CuS(s) + H2 SO4 (aq)

CHEMICAL PROPERTIES OF SULPHIDES

1. Sulphides produce hydrogen sulphide when heated with hydrochloric acid.

FeS(s) + 2HCl(aq) → FeCl2 (aq) + H2 S(g)
2. Most metallic sulphides react with oxygen when heated to give the corresponding oxides and sulphur
dioxide. e.g.
2CuS(s) + 3O2 (g) → 2CuO(s) + 2SO2 (g)
Mercury (II) sulphide however gives metallic mercury instead of the oxide.
HgS(s) + O2 (g) → Hg(l) + SO2 (g)
USES OF SULPHIDES
 Zinc blende (ZnS) is used in the commercial production of paint.
 Carbon disulphide (CS2 ) is used as a solvent and as a pesticide.
B. SULPHUR DIOXIDE, 𝐒𝐎𝟐

Sulphur dioxide is an acidic gas. It is usually present in volcanic gases and in some sulphur springs. It may be
present in air as a pollutant in cities and towns, from vehicles and industries.

LABORATORY PREPARATION OF SULPHUR DIOXIDE

Apparatus: Sodium sulphite is put in a round-bottomed flask and the apparatus is set up as shown below in
a fume cupboard because sulphur dioxide is a poisonous gas.

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Procedure:

 Dilute hydrochloric acid is poured through the thistle funnel to the sodium sulphite and the mixture is
heated gently.
 Effervescence occurs as sulphur dioxide gas is produced.
Na2 SO3 (aq) + 2HCl(aq) → 2NaCl(aq) + H2 O(l) + SO2 (g)
 The gas evolved is dried by bubbling it through concentrated sulphuric acid.
 The dry gas is then collected by downward delivery since sulphur dioxide is denser than air.

Alternatively, Sulphur dioxide can also be prepared in the laboratory by heating copper turnings with
concentrated sulphuric acid.

Cu(s) + 2H2 SO4 (aq) → CuSO2 (aq) + 2H2 O(l) + SO2 (g)

INDUSTRIAL MANUFACTURE

Industrially, sulphur dioxide is manufactured industrially by burning sulphur in air.

S(s) + O2 (g) → SO2 (g)

PROPERTIES OF SULPHUR DIOXIDE

A. PHYSICAL PROPERTIES
 It is a colourless and poisonous gas with an irritating smell.
 It turns moist blue litmus paper red since it is an acidic gas.
 It denser than air.
 It is easily liquefied under pressure at room temperature.
 It dissolves readily in water.

B. CHEMICAL PROPERTIES
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Page 12 of 20 SULPHUR AND ITS COMPOUNDS

1. Reaction with water: It dissolves in water readily forming sulphurous acid.

SO2 (g) + H2 O(l) → H2 SO3 (aq)

⏟
𝐒𝐮𝐥𝐩𝐡𝐮𝐫𝐨𝐮𝐬 𝐚𝐜𝐢𝐝

2. Acidic properties: Sulphur dioxide is an acidic gas and hence neutralizes alkalis to form salts (sulphites)
and water only. examples:

2NaOH(aq) + SO2 (g) → Na2 SO3 (aq) + H2 O(l)

2KOH(aq) + SO2 (g) → K 2 SO3 (aq) + H2 O(l)

3. As a reducing agent: Sulphur dioxide is a strong reducing agent in aqueous solution where it forms
sulphurous acid that readily donates electrons or removes oxygen from a substance thus reducing it.
Whenever sulphur dioxide acts as a reducing agent, it oxidized to sulphuric acid.
 It decolourises acidified potassium permanganate solution with no yellow deposition of sulphur. The
change in colour is due to the reduction of the purple manganate (VII) ions (MnO−
4 ) to the very pale pink

manganese (II) ions (Mn2+ ).

5SO2 (g) + 2KMnO4 (aq) + 2H2 O(l) → K 2 SO4 (aq) + 2MnSO4 (aq) + 2H2 SO4 (aq)

 It changes the colour of acidified potassium dichromate solution from orange to green with no yellow
deposit of sulphur. The colour change is due to the reduction of orange dichromate ions (Cr2 O2−
7 ) to

the green chromium (III) ions (Cr 3+ )

3SO2 (g) + H2 SO4 (aq) + K 2 Cr2 O7 (aq) → K 2 SO4 (aq) + Cr2 (SO4 )3 (aq) + H2 O(l)

 It reduces brown iron (III) chloride solution to green iron (II) chloride solution.

2FeCl3 (aq) + SO2 (g) + 2H2 O(l) → 2FeCl2 (aq) + 2HCl(aq) + H2 SO4 (aq)

 It reduces concentrated nitric acid to nitrogen dioxide which is liberated as brown fumes.

2HNO3 (aq) + SO2 (g) → H2 SO4 (aq) + 2NO2 (g)

4. As an oxidizing agent: Sulphur dioxide can act as an oxidizing agent in the presence of a stronger
reducing agent than itself. Examples:
 It oxidizes moist hydrogen sulphide to yellow sulphur.

2H2 S(g) + SO2 (g) → 2H2 O(l) + 3S(s)

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 It combines with certain metals to form their oxides e.g.

2Mg(s) + SO2 (g) → 2MgO(s) + S(s)

 It combines with oxygen in the presence of a catalyst to form sulphur trioxide.

2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

5. As a bleaching agent: Sulphur dioxide is a strong bleaching agent in aqueous solution where It forms
sulphurous acid which donates electrons to a dye bleaching it (i.e. it becomes decolorized). Sulphur
dioxide therefore bleaches by reduction and in the process in oxidized to sulphuric acid.

H2 SO3 (aq) + Dye(aq)

⏟ → H2 SO4 (aq) + ⏟
bleached Dye(aq)
coloured colourless

SULPHITES

Sulphites are normal salts formed when sulphurous acid or sulphur dioxide reacts with excess alkalis, e.g.

H2 SO3 (aq) + 2NaOH(aq) → Na2 SO3 (aq) + H2 O(l)

SO2 (g) + 2NaOH(aq) → Na2 SO3 (aq) + H2 O(l)

If the alkali is limited or the sulphur dioxide is in excess, an acid salt (a hydrogen sulphite) is formed.

SO2 (g) + NaOH(aq) →

⏟ NaHSO3 (aq)
𝐄𝐱𝐜𝐞𝐬𝐬

The sulphites of calcium, potassium, sodium and ammonium are soluble in water while the other metallic
sulphites are insoluble in water.

ACTION OF DILUTE ACIDS ON SULPHITES

When sulphites are warmed with dilute acids, they form salts, water and sulphur dioxide. The reaction is
faster when concentrated acids are used.

CaSO3 (s) + 2HCl(aq) → CaCl2 (s) + H2 O(l) + SO2 (g)

K 2 SO3 (aq) + H2 SO4 (aq) → K 2 SO4 (aq) + H2 O(l) + SO2 (g)

TEST FOR SULPHITES

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Warm the unknown substance with a dilute acid. If effervescence occurs and a colourless gas (sulphur
dioxide) which turns damp blue litmus paper red is given off, then the substance is a sulphite.

2H + (aq) + SO2−
3 (aq) → H2 O(l) + SO2 (g)

Alternatively, add a few drops of barium chloride solution to the unknown substance. If a white precipitate
of barium suphite is formed, which dissolves in excess dilute hydrochloric acid, then the substance is a
sulphite.

Ba2+ (aq) + SO2−

3 (aq) → BaSO3 (s)

C. SULPHURIC ACID
Sulphuric acid is a thick oily liquid often called the oil of vitriol. It is a very important industrial chemical. In
fact the amount of sulphuric acid used in a country can be taken as a rough measure of its technological
development.

THE INDUSTRIAL MANUFACTURE OF SULPHURIC ACID

THE CONTACT PROCESS

Most of the world’s supply of sulphuric acid is produced by the contact process.

RAW MATERIALS:

 Sulphur from the Frasch process.

 Oxygen from the atmosphere.
 Distilled water.
 Concentrated sulphuric acid.

THE CONTACT PROCESS TAKES PLACE IN FOUR STAGES:

1. THE PRODUCTION OF SULPHUR DIOXIDE

It is produced by burning sulphur obtained by the Frasch process in air.
S(s) + O2 (g) → SO2 (g)
Sulphur dioxide for the process can also be obtained by the following methods;
 Burning hydrogen sulphide obtained from crude oil in air.

2H2 S(g) + 3O2 (g) → 2SO2 (g) + 2H2 O(l)

 Burning sulphur-containing ores such as Zinc blende (ZnS) and Iron pyrites (FeS) in air

FeS(aq) + 11O2 (g) → 2Fe2 O3 (s) + 8SO2 (g)

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ZnS(s) + 3O2 (g) → 2ZnO(s) + 2SO2 (g)

2. THE PURIFICATION OF SULPHUR DIOXIDE

The sulphur dioxide obtained is mixed with access air and passed through an electrostatic dust
precipitator to remove dust particles and traces of arsenic (III) oxide which can poison the catalyst (i.e.
greatly reduce its catalytic activity).
3. THE CATALYTIC OXIDATION OF SULPHUR DIOXIDE TO SULPHUR TRIOXIDE
(THE CONTACT PROCESS)
The purified mixture of sulphur dioxide and excess air at a pressure of 1atm is passed through a catalyst
chamber maintained at a temperature of 450 − 500℃. In this chamber, sulphur dioxide combines
reversibly with oxygen in the presence of the catalyst to form sulphur trioxide.

2SO2 (g) + O2 (g) ⇌ 2SO3 (g)

The most efficient catalyst for this process is platinised abestors, however platinum is:
 Very expensive.
 Easily poisoned by impurities such as arsenic compounds.
The catalyst that is usually preferred is vanadium (v) oxide, 𝑉2 𝑂5 because it is less expensive and more
resistant to impurities than platinum.

4. THE CONVERSION OF SULPHUR TRIOXIDE TO SULPHURIC ACID

If sulphur trioxide is dissolved in water, sulphuric acid is formed.

SO3 (g) + H2 O(l) → H2 SO4 (aq)

However this is not done because the reaction is strongly exothermic and the heat produced will
vaporize the acid forming a mist of acid droplets which will constitute a serious pollution problem and
will also pervade the factory.
In practice, the sulphur trioxide is first safely dissolved in concentrated sulphuric acid forming a thick
liquid called oleum.
SO3 (g) + H2 SO4 (l) → H2 S2 O7 (l)
⏟
Oleum

The oleum is then diluted with a calculated amount of water to produce 98% sulphuric acid.
H2 S2 O7 (l) + H2 O(l) → 2H2 SO4 (l)

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USES OF SULPHURIC ACID

 In the manufacture of fertilizers such as ammonium sulphate and superphosphate.
 In the manufacture of paints and pigments.
 In the manufacture of man-made fibers like rayon.
 To “pickle” iron and steel (clean the surface) prior to electroplating.
 In the manufacture of soapless detergents.
 As electrolytes in batteries.

PROPERTIES OF SULPHURIC ACID

A. PHYSICAL PROPERTIES

 Concentrated sulphuric acid is a colourless, odourless glacial liquid.

 Concentrated sulphuric acid is very corrosive i.e. it can eat away clothing, paper, wood and can causes
severe burns if it comes into contact with the skin.
 Dilute sulphuric acid, turns blue litmus red and is sour in taste.
 Concentrated sulphuric acid is hygroscopic i.e. it absorbs water vapour from the surroundings and
become more dilute in the process. Due to this hygroscopic nature, concentrated sulphuric acid is used
as a drying agent for gases.
 Concentrated sulphuric acid has a great affinity for water and evolves a large amount of heat as it
dissolves in water. Hence when diluting concentrated sulphuric acid, “Never add water to the acid;
always add the acid slowly to the water with constant stirring.” If water is added to concentrated
sulphuric acid, the great amount of heat produced may change some of the water into pockets of steam
which might scatter the acid.
B. CHEMICAL PROPERTIES OF SULPHURIC ACID

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Page 17 of 20 SULPHUR AND ITS COMPOUNDS
1) ACIDIC PROPERTIES : Only dilute sulphuric acid behaves as an acid because it ionizes completely in
aqueous solution as follows:
H2 SO4 (aq) → 2H + (aq) + SO2−
4 (aq)

Concentrated sulphuric acid is only slightly ionized and hence does not behave as an acid.
 Reactions with bases: Dilute sulphuric acid is dibasic and hence neutralizes alkalis to form normal salts
and acid salts. Examples:

2NaOH(aq)
⏟ + H2 SO4 (aq) → Na2 SO4 (aq) + H2 O(l)
⏟
𝐄𝐱𝐜𝐞𝐬𝐬 𝐍𝐨𝐫𝐦𝐚𝐥 𝐬𝐚𝐥𝐭

NaOH(aq)
⏟ + H2 SO4 (aq) → NaHSO
⏟ 4 (aq) + 2H2 O(l)
𝐋𝐢𝐦𝐢𝐭𝐞𝐝 𝐀𝐜𝐢𝐝 𝐬𝐚𝐥𝐭

It also reacts with metallic oxides to form salts and water only e.g.
CuO(s) + H2 SO4 (aq) → CuSO4 (aq) + H2 O(l)

 Reaction with carbonates: Dilute sulphuric acid reacts with carbonates to form salts, water and carbon
dioxide gas e.g.
CuCO3 (aq) + H2 SO4 (aq) → CuSO4 (aq) + H2 O(l)+CO2 (g)

 Reaction with metals: Dilute sulphuric acid reacts with metals above hydrogen in the reactivity series
liberating hydrogen gas. Examples:
Zn(s) + H2 SO4 (aq) → ZnSO4 (aq) + H2 (g)

Fe(s) + H2 SO4 (aq) → FeSO4 (aq) + H2 (g)

2) As an oxidizing agent: Concentrated sulphuric acid is a strong oxidizing agent. When it oxidizes, it is
reduced to water and sulphur dioxide. Examples:
 It oxidizes metals to the corresponding metallic sulphates, e.g.
Zn(s) + 2H2 SO4 (aq) → ZnSO4 (aq) + 2H2 O(l) + SO2 (g)

Cu(s) + 2H2 SO4 (aq) → CuSO4 (aq) + 2H2 O(l) + SO2 (g)
 It oxidizes non-metals to the corresponding oxides, e.g.
C(s) + 2H2 SO4 (aq) → CO2 (g) + 2H2 O(l) + 2SO2 (g)

 It oxidizes hydrogen sulphide to sulphur.

H2 S(g) + H2 SO4 (aq) → SO2 (g) + 2H2 O(l) + S(s)

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Page 18 of 20 SULPHUR AND ITS COMPOUNDS
3) As a dehydrating agent: A dehydrating agent removes water from a substance causing a change in the
chemical composition of the substance.

Dehydration and drying result in the removal of water molecules from a substance, but dehydration
causes the decomposition of the substance while drying does not.

Concentrated sulphuric acid is a strong dehydrating agent due to its high affinity for water. This is
shown in the following examples:
 It removes water of crystallization from blue crystals of copper (II) sulphate pentahydrate, converting
them into a white anhydrous powder.

𝐶𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
CuSO4 . 5H2 O(s) → CuSO4 (s)
−5𝐻2 𝑂
 It removes the elements of water from various compounds such as sugar, ethanol, methanoic acid and
ethanedioic acid, decomposing them e.g.

𝐶𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
C12 H22 O11 (s) → 12C(s)
sugar (white) −11𝐻 𝑂 sugar charcoal(black)
2

𝐶𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
HCOOH(s) → CO(g)
Methanoic acid −𝐻2 𝑂 Carbon monoxide

𝐶𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
C2 H5 OH(l) → C2 H4 (g)
Ethanol −𝐻2 𝑂 Ethene

The corrosive action of concentrated sulphuric acid on paper, clothes, wood and the skin is due to its
strong dehydrating ability. If concentrated sulphuric acid accidentally spills on the skin, it should be
washed away with plenty of water.
SULPHATES

Sulphates are the normal salts of sulphuric acid. All common sulphates are soluble in water except those of
calcium, barium and lead.

LABORATORY PREPARATION OF SULPATES

The method used to prepare a metallic sulphate depends on the position of the metal in the reactivity
series and in the nature of the sulphate.

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Page 19 of 20 SULPHUR AND ITS COMPOUNDS
 By the action of sulphuric acid on a metal:
The sulphates of metals above hydrogen in the reactivity series such as magnesium and zinc are
prepared by the action of dilute sulphuric acid on the corresponding metals. Hydrogen is displaced from
the acid by the metals, e.g.
Mg(s) + H2 SO4 (aq) → MgSO4 (aq) + H2 (g)

Zn(s) + H2 SO4 (aq) → ZnSO4 (aq) + H2 (g)

The sulphates of metals below hydrogen in the reactivity series such as copper, mercury and silver are
prepared by the action of hot concentrated sulphuric acid on the corresponding metals. The metals are
oxidized by concentrated sulphuric acid to the corresponding sulphates.

Cu(s) + 2H2 SO4 (aq) → CuSO4 (aq) + 2H2 O(l) + SO2 (g)

Hg(l) + 2H2 SO4 (aq) → HgSO4 (aq) + 2H2 O(l) + SO2 (g)

 By the action of sulphuric acid on the oxides, hydroxides and carbonates of some metals: This method
is used to prepare the sulphates of the highly reactive metals such as potassium, sodium and calcium.
The sulphates of these metals are never prepared by the action of dilute sulphuric acid on the metals
because the reactions are too vigorous and dangerous.

2NaOH(aq) + H2 SO4 (aq) → Na2 SO4 (aq) + 2H2 O(l)

K 2 CO3 (aq) + H2 SO4 (aq) → K 2 SO4 (aq) + H2 O(l)+CO2 (g)

CaO(s) + H2 SO4 (aq) → CaSO4 (aq) + H2 O(l)

 By double decomposition: Insoluble sulphates such as lead (II) sulphate and barium sulphate, are
prepared by this method.
Pb(NO3 )2 (aq) + Na2 SO4 (aq) → PbSO4 (s) + 2NaNO3 (aq)
⏟
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭𝐞

BaCl2 (aq) + K 2 SO4 (aq) → BaSO4 (s) + 2KCl(aq)

⏟
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭𝐞

Summary for the preparation of sulphates

METAL METHOD OF PREPARATION

K, Na, Ca By the action of dilute sulphuric acid on CO3, OH, O2- ect
Mg, Al, Zn, Fe By the action of dilute sulphuric acid on metals, their CO3, O2- However, Al
requires the action of concentrated sulphuric acid
Pb, Ba By double decomposition reaction (insoluble sulphtes)
Cu, Hg, Au By the action of hot concentrated sulphuric acid on metals

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Page 20 of 20 SULPHUR AND ITS COMPOUNDS
PROPERTIES OF SULPHATES

 Action of heat: The sulphates of potassium and calcium are stable to heat. The sulphates of metals
which are fairly low in the reactivity series decompose on strong heating to form the oxides of the
metals, sulphur dioxide and/or sulphur trioxide, e.g.
∆
2FeSO4 (s) → Fe2 O3 (s) + SO2 (g) + SO3 (g)

 Solubility in water: Most sulphates are colourless except those with coloured metallic ions such as blue
CuSO4 (aq), Green FeSO4 (aq) , Reddish-brown Fe2 (SO4 )3 (aq) etc.

THE BARIUM CHLORIDE TEST FOR SULPHATES

To an aqueous solution of the unknown sample in a test-tube, add excess dilute hydrochloric acid, followed
by barium chloride solution. If a white precipitate which is insoluble in excess dilute hydrochloric acid is
formed, then sulphate ions are present in the aqueous solution and hence the substance is a sulphate.

Ba2+ (aq) + SO4 2− (aq) → BaSO4 (s)

⏟
𝐖𝐡𝐢𝐭𝐞 𝐩𝐩𝐭𝐞

The acidification process is necessary to prevent the precipitation of other insoluble barium salts such as
barium carbonate and barium sulphite, which are soluble in acidic solutions unlike the sulphate which is
insoluble.

USES OF SULPHATES
 Na2 SO4 . 10H2 O and MgSO4 . 7H2 O are used as laxatives.
 Ammonium sulphate (NH4 )2 SO4 is used as a fertilizer and in a more concentrated form as a weed
killer.
 Plaster of Paris (CaSO4 . H2 O) is widely used to make plaster casts to set broken bones.
 BaSO4 is used for the production of paints.

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