SULPHUR
Sulphur is found in group VI period II in the Periodic Table. It occurs as a free element found in underground deposits. It is also found in the combined state as metallic Sulphide and as tetraoxosulphate (IV).
ELECTRONIC STRUCRURE OF SULPHUR
Extraction of Sulphur by the Frasch Process
The Frasch Process is an industrial method used to extract sulphur from underground deposits. It is especially useful when sulphur is found deep below the earth’s surface, making traditional mining difficult.
In this process, a set of three concentric pipes is drilled down into the sulphur deposit. Superheated water (at about 160–170°C) is pumped through the outermost pipe to melt the sulphur underground, since sulphur has a relatively low melting point.
Next, hot compressed air is forced down the innermost pipe. This creates pressure that pushes the molten sulphur up through the middle pipe to the surface.
The sulphur obtained is usually very pure (about 99.5%) and requires little further purification.
Key Advantages
I. Produces high-purity sulphur
ii. Reduces the need for traditional mining
iii Efficient for deep underground deposits
Simple Summary
The Frasch Process melts underground sulphur using hot water and then forces it to the surface using compressed air.
ALLOTROPES OF SULPHUR
There are two main crystalline allotropes of Sulphur they are: -
1 Rhombic
Sulphur: This is a bright yellow octahedral crystalline solid made up of S8 molecules. It is stable below 96oC.
2 Monoclinic Sulphur: This is a needle like crystalline molecule
consisting of S8. It has an amber colour and is stable at temperatures above 96oC.
It easily reverts to Rhombic below 96oC. The transition temperature
between Rhombic and Monoclinic is 96oC.
Comparison of the Physical Properties of Rhombic and
Monoclinic Sulphur
|
Rhombic sulphur
|
Monoclinic sulphur
|
|
Colour
|
Bright yellow
|
Amber
|
|
Shape
|
Octahedral
|
Needle-shaped
|
|
Density
|
2.80 g/cm3
|
1.98g/cm3
|
|
Melting point
|
1130C
|
119oC
|
|
Stability
|
Stable below 96oC
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Stable above 96oC
|
There are other non crysatlline allotropes of Sulphur such as
1. Amorphous
sulphur: formed when sulphur is dissolved in carbon(IV) sulphide and the solution is allowed to evaporate.
2. Plastic
sulphur: formed when molten Sulphur is suddenly poured into cold water:00
PHYSICAL PROPERTIES
1. Sulphur
is a yellow solid.
2. It melts at 119oC and boils at 444oC
3. It is
insoluble in water but soluble in carbon (IV) sulphide and toluene
3. It is a
poor – conductor of heat and electricity.
CHEMICAL PROPERTIES
1. It reacts directly with metals to form sulphide (S2-)
Fe(s) + S(s) → FeS(s)
2 It reacts with hydrogen
to form hydrogen sulphide;
H2(g) + S(s) → H2S(g)
3. It reacts with excess oxygen to form sulphur (IV) oxide
O2(g) + S(s) →SO2(g)
4. It reacts with coke (carbon) to form carbon (II)
sulphide
C(s) + S(s) → CS2
USES
1. It used in manufacturing tetraoxosulphate (IV) acid
2. It used in vulcanization of rubber
3. It used as germicides
4. It used in manufacturing bleaching agent
COMPOUNDS OF SULPHUR
1. HYDROGEN SULPHIDE, H2S
Hydrogen sulphide is found in volcanic gases, sulphur
springs, coal gas and natural gas.
LABORATORY PREPARATION
Hydrogen sulphide is prepared in the laboratory by the
action of dilute acids on metallic sulphide like Iron (II) sulphide
2HCl(aq)+ FeS(s)
→ FeCl2(aq) + H2S(g)
The Kipp’s apparatus is used for regular supply of hydrogen sulphide in the laboratory.
PHYSICAL PROPERTIES of Hydrogen sulphide
1. It is a colourless gas
2. It smells like that of rotten egg.
2. It
is a poisonous gas
3. It
is about 1.18 times denser than air.
4. It
is moderately soluble in water to form very weak acidic solution.
5. It
burns with pale blue flame.
CHEMICAL PROPERTIES
1. As an acid it reacts with alkali to form a normal
salt and water
2NaOH(aq) + H2S(g)
→ Na2S(aq) +2H2O(l)
2. It reacts with excess oxygen to form sulphur (VI)
oxide but forms deposit of sulphur with limited oxygen
2H2S(g) + 3O2(g) → 2H2O(l) +
2SO2(g)
2H2S(g) + O2(g) → 2H2(l)
+ 2S(s)
3. As
a reducing agent, it reacts with many oxidizing agents such
as acidified KMnO4,
acidified K2Cr2O7, chlorine gas, FeCl2,
SO2, H2SO4 and HNO3
TEST FOR HYDROGEN SULPHIDE
Moistened a piece of filter paper with lead (II)
trioxonitrate (V) solution and dropped it into a gas jar of the unknown gas. If
the paper turns black, then the gas is H2S.
SULPHUR (IV) OXIDE, SO2
LABORATORY PREPARATION
It is prepared in the laboratory by heating
sodium or potassium trioxosulphate (IV) with tetraoxosulphate (VI) acid or
hydrochloric acid.
Na2SO3(aq)+2HCl(aq) → 2NaCl(aq)+ H2O(l) + SO2(g)
Physical Properties of sulphur (IV) oxide
1. Sulphur
(IV) oxide is a colourless poisonous gas.
2. It smell like that of burning
matches.
2. It
is very soluble in water.
3. It
is about 2.5 times denser than air.
Chemical Properties
1. As
an acid: - it reacts with alkali to form normal salt and water
only.
2NaOH(aq)+ SO2(g) →
Na2SO3(aq) + H2O(l)
2. As
reducing agent: - Sulphur (IV) oxide reduces oxidizing agents such as
acidified KMnO4; acidified K2Cr2O7;
FeCl3, HNO3, chlorine gas. It decolorizes acidified
purple KMnO4 and turns acidified orange K2Cr2O7
to green.
3. As an oxidizing agent: -Sulphur (IV) oxide reacts as oxidizing agent in the presence of strong reducing agent such as hydrogen sulphide.
2H2S(g) + SO2(g) → 2H2O(l) + 3S(s)
C(s)+ SO2(g)→CO2(g)+ S(s)
4. As a bleaching agent: - It decolourising dye by its bleaching action. The
bleaching action is similar to that of chlorine becausewater must be present.
But, while chlorine bleaches by oxidation sulphur IV oxide bleaches by
reduction.
USES of sulphur (IV) oxide
1.It is used in manufacture of tetraoxosulphate (VI) acid.
2. It is used as a germicide and a fumigant especially for destroying termites.
3. It is used as bleaching agent for straw, silt and wood.
4. It is used as preservative in some liquid e.g orange juice.
5. Liquid sulphur (IV) oxide is used as refrigerant.
Test for SO2
1. When sulphur (IV) oxide gas is bubbled through a solution of either acidified potassium
heptaoxodichromate (VI) or potassium tetraoxomanganate (VII), it changes the colour of acidified K2Cr2O7 from orange to green or it changes the colour of acidified KMnO4 purple to colourless.
SULPHUR (VI) OXIDE, SO3
Sulphur (VI) oxide is prepared by reacting sulphur (IV)
oxide and oxygen at 450oC and 1 atm pressure in the presence
of vanadium (V) oxide or platinized asbestos as catalyst
2SO2(g) + O2(g) →2SO3(g)
PHYSICAL PROPERTIES OF SO3
1. It is a white needle-like crystal at room temperature.
2. It
has a low boiling point and vapourizes on gentle heating.
3 It
dissolves readily in water to give tetraoxosulphate (VI) acid.
TRIOXOSULPHATE (IV) ACID, H2SO3
Trioxosulphate (IV) acid is a dibasic acid with a molecular
formula H2SO3
Laboratory Preparation OF H2SO3
It is prepared in the lab by the action of dilute hydrochloric acid on
heated sodium trioxosulphate (IV) to produce sulphur (IV) oxide, which is then
dissolved in water.
Na2SO3(s)+2HCl(aq)→2NaCl(aq) +
H2O(l) + SO2(g)
H2O(l)+ SO2(g) → H2SO3(aq)
Sulphur (IV) Oxide is the acid anhydride of trioxosulphate
(IV) acid.
PHYSICAL PROPERTIES OF H2SO3
1. It
is colourless liquid.
2. It
is readily soluble in water.
3. It
has an irritating and choking smell.
Chemical Properties oF H2SO3
1. It reacts with alkalis to form salt and water.
2NaOH(aq) + H2SO3(aq)→ Na2SO3(aq) +
2H2O(l)
2. It oxidises in air to tetraoxosulphate (VI) acid
2H2SO3(aq) + O2(g) → 2H2SO4(aq)
3. As a reducing agent: - It
reduces oxidizing agent like acidified KMnO4 and acidified K2Cr2O7
4 It
bleaches dyes in the presence of water.
Test for SO32-
Add a little amount of barium chloride solution to a solution of the
unknown substance. If a white precipitate is formed which is soluble in dilute hydrochloric acid then the presence of a trioxosulphate (IV) ion is confirmed.
USES OF H2SO3
1. It
is used for bleaching straw and other fabrics.
2. It
is used as a germicide.
TETRAOXOSULPHATE VI ACID, H2SO4
Tetraoxosulphate VI acid is one of the most important
chemical compounds known. It is used in almost every manufacturing process;
hence it is mostly prepared industrially.
INDUSTRIAL PREPARATION OF H2SO4
It is manufactured industrially by
Contact process. The following equations summarizes the steps involved in the Contact process.
1. Sulphur is burnt in dry air to obtain sulphur (IV) oxide, SO2
S(s) + O2(g) →
SO2(g)
2.The Sulphur (IV) oxide produced is combined with excess oxygen in the presence of vanadium V oxide (V2O5 ) as catalyst at a temperature of 450oC to yield sulphur (VI) oxide.
SO2(g) + O2(g) → 2SO3(g) + heat
3. The
sulphur (VI) oxide is then dissolved in concentrated H2SO4 to
produce a thick oily liquid called Oleum.
H2SO4(aq) + SO3(g)→ H2S2O7(aq)
4. The
Oleum is then combined with one mole of water to produce about 98% tetraoxosulphate
(VI) acid.
H2O(l)+ H2S2O7(aq) 2H2SO4(aq)
NOTE: Dissolving Sulphur (VI) oxide in water directly is highly exothermic and will cause the acid to vaporize, producing a mist of droplets of the concentrated acid which can spread and cause acid
burns.
PHYSICAL PROPERTIES
1. It
is a colourless, viscous liquid with density of 1.84gcm-3
2. It
is corrosive and cause burns when in contact with the skin.
3. It
is highly soluble in water evolving large amount of heat.
CHEMICAL PROEPERTIES
1. As
an acid,
i. It reacts with metals higher than hydrogen in the electrochemical
series to liberate hydrogen gas
Mg(s)+ H2SO4(aq)→ MgSO4(aq)+ H2(g)
ii. It
reacts with bases to form salts and water ZnO(s)+H2SO4(aq) →ZnSO4(aq)+H2O(l)
iii. It
reacts with alkali to form normal and acidic salt
H2SO4(aq)+KOH(aq)→NaHSO4(aq)+ H2O(l)
H2SO4(aq)+ KOH(aq)→ Na2 SO4(aq) + 2H2O(l)
iv.. It reacts with trioxocarbonate (IV) to liberate carbon (IV) oxide
H2SO4(aq)+CuCO3(aq)→CuSO4(aq)+ H2O(l) +
CO2(g)
2. As
oxidizing agent: - Concentrated H2SO4 oxidise metals and non –metals to yield the corresponding tetraoxosulphate VI and itself reduced to SO2. It oxidises hydrogen sulphide to Sulphur.
Cu(s)+ 2H2SO4(aq)→ CuSO4(aq)+ 2H2O(l)+SO2(g)
C(s) +
2H2SO4(aq)→2H2O(l) + CO2(g)+ 2SO2(g)
H2SO4(aq)+ H2S(g)→S(s)+H2O(l)+ SO2(g)
3. As a dehydrating agent: - Concentrated
tetraoxosulphate (VI) acid also behaves as a dehydrating agent, removing components of water from
compounds like sugar and ethanedioic acid
C12H22O11(s)→12C(s) +11H2O(l)
sugar charcoal
COOH
| + H2SO4 → CO2 + CO + H2O
COOH conc
4. Concentrated
tetraoxosulphate (VI) displaces volatile acids from their salts
NaCl(s)+H2SO4(aq)→NaHSO4(aq) + HCl(g)
Test for SO42-
Add Barium chloride solution to a solution of the
unknown salt. If a white precipitate is formed which is insoluble in excess dilute hydrochloric
acid, then the presence of a tetraoxosulphate (VI) ion is confirmed.
USES OF H2SO4
1. It is used as an electrolyte in lead accumulator.
2. It
is used in production of fertilizers e.g ammonium tetraoxosulphate (VI).
3. It
is used in purification of crude oil.
4. It
is used as drying agent for many gases except NH3 and H2S
gas.
5 It
is used to clean metals before electroplating.
6. It is used in the production of fibres
7. It is used in the manufacture of synthetic detergents
TETRAOXOSULPHATE (VI) SALTS: -
These are the salts formed when metals, bases or alkalis and trioxocarbonate IV reacts with H2SO4
USES OF TETRAOXOSULPHATE (VI) SALTS
1. Ammonium
tetraoxosulphate (VI) (NH4)2SO4 used as fertilizers
2. Sodium
tetraoxosulphate (VI) (Na2SO4) is used in paper manufacture and as a purgative
3. Calcium
tetraoxosulphate (VI) (CaSO4) is mined as gypsum and is used as plaster of Paris (POP) used to set broken bones.
4. Aluminum
tetraoxosulphate (VI) (Al2(SO4)3) is used to coagulate precipitate in purification of water (alum)
5. Iron
II tetraoxosulphate (VI) is used to treat anemia.
OBJECTIVE QUESTIONS
1. Sulphur belongs to which group in the periodic table?
A. Group I
B. Group IV
C. Group VI
D. Group VII
2. The most common allotrope of sulphur at room temperature is:
A. Monoclinic sulphur
B. Plastic sulphur
C. Rhombic sulphur
D. Amorphous sulphur
3. Which colour is associated with sulphur?
A. Red
B. Yellow
C. Blue
D. Green
4. Sulphur is mainly extracted using the because:
A. It is cheap
B. It produces impure sulphur
C. Sulphur is found underground
D. It requires no heat
5. Which of the following is NOT an allotrope of sulphur?
A. Rhombic
B. Monoclinic
C. Plastic
D. Diamond
6. Sulphur dioxide has the chemical formula:
A. SO
B. SO₂
C. SO₃
D. S₂O
7. The oxidation state of sulphur in SO₂ is:
A. +2
B. +4
C. +6
D. −2
8. Sulphur dioxide acts mainly as a:
A. Reducing agent
B. Oxidizing agent
C. Catalyst
D. Base
9. Which gas is formed when sulphur burns in air?
A. Hydrogen sulphide
B. Sulphur trioxide
C. Sulphur dioxide
D. Carbon dioxide
10. The gas with a rotten egg smell is:
A. SO₂
B. H₂S
C. CO₂
D. NH₃
11. Hydrogen sulphide turns lead(II) ethanoate paper:
A. Blue
B. Red
C. Black
D. White
12. The contact process is used in the manufacture of:
A. Hydrochloric acid
B. Nitric acid
C. Sulphuric acid
D. Carbonic acid
13. The catalyst used in the is:
A. Iron
B. Nickel
C. Vanadium(V) oxide
D. Platinum
14. Oleum is a solution of:
A. SO₂ in water
B. SO₃ in H₂SO₄
C. H₂SO₄ in water
D. SO₂ in H₂SO₄
15. Sulphuric acid is best described as:
A. Weak acid
B. Strong acid
C. Neutral compound
D. Organic acid
16. Which of the following reacts with dilute sulphuric acid to produce hydrogen gas?
A. Copper
B. Zinc
C. Silver
D. Gold
17. The drying agent commonly used in laboratories is:
A. NaCl
B. H₂SO₄ (conc.)
C. HCl
D. NaOH
18. Sulphur trioxide reacts with water to form:
A. H₂SO₃
B. H₂SO₄
C. H₂S
D. SO₂
19. Acid rain is mainly caused by:
A. CO₂
B. SO₂
C. O₂
D. H₂
20. Plastic sulphur is formed when:
A. Sulphur is slowly cooled
B. Molten sulphur is rapidly cooled
C. Sulphur reacts with oxygen
D. Sulphur is heated gently
THEORY QUESTIONS
1.
(I). Name the process represented by the chart
ii). Identify reactant X and product Y.
iii). What are the operating temperature and pressure at stage II
iv). Mention the stage which requires a catalyst and state the catalyst used.
v) give the reason why the SO3 produced in stage II is not dissolved directly in water.
2.(a). State two physical properties of hydrogen sulphide
(ii). Name the laboratory equipment used for intermittent production of hydrogen sulphide?
b. What property of hydrogen sulphide is illustrated in the reaction represented by the following equation?
H2S + 2NaOH ---> Na2S + H2O