Sulphur and Its Compounds
Sulphur and Its Compounds
Sulphur and Its Compounds
Sulphur is the second member of group VI elements. It is placed just below oxygen in the
periodic table. It has an atomic number 16 hence its electron arrangement is 2.8.6.
Sulphur occurs naturally as an element in deposits in places such as Texas and Louisiana in
U.S.A, Sicily in Italy, and various places in Japan.
Sulphur also occurs in combination with other elements as sulphides and sulphates. The
sulphide ores include copper pyrites (CuFeS2) and iron pyrites (FeS2).
The sulphate ores include gypsum (CaSO4.2H2O)and anhydrite (CaSO4). Petroleum gas and
coal mines contain sulphur in the form of hydrogen sulphide gas.
Water is heated to about 170°C under pressure of about 10 atmospheres and is forced down
the outermost pipe. The pressure ensures that the water remains in liquid state at such
high temperature.
Hot air at a pressure of 15 atmospheres is forced down the innermost pipe. This produces a
light froth consisting of a mixture of molten sulphur and water. The high pressure forces
the mixture up the middle pipe.The mixture is run into large tanks on the surface where
the sulphur solidifies at 115°C, Separates from the water and is stored. Sulphur obtained
this way in usually over 99% pure.
Allotropes of Sulphur
Sulphur exhibits allotropy. The main allotropes are rhombic and monoclinic sulphur
Rhombic Sulphur
Rhombic sulphur is also referred to as octahedral or α-sulphur. It is a bright yellow
crystalline solid with an octahedral shape.
(a) A crystal of rhombic sulphur. (b) Packing of rhombic sulphur molecules in a crystal
Monoclinic Sulphur
Monoclinic sulphur is also referred to as prismatic or ß - sulphur. It is a pale yellow
crystalline solid. The crystals appear needle-like when observed using a hand lens. The
actual shape of the crystal is a hexagonal prism.
Immediately pour out the molten sulphur. Remove the crust by cutting round the edge of
the dish with a knife. Use a hand lens to observe the crystals that have formed on the
underside of the crust.
Monoclinic sulphur has a melting point of 119°C and a density of 1.98 g/cm3. Below 96°C
monoclinic sulphur gradually changes to rhombic sulphur. This temperature of 96°C is
the transition temperature for rhombic and monoclinic sulphur.
The temperature at which one allotrope of an element changes to another is called the
transition temperature.
Non-crystalline – (amorphous) forms of Sulphur
Include plastic, colloidal, and powdery sulphur.
Plastic sulphur is prepared by heating powdered sulphur until it boils. The boiling sulphur
is then poured in a thin continuous stream into a beaker containing cold water. Long elastic
yellow threads of plastic sulphur are formed.
This form of sulphur is insoluble in carbon(IV) sulphide. It turns into hard rhombic sulphur
if left for a few days.
When dilute hydrochloric acid is added to a test-tube containing a dilute solution of
sodium thiosulphate, Na2S2O3, a yellow precipitate of colloidal sulphur is deposited.
N2S2O3,(aq) + 2HCl(aq) 2NaCl(aq) + H2O(l) + SO2(g) + S(s)
Powdery sulphur may be prepared by saturating distilled water with hydrogen sulphide.
The solution is then exposed to air. A white powder is deposited.
H2S(g) + Water H2S(aq)
2H2S(aq) + O2(g) 2H2O(l) + 2S(s)
Above 160°C, the liquid darkens further and becomes almost black. Near the boiling point
the liquid becomes more mobile. This is due to the breaking of the long chains to shorter
chains.
The liquid boils at 444°C and forms a reddish-brown vapour consisting of S8, S6 and S2
molecules which cools to form a yellow sublimate. This sublimate is known as “flowers of
sulphur” and consists mainly of S8 rings.
The moist blue litmus paper turns red indicating that the oxides produced when sulphur
burns are acidic.
Sulphur combines directly with some elements to form sulphides.
When a mixture of sulphur, and iron powder is heated, a highly exothermic reaction
occurs. Once the reaction has started at one point, the glow spreads through the mixture
without further heating, forming iron(II) sulphide. This is because the heat produced
during the reaction is high enough to sustain the reaction.
Hot powdered copper similarly combines with heated sulphur forming copper(I)
sulphide.
Sulphur also combines with some non-metals such as carbon and hydrogen forming
non-metallic sulphides.
Carbon combines with sulphur at high temperatures to form carbon(IV) sulphide.
Hydrogen combines with sulphur to form hydrogen sulphide.
Uses of Sulphur
• Manufacture of sulphuric(VI) acid.
• Manufacture of sulphur-drugs, explosives, matches and fireworks
• Manufacture of bleaching agent used to bleach wood pulp in the paper industry.
• Vulcanization (hardening) of rubber.
• Manufacture of artificial hair dyes.
Manufacture of sodium thiosulphate which is used in photography
Oxides of Sulphur
Sulphur forms two oxides namely sulphur(IV) oxide, SO2, and sulphur(VI) oxide SO3.
The gas may also be prepared by the action of concentrated sulphuric(VI) acid on copper
turnings. The reaction should be carried out in a fume cupboard.
Cu(s) + 2H2SO4(aq) SO2(g) + 2H2O(l) + CuSO4(aq)
Sulphur(IV) oxide is dried by passing it through concentrated sulphuric(IV) acid and
collected by downward delivery. The gas jar is confirmed to be full of the gas when the
paper soaked in orange potassium chromate(VI) turns green.
(iii) Acidified bromine water followed by a few drops of barium chloride solution.
Red brown acidified bromine water is decolourised when reacted with sulphur(IV) oxide.
The bromine water is reduced to hydrobromic acid as the sulphur(IV) oxide is oxidised to
sulphate.
The nitric(V) acid is reduced to nitrogen(IV) oxide while the sulphuric(IV) acid is oxidised
to sulphuric(VI) acid. When a solution of barium chloride is added to the mixture, a white
precipitate of barium sulphate is formed indicating the presence of sulphate, ions.
(Iv) A burning splint is lowered into a gas jar containing Sulphur (IV) oxide.
When a burning splint is lowered into a test-tube containing sulphur(IV) oxide, it is put off
showing that the gas does not support combustion or burn. However, in the presence of a
catalyst, the gas is oxidised to sulphur(VI) oxide.
In this reaction, sulphur (IV) oxide is an oxidising agent, supplying oxygen to magnesium.
Explain the observations made when a gas jar of dry hydrogen sulphide gas is inverted
over a test-tube containing Sulphur (IV) Oxide and a few drops of water added.
When a gas jar of dry hydrogen sulphide gas is inverted over a test-tube containing dry
sulphur(IV) oxide, there is no observable change. When a few drops of water are added
into each gas jar and the mixture is shaken, a yellow deposit of sulphur is produced.
2H2S(g) + SO2(g) 3S(s) + 2H2O(l)
The reaction only takes place when the gases are moist. Sulphur(IV) oxide acts as an
oxidising agent.
Discussion Questions
1. State the purpose of the following in the set up.
(a) Concentrated sulphuric(VI) acid.
Sulphur(IV) oxide and oxygen gases are dried by passing them through
concentrated sulphuric(VI) acid
(b) Freezing salt ice mixture.
The sulphur(VI) oxide is cooled by the freezing salt-ice mixture and it solidifies.
(c) Anhydrous calcium chloride.
Since sulphur(VI) oxide is deliquescent, calcium chloride is used to keep it free from
moisture
2. Write an equation for the reaction that takes place in the combustion tube.
2SO2(g)+ O2(g) 2SO3(s)
3. Comment on the method of collection of sulphur(VI) oxide.
The sulphur(VI) oxide is cooled by the freezing salt-ice mixture and it solidifes. This
allows it to be collected as illustrated.
sulphite precipitate, the precipitate dissolves. This is the test for sulphite ions.
The raw materials for its manufacture are sulphur(IV) oxide and air.
Sulphides or sulphur are burnt in air to produce sulphur(IV) oxide.
Burning of sulphur is the most convenient method of producing sulphur(IV)
oxide.
S(s) + O2(g) SO2(g)
The sulphur(IV) oxide contains dust particles as impurities.
The impurities reduce the surface area of the catalyst, thus impairing its
efficiency. These impurities are said to poison the catalyst.
The dust impurities are removed by electrostatic precipitation.
The mixture of gases is passed through concentrated sulphuric(VI) acid in order to dry it.
After purification, the gaseous mixture is pre-heated in the heat exchanger to attain
suitable reaction temperature before being passed into the catalytic chamber.
In the catalytic chamber, sulphur(IV) oxide and oxygen react to form sulphur(VI)
oxide.
However, the vanadium (V) oxide (V2O5) is preferred because it is cheaper and
less easily poisoned.
For maximum yield of sulphur (VI) oxide in the contact process, low temperature and high
pressure are necessary.
However, at low temperature the reaction is slow while high pressure is expensive
to maintain. A temperature of 450°C and pressure of 2 to 3 atmospheres are used
and are referred to as optimum conditions.
The sulphur (VI) oxide is not dissolved directly in water because the excessive heat
generated could boil the acid to produce a mist of fine droplets of sulphuric (VI) acid in
air. Hence, the gas is dissolved in concentrated sulphuric (VI) acid to form oleum
(H2S2O7).
Sulphuric(VI) acid is obtained by diluting oleum with water.
H2S2O7(1) + H2O(l) 2H2SO4(l)
During the contact process, not all the sulphur(IV) oxide is converted into sulphur (VI)
oxide: only 98% conversion of sulphur(IV) oxide to sulphur(VI) oxide occurs.
Sulphur(IV) oxide is a pollutant, passing the exhaust gases through chimneys lined
with calcium hydroxide reduces the amount of sulphur(IV) oxide released to the
atmosphere. This is referred to as scrubbing the gas.
Ca(OH)2(aq) + SO2(g) CaSO3(s) + H2O(l)
In some industries, filters fitted with strong alkalis are installed to remove any traces
of acid or mist from exhaust gases.
Properties of Sulphuric(VI) acid
Concentrated sulphuric (VI) acid is a colourless oily liquid.
It has a density of 1.84 g/cm3 and boils at 338°C.
It is very soluble in water. It dissolves with evolution of heat (exothermic reaction)
Concentrated sulphuric (VI) acid is hygroscopic. This property makes the acid a suitable
drying agent for gases which do not react with it. The acid readily removes water from
hydrated salts.
Concentrated sulphuric (VI) acid is a strong dehydrating agent.
A dehydrating agent is a substance which is capable of removing chemically combined
water or the elements of water from a compound.
The process of removing water or its elements from a compound is called
dehydration.
The acid dehydrates alcohols to to alkenes, methanoic acid to carbon (II) oxide and sugar to
carbon. The sugar crystals are charred to a black mass when concentrated sulphuric (VI)
acid is added to it.
Hot concentrated sulphuric (VI) acid is a strong oxidising agent. It oxidises metals such as
copper and non-metals such as carbon and sulphur.
It is also a less volatile acid and displaces more volatile acids from their salts.
Discussion Questions
1. Explain why the acid should be added to water and not water to acid.
If water is added to the acid, fumes are produced since the reaction is quite
exothermic. For this reason, dilution of the concentrated acid should always be
carried out by adding small portions of the acid slowly to a large volume of water
with constant stirring.
2. Explain the observation made when concentrated sulphuric(VI) acid was added to:
(a) Copper (II) sulphate crystals.
When the acid is added to blue crystals of copper(II) sulphate pentahydrate,
CuSO4.5H2O, a white powder of the anhydrous salt is formed.
3. Explain the observations made when concentrated sulphuric(IV) acid was reacted
with:
(a) Copper and zinc metals
When copper or zinc metal is added to concentrated sulphuric(IV) acid, a gas is
produced which turns acidified potassium chromate(VI) solution from orange to
green and decolourises acidified potassium manganate(VII) solution.
Cu(s) + 2H2SO4(l) CuSO4(aq) + SO2(g) + 2H2O(l)
Zn(s) + 2H2SO4(l) ZnSO4(aq) + SO2(g) + 2H2O(l)
(b) Carbon and Sulphur powder.
Hot concentrated sulphuric (VI) acid oxidises non-metals such as sulphur and
carbon.
S(s) + 2H4SO4(l) 3SO2(g) + 2H2O(l)
C(s) + 2H2SO4(l) 2SO2(g) + CO2 (g) + 2H2O(l)
4. Explain the observation made when concentrated sulphuric(VI) acid was added to
Potassium nitrate crystals and Sodium chloride.
Concentrated sulphuric(IV) acid is a less volatile acid. It displaces more volatile
acids from their salts.
KNO3(s) + H2SO4(l) HNO3(g) + KHSO4(s)
NaCl(s) + H2SO4(l) HCl(s) + NaHSO4(s)
.
Hydrogen sulphide is formed when dilute hydrochloric acid is added to iron(II) sulphide.
FeS(s) + 2HCl(aq) FeCl2(aq) + H2S(g)
However, any metal sulphide, and dilute acid can be used to prepare hydrogen sulphide
gas.
The gas is collected over warm water since it dissolves in cold water.
The gas can be dried by passing it through a U-tube packed with anyhydrous calcium
chloride.
The gas cannot be dried using concentrated sulphuric (VI) acid because it would be
oxidised to sulphur.
3H2S(g) + H2SO4(l) 4S(s) + 4H2O(l)
Similarly, acidified orange chromate (VI) is reduced to green chromium(III) ions solution.
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