Sulphur

Presented by Hikmat Khanal

L.R.I school, Kalanki, KTM
 Syllabus according to NEB

9.8 Sulphur
9.8.1 Allotropes of sulphur (name only) and uses of sulphur
9.8.2 Hydrogen sulphide (preparation from Kipp's apparatus with diagram,) properties (Acidic nature, reducing
nature, analytical reagent) and uses
9.8.3 Sulphur dioxide its properties (acidic nature, reducing nature, oxidising nature and bleaching action) and
uses
9.8.4 Sulphuric acid and its properties (acidic nature, oxidising nature, dehydrating nature) and uses
9.8.5 Sodium thiosulphate (formula and uses)
SULPHUR
 What are allotropes and allotropy?
The two or more forms of same element having similar
chemical properties but different physical properties are
called allotropes and the phenomenon is called allotropy. For
example- Rhombic sulphur and Monoclinic sulphur are two
allotropes of sulphur.
 γ-sulphur
α-sulphur

β-sulphur δ- sulphur
 Rhombic sulphur/octahedral sulphur/α-sulphur Monoclinic/prismatic/β sulphur

 It is soluble in CS2 but insoluble in H2O.

It is stable above 95.5°C and below this it changes
into rhombic sulphur.
 It is the most stable form of sulphur at Hence 95.5°C is the temperature at which both α
ordinary condition. But, it is not stable and β form co-exist.
above 95.5°C.
It is soluble in CS2 but insoluble in H2O
Above 95.5°C
rhombic sulphur monoclinic
Below 95.5°C

rhombic sulphur consist of S8 molecule

that is puckered or crown shaped.

Both alpha and beta form of sulphur are bad conductor of heat and electricity
Uses of sulphur

• Used to prepare sulphuric acid.

• It is most abundant part of human body.
• Used to prepare gun powder.
• Used to prepare sulpha drug.
• Used in vulcanization of rubber.
• Used to prepare sulphur containing fertilizers.
Vulcanization of rubber
 Hydrogen sulphide (H2S)

Intermittent supply of H2S gas by Kipp’s apparatus :

(Working principle of Kipp’s apparatus )
{Intermittent = Stopping and starting at irregular intervals}
• H2S gas is frequently required for salt analysis in the
laboratory. The special apparatus which is used for the
preparation of H2S is called Kipp’s apparatus.
Kipp’s apparatus for H2S gas production
Kipp’s apparatus consist of three bulbs A, B and C. The bulbs are
interconnected with each other. The upper bulb A contains a long
stem which reaches upto bulb C. When dil. H2SO4 is poured from
bulb A, liquid level rises in bulb C and reaches upto bulb B just to
cover iron sulphide. Then the reaction between iron sulphide and
H2SO4 takes place to form H2S gas. As H2S gas is formed, the
pressure inside bulb B increases and forces the dil. H2SO4 up into
the upper bulb A. Then the contact between FeS and dil. H2SO4
breaks and the formation of gas is stopped(ceased). When the tap
is opened H2S comes out and the pressure decreases. As a result
liquid level again rises at bulb B and H2S gas start to evolve again. In
this way H2S gas is prepared intermittently by Kipp’s apparatus.
 Physical Properties of H2S :

• It is colourless gas with rotten egg smell.

• It is soluble in water.
• It is poisonous gas.
NOTE: In its low concentration it causes nausea, dizziness and
headache. At high concentration it is fatal (i.e. deadly poisonous).
Conc. of H2S in air 1 part in 1000 parts of air may be fatal.
• It is heavier than air(with vapour density 17).
 Chemical Properties of H2S :
1. Acidic character of H2S :
• It acts as a weak diprotic (dibasic) acid. It ionizes in two
steps to give two protons.

• H2S reacts with base to form two series of salts. Eg.

• H2S reacts with basic oxides to give salt.

2. H2S as reducing agent :-

• Sulphur in H2S bears -2 oxidation state which in minimum
oxidation state of sulphur. In chemical reaction, H2S tends to
get oxidized . So H2S acts as reducing agent.
• It reduces halogens into halogen acids(haloacids).
• It reduces sulphur dioxide to sulphur.

• It reduces ferric salt to ferrous salt.

• It reduces conc. HNO3 to NO2.

• It reduces conc. H2SO4 to SO2.

• It reduces acidified potassium permanganate solution and pink

colour of KMnO4 is discharged.
• It reduces acidified K2Cr2O7 solution and orange color
of K2Cr2O7 changes to green.

3. H2S as analytical reagent in salt analysis (Precipitation of

metal sulphide) :
H2S gas is used as analytical agent to detect group II basic radicals
in acidic medium i.e. HCl and group IIIB basic radicals in alkaline
medium i.e. NH4Cl and NH4OH.
Group II basic radicals :

Group II basic radicals consists of Cu⁺⁺ , Hg⁺⁺, Pb⁺⁺, Cd⁺⁺, Sn⁺⁺, As⁺⁺⁺,
Sb⁺⁺⁺, Bi⁺⁺⁺. In qualitative salt analysis this group II radicals are
precipitated in the form of their sulphide in acidic medium. By
noting the colour of ppt., we can identify the metal cations.
• Group IIIB basic radicals : Group IIIB basic radicals consist of Zn⁺⁺, Co⁺⁺,
Ni⁺⁺, Mn⁺⁺. These are precipitated by passing H2S in alkaline medium ( i.e.
NH4Cl + NH4OH).
 • Structure of H2S :

• Uses of Hydrogen sulphide (H2S) :

1. It is used as analytical reagent in laboratory.
2. It is used as reducing agent.
3.It is used to prepare metallic sulphide, which can be used as
pigment.
Sulphur Dioxide (SO2):
• Physical properties:
1. It is colourless gas having suffocating smell.
2. It is highly soluble in water.
3. Its melting point is -75.5°C and boiling point is -10°C.
• Chemical Properties of sulphur dioxide:
1. Weak acidic nature: It dissolves in water to give sulphurous acid, a weak
diprotic (dibasic) acid.

Sulphurous acid ionizes in two steps:

It produces two series of salts if reacted with base. Eg.

Sod. bisulphite

Sod. bisulphite
2. SO2 as a reducing agent:
Aqueous sulphur dioxide shows reducing character and SO2 itself
gets oxidized to H2SO4.
• It reduces halogens (Cl2, Br2, I2) in aq. Solution to respective
halides. Eg.
• It reduces acidified potassium permanganate solution and pink colour of
KMnO4 is discharged.
• It reduces acidified K2Cr2O7 solution and orange color of K2Cr2O7 changes
to light green.
• It reduces ferric salt to ferrous salt and colour changes from yellow to light
green.
• It reduces potassium iodate (KIO3) solution to iodine.

3. SO2 as an oxidizing agent:

SO2 oxidizes powerful reducing agents like H2S, HI, Mg, Fe, etc. and itself get
reduced to sulphur or sulphide.
4. SO2 as bleaching agent:

Formation of colourless product from colouring substance is called

bleaching. Chemical substances such as SO2, H2O2, CaOCl2, Cl2, etc. show
bleaching action.

SO2 can act as a bleaching agent in presence of moisture. It can bleach

coloured wool, silk, flower, hair, etc. The bleaching action of sulphur dioxide is
due to the formation of nascent hydrogen in presence of moisture, which
reduces colouring substance to colourless reduced product.
In some cases, bleaching action of SO2 is due to formation of
colourless addition product.
Sulphur dioxide (SO2) Chlorine(Cl2)
1.Sulphur dioxide reacts with water to yield 1.Chlorine reacts with water to yield nascent oxygen
nascent hydrogen which bleaches coloured which bleaches coloured substance to colourless product
substance to colourless product by reduction. by oxidation.
SO2 + 2H2O  H2SO4 + 2 [H] Cl2 + H2O  2HCl + 2[O]

2.Bleaching by SO2 may be sometimes due to 2.No such colourless addition product is formed with
formation of colourless addition products. chlorine.

3.Bleaching by SO2 is reversible i.e. a temporary 3. Bleaching by Cl2 is irreversible ie. a permanent process.
process.
4. Cl2 is strong bleaching agent.
4. SO2 is mild bleaching agent.
5. It is used to bleach wood, textiles, paper, etc.
5.It is used to bleach delicate articles such as wool,
silk, cane sugar, etc.
 Test for SO2 :
Potassium dichromate paper test : When SO2 comes in contact with acidified
potassium dichromate paper, the orange coloured paper turns to green due to
formation of chromium sulphate.
Uses of SO2:

• It is used as bleaching agent.

• It is used in the manufacture of sulphuric acid.
• It can be used as disinfectant, fungicide and food
preservative.
 Sulphuric acid (H2SO4)

• Sulphuric acid is widely used chemical in industries. It is used in the

manufacture of fertilizers, drugs, dyes, polymers, etc. thousands of tons of
sulphuric acid is manufactured every year world wide. Due to its wide
range of uses, it is called king of chemicals. It is also called oil of vitriol.

Manufacture of sulphuric acid by contact process(from last unit:

modern chemical manufacture):
• In early days, sulphuric acid used to be manufactured by lead chamber
process.
• Contact process is modern method. The acid obtained is pure ( free
from impurities) and is quite concentrated (96-99%).
The contact process, it’s name is mainly from the fact that the conversion of
sulphur dioxide into sulphur trioxide is carried out in contact with surface of
catalyst.

Principle :
1. Production of sulphur dioxide:
Sulphur dioxide gas can be prepared either by burning sulphur or roasting of
iron pyrites.
2. Catalytic oxidation of sulphur dioxide:
Sulphur dioxide is oxidized to sulphur trioxide in presence of catalyst vanadium
pentoxide at about 450°C temperature and 2 atm pressure.

3. Conversion of SO3 into H2SO4:

Sulphur trioxide obtained is absorbed in 98% H2SO4 to produce oleum or
fuming sulphuric acid. The oleum is diluted with calculated amount of water
to get desired concentration of H2SO4.
Conditions for optimum yield of H2SO4:

Formation of SO2 to SO3 is one of the must important steps in the manufacture
of sulphuric acid. The production of H2SO4 entirely depends on the amount of
SO3 formed. As reaction is reversible, exothermic and proceeds with decrease
in volume, Le- Chatelier’s principle can be applied for the maximum yield of
sulphur trioxide.
• Low temperature : This reaction is exothermic . So, low temperature is
required for maximum yield. But too low temperature is too slow to attain
equilibrium. So an optimum temperature of about 450°C is supplied.

• High concentration of reactants : High concentration of SO2 and O2 is used

for more production of SO3 .

• High pressure : High pressure favours the reaction because the product
formed has less volume than reactant . But the acid resistant tower which
are able to withstand high pressure are difficult to build. Hence, an
optimum pressure of about 2 atm is applied.

• Use of catalyst: Rate of reaction is increased by the use of positive catalyst.

So, vanadium pentoxide is used as catalyst for higher yield of H2SO4.
Flow sheet diagram for the manufacture of sulphuric acid via contact process
Flow-sheet diagram
Details of the plant or process:
1. Sulphur or pyrite burner:
SO2 gas is obtained by burning sulphur or iron pyrite with air
in sulphur or pyrite burner.

2.Purification unit: The impure SO2 gas obtained is purified by the

purification unit.
a. Electrical dust precipitator: Dust particles present in sulphur dioxide gas
is precipitated in electrical dust precipitator by the influence of high
potential difference applied between the metallic conductors fitted in the
chamber.
b.Steam chamber: The lighter dust particles are settled down by using
steam in steam chamber.

c.Cooler: The gases coming out from the steam chamber are passed through
cooler. The gases get cooled down to about 100°C.

d.Washing tower(scrubber): The cooled SO2 gas is then passed into a tower
called scrubber which is packed with quartz and water is sprayed from the
top. The water soluble impurities are washed away.

e.Drying tower: The moisture present in sulphur dioxide is absorbed by the

spray of conc.H2SO4 in drying tower.

f.Arsenic purifier: Arsenous oxide ( As2O3) present in gas is absorbed by

ferric hydroxide( because it may causes catalytic poisoning).
3.Testing box: The purity of sulphur dioxide is checked in testing box by
passing through a darkened box.

4. Preheater: The purified mixture of SO2 and O2 is heated upto 450°C.

5.Contact chamber: The SO2 gas is catalytically oxidized to sulphur trioxide

(SO3) in the presence of V2O5 as catalyst at 450°C temperature and 2 atm
pressure.

6.Absorption tower: This tower is packed with quartz (or acid proof stone)
in which 98% H2SO4 is sprayed from the top of the tower. Concentrated
H2SO4 absorbs sulphur trioxide to form oleum (or pyrosulphuric acid).
Oleum is then treated with calculated amount of water to form sulphuric
acid of desired concentration.
 Physical Properties of H2SO4:
• It is colourless, hygroscopic, syrupy liquid.

• It is highly soluble in water (due to formation of intermolecular hydrogen

bond). It dissolves in water with the liberation of large quantity of
heat(19Kcal/mol) which may causes the explosion or spurt the acid out
of the container.
H2SO4 + nH2O H2SO4.nH2O + Heat
Therefore, sulphuric acid is diluted by adding the acid slowly to water
with constant stirring and not by adding water to the acid.
• It’s melting point is 10.5°C and boiling point is 338°C.

• Pure H2SO4 is covalent compound and bad conductor of

electricity. However aqueous H2SO4 conducts electricity.

• Litmus test : Sulphuric acid is covalent compound. In pure state it

does not change the colour of the blue litmus paper. However,
aqueous acid gets ionized and produces hydrogen(or hydronium)
ion into solution. Due to which it can change the colour of blue
litmus paper to red.
 Chemical properties of H2SO4:
1. Acidic nature:

H2SO4 is a strong dibasic (diprotic) acid and ionizes in two steps.

It gives two series of salts like bisulphate and sulphate when reacted
with base.Eg.
2. H2SO4 as an oxidizing agent:
• Action with metals:
More electropositive metals ( i.e. metals lying above hydrogen in
electrochemical series) like Zn, Fe, Mg, Al, etc. react with dil. H2SO4 to produce
hydrogen gas. Here H2SO4 reduces to H2 and metals oxidize to metal sulphates.
Conc. H2SO4 oxidizes Zn, Cu, Ag, Hg, etc. to respective metal sulphates and
H2SO4 gets reduced to SO2.
2. Action with non metals:
• Carbon is oxidized to carbon dioxide.
• Sulphur is oxidized to sulphur dioxide.

• Phosphorus is oxidized to phosphoric acid.

3. Action with some other reducing agents:

• H2SO4 oxidizes H2S to S and itself reduces to SO2.

• HBr and HI are oxidized to Br2 and I2 respectively.

 {Note : HCl can not be oxidized to Cl2 because of strong bond.}

4. Sulphuric acid as dehydrating agent:

H2SO4 is a good dehydrating agent. It absorbs water molecules from sugar,
cellulose, copper sulphate crystals, etc.

• With sugar (charring action):

When conc. H2SO4 is treated with sugar, wood, paper, etc. it absorbs water
and a black mass of carbon is formed. This process is called charring.
• With copper sulphate crystals:
It removes water of crystallization from hydrated salts.

• With oxalic acid crystals and formic acid:

• Uses of sulphuric acid:
1. It is used for the manufacture of fertilizers.
2. It is used in manufacture of HCl, HNO3, H3PO4,
etc.
3. It is used as an oxidizing agent.
4. It is used as a drying and dehydrating agent.
Sodium thiosulphate:

• Molecular formula: Na2S2O3. 5H2O. It is commonly called hypo.

Uses of sodium thiosulphate:

1. It is used as a fixer in photography. { i.e. for fixing silver bromide in
photographic plate}

2. It is used in (iodometric) titration for the estimation of iodine.

3. It is used as an antichlor agent to remove excess of chlorine from

bleached textiles/fibers.