Allotropes of sulphur

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.
Sulphur exists on following allotropic forms:
 Uses of sulphur

•It is used for the manufacture of sulphuric acid, sulphur dioxide and other sulphur
compounds.
•It is used in medicine to manufacture sulpha drugs and ointments for skin disease.
•It is used for the vulcanization of rubber.
Note: Vulcanization is a process of heating raw rubber with sulphur or its compounds to destroy its sticky nature
and to increase the durability of rubber products.
•It is used for the manufacture of black gun powder which is a mixture of carbon
(charcoal), sulphur and nitre (KNO ). 3

•It is used in the manufacture of fungicides and insecticides.

 Hydrogen sulphide (H2S)
Working principle of Kipp’s apparatus : Intermittent production of H2S gas by
Kipp’s apparatus
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. It follows following principle reaction;

Intermittent = Stopping
and starting at irregular
intervals
Kipp’s apparatus consist of three bulbs A, B and C. The bulbs are interconnected with each
other. The upper bulb C contains a long stem which reaches upto bulb A. At first the outlet
tap is closed and dil. H2SO4 is poured from bulb C, liquid level rises in bulb A and reaches
upto bulb B where it comes in contact with iron sulphide. Then the reaction between iron
sulphide and H2SO4 takes place to form H2S gas. As H2S gas is formed, the gas pressure
inside bulb B increases and displaces the dil. H2SO4 to bulb A and then into the upper bulb C.
Increase in volume of H2S gas displaces acid as the result contact between FeS and dil. H2SO4
break and the formation of gas is stopped (ceased). When the tap is opened H 2S comes out
and the pressure decreases. As a result liquid level again rises at bulb B and H 2S gas start to
evolve again. In this way H2S gas is prepared intermittently by Kipp’s apparatus.

Q. Why conc sulphuric acid and nitric acid is not used to prepare H 2S?
Because they oxidise H2S to free Sulphur.
 Phsical Properties of hydrogen sulphide
1. It is colourless gas with rotten egg smell.
2. It is soluble in water.
3. It is poisonous gas.
4. It is heavier than air

Structure of H2S:

Chemical Properties of hydrogen sulphide

1. Acidic character : It acts as a weak diprotic(dibasic) acid. It ionizes in two steps to give two protons .
 *H S reacts with base to form two series of salts. Eg.
2

*H S reacts with basic oxides to give salt. eg.

2

H2S as reducing agent :

ulphur in H2S bears -2 oxidation state which in minimum oxidation state of sulphur. In chemical reaction, H 2S tends to get oxidized. So H2S
t reduces halogens into halogen acids.
* 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 KMnO 4 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 in alkaline medium i.e. NH 4Cl 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.

Why alkaline medium is not used?

Because they form respective hydroxide which
prevents formation of their sulphide.

orangeppt
oup IIIB basic radicals:
up IIIB basic radicals consist of Zn++, Co++, Ni++, Mn++. These are precipitated by passing H2S in alkaline medium ( i.e. NH4Cl+ NH4OH).

Why acidic medium is not used?

In acidic medium H2S is a weak acid dissociates
partially and produce less S– and less sulphide ppt.
 Uses of H2S:
•It is used as analytical reagent in laboratory.
•It is used as reducing agent.
•It is used to prepare metallic sulphide, which can
be used as pigment.

Sulphur
Chemical dioxide
Properties of sulphur (SO 2)
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.

2. SO as a reducing agent: Aqueous sulphurdioxide shows reducing character and

2

SO itself gets oxidized to H SO .

2 2 4

* It reduces halogens (Cl , Br , I ) in aq. Solution to respective halides. Eg.

2 2 2
* It reduces acidified potassium permanganate solution and pink colour of KMnO 4 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 (KIO ) solution to iodine.

3
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.

. SO2 as bleaching agent:

ormation of colourless product from coloured substance is called bleaching. Chemical substances such as SO 2, 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.

→ The bleaching action of SO2 is temporary. The bleached colourless compound will regain its
original colour slowly on standing in air due to oxidation by air.
Comparison of bleaching action of SO2 and Cl2:

Sulphur dioxide (SO2) Chlorine (Cl2)

1. Sulphur dioxide reacts with water to 1. Chlorine reacts with water to yield
yield nascent hydrogen which bleaches nascent oxygen which bleaches coloured
coloured substance to colourless substance to colourless product by
product by reduction. oxidation.
SO2 + 2H2O –> H2SO4 + 2 [H] Cl2 + H2O –> 2HCl + 2[O]

2. Bleaching by SO2 may be sometimes 2. No such colourless addition product is

due to formation of colourless addition formed with chlorine.
products.
3. Bleaching by Cl2 is irreversible ie. a
3. Bleaching by SO2 is reversible i.e. a permanent process.
temporary process.
4. Cl2 is strong bleaching agent.
4. SO2 is mild bleaching agent.
5. It is used to bleach wood, textiles,
5. It is used to bleach delicate articles paper, etc.
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.
20
Do Briefing of each step by yourself from class instructions.
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 4500C is supplied.
•High concentration of reactants : High concentration of SO 2 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.
 Physical Properties of H2SO4:

•It is colourless, hygroscopic, syrupy liquid.

•It is highly soluble in water and dissolves in water with the liberation of large quantity
of heat 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.
•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 of H SO : 2 4

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. H SO as an oxidizing agent :
2 4

i. 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 H 2SO4 gets reduced to SO2.
ii. Action with non metals :

•Carbon is oxidized to carbondioxide.

•Sulphur is oxidized to sulphurdioxide.

•Phosphorus is oxidized to phosphoric acid.

iii. 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:

Structure : Lewis structure of H SO

2 4
Uses of sulphuric acid

•It is used for the manufacture of fertilizers.

•It is used in manufacture of HCl, HNO3, H3PO4, etc.
•It is used as an oxidizing agent.
•It is used as a drying and dehydrating agent.

Test of H SO : 2 4

Sulphuric acid gives H+ ions and SO4– – ions in aqueous solution. The presence of H+ ion can be detected
by litmus paper. The presence of SO4– – can be detected by BaCl2 solution which gives white precipitate.
 Sodium thiosulphate(hypo) :

Molecular formula : Na2S2O3. 5H2O

It is commonly called hypo.

Uses of sodium thiosulphate(hypo) :

•It is used as a fixer in photography. { i.e. for fixing silver bromide in photographic plate}
•It is used in (iodometric) titration for the estimation of iodine.
•It is used as an antichlor agent to remove excess of chlorine from bleached textiles/fibers.