Class 12th

7.57

The general electronic configuration of halogens is np⁵, where n = 2-6. Thus, halogens need only one more electron to complete their octet and to attain the stable noble gas configuration.

Also, halogens are highly electronegative with low dissociation energies and high negative electron gain enthalpies. Therefore, they have a high tendency to gain an electron.

Whenever an atom accepts an electron from another atom, the atom accepting the electron is getting reduced and the atom donating the electron is oxidized.

But the electron accepting atom acts as an oxidizing agent while the electron donating atom acts as reducing agent. Hence, they act as strong oxidizing agents.

7.56

SO₂ is a highly irritating gas and causes serious respiratory problems, and may cause a fit of coughing.

1. It reacts with water vapour present in the atmosphere to form sulphuric acid. This causes acid rain. Acid rain damages soil [soil become more acidic], plants, and buildings get corroded, especially those made of marble.

In the air, SO₂ is oxidized to SO₃ which is also an irritant.

2SO₂ + O₂  2SO₃ SO₃ + H₂O H₂SO₄

2. Even in very low concentrations, SO₂ causes irritation in the respiratory It causes throat and eye irritation and can also affect the larynx to cause breathlessness.

3. It is extremely harmful to plants. Plants exposed to sulphur dioxide for a prolong time lose colour from their This condition is known as chlorosis. This is because the formation of chlorophyll is retarded in presence of sulphur dioxide.

(i) Zone refining Is the method based on the principle that the impurities are more soluble in the melt than in the solid state of the metal.

(ii) Electrolytic refining works on the principle of refining impure metals by the use of electricity. In Electrolytic refining, the impure metal is made the anode and a strip of pure metal is made as the A solution of a soluble salt of the same metal is taken as the electrolyte. When an electric current is passed, metal ions from the electrolyte are deposited at the cathode as a pure metal and the impure metal from the anode dissolves into the electrolyte in the form of ions. The impurities present in the impure metal gets collected below the anode.

(iii) Vapour refining is the process of refining metal by converting it into its volatile compound and then, decomposing it to obtain a pure metal. To carry out this process,

1. The metal should form a volatile compound with an available reagent, and
2. The volatile compound should be easily decomposable so that the metal can be easily recovered
3. Nickel, Zirconium and titanium are refined using this method.

7.55

Theory: This process involves the catalytic oxidation of sulphur dioxide into sulphur trioxide by atmospheric air.

2SO₂ + O₂  2 SO_3; A_H = - 196.6 kJ

The reaction is reversible, exothermic and involves a decrease in the number of moles. Therefore, according to the Le-Chatelier's principle, the favourable conditions for the maximum yield of sulphur trioxide are as follows.

[i]. Low temperature: A decrease in temperature would favour the forward reaction. The optimum temperature is experimentally found to be 670-720 K.

[ii]. High pressure: An increase in pressure should favour the forward reaction because the reaction involves a decrease in a number of moles. In practice, about 2-atmosphere pressure is maintained.

[iii]. Excess of oxygen: An increase in the concentration of reactants favours the forward reaction. Hence, oxygen [air] is used in excess.

[iv]. Use of catalyst:

1] Even at low temperature and high pressure, the yield of sulphur trioxide is not very satisfactory. 2] Hence, a suitable catalyst must be used to increase the rate of formation of sulphur trioxide.

Several catalysts such as platinized asbestos, platinized silica gel, vanadium pentoxide, may be used for the purpose.

Nowadays, vanadium pentoxide is extensively used as a catalyst in this It gives good results at 67-72 K and is less susceptible to poisoning.

The sulphur trioxide obtained as above is dissolved in concentrated sulphuric acid to get oleum. Sulphuric acid of desired concentration can be obtained by diluting it with water.

The plant used in the process consists of following parts.

[i]. Sulphur burners: In these burners, sulphur is burnt to produce sulphur dioxide. S + O₂ SO₂

Iron pyrites may also be used in place of sulphur. 4FeS₂ + 11O₂  2Fe₂O₃ + 8SO₂

Sulphur dioxide thus produced is mixed with air and is taken to the purification unit.

[ii]. Purification unit: The impurities present in the mixture of sulphur dioxide and air coming from sulphur burners are removed in this unit. The unit consists of following parts.

Dust precipitator: It makes the dust particles to settle

Washing and cooling tower: The dust-free gases are washed with water to remove the impurities and to cool the gases.

Drying Tower: In this tower, the incoming gases are dried by a spray of H₂SO₄.

Arsenic purifier: It consists of gelatinous ferric hydroxide and absorbs any impurity of arsenic oxide present in the gases.

Testing box: This box detects the presence of solid particles in the incoming When the gases are found free from solid particles, they are allowed to move onwards to the contact tower.

[iii] Contact tower:

It consists of iron pipes packed with vanadium

The gases coming out of the testing box are heated to 725 K in a pre-heater and then allowed to enter into this

As the mixture of sulphur dioxide and air passed through the pipes containing the catalyst, sulphur dioxide gets oxidized to sulphur trioxide.

The conversion of SO₂ into SO₃is exothermic and heat generated in the reaction is sufficient to maintain the temperature of the catalyst.

Therefore, once the process has started, the gases are not heated in the pre-heater and are passed directly into the contact

[iv]. Absorption tower:

The sulphur trioxide formed in the contact tower is now led to the absorption tower where it is brought in contact with conc. H₂SO₄which is sprayed from the top of the

Sulphur trioxide gets dissolved in conc. Sulphuric acid to give oleum. This can be converted into sulphuric acid of desired concentration by diluting it with a calculated amount of

Sulphur trioxide is not absorbed in water directly because it results in the formation of the dense fog of sulphuric acid particles which makes the operation difficult to

This is why it is preferred to dissolve SO₃ into Sulphuric acid to obtain oleum.

Thermodynamic factors help us in choosing a suitable reducing agent for the reduction of a particular metal state as described below.

From Ellingham diagram, it is evident that metals for which the standard free energy of formation of their oxides is more negative can reduce those metal oxides for which the standard free energy of formation of their respective oxides is less negative. In other words, any metal will reduce the oxides of other metals which lie above in the Ellingham Diagram because the standard free energy change of the combined redox reaction will be negative by any amount of equal to the difference in Δ _fG⁰ of the two metal oxides. Hence, both Al, Zn can reduce FeO to Fe, but Fe cannot reduce Al₂O₃ to Al and ZnO to Zn.