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In the electrolysis of aqueous sodium chloride solution which of the half-cell reaction will occur at anode?

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By Expert Faculty of Sri Chaitanya
a
Na+(aq)+e−⟶Na(s);Ecell∘=−2.71V
b
2H2O(l)⟶O2(g)+4H+(aq)+4e−;Ecell∘−1.23V
c
H+(aq)+e−⟶12H2(g);Ecell∘=0.00V
d
Cl−(aq)⟶12Cl2(g)+e−;Ecell ∘=1.36V

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detailed solution

Correct option is D

In case of electrolysis of aq .NaCl oxidation reaction occurs at anode as follows:                        Cl−(aq)⟶12Cl2(g)+e−;E∘=1⋅36V2H2O(l)⟶O2(g)+4H+(aq)+4e−⋯; Ecell∘=1.23VBut due to lower Ecello value, water should get oxidised in preference of Cl- (aq)However, the actual reaction taking place is the first one i.e. Cl2 is produced.This unexpected result is explained on the basis of the concept of 'over voltage', i.e. water needs greater voltage for oxidation to O2 (as it is kinetically slow process) than that needed for oxidation of Cl- ions to Cl2.

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Similar Questions

Statement 1 : Electrolysis of NaCl solution gives chlorine at anode instead of O2.
Statement 2 : Formation of oxygen at anode requires over voltage.
 

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