Answer :

In the electrolysis of NaCl by Down’s process, chlorine is obtained as a by-product. This process involves the electrolysis of a fused mixture of NaCl and CaCl2 at 873K. during electrolysis, sodium is liberated at the cathode and Cl2 is liberated at the anode.

If an aqueous solution of NaCl is electrolysed, H2 is evolved at the cathode and Cl2 is obtained at the anode. the reason being that E0 of Na+/Na redox couple is much lower (E0 = - 2.71 V) than that of H2O (E0H2O/H2) = - 0.83V ) and hence water is reduced to H2 in presence of Na+ ions. However, NaOH is obtained in the solution.

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