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Electrochemistry

Question
CBSEENCH12005965

Explain why electrolysis of aqueous solution of NaCl gives H2 at cathode and Cl2 at anode. Write overall reaction.

Solution
Sodium chloride and water ionize as follows:
NaCl Na+ + Cl-H2O H+ + OH-
At cathode: Both Na+ and H+ ions are present near the cathode. But the discharge potential of H+ is lower than that of Na+ ion. So H+ ions are discharged in preference to Na+ ions.
H+ +e-  HH + H  H2
Thus H2 gas is liberated at the cathode and Na+ ions remain in the solution.
At the anode: Both Cl and OH ions are present near the anode. As the discharge potential of Cl ions is lower than that of OH- ions, so Cl ions are discharged in presence to OH ions.

Cl- + e-  ClCl   + Cl   Cl2

Thus Cl
2 is liberated at anode and OH ions remain in the solution.
The overall reaction is:
NaCl(aq) + H2 O(l) → Na+ (aq) + OH– (aq)
+12H2(g)+12Cl2(g)