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Question

Which of the following statements is/are true for the electrolysis of aq.LiCl with Ag electrodes?

A
Ag is deposited at cathode
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B
O2 is liberated at anode
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C
Cl2 is liberated at anode
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D
None of the above
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Solution

The correct option is A Ag is deposited at cathode
When the electrolysis of aq.LiCl is done with Ag electrodes, there are three possible reaction to occur at both anode and cathode.
Here, the silver electrode used is a active electrode. It is involved in the cell reaction.
At cathode:
1. Li+(aq)+eLi(s)
E0Li+/Li=3.04 V

2. 2H2O(l)+2eH2(g)+2OH(aq)
E0H2O/H2=0.83 V

3. Ag+(aq)+eAg(s)E0Ag+/Ag=0.80 V

The reaction with a higher reduction value of E0 takes place at the cathode. Therefore, deposition of silver will take place at the cathode.
At cathode : Ag+(aq)+eAg(s)

At anode:
1. 2Cl(aq)Cl2(g)+2e
E0Cl/Cl2=1.36 V

2. 2H2O(l)4H+(aq)+O2(g)+4e
E0H2O/O2=1.23 V

3. Ag(s)Ag+(aq)+e
E0Ag/Ag+=0.8 V

The reaction with a higher oxidation value of E0 takes place at the anode. Therefore, silver is dissolved at anode.
At anode: Ag(s)Ag+(aq)+e

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