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OXIDATION HALF REACTION AT THE ANODE AQUEOUS NaCl

Electrochemistry

Electrochemical Cells 

Electrolytic cell

Electrolysis of aqueous NaCl 

Oxidation half-reaction at the anode

At anode there will be a competition between oxidation of CI- to CI2, as in the case of molten NaCl and oxidation of water to O2 gas

2CI-(aq) → CI2(g) + 2e- = -1.36 V            E0oxi = -1.36 V

2H2O(l) → O2(g) + 4H+(aq) + 4e-              E0oxi = -0.4 V

The standard electrode potential for oxidation of water is greater than that for oxidation of CI-.

This means that water has a greater tendency to undergo oxidation than CI- ion.

It is, therefore, expected that the cathode half-reaction must be oxidation of water to O2, gas.

However, the experimental observation shows that the gas produced at the anode is Cl2, gas, and not O2, gas.

This indicates that the reaction that occurs is the oxidation of Cl- to Cl2.

This is because of the phenomenon of overvoltage.

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