Why positive and negative are different in galvanic cell and electrolytic cell?

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Why positive and negative are different in galvanic cell and electrolytic cell?

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Why positive and negative are different in galvanic cell and electroly...

Galvanic cell

Now, in a galvanic cell the reaction proceeds without an external potential helping it along. Since at the anode you have the oxidation reaction which produces electrons you get a build-up of negative charge in the course of the reaction until electrochemical equilibrium is reached. Thus the anode is negative.

At the cathode, on the other hand, you have the reduction reaction which consumes electrons (leaving behind positive (metal) ions at the electrode) and thus leads to a build-up of positive charge in the course of the reaction until electrochemical equilibrium is reached. Thus the cathode is positive.

Electrolytic cell

In an electrolytic cell, you apply an external potential to enforce the reaction to go in the opposite direction. Now the reasoning is reversed. At the negative electrode where you have produced a high electron potential via an external voltage source electrons are "pushed out" of the electrode, thereby reducing the oxidized species Ox, because the electron energy level inside the electrode (Fermi Level) is higher than the energy level of the LUMO of Ox and the electrons can lower their energy by occupying this orbital - you have very reactive electrons so to speak. So the negative electrode will be the one where the reduction reaction will take place and thus it's the cathode.

At the positive electrode where you have produced a low electron potential via an external voltage source electrons are "sucked into" the electrode leaving behind the the reduced species Red because the electron energy level inside the electrode (Fermi Level) is lower than the energy level of the HOMO of Red. So the positive electrode will be the one where the oxidation reaction will take place and thus it's the anode.

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