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When you're relating free energy to the cell potential, as given by , the cell potential (E) comes from the galvanic cell. So, you'd need to calculate the cell potential from the galvanic cell and its two electrodes – the anode and the cathode. Using the two electrodes, you can find the half reactions to find the cell potential of the galvanic cell.
The importance of a galvanic cell is that charge is being transferred from one species to another, or from anode to cathode and as electrons are transferred from one species to another there is a buildup of charge and a voltage associated with that. Therefore electricity is generated when electrons are transferred from one species to the next and allows for the transfer of energy.
I found that this Khan Academy video may be helpful/relevant in answering your question: https://www.khanacademy.org/science/che ... ree-energy
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