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E°cell= E°cathode − E°anode is used when the half reactions are both in reduction form so ie: Cu ^2+ + 2e -> Cu. E°cell= E°cathode + E°anode is used when the half reaction of the anode is in its real state, oxidized, ie: Cu -> Cu^2+ + 2e. if done right, both ways give you the same answer.
The first way is taking the standard reduction potentials of each (when both are going in same direction). The second way also works bc you switch the reduced half equation and flip the E sign so it still holds to be true.
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