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It is true that the cathode will be the Ecell that is more positive. You can also to see which part of the reaction is oxidized and which part is reduced to figure out what will be the anode or cathode in the half reactions.
In addition, you want a galvanic cell with a positive E (naught) for the reaction. So after you see the the E (naught) of the two half reactions, you can figure out which reaction will be the reduction and which reaction will be the oxidation.
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