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The Ecell must be positive, and so you use the Ecathode -Eanode equation to determine which reaction is the cathode and anode by looking at the values you get when you put the E of one reaction in the cathode place and the other in the anode place. If the value is positive, the place you have the E values in are correct and you can look at the corresponding reactions to see which is cathode and which is anode.
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