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Just to be clear, given two half equations, the Cathode consists of the more electronegative atom right? Also, for all of the half equations, are the E(cathode)/E(anode) values flipped if we were to flip the sign of the equation?
The cathode equations should have a more positive value of standard potential then the anode half reactions. This makes sense because when you go to determine the standard cell potential then you will arrive at the most energetically favorable number.
The anode has the element that is most likely oxidized while the cathode has the element that is reduced. The half-reaction with the element that is most likely reduced has a higher standard potential (more V) so it forms the cathode. The half-reaction with the element that is less likely reduced has a lower standard potential and that forms the anode. A half-reaction that is a reduction equation can be flipped to form an oxidation equation, also flipping the standard potential as well.
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