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Just to confirm. When comparing a species couple, to determine which would be the anode and which would be the cathode, the higher/more positive standard potential would represent the cathode while the lower/more negative standard potential would represent the anode.
Yes you can do it like that, but not all the time. In an electrolytic cell, the potential is supposed to be negative; so, if you did it like you said, then you would mix them up because you are solving for the standard potential to be negative. It is a more safe bet to look at the overall reaction and [censored] whether the ion is being oxidized or reduced and go from there.
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