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When using the equation , does the number of moles of electrons we plug in depend on the moles of ions we start out with? Or do we only look at the moles of electrons transferred within the overall reaction?
Not sure if I understand your question, but you should look at both! For example if 2Ce^4+(aq) --> 2Ce^3+(aq), then n should equal 2. Even though one electron was needed to lower the charge, there were two moles of the ions.
n is the number of electrons transferred, to find it you would find the two half reactions, and balance them out for an equal #e. for example if cathode reaction has 2e transfer and anode reaction has 3e transfer, you would balance them for both of them to have a 6e transfer, in which case your n would be 6.
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