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When oxidation and reduction reactions are run through a singular electrode that has a voltage applied across it it will run only one of the reaction at a time. What determines whether it goes through oxidation or reduction. Obviously the solution being used needs to be capable of going up or down. What voltage range encourages each reaction?
If you look at the standard reduction potentials (pg A17 in Appendix 2 in the book) the reduction half-reactions are listed in order of strongly oxidizing to strongly reducing. The stronger the reduction rxn (more positive voltage) and the less favorable the oxidation rxn (less positive voltage) the more favorable the overall reaction. Depending on these potentials, the reactions will sway in one direction or the other. The key is that the most positive voltage is optimal for driving the reaction.
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