[Mr. Raru]

In the electrolysis of AgNO3 with inert electrodes, why is the silver ion reduced rather than the nitrate ion when the nitrate has a higher standard electrode potential?

[Bakegaku]

A substance is reduced when electrons (or just one) are added to it.  Which ion can accept electrons?

[Mr. Raru]

A substance is reduced when electrons (or just one) are added to it.  Which ion can accept electrons?

Yes, I know this but:
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l)   0.96
Ag+(aq) + e- -> Ag(s) 0.80

Ah, but I think I answered my own question. I am not in acidic solution, correct? so the reduction of nitrate is not possible. And Ag+ is more readily reduced than H₂O to H₂.
2H2O(l) + 2e- -> H2(g) + 2OH-(aq) -0.83

[AWK]

During electrolysis you have anions close to anode and cations close to cathode. During electrolysis of AgNO3 you should add some acid (HNO3) to prevent precipitation of Ag2O.

[xiankai]

just wondering, how does the Ag2O form? isnt Ag supposed to be a non-reactive metal?

[Alberto_Kravina]

just wondering, how does the Ag2O form? isnt Ag supposed to be a non-reactive metal?

Ag₂O exists. Although silver is a "non-reactive" metal it forms ions (Au, Pt, and some other "non-reactive" metals form ions as well)

[AWK]

During electrolysis you have cathode compartment and anode compartment.
At cathode the following reactions take place
Ag+ + e = Ag(s)
and
2H2O(l) + 2e- = H2(g) + 2OH-(aq)
without mixing of solution from both compartment
2Ag+ + 2OH- = Ag2O(s) + H2O as a side reaction
when mixing
OH- + H3O+ = 2H2O

At anode
6H2O = O2 + 4H3O+ + 4e-