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Metal-electrolyte interface
An interface is created when a metal (solid) electrode is
by
i io RT ln ai
G
i
ni P ,T ,ni n j
G n i i
i
i ( I ) i ( II )
If above equality is not fulfilled, then spontaneous reaction
When metal (M)is in contact with its ions (Mz+) in solution then the
Cu Cu e
2
( aq)
(m)
(a)
(b)
i ( I ) zi Fi ( I ) i ( II ) zi Fi ( II )
where i(I)and I(II) are the electrical potential in the interior
of phases (I) and (II)
ziFI the electrical work needed to bring one mole of ions
with z charge from infinity to the region of where the
potential I exists
I is called Galvani potential
i zi Fi i RT ln ai zi Fi
o
i 0
0
2
Cu
Cu
For the reaction
(s)
( aq) 2e( m ) we write:
o
o
Cu
RT ln aCu 0FCu Cu
RT ln aCu 2FCu eo RT ln ae 2Fe
2
M sol
and called Galvani potential
By rearrangement
o
o
Cu
2eo Cu
2
2F
RT aCu2
ln
2F
aCu
RT aCu2
ln
2F
aCu
o
question
If two different metal/solution interfaces are connected, how the
potential difference is expressed?