Under standard conditions (pressure of
hydrogen gas 1 atm, acid concentration of 1 mol
L-1), the potential for the reduction reaction
below is assigned a value of zero vaults
2H+(aq) + 2e- <--> H2(g) Eo = 0.00V
For any redox couple, the standard electrode
(reduction) potential is the voltage obtained
under standard conditions when that half-cell is
connected to the standard hydrogen electrode
Experimentally, the more positive terminal is always
where reduction is occurring in a spontaneous reaction
Example
The cell potential for the electrochemical cell below is +0.76V:
Zn(s) | Zn2+(aq) || H+(aq) | H2(g) | Pt(s)
The Zn electrode is the negative and
the standard reduction potential for
the Zn2+/Zn half cell is -0.76V
If the Zn2+/Zn electrode is replaced
with a Cu2+/Cu electrode, the Cu2+ is
reduced and the H2 gas is oxidised
The Cu electrode is positive and
the Cu2+ | Cu couple will have a
positive reduction potential
The voltmeter has a reading of +0.34V:
Pt(s) | H+(aq) | H2(g) || Cu2+(aq) | Cu(s)
When comparing standard reduction potentials, the species
on the left in the couple with the most positive reduction
potential will be the strongest oxidising agent or oxidant
As the electrode potential
decreases, the strength of
oxidant species decreases,
while strength of reductant
species increases
When comparing standard reduction
potentials, the species on the left in the couple
with the most positive reduction potential will
be the strongest oxidising agent or oxidant
As the electrode potential decreases, the
strength of the oxidant species decreases,
while strength of reductant species increases
Using reduction potentials
to determine Eo cell
In any electrochemical cell, Eo
cell = Eo (reduction half-cell) -
Eo (ocidation half-cell) or Eo
cell = Eo (cathode) - Eo (anode)
The couple with the more positive
reduction potential will be the
reduction half-cell (cathode)
A more reactive metal will reduce
the cation of a less reactive metal,
as the Eo cell value for the reaction
will be positive (the more reactive
metal is the reductant in the redox
couple with the lower Eo value
Despite a positive standard
cell potential, a reaction
may be very slow due to a
high activation energy
A reaction may not
proceed if the surface
of the metal is
coated with an oxide