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Standard Electrode
Potentials
In an electrochemical cell, an electric potential is
created between two dissimilar metals. This
potential is a measure of the energy per unit
charge which is available from the
oxidation/reduction reactions to drive the reaction.
It is customary to visualize the cell reaction in
terms of two half-reactions, an oxidation
half-reaction and a reduction half-reaction.
Reduced species -> oxidized
species + ne-
Oxidation at
anode
Index
Reduction at
cathode
Oxidation/
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19
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ECell
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Standard
Potential
E (volts)
-3.04
-2.92
-2.76
-2.71
-0.76
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0.34
2.07
2.87
Calculation of Voltaic
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Index
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Cell Potentials
When an electrochemical cell is arranged with the
two half-reactions separated but connected by an
electrically conducting path, a voltaic cell is
created. The maximum voltage which can be
produced between the poles of the cell is
determined by the standard electrode potentials
under the standard conditions under which those
potentials are dened.
Consider the historic Daniell cell in which zinc and
copper were used as electrodes. The data from the
table of standard electrode potentials is
Cathode (Reduction)
Half-Reaction
Standard Potential
E (volts)
-0.76
0.34
Oxidation/
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19
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Ecell =
volts
M, then the
For temperature =
C =
K
,
volts
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Index
Oxidation/
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19
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Consider a concentration of
10-5Molar for Zn2+(aq) and
0.1 Molar for Cu2+(aq) as a
test case for temperature
dependance. We can see
that the cell potential tends
to increase with
temperature, or that a
colder cell prodices less
voltage - a commonly
observed phenomenon with
dry cell batteries. The
variation with temperature
is linear with temperature,
but quite small for this cell.
The large variations of
practical output voltage
with temperature for dry
cells does not arise from the
Nernst equation alone.
Background for the Nernst equation
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Index
Oxidation/
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Nernst Equation
The Nernst equation allows us to predict the cell
potential for voltaic cells under conditions other
than standard conditions of 1M, 1 atmosphere,
25C. The eects of dierent temperatures and
concentrations may be tracked in terms of the
Gibbs free energy change G. This free energy
change depends upon the temperature and
concentrations according to
where
is the free energy change under
standard conditions and Q is the thermodynamic
reaction quotient. The free energy change is
related to the cell potential Ecell by
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19
or
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