Standard Electrode Potentials

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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

Oxidized species + ne- ->

reduced species

Reduction at
cathode

Oxidation/
Reduction
concepts

The cell potential (often called the electromotive

force or emf) has a contribution from the anode
which is a measure of its ability to lose electrons it will be called its "oxidation potential". The
cathode has a contribution based on its ability to
gain electeons, its "reduction potential". The cell
potential can then be written
Ecell = oxidation potential + reduction potential

Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19

If we could tabulate the oxidation and reduction

potentials of all available electrodes, then we could
predict the cell potentials of voltaic cells created
from any pair of electrodes. Actually, tabulating
one or the other is suicient, since the oxidation
potential of a half-reaction is the negative of the
reduction potential for the reverse of that reaction.
Two main hurdles must be overcome to establish
such a tabulation
1. The electrode potential cannot be determined
in isolation, but in a reaction with some other
electrode.
2. The electrode potential depends upon the
concentrations of the substances, the

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Standard Electrode Potentials

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temperature, and the pressure in the case of a

gas electrode.
In practice, the rst of these hurdles is overcome
by measuring the potentials with respect to a
standard hydrogen electrode. It is the nature of
electric potential that the zero of potential is
arbitrary; it is the dierence in potential which has
practical consequence. Tabulating all electrode
potentials with respect to the same standard
electrode provides a practical working framework
for a wide range of calculations and predictions.
The standard hydrogen electrode is assigned a
potential of zero volts.
The second hurdle is overcome by choosing
standard thermodynamic conditions for the
measurement of the potentials. The standard
electrode potentials are customarily determined at
solute concentrations of 1 Molar, gas pressures of
1 atmosphere, and a standard temperature which
is usually 25C. The standard cell potential is
denoted by a degree sign as a superscript.

ECell

1. Measured against standard

hydroden electrode.
2. Concentration 1 Molar
3. Pressure 1 atmosphere
4. Temperature 25C

The example below shows some of the extreme

values for standard cell potentials.
Cathode (Reduction)
Half-Reaction

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Standard
Potential
E (volts)

Li+(aq) + e- -> Li(s)

-3.04

K+(aq) + e- -> K(s)

-2.92

Ca2+(aq) + 2e- -> Ca(s)

-2.76

Na+(aq) + e- -> Na(s)

-2.71

Zn2+(aq) + 2e- -> Zn(s)

-0.76

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Standard Electrode Potentials

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Cu2+(aq) + 2e- -> Cu(s)

0.34

O3(g) + 2H+(aq) + 2e- -> O2(g)

+ H2O(l)

2.07

F2(g) + 2e- -> 2F-(aq)

2.87

The values for the table entries are reduction

potentials, so lithium at the top of the list has the
most negative number, indicating that it is the
strongest reducing agent. The strongest oxidizing
agent is uorine with the largest positive number
for standard electrode potential. The link below
takes you to a more extensive table.
Table of Standard Electrode Potentials
Useful applications of the standard electrode
potentials include the following.
Strengths of oxidizing and reducing agents
Electrode potentials under non-standard
conditions
Potentials for voltaic cells
Relationship to Gibbs free energy
Relationship to equilibrium constants
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Calculation of Voltaic
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Index

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Standard Electrode Potentials

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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)

Zn2+(aq) + 2e- -> Zn(s)

-0.76

Cu2+(aq) + 2e- -> Cu(s)

0.34

The cell potential can be written

Ecell = oxidation potential + reduction potential
Since the tabulated standard electrode potentials
are reduction potentials, the one which is most
negative will need to be reversed in sign to get its
oxidation potential. When that is done, it is clear
that the theoretical standard cell potential for the
zinc-copper cell is 1.10 volts.

Oxidation/
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19

In general, a real voltaic cell will dier from the

standard conditions, so we need to be able to
adjust the calculated cell potential to account for
the dierences. This can be done with the
application of the Nernst equation.

Presuming that there are two metal electrodes

with their ions, the standard potential for a cell

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with anode potential

potential

volts and cathode

volts is

Ecell =

volts

If the ion concentration at the anode is [A] =

M and the concentration at the
cathode is [C] =

M, then the

thermodynamic reaction quotient Q = [A]/[C] =

For temperature =

C =

and number of electrons exchanged n =

K
,

the calculated cell potential is

Ecell =

volts

By numerically exploring the above calculation,

you can conrm that large concentration
dierences between the anions and the cations can
cause the voltage to dier signicantly from the
standard cell potential, and that such large
concentration dierences also make the cell
potential more temperature dependent.
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The Nernst Equation

The cell potential for a voltaic cell under standard
conditions can be calculated from the standard
electrode potentials. But real voltaic cells will
typically dier from the standard conditions. The
Nernst equation relates the cell potential to its
standard cell potential.
R = gas constant
T = temperature in
Kelvins
Q = thermodynamic
reaction quotient
F = Faraday's constant
n = number of electrons
transferred
The quantity Q, the thermodynamic reaction
constant, is like a dynamic version of the
equilibrium constant in which the concentrations
and gas pressures are the instantaneous values in
the reaction mixture. For a reaction

Index
Oxidation/
Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8

the reaction quotient has the form

Ebbing
Ch 19

where [C] is understood to be the molar

concentration of product C, or the partial pressure
in atmospheres if it is a gas.
Applied to the Daniell cell where zinc and copper
form the electrodes, the reaction is
Zn(s) + Cu2+(aq) <-> Zn2+(aq) + Cu(s)
the form of Q is

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since the concentrations of the pure metal solids

are assigned the value 1. This implies that the
departure of the cell potential from its standard
value of 1.10 volts will be inuenced by the
temperature and the ion concentrations.
One implication is that the
cell potential will be
reduced from the standard
value if the concentration of
Zn2+(aq) is greater than
that of Cu2+(aq) at the
standard temperature. An
excess concentration of
Cu2+(aq) will give a higher
voltage. The graph at right
shows the increase in cell
voltage with increasing
concentration of the cation.
Note that the horizontal
axis is logarithmic, and that
the straight line variation of
the voltage represents an
logarithmic variation with
Q. Note that the cell
potential is equal to the
standard value if the
concentrations are equal
even if they are not equal to
the standard value of 1M,
since the logarithm gives
the value zero.

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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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Background for the

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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

so for non-standard conditions

Reduction
concepts
Electrochemistry
concepts
Reference
Hill & Kolb
Ch 8
Ebbing
Ch 19

or

which is called the Nernst equation.

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