Overpotentials in Electrochemical Cells

Electrochemical devices – whether a reaction cell, battery, or fuel cell – operate

at potentials substantially different than their reversible potentials. The
difference between actual potential and reversible potential is called the
overpotential.
An overpotential is the potential beyond a reversible potential
that produces an increased thermodynamic driving force for
the process.

Overpotentials may be positive or negative. The sign is determined by the

nature of the process: overpotentials for reduction are negative, since a more
negative potential is more reducing. Conversely, overpotentials for oxidation are
positive, since a more positive potential is more oxidizing. Overpotentials are
not limited to reactions. They can be applied to electrode and electrolyte
resistance, and to more complex processes, such as mass transfer limitations.
Thus, overpotentials for cathodes are negative, whereas those for anodes are
positive.
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