Overpotential

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This article is about a concept in electrochemistry. For the fault condition in electrical engineering,
see Overvoltage.
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In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's

thermodynamically determined reduction potential and the potential at which the redox event is
experimentally observed.[1] The term is directly related to a cell's voltage efficiency. In an electrolytic
cell the existence of overpotential implies the cell requires more energy than thermodynamically
expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is
recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The
quantity of overpotential is specific to each cell design and varies across cells and operational
conditions, even for the same reaction. Overpotential is experimentally determined by measuring the
potential at which a given current density (typically small) is achieved.

Contents

 1Thermodynamics
 2Varieties
o 2.1Activation overpotential
 2.1.1Reaction overpotential
o 2.2Concentration overpotential
 2.2.1Bubble overpotential
o 2.3Resistance overpotential
 3See also
 4References

Thermodynamics[edit]
The four possible polarities of overpotentials are listed below.

 An electrolytic cell's anode is more positive, using more energy than thermodynamics require.
 An electrolytic cell's cathode is more negative, using more energy than thermodynamics
require.
 A galvanic cell's anode is less negative, supplying less energy than thermodynamically
possible.
 A galvanic cell's cathode is less positive, supplying less energy than thermodynamically
possible.
The overpotential increases with growing current density (or rate), as described by the Tafel equation.
An electrochemical reaction is a combination of two half-cells and multiple elementary steps.
Each step is associated with multiple forms of overpotential. The overall overpotential is the
summation of many individual losses.
Voltage efficiency describes the fraction of energy lost through overpotential. For an electrolytic cell
this is the ratio of a cell's thermodynamic potential divided by the cell's experimental potential
converted to a percentile. For a galvanic cell it is the ratio of a cell's experimental potential divided by
the cell's thermodynamic potential converted to a percentile. Voltage efficiency should not be
confused with Faraday efficiency. Both terms refer to a mode through which electrochemical systems
can lose energy. Energy can be expressed as the product of potential, current and time
(joule = volt × Ampere × second). Losses in the potential term through overpotentials are described
by voltage efficiency. Losses in the current term through misdirected electrons are described by
Faraday efficiency.

Varieties[edit]
Overpotential can be divided into many different subcategories that are not all well defined. For
example, "polarization overpotential" can refer to the electrode polarization and the hysteresis found
in forward and reverse peaks of cyclic voltammetry. A likely reason for the lack of strict definitions is
that it is difficult to determine how much of a measured overpotential is derived from a specific
source. Overpotentials can be grouped into three categories: activation, concentration, and
resistance.[2]
Activation overpotential[edit]
Activation overpotential for the evolution of selected gases on various electrode materials at 25 °C[citation needed]

Material of the electrode Hydrogen Oxygen Chlorine

Platinum (platinized) −0.07 V +0.77 V +0.08 V

Palladium −0.07 V +0.93 V

Gold −0.09 V +1.02 V

Iron −0.15 V +0.75 V

Platinum (shiny) −0.16 V +0.95 V +0.10 V

Silver −0.22 V +0.91 V

Nickel −0.28 V +0.56 V

Graphite −0.62 V +0.95 V +0.12 V

Lead −0.71 V +0.81 V

Zinc −0.77 V
Mercury −0.85 V

The activation overpotential is the potential difference above the equilibrium value required to
produce a current that depends on the activation energy of the redox event. While ambiguous,
"activation overpotential" often refers exclusively to the activation energy necessary to transfer an
electron from an electrode to an anolyte. This sort of overpotential can also be called "electron
transfer overpotential" and is a component of "polarization overpotential", a phenomenon observed
in cyclic voltammetry and partially described by the Cottrell equation.
Reaction overpotential[edit]
Reaction overpotential is an activation overpotential that specifically relates to chemical reactions that
precede electron transfer. Reaction overpotential can be reduced or eliminated with the use
of electrocatalysts. The electrochemical reaction rate and related current density is dictated by the
kinetics of the electrocatalyst and substrate concentration.
The platinum electrode common to much of electrochemistry is electrocatalytically involved in many
reactions. For example, hydrogen is oxidized and protons are reduced readily at the platinum surface
of a standard hydrogen electrode in aqueous solution. Substituting an electrocatalytically inert glassy
carbon electrode for the platinum electrode produces irreversible reduction and oxidation peaks with
large overpotentials.
Concentration overpotential[edit]
Concentration overpotential spans a variety of phenomena that involve the depletion of charge-
carriers at the electrode surface. Bubble overpotential is a specific form of concentration overpotential
in which the concentration of charge-carriers is depleted by the formation of a physical bubble. The
"diffusion overpotential" can refer to a concentration overpotential created by slow diffusion rates as
well as "polarization overpotential", whose overpotential is derived mostly from activation
overpotential but whose peak current is limited by diffusion of analyte.
The potential difference is caused by differences in the concentration of charge-carriers between bulk
solution and the electrode surface. It occurs when electrochemical reaction is sufficiently rapid to
lower the surface concentration of the charge-carriers below that of bulk solution. The rate of reaction
is then dependent on the ability of the charge-carriers to reach the electrode surface.
Bubble overpotential[edit]
Bubble overpotential is a specific form of concentration overpotential and is due to the evolution of
gas at either the anode or cathode. This reduces the effective area for current and increases the local
current density. An example is the electrolysis of an aqueous sodium chloride solution—
although oxygen should be produced at the anode based on its potential, bubble overpotential
causes chlorine to be produced instead, which allows the easy industrial production of chlorine
and sodium hydroxide by electrolysis.
Resistance overpotential[edit]
Resistance overpotentials are those tied to a cell design. These include "junction overpotentials" that
occur at electrode surfaces and interfaces like electrolyte membranes. They can also include aspects
of electrolyte diffusion, surface polarization (capacitance) and other sources of counter electromotive
forces.

See also[edit]
 Electrolysis