Reduction-Potential

Reduction potential 1
Reduction potential
Reduction potential (also known as redox potential, oxidation / reduction potential, ORP or ) is a measure
of the tendency of a chemical species to acquire electrons and thereby be reduced. Reduction potential is measured in
volts (V), or millivolts (mV). Each species has its own intrinsic reduction potential; the more positive the potential,
the greater the species' affinity for electrons and tendency to be reduced.
Measurement and Interpretation

In aqueous solutions, the reduction potential is a measure of the tendency of the solution to either gain or lose
electrons when it is subject to change by introduction of a new species. A solution with a higher (more positive)
reduction potential than the new species will have a tendency to gain electrons from the new species (i.e. to be
reduced by oxidizing the new species) and a solution with a lower (more negative) reduction potential will have a
tendency to lose electrons to the new species (i.e. to be oxidized by reducing the new species). Just as the transfer of
hydrogen ions between chemical species determines the pH of an aqueous solution, the transfer of electrons between
chemical species determines the reduction potential of an aqueous solution. Like pH, the reduction potential
represents an intensity factor. It does not characterize the capacity of the system for oxidation or reduction, in much
the same way that pH does not characterize the acidity.
Because the absolute potentials are difficult to accurately measure, reduction potentials are defined relative to a
reference electrode. Reduction potentials of aqueous solutions are determined by measuring the potential difference
between an inert sensing electrode in contact with the solution and a stable reference electrode connected to the
solution by a salt bridge. The sensing electrode acts as a platform for electron transfer to or from the reference half
cell. It is typically platinum, although gold and graphite can be used. The reference half cell consists of a redox
standard of known potential. The standard hydrogen electrode (SHE) is the reference from which all standard redox
potentials are determined and has been assigned an arbitrary half cell potential of 0.0 mV. However, it is fragile and
impractical for routine laboratory use. Therefore, other more stable reference electrodes such as silver chloride and
saturated calomel (SCE) are commonly used because of their more reliable performance.
Although measurement of the reduction potential in aqueous solutions is relatively straightforward, many factors
limit its interpretation, such as effects of solution temperature and pH, irreversible reactions, slow electrode kinetics,
non-equilibrium, presence of multiple redox couples, electrode poisoning, small exchange currents and inert redox
couples. Consequently, practical measurements seldom correlate with calculated values. Nevertheless, reduction
potential measurement has proven useful as an analytical tool in monitoring changes in a system rather than
determining their absolute value (e.g. process control and titrations).
Standard reduction potential,

The standard reduction potential ( ) is measured under standard conditions: 25°C, a 1 M concentration for each
ion participating in the reaction, a partial pressure of 1 atm for each gas that is part of the reaction, and metals in their
pure state. The standard reduction potential is defined relative to a standard hydrogen electrode (SHE) reference
electrode, which is arbitrarily given a potential of 0.00 volts. Historically, many countries, including the United
States and Canada, used standard oxidation potentials rather than reduction potentials in their calculations. These are
simply the negative of standard reduction potentials, so it is not a major problem in practice. However, because these
can also be referred to as "redox potentials", the terms "reduction potentials" and "oxidation potentials" are preferred
by the IUPAC. The two may be explicitly distinguished in symbols as and .
Converting potentials between different types of reference electrodes

Often a reduction potential is quoted as measured against a different reference electrode than the one desired and it
becomes necessary to convert to the desired reference potential. Alternatively, it may be necessary to convert
measurements to the standard reduction potential for reporting purposes. This is easily done by recognizing that the
observed potential represents the difference between the potential at the sensing electrode and the potential at the
reference electrode, i.e.
Where is the observed reaction, is the reference used in experiment, and is the reference that is
desired. The voltage relationships for several different reference electrodes at 25 °C can be interrelated as follows:
Reference electrode Electrode potential with respect to SHE (mV)
Standard hydrogen electrode (SHE) 0
Saturated calomel electrode (SCE) + 241
Ag/AgCl, 1 M KCl + 236
Ag/AgCl, 4 M KCl + 200
Ag/AgCl, sat. KCl +197
For example, if one measured 300 mV using a saturated KCl Ag/AgCl reference(ref2) and wanted to refer it to the
standard reduction potential ( ) measured using a SHE reference electrode (ref1), then 197 mV should be added
to the 300 mV to obtain 497 mV, since
it follows that
and therefore
Likewise, if one measured 300 mV using a saturated KCl Ag/AgCl reference (ref2) and wanted to determine the
corresponding measurement using an SCE reference (ref1), then given
it follows that
and therefore
Half cells
The relative reactivities of different half cells can be compared to predict the direction of electron flow. A higher
means there is a greater tendency for reduction to occur, while a lower one means there is a greater tendency for
oxidation to occur.
Any system or environment that accepts electrons from a normal hydrogen electrode is a half cell that is defined as
having a positive redox potential; any system donating electrons to the hydrogen electrode is defined as having a
negative redox potential. is measured in millivolts (mV). A high positive indicates an environment that
favors oxidation reaction such as free oxygen. A low negative indicates a strong reducing environment, such as
free metals.
Sometimes when electrolysis is carried out in an aqueous solution, water, rather than the solute, is oxidized or
reduced. For example, if an aqueous solution of NaCl is electrolyzed, water may be reduced at the cathode to
produce H2(g) and OH- ions, instead of Na+ being reduced to Na(s), as occurs in the absence of water. It is the
reduction potential of each species present that will determine which species will be oxidized or reduced.
Absolute reduction potentials can be determined if we find the actual potential between electrode and electrolyte for
any one reaction. Surface polarization interferes with measurements, but various sources give an estimated potential
for the standard hydrogen electrode of 4.4 V to 4.6 V (the electrolyte being positive.)
Half-cell equations can be combined if one is reversed to an oxidation in a manner that cancels out the electrons to
obtain an equation without electrons in it.
Nernst equation
The and pH of a solution are related. For a half cell equation, conventionally written as reduction (electrons on
the left side):
The half cell standard potential is given by:
where is the standard Gibbs free energy change, is the number of electrons involved, and is Faraday's
constant. The Nernst equation relates pH and :
where curly brackets indicate activities and exponents are shown in the conventional manner. This equation is the
equation of a straight line for as a function of pH with a slope of volt (pH has no units.) This
equation predicts lower at higher pH values. This is observed for reduction of O2 to OH− and for reduction of
H+ to H2. If H+ were on the opposite side of the equation from H+, the slope of the line would be reversed (higher
at higher pH). An example of that would be the formation of magnetite (Fe3O4) from HFeO:[1]
3 HFeO + H+ = Fe3O4 + 2 H2O + 2 e<sup>−</sup>
where = −1.1819 − 0.0885 log[HFeO] + 0.0296 pH. Note that the slope of the line is −1/2 the −0.05916 value
above, since = −1/2.
In biochemistry
Many enzymatic reactions are oxidation-reduction reactions in which one compound is oxidized and another
compound is reduced. The ability of an organism to carry out oxidation-reduction reactions depends on the
oxidation-reduction state of the environment, or its reduction potential ( ).
Strictly aerobic microorganisms are generally active at positive values, whereas strict anaerobes are generally
active at negative values. Redox affects the solubility of nutrients, especially metal ions.
There are organisms that can adjust their metabolism to their environment, such as facultative anaerobes. Facultative
anaerobes can be active at positive Eh values, and at negative Eh values in the presence of oxygen bearing inorganic
compounds, such as nitrates and sulfates.
In geology
Eh-pH (Pourbaix) diagrams are commonly used in mining and geology for assessment of the stability fields of
minerals and dissolved species. Under conditions where a mineral (solid) phase is the most stable form of an
element, these diagrams show that mineral. As with results from all thermodynamic (equilibrium) evaluations, these
diagrams should be used with caution. Although the formation of a mineral or its dissolution may be predicted to
occur under a set of conditions, the process may be negligible because its rate is so slow. Under those circumstances,
kinetic evaluations are necessary. However, the equilibrium conditions can be used to evaluate the direction of
spontaneous changes and the magnitude of the driving force behind them.
References
[1] Garrels, R.M.; Christ, C.L. (1990). Minerals, Solutions, and Equilibria. London: Jones and Bartlett.
External links
• Redox potential definition (http://users.rcn.com/jkimball.ma.ultranet/BiologyPages/R/RedoxPotentials.
html)
• Large table of potentials (http://www.northland.cc.mn.us/Chemistry/standard_reduction_potentials.htm)
(Site broken. Archived version (http://web.archive.org/web/20070518092613/http://www.northland.cc.
mn.us/Chemistry/standard_reduction_potentials.htm) on the Internet Archive.)
Article Sources and Contributors 5
Article Sources and Contributors

Reduction potential Source: http://en.wikipedia.org/w/index.php?oldid=483575198 Contributors: Adrian J. Hunter, Anuran, Aushulz, Avij, BeteNoir, BirgitteSB, Calanos, Corpx, Cybercobra,
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Reduction potential 1

Measurement and Interpretation

Standard reduction potential,

Converting potentials between different types of reference electrodes

Reference electrode Electrode potential with respect to SHE (mV)

Standard hydrogen electrode (SHE) 0

Saturated calomel electrode (SCE) + 241

Ag/AgCl, 1 M KCl + 236

Ag/AgCl, 4 M KCl + 200

Ag/AgCl, sat. KCl +197

The half cell standard potential is given by:

Article Sources and Contributors

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