9/30/2019 Reduction potential - Wikipedia

Reduction potential
Redox potential (also known as oxidation / reduction potential, ORP, pe, ε, or ) is a measure of the
tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or
oxidised, respectively. Redox potential is measured in volts (V), or millivolts (mV). Each species has its own intrinsic
redox potential; for example, the more positive the reduction potential (reduction potential is more often used due to
general formalism in electrochemistry), the greater the species' affinity for electrons and tendency to be reduced. ORP
can reflect the antimicrobial potential of the water.[1]

Contents
Measurement and interpretation
Explanation
Standard reduction potential
Half cells
Nernst equation
Biochemistry
Environmental chemistry
Water quality
Geology
See also
Weblinks
References
Additional notes
External links

Measurement and interpretation

In aqueous solutions, redox potential is a measure of the tendency of the solution to either gain or lose electrons when
it is subjected 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). Because the absolute potentials are next to
impossible 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.[2]

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 as well. 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.

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Although measurement of the redox 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).

Explanation
Similar to the concentration of hydrogen ion determines the acidity or pH of an aqueous solution, the tendency of
electron transfer between a chemical species and an electrode determines the redox potential of an electrode couple.
Like pH, redox potential represents how easily electrons are transferred to or from species in solution. Redox potential
characterises the ability under the specific condition of a chemical species to lose or gain electrons instead of the
amount of electrons available for oxidation or reduction.

In fact, it is possible to define pe, the negative logarithm of electron concentration (-log[e]) in a solution, which will be
directly proportional to the redox potential.[2][3] Sometimes pe is used as a unit of reduction potential instead of ,
for example in environmental chemistry.[2] If we normalize pe of hydrogen to zero, we will have the relation pe=16.9
at room temperature. This point of view is useful for understanding redox potential, although the transfer of
electrons, rather than the absolute concentration of free electrons in thermal equilibrium, is how one usually thinks of
redox potential. Theoretically, however, the two approaches are equivalent.

Conversely, one could define a potential corresponding to pH as a potential difference between a solute and pH
neutral water, separated by porous membrane (that is permeable to hydrogen ions). Such potential differences
actually do occur from differences in acidity on biological membranes. This potential (where pH neutral water is set to
0 V) is analogous with redox potential (where standardized hydrogen solution is set to 0 V), but instead of hydrogen
ions, electrons are transferred across in the redox case. Both pH and redox potentials are properties of solutions, not
of elements or chemical compounds per se, and depend on concentrations, temperature etc.

Standard reduction potential

The standard reduction potential ( ) is measured under standard conditions: 25 °C, a 1 activity for each ion
participating in the reaction, a partial pressure of 1 bar 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 V. 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 .

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.

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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, n is the number of electrons involved, and F 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 HFeO2 (aq):[4]

3 HFeO−2 + H+ = Fe3O4 + 2 H2O + 2 [[e−]]

−
where Eh = −1.1819 − 0.0885 log([HFeO2 ]3) + 0.0296 pH. Note that the slope of the line is −1/2 the −0.05916
value above, since h/n = −1/2.

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.[5]

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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.

Environmental chemistry
In the field of environmental chemistry, the reduction potential is used to determine if oxidizing or reducing
conditions are prevalent in water or soil, and to predict the states of different chemical species in the water, such as
dissolved metals. pe values in water range from -12 to 25; the levels where the water itself becomes reduced or
oxidized, respectively.[2]

The reduction potentials in natural systems often lie comparatively near one of the boundaries of the stability region of
water. Aerated surface water, rivers, lakes, oceans, rainwater and acid mine water, usually have oxidizing conditions
(positive potentials). In places with limitations in air supply, such as submerged soils, swamps and marine sediments,
reducing conditions (negative potentials) are the norm. Intermediate values are rare and usually a temporary
condition found in systems moving to higher or lower pe values.[2]

In environmental situations, it is common to have complex non-equilibrium conditions between a large number of
species, meaning that it is often not possible to make accurate and precise measurements of the reduction potential.
However, it is usually possible to obtain an approximate value and define the conditions as being in the oxidizing or
reducing regime.[2]

In the soil there are two main redox constituents: 1) anorganic redox systems (mainly ox/red compounds of Fe and
Mn) and measurement in water extracts; 2) natural soil samples with all microbial and root components and
measurement by direct method [Husson O. et al.: Practical improvements in soil redox potential ( ) measurement
for characterisation of soil properties. Application for comparison of conventional and conservation agriculture
cropping systems. Anal. Chim. Acta 906 (2016): 98-109].

Water quality
Oxidation reduction potential (ORP) can be used for water system monitoring with the benefit of a single-value
measure of the disinfection potential, showing the activity of the disinfectant rather than the applied dose.[1] For
example, E. coli, Salmonella, Listeria and other pathogens have survival times of under 30 s when the ORP is above
665 mV, compared against >300 s when it is below 485 mV.[1]

A study was conducted comparing traditional parts per million chlorination reading and ORP in Hennepin County,
Minnesota. The results of this study argue for the inclusion of ORP above 650mV in local health codes.[6]

Geology
Eh-pH (Pourbaix) diagrams are commonly used in mining and geology for assessment of the stability fields of
minerals and dissolved species. Under the conditions where a mineral (solid) phase is predicted to be the most stable
form of an element, these diagrams show that mineral. As the predicted results are all from thermodynamic (at
equilibrium state) 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 practically be negligible because its
rate is too slow. Consequently, kinetic evaluations at the same time are necessary. Nevertheless, the equilibrium
conditions can be used to evaluate the direction of spontaneous changes and the magnitude of the driving force behind
them.

See also

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Galvanic cell
Electrolytic cell
Electromotive force
Electrochemical potential
Standard electrode potential
Solvated electron

Table of standard electrode potentials

Oxygen radical absorbance capacity
Redox
Fermi level

Weblinks
Online Calculator Redoxpotential („Redox Compensation”) (http://www.wolkersdorfer.info/en/redoxprobes.html)

References
1. Trevor V. Suslow, 2004. Oxidation-Reduction Potential for Water Disinfection Monitoring, Control, and
Documentation, University of California Davis, http://anrcatalog.ucdavis.edu/pdf/8149.pdf
2. vanLoon, Gary; Duffy, Stephen (2011). Environmental Chemistry -(*Gary Wallace) a global perspective (3rd ed.).
Oxford University Press. pp. 235–248. ISBN 978-0-19-922886-7.
3. 1981 Stumm, W. and Morgan, J. J. (1981): Aquatic chemistry, 2nd Ed.; John Wiley & Sons, New York
4. Garrels, R.M.; Christ, C.L. (1990). Minerals, Solutions, and Equilibria. London: Jones and Bartlett.
5. Chuan, M.; Liu, G. Shu. J (1996). "Solubility of heavy metals in a contaminated soil: Effects of redox potential and
pH". Water, Air, & Soil Pollution. 90: 543–556. Bibcode:1996WASP...90..543C (https://ui.adsabs.harvard.edu/abs/
1996WASP...90..543C). doi:10.1007/BF00282668 (https://doi.org/10.1007%2FBF00282668).
6. Bastian, Tiana; Brondum, Jack (2009). "Do Traditional Measures of Water Quality in Swimming Pools and Spas
Correspond with Beneficial Oxidation Reduction Potential?" (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2646
482). Public Health Rep. 124: 255–61. PMC 2646482 (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2646482).
PMID 19320367 (https://www.ncbi.nlm.nih.gov/pubmed/19320367).

Additional notes
Onishi, j; Kondo W; Uchiyama Y (1960). "Preliminary report on the oxidation-reduction potential obtained on
surfaces of gingiva and tongue and in interdental space". Bull Tokyo Med Dent Univ (7): 161.

External links
Redox potential definition (http://www.biology-pages.info/R/RedoxPotentials.html)
Large table of potentials (http://www.northland.cc.mn.us/Chemistry/standard_reduction_potentials.htm) (Site
broken. Archived version (https://web.archive.org/web/20070518092613/http://www.northland.cc.mn.us/Chemistr
y/standard_reduction_potentials.htm) on the Internet Archive.)

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