1/31/2014 Reduction potential - Wikipedia, the free encyclopedia

Reduction potential
From Wikipedia, the free encyclopedia

Reduction potential (also known as redox potential, oxidation / reduction potential, ORP, pE, ε, 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. ORP is a common
measurement for water quality.[1]

Contents
1 Measurement and interpretation
2 Explanation
3 Standard reduction potential
4 Converting potentials between different types of reference electrodes
5 Half cells
6 Nernst equation
7 Biochemistry
8 Environmental chemistry
9 Water quality
10 Geology
11 See also
12 References
13 Additional notes
14 External links

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). 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.[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. 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

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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).

Explanation
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 buffering capacity.

In fact, it is possible to define pE, logarithm of electron concentration 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 Eh, for
example in environmental chemistry.[2]

The actual value of electron concentration is not measurable as it is of order of 10^-55 M, yet it is
thermodynamically a well defined quantity. What matters is the logarithm of the quotient of concentration of
electrons in one solute with respect to the other, and that is, via Nernst equation, proportional to the redox
potential. If we normalize pE of hydrogen to zero, we will have the relation pE=16.9 Eh 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 0V) is analogous with redox potential (where standardized hydrogen solution is set to 0V), 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

See also: Standard hydrogen electrode

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[citation needed], 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
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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
See also: Saturated calomel electrode

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[citation needed]
Ag/AgCl, 1 M KCl +192[citation needed]
Ag/AgCl, 4 M KCl +228[citation needed]
Ag/AgCl, sat. KCl +236[citation needed]

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

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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
Main article: 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:

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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 HFeO2 (aq):[4]

−
3 HFeO2 + H+ = Fe3O4 + 2 H2O + 2 [[e−]]

−
where = −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 = −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.[citation needed]

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 to.[citation needed]

Environmental chemistry
See also: Pourbaix diagram

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 ranges 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]

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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]

Water quality
ORP is measured in millivolts.

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.[5]

Geology
See also: Pourbaix diagram

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.

See also
Galvanic cell
Electrolytic cell
Electromotive force
Electrochemical potential
Standard electrode potential
Table of standard electrode potentials
Oxygen radical absorbance capacity
Redox

References
1. ^ a b c 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. ^ a b c d e f vanLoon, Gary; Duffy, Stephen (2011). Environmental Chemistry - a global perspective (3rd ed.).

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1/31/2014 Reduction potential - Wikipedia, the free encyclopedia

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. ^ Bastian, Tiana; Brondum, Jack. "Do Traditional Measures of Water Quality in Swimming Pools and Spas
Correspond with Beneficial Oxidation Reduction Potential?"
(http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2646482/). Retrieved 21 January 2014.

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://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_reductio
n_potentials.htm) on the Internet Archive.)

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Categories: Electrochemistry Potentials

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