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.
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.
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. Sometimes pe is used as a unit of reduction potential instead of , for example in environmental chemistry. 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.
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 HFeO−
2 (aq):
2 (aq):
- 3 HFeO−
2 + H+ = Fe3O4 + 2 H2O + 2 [[e−]]
where Eh = −1.1819 − 0.0885 log([HFeO−
2]3) + 0.0296 pH. Note that the slope of the line is −1/2 the −0.05916 value above, since h/n = −1/2.
2]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.
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.
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.
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.
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. 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.
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.
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.