Reduction potential

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Reduction potential (also known as redox potential) is the tendency of a chemical species to acquire electrons and thereby be reduced. 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.

A reduction potential is measured in volts (V) and is defined relative to the standard hydrogen electrode (SHE), which is arbitrarily given a potential of 0.00 volts. Standard reduction potential (E0), is measured under standard conditions: 25°C, a 1M concentration 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. Historically, many countries, including the United States, 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 Er0 and Eo0.

The relative reactivities of different half-cells can be compared to predict the direction of electron flow. A higher E0 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. Eh is measured in millivolts (mV). A high positive Eh indicates an environment that favors oxidation reaction such as free oxygen. A low negative Eh 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.

Reduction potential 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 (Eh).

Strictly aerobic microorganisms can be active only at positive Eh values, whereas strict anaerobes can be active only at negative Eh values. Redox affects the solubility of nutrients, especially metal ions. Oxygen strongly affects redox potential.

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