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). Because the true or absolute potentials are difficult to accurately measure, reduction potentials are 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 atm 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 E_r⁰ and E_o⁰.

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. E_h is measured in millivolts (mV). A high positive E_h indicates an environment that favors oxidation reaction such as free oxygen. A low negative E_h 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 H_2(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 4.4V to 4.6V (the electrolyte being positive.)

[edit] 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 (E_h).

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