6.

OXIDATION-REDUCTION (REDOX) REACTIONS The term oxidation-reduction or redox reactions is used to designate a class of chemical reactions during which one or more electrons (e-) are lost by an atom or molecule and acquired by a different atom or molecule. Since chemical reactions neither create nor destroy electrons, and there are no free electrons in solution, these two events must be coupled the electrons must be removed from one species and transferred to another. Thus, redox reactions are also called "electron transfer" reactions. Clearly, not all atoms or molecules are capable of participating in such reactions under physiological conditions. Those that can do so are called "redox active" and have two stable forms. One form is called "reduced" and contains at least one transferable electron per molecule; the other is called "oxidized" and can accept at least one electron (see below). Concepts and Definitions Suppose A and B are two different "redox active" or "electron carrier" molecules. Suppose further that molecule B has a greater affinity for electrons than molecule A. Under the appropriate circumstances, the reactions diagrammed below will occur. An oxidation-reduction (redox or electron transfer) reaction is one in which one molecule or atom (here A) loses electrons, and a molecule or atom of a different species (here B) gains them. Since there are no free electrons in solution, these two processes must be coupled and oxidation is always accompanied by reduction.
Oxidation-Reduction Reaction A (reduced) B (oxidized)

Oxidation Reaction

Reduction Reaction

A (oxidized)

B (reduced)

Oxidation is the loss of electrons. Reduction is the gain of electrons.

Fig. 1. Schematic of an electron transfer (oxidation-reduction, redox) reaction.

The reductant, here A (reduced), is a molecule or atom that reduces a different atom or molecule, here B (oxidized). Thus, the reductant loses electrons and becomes oxidized. An oxidant, here B (oxidized), is an atom or molecule that oxidizes a different atom or molecule, here A. Thus, the oxidant gains electrons and becomes reduced. An oxidation-reduction (redox) couple (pair) is composed of both the oxidized and reduced forms of an electron carrier atom or molecule, e.g., A (oxidized) and A (reduced) 1

or B (oxidized) and B (reduced). The reduction (redox) potential of an atom or molecule (actually of the redox pair) reflects its affinity for electrons. The atom or molecule with the higher (more positive) reduction potential becomes reduced. The reaction is: oxidant + e- reductant. The larger or more positive this number, the greater the affinity of the oxidized species for electrons. Electrons flow from a reduced atom or molecule of lower reduction potential to an oxidized atom or molecule of higher reduction potential. In the example above, the reduction potential of B is greater than that of A. Two factors determine whether one redox active substance will give electrons to a different redox active substance. The first factor is which of the two substances has the higher affinity for electrons. Obviously, all other factors being equal, the substance with the higher affinity for electrons will take them from the substance with lower affinity. This affinity is quantitated by a number, the standard reduction potential (E0'); this number depends on the particular molecular species and cannot be altered by the cell or organism. The second factor is the ratio of concentrations of the electron-containing and the electron-deficient forms of the redox active molecule. The cell can control these concentrations and thereby regulate oxidation-reduction reactions. The influence of this factor is apparent from the limiting case. Suppose B has a much higher affinity for electrons than A but that all the molecules of B contain electrons and all the molecules of A are electron deficient. Under these circumstances, no reaction can occur. Table of Standard Reduction Potentials (pH = 7.0, T = 25 C) Oxidant + ne- Reductant Oxidized Form Reduced Form n Eo' in Volts (Oxidant) (Reductant) (Number of Electrons) (Standard Reduction Potential) NAD(P)+ NAD(P)H + H+ 2 -0.32 pyruvate lactate 2 -0.19 oxaloacetate malate 2 -0.18 fumarate succinate 2 +0.03 cyt b (ox) cyt b (red) 1 +0.07 ubiquinone (Q) ubiquinol (QH2) 2 +0.10 cyt c (ox) cyt c (red) 1 +0.25 cyt a (ox) cyt a (red) 1 +0.29 cyt a3 (ox) cyt a3 (red) 1 +0.55 1/2 O2 + 2H+ H2O 2 +0.82 Some examples of biologically important electron carriers are shown above. Note that the values shown are E0' values. The actual reduction potential (E') observed in vivo may differ from E0' because the molecules in the redox pair may not be present at the same concentration as each other. E0' thus characterizes the redox couple under standard conditions. It is the actual, measured reduction potential of the redox couple in a solution where the reductant and oxidant are present at the same concentration. For the reverse reaction, Reductant Oxidant + ne-, the numerical value of Eo' remains the same, but the sign is changed. 2