Mechanisms of redox reactions

Some of the problems associated with formulating descriptions of the mechanisms are illustrated by the reaction between two metal ions that undergo complementary, one-unit changes in oxidation state:

There are many different metal ions, designated with the letters M and N, which participate in redox reactions with this basic stoichiometry. To define the possible mechanisms with any precision, it is necessary to identify the groups that are directly bonded to the metals, as well as to specify which particular metals take part in the reactions. One relatively simple example is the chromium(II)-iron(III) reaction. Both chromium and iron aquo ions are surrounded by six water molecules in both the +2 and +3 oxidation states.

The reaction appears from its stoichiometry to entail simple electron transfer from Cr(II) to Fe(III). There are, however, other possibilities. Their variety is most evident if it is assumed that the oxidizing agent, hexaaquoiron(III) (Fe[H₂O]₆³⁺), dissociates a hydrogen ion before reacting with hexaaquochromium(II) (Cr[H₂O]₆²⁺). The hexaaquoiron(III) ion is then converted to a hydroxopentaaquoiron(III) ion, known to be an important reactant in the Fe(III)-Cr(II) reaction. Its formation requires no change in the oxidation state of iron and should be regarded as a simple acid-base reaction. With hydroxopentaaquoiron(III) ion, (H₂O)₅FeOH²⁺, as the oxidizing agent, simple electron transfer does provide one plausible means for the reaction. All the steps in the mechanism must add up to give the overall reaction. Intermediate species such as hydroxopentaaquoiron(III) must cancel out in the addition process by occurring as products in one step and reactants in another:

An alternative to simple electron transfer is the transfer of a hydrogen atom from a water molecule bound to chromium(II) to the hydroxide ion (OH⁻) bound to iron(III). A third possibility is the transfer of a neutral OH group (called a hydroxyl radical) from iron(III) to chromium(II). Oxygen and hydrogen occur as oxygen(−II) and hydrogen(I) in both reactants and products. These oxidation states correspond to those present in the hydroxide ion OH⁻. Therefore, when an OH group transfers, it must leave an electron behind, reducing the iron, and then reaccept an electron from chromium, oxidizing it. Since both the aqueous iron and chromium ions have a strong tendency to remain surrounded by six oxygen molecules, the most likely method of OH transfer would be the sharing of the transferred oxygen between the two metals at an intermediate stage of the reaction. But iron(III) is not a strong enough oxidizing agent to produce a significant concentration of neutral OH groups from OH⁻ ions. A more acceptable description of the OH transfer mechanism, therefore, is to regard OH⁻ as a bridging group through which electron transfer is accomplished as the two metal ion groups share a bonded oxygen atom.

Experimentally, it is difficult to distinguish between the alternative mechanisms posed above. Classification schemes for reaction mechanisms are of little value unless they offer alternatives that can be experimentally verified. For that reason the most successful system for classifying the mechanisms of redox reactions between metal ions has been the inner sphere–outer sphere dichotomy. Outer-sphere reactions are those that take place without breaking any bonds between a metal and a group such as water or hydroxide ion bound to it. Both the simple electron- and hydrogen-atom-transfer mechanisms are outer-sphere processes. If, on the other hand, the oxidation-state changes take place within an intermediate product in which the two metals are directly bonded to a common bridging group (such as shown in the equation above), the mechanism is inner-sphere. Formation of the intermediate requires loss of a bound water molecule by one of the metals. The inner sphere–outer sphere distinction can be tested experimentally in some redox systems.