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Oxidation and Reduction A Matter of Electrons Both catabolic and anabolic pathways include key reactions in which electrons

are transferred from one reactant to another. Reactions that involve a change in the electronic state of the reactants are called oxidation-reduction (or redox) reactions. Changes of this type are accompanied by the gain or loss of electrons. Consider the conversion of metallic iron (fe) to the ferrous state (fe2+). This conversion involves the loss of a pair of electrons by the iron atom, which thereby attains a more positive state; when an atom loses one or more electrons, it is said to be oxidized. The reaction is reversible. Ferrous ions can be converted to metllic iron, a more negative state, by the acquisition of a pair of electrons; when an atom gains one or more electrons it is said to be reduced. For metallic iron to be oxidized, there must besome substance to accept the electrons that are released. Conversely,for ferrous ions to be reduced, there must be some substance to donate the necessary electrons. In other words, the oxidation of one reactant must a be accompanied by the simultaneous reduction of some other reactant, and vice versa. One possible reaction involving iron might be Fe + Cu2+ Fe2+ + Cu The substance that loses electorns during an oxidation reduction reaction, that is, the one that becomes oxidized, is called a reducing agent, and the one that gains electrons, that is, the one that becomes reduced, is called an oxidizing agent. The oxidation or reduction of metals,such as iron or copper, involve the loss or gain of entire electrons. The oxidation and reduction of organic substrates during cellular metabolism involve carbon atoms that are convalently bonded to other atoms. As discussed in Chapter 2, when a pair of electrons is shared by two different atoms, the electrons generally attracted more strongly to one of the two atoms of the polarized bond. In a CH bond, the carbon atom has the strongest pull on the electrons, thus it can be said that the carbon atom is in a reduced state. In contrast, if a carbon atom is bonded to a more electronegative atom, asin a C-O or C-N bond, the electrons are pulled away from the carbon atom, which is thust in an oxidized state. Since carbon has four outer shell electrons it can share with others atoms, it can exist in a variety of oxidation states. This is illustrated by the carbon atom in a series of one carbon molecules (figure 3.21) ranging from the fully reduced state in methane (CH4) to the fully oxidized state in carbon dioxide (CO2). The relative oxidation state of an organic molecule can be roughly determined by counting the number of hydrogen versus oxygen and nitrogen atoms per carbon atom. As we will see shortly, the oxygen state of the carbon atoms in an organic molecule provides a measure of the molecules free energy content.

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