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Supplemental notes for IVMS Intro to Biochemistry Course This is a comprehensive introduction to medical biochemistry suitable for AP High School, Premed Students and Biomedical Science Majors

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Redox Reactions
What is a redox reaction?
The formal name for a redox reaction is "oxidation reduction reaction," and you can see that "redox" is just shorthand for the words reduction and oxidation. Thus, in a redox reaction, two things happen. You guessed it -- oxidation and reduction. These two have to happen together. You cannot have an oxidation reaction without a corresponding reduction reaction. Its a bit like the idea behind a blood transfusion or an organ transplant. You cannot have a recipient unless you have a donor, and it does not make any sense to be a donor unless there is a recipient. You may have noticed that "oxidation" starts with the same prefix as oxygen, suggesting that oxygen may be somehow involved in this process. Indeed, one definition of oxidation states that: Oxidation is the gaining of bonds to oxygen Organic fuel substances (such as wood, coal or gas) are examples of compounds that can be oxidized. In the process of burning, the carbon in these substances becomes bonded with oxygen, while some of the oxygen used to "burn" the fuel bonds to the hydrogen atoms from the fuel. Thus, one of the definitions of reduction states that: Reduction is the gaining of hydrogen Therefore, combustion reactions are good examples of redox reactions where one molecule gains oxygen (is oxidized) and one molecule gains hydrogen (is reduced). For example, lets look at what happens when gasoline in your car is burned as you drive around town (heptane is a common hydrocarbon component of gasoline): C7H12 + 11 O2 heptane
Redox Reactions

7 CO2 carbon dioxide

+ 8 H2O water

oxygen

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Note how the carbon atoms in heptane are oxidized (because the carbon atoms in heptane become bonded with oxygen atoms), while the oxygen is reduced (becomes bonded with hydrogen atoms). These definitions of oxidation and reduction are useful. However, more general definitions of oxidation and reduction involve the movement of electrons between the compounds involved in the redox reaction. In the most broad definition of redox reactions: Oxidation is the loss of electrons Reduction is the gain of electrons Because electrons are negatively charged, an increase in electrons means a decrease in overall charge (the compound becomes more negatively charged). On the other hand, an atom that is oxidized has given up some of those negatively charged electrons, which will increase its overall charge (the compound becomes more positively charged). Notice that these definitions do not involve oxygen and hydrogen. Thus, redox reactions can occur with compounds that do not contain oxygen or hydrogen atoms. An everyday example of a redox reaction that we are all familiar with is the process of rusting. Rust is the flaky brown substance that forms on iron objects left exposed to the elements for too long, especially if the objects get wet. Rust doesnt just form on the iron object, the iron actually turns into rust (rust is actually a form of oxidized iron). We all intuitively know the chemical reaction of rusting: iron + water + air Fe + H2O + O2 = rust Fe2O3

Lets examine the oxidation and reduction reactions that are involved in the redox reaction of rusting. First, iron, in the presence of moisture (H2O) will lose electrons, becoming a positively charged ion in water: Oxidation reaction: Iron is oxidized (loses e-) Fe(s) Fe2+(aq) + 2 e-

Those electrons are then used to reduce the oxygen dissolved in the water (remember that water will have some dissolved oxygen and also H+ and OH- ions): Reduction reaction: Oxygen is reduced (gains e-) O2 + 4e- + 4 H+
Redox Reactions

2 H2O

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Those Fe2+ ions react with the OH- ions in water to produce iron hydroxide, which will dry in several steps to produce rust: Fe2+ + 2OHFe(OH)2 Fe2O3 (rust)

Notice that the redox reaction needs water, which explains why a moist environment speeds up the rusting process. Rusting can occur in dry climates, but it tends to happen much more slowly due to the relatively low humidity in the air. Because it is difficult to remember the definitions of oxidation and reduction that involve the movement of electrons, a common mnemonic that can help you keep these rules in mind is:

"OIL RIG"
O I L R I G

Oxidation Is Loss of electrons Reduction Is Gain of electrons

This is an especially appropriate mnemonic for remembering redox reactions because the burning of oil (a hydrocarbon fuel) is a redox reaction!

Reduction Potentials
We just discussed in the last section how a redox reaction is really two reactions that happen together, an oxidation and a reduction. It makes sense that they occur together if we think about how oxidations lose electrons while reductions gain electrons (remember OIL RIG). The two reactions must be coupled because you cant have an electron donor without an electron recipient. Because of this, these two reactions (oxidation and reduction) are considered to be two halves of a whole. In other words, a redox reaction consists of an oxidation half reaction and a reduction half reaction.

The redox pie: two half reactions make a whole

Redox Reactions

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Lets return to the OIL RIG definition of redox reactions for a moment. It can tell us which compounds are oxidized or reduced, depending on whether electrons are gained or lost. But which atoms gain electrons, and which ones lose them? Remember that electrons are tiny charged particles that orbit the nucleus of an atom at dizzying speeds. Depending on how many electrons are orbiting the nucleus, and in which orbitals (at what distance from the nucleus), some atoms hold on to some of their electrons very loosely, and have a higher tendency to give them away. Other atoms hold onto their electrons very tightly, and are in fact able to attract nearby electrons into their orbitals. The potential, or tendency, to gain electrons, is the reduction potential. The reduction potential is the tendency of a compound to be reduced. The reduction potential is experimentally determined for the oxidation and reduction half reactions, and is called E0. To remember the relationship of E0 and oxidation and reduction, consider the reduction potential as how much a compound wants to get reduced (it has a lot of potential for reduction). Remember, reduction is a gain of electrons (OIL RIG), so the larger (more positive) the E0, the more likely the compound in the half reaction is to gain electrons (be reduced). Think of it as being like a large magnet. A large magnet attracts nails more strongly, and holds them more tightly, than a small magnet. Similarly, a compound with a large (positive) reduction potential attracts electrons more strongly than a small (or even a negative) reduction potential.

The E0 values can be looked up in tables, and are always given for reduction halfreactions (reactions gaining electrons). For example: S + 2H+ + eH2S E0 = -0.23 V

We know that a redox reaction consists of both a reduction and an oxidation. Shouldnt there be such a thing as an "oxidation potential," too? As it turns out, you can tell how likely a compound is to be oxidized from the reduction potential. Since, as mentioned above, a high (large positive) reduction potential means a high tendency to be reduced, it must follow that a
Redox Reactions

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lower reduction potential must mean that a compound is less likely to be reduced. If a compound is less likely to be reduced, it is more likely to be oxidized. Thus, in a redox reaction, when two half-reactions are coupled together, the half-reaction (with the higher E0) will be the reduction reaction, while the half-reaction with a smaller (or more negative) E0 will then be forced backwards and act as the oxidation reaction. A knowledge of the half-reaction reduction potentials can therefore tell you whether compounds are more likely to be oxidized or reduced. Its like a tug-of-war. The strongest team always pulls the weaker team into the mud pit. In the same way, the compound with the larger reduction potential pulls the electrons over to its side.

Finally, the tendency of the whole reaction to proceed can be calculated from reduction potentials of half reactions, which have been determined experimentally, using the formula: E0 = (E0 from reaction where e- are gained) - (E0 from reaction where e- are released) A positive E0 tells you that the reaction will proceed in the direction it is written. Lets do an example to make all these rules seem a little more clear. In a reaction that is needed for ATP generation in our bodies, cytochrome C molecules are oxidized in a redox reaction where oxygen that we breathe is reduced: 4 cytochrome c2+ + 4 H+ + O2 The two half-reactions are: cytochrome c3+ + eO2 + 2 H + 2 e
+ -

4 cytochrome c3+ + 2 H2O

cytochrome c2+ H2O

E0 = 0.235 volts E0 = 0.815 volts

Which of the half reactions is more likely to gain electrons? What is the overall E0 of the redox reaction? Notice how the half reactions are both written as reductions. The positive (larger) value for E0 means that the half reaction will insist on gaining electrons, and act as the reduction. Reaction (2)
Redox Reactions

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has the higher E0, and is thus more likely to gain electrons. Because reaction (1) is by comparison less likely to gain electrons, reaction (1) will be forced backwards, becoming an oxidation reaction, by reaction (2). Thus, in order to "add" the two half reactions together to get the whole reaction, we will have to reverse half reaction (1): cytochrome c2+ cytochrome c3+ + e[reverse of (1)]

Now lets add the two half reactions to get the whole redox reaction. Notice that we will have to multiply the above reaction [reverse of (1)] by 4, and reaction (2) by 2, to get the final reaction. However, the E0 values are not multiplied! This is because the E0 value is independent of the numbers of electrons that are in the half reactions. [reverse of (1)] (2) (SUM) 4 cytochrome c2+ O2 + 4 H+ + 4 e4 cytochrome c3+ + 4 e2 H2O 4 cytochrome c3+ + 2 H2O (e- released) (e- gained)

4 cytochrome c2+ + 4 H+ + O2

E0 = (E0 from reaction where e- are gained) - (E0 from reaction where e- are released) E0 = (0.815 V) - (0.235 V) E0 = 0.580 V

Energy on Tap
Redox reactions are powerful things. Thats not just a figure of speech. Redox reactions really are useful for generating power. Remember how we defined redox reactions as being comprised of the transfer of electrons? Thats exactly what electricity is, the movement of electrons. You may have noticed that the reduction potential (E0) of half reactions is in Volts, which we use as a measure of electricity? Heres an example. Lets say you buy some alkaline batteries to
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power your electric toothbrush. When you hit the "on" switch, how do batteries generate the electricity to run that gadget?

The battery has zinc powder at one end, and manganese dioxide at the other end. The two ends are connected by a potassium hydroxide (KOH) solution that provides OH- ions. (1) Zn + 2 OHZn(OH)2 + 2 eZn loses e- (oxidation)

The electrons flow out of the battery, and this electric current powers those motorized bristles, letting you get those pearly whites sparkling clean. Moving along the circuit, the electrons then re-enter the battery: (2) 2MnO2 + H2O + 2 eMn2O3 + 2 OHMn gains e- (reduction)

The OH- ions are regenerated, and are free to flow through the KOH solution to the Zn to generate more electrons. Your body uses redox reactions to create energy, too, although in a different way. The majority of the energy generated in our bodies comes from aerobic metabolism, which uses the O2 that we breathe to "burn" the fuel that we eat. The oxidation of compounds such as carbohydrates in redox reactions makes the generation of ATP, our "energy currency", possible. There are other energy-producing redox reactions in the body that do not utilize oxygen directly. For example, lets say you start to get ready for the upcoming ski season by doing some leg lifts. Under non-strenuous conditions, aerobic metabolism uses O2 to generate ATP to power the muscle. However, during vigorous exercise where O2 demand is very high in the muscles, an interesting reaction called homolactic fermentation is responsible for allowing our muscles to keep working hard even when oxygen starts to run low (such as by the time you get to your 100th leg lift!). The overall reaction is: Pyruvate + NADH + H+ lactate + NAD+

This is a redox reaction that consists of two half reactions: (1)

Redox Reactions

Pyruvate + 2 H+ + 2 e-

lactate

pyruvate gains e- (is reduced)

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(2)

NADH + H+

NAD+ + 2H+ + 2e-

NADH loses e- (is oxidized)

The NAD+ that is generated is then used in other metabolic reactions to generate more ATP. The lactate (lactic acid) generated by this reaction is believed to be responsible for the "burn" that you feel in muscles that you worked too hard.

Conclusion
A redox reaction, also known as an oxidation-reduction reaction, is a type of chemical reaction where one of the reactants is oxidized and one of the reactants is reduced. Oxidation of a compound can be defined in several ways, one of which is that it is the gain of bonds to oxygen, another of which is that it is the loss of electrons. Similarly, two useful definitions of reduction, (the opposite of oxidation), are the gain of hydrogen or the gain of electrons. The mnemonic OIL RIG can help you remember these definitions: Oxidation Is Loss (of electrons), Reduction Is Gain (of electrons). Oxidation and reduction reactions always occur together, because the electrons that are donated from one compound, must be received by another compound. This is why redox reactions are said to be the product of two half reactions, the oxidation half reaction and the reduction half reaction. Each half reaction has a measurable reduction potential E0, which is a measure in volts of how easily the compound is reduced (how easily it gains electrons). Remember, the reduction potential is how much a species "wants" to get reduced, and the higher the number, the greater the potential. Redox reactions play an important part in our lives. Combustion reactions that generate heat and electricity, such as the burning of natural gas, oil, gasoline or wood, are redox reactions, and in our bodies, redox reactions are needed to generate ATP to power our metabolism and our muscles.

Redox Reactions