11.1 Oxidation–Reduction Reactions

Learning Objectives

After Chapter 11.1, you will be able to:

Reactions that involve the transfer of electrons from one chemical species to another can be classified as oxidation–reduction (redox) reactions.

Oxidation and Reduction

The law of conservation of charge states that electrical charge can be neither created nor destroyed. Thus, an isolated loss or gain of electrons cannot occur; oxidation (loss of electrons) and reduction (gain of electrons) must occur simultaneously, resulting in an electron transfer called a redox reaction. An oxidizing agent causes another atom in a redox reaction to undergo oxidation and is itself reduced. A reducing agent causes the other atom to be reduced and is itself oxidized. There are various mnemonics to remember these terms, as highlighted in the sidebar.

Mnemonic

Redox reactions: choose one of the mnemonics and stick with it!

Being familiar with some common oxidizing and reducing agents can save significant time on Test Day, especially in organic chemistry reactions. Some of the commonly used agents on the MCAT are listed in Table 11.1. Note that almost all oxidizing agents contain oxygen or another strongly electronegative element (such as a halogen). Reducing agents often contain metal ions or hydrides (H).

Table 11.1. Common Oxidizing and Reducing Agents
Oxidizing Agents Reducing Agents
O2 CO
H2O2 C
F2, Cl2, Br2, I2 (halogens) B2H6
H2SO4 Sn2+ and other pure metals
HNO3 Hydrazine*
NaClO Zn(Hg)*
KMnO4* Lindlar’s catalyst*
CrO3, Na2Cr2O7* NaBH4*
Pyridinium chlorochromate (PCC)* LiAlH4*
NAD+, FADH** NADH, FADH2**
* These oxidizing agents and reducing agents are commonly seen in organic chemistry reactions. ** These and other biochemical redox reagents often act as energy carriers in biochemistry reactions.

Note that biochemical redox reagents such as NAD+ tend to act as both oxidizing and reducing agents at different times during metabolic pathways. As such, they act as mediators of energy transfer during many metabolic processes, as shown in Figure 11.1.

energy transfered from food molecules to ATP, NAD(P)H, and then transfered to cell components
Figure 11.1. Oxidation and Reduction of Biochemical Compounds Serves as a Method of Energy Transfer

On a technical level, the term oxidizing agent or reducing agent is applied specifically to the atom that gains or loses electrons, respectively. However, many science texts will describe the compound as a whole (CrO3, rather than Cr6+) as the oxidizing or reducing agent.

Assigning Oxidation Numbers

It is important, of course, to know which atom is oxidized and which is reduced. Oxidation numbers are assigned to atoms in order to keep track of the redistribution of electrons during chemical reactions. Based on the oxidation numbers of the reactants and products, it is possible to determine how many electrons are gained or lost by each atom.

Bridge

In Chapter 3 of MCAT General Chemistry Review, we illustrated that metals form cations and nonmetals form anions. To form a cation, a metal must lose electrons. Therefore, metals like to get oxidized (lose electrons) and act as good reducing agents. Nonmetals, on the other hand, like to get reduced (gain electrons) and act as good oxidizing agents.

The oxidation number of an atom in a compound is assigned according to the following rules:

  1. The oxidation number of a free element is zero. For example, the atoms in N2, P4, S8, and He all have oxidation numbers of zero.
  2. The oxidation number for a monatomic ion is equal to the charge of the ion. For example, the oxidation numbers for Na+, Cu2+, Fe3+, Cl, and N3– are +1, +2, +3, –1, and –3, respectively.
  3. The oxidation number of each Group IA element in a compound is +1.
  4. The oxidation number of each Group IIA element in a compound is +2.
  5. The oxidation number of each Group VIIA element in a compound is –1, except when combined with an element of higher electronegativity. For example, in HCl, the oxidation number of Cl is –1; in HOCl, however, the oxidation number of Cl is +1.
  6. The oxidation number of hydrogen is usually +1; however, its oxidation number is –1 in compounds with less electronegative elements (Groups IA and IIA). Hydrogen is +1 in HCl, but –1 in NaH.
  7. In most compounds, the oxidation number of oxygen is –2. The two exceptions are peroxides (O22−), for which the charge on each oxygen is –1, and compounds with more electronegative elements, such as OF2, in which oxygen has a +2 charge.
  8. The sum of the oxidation numbers of all the atoms present in a neutral compound is zero. The sum of the oxidation numbers of the atoms present in a polyatomic ion is equal to the charge of the ion. Thus, for (SO42−), the sum of the oxidation numbers must be –2.

MCAT Expertise

Think of the oxidation number as the typical charge of an element based on its group number, metallicity, and general location in the periodic table.

Key Concept

The conventions of formula writing put cation first and anion second. Thus HCl implies H+, and NaH implies H. Use the way the compound is written on the MCAT along with the periodic table to determine oxidation states.

MCAT Expertise

Don’t forget that you can click on “Periodic table” to pull it up on Test Day. Note the trends for assigning oxidation numbers; these general rules will help reduce the need to memorize individual oxidation numbers. Be aware that the transition metals can take on multiple oxidation states and therefore multiple oxidation numbers.

Oxidation number is often confused with formal charge, discussed in Chapter 3 of MCAT General Chemistry Review. Both account for the perceived charge on an element, but do so in different ways. Oxidation number assumes unequal division of electrons in bonds, “awarding” the electrons to the more electronegative element. Formal charge, on the other hand, assumes equal division of electrons in bonds, “awarding” one electron to each atom in the bond. In reality, the distribution of electron density lies somewhere between these two extremes. The assigning of oxidation number can be seen in Figure 11.2.

"award" electrons to bonds in oxygen, giving each oxygen an oxidation number of -2 and carbon +4.
Figure 11.2. Assigning Oxidation Numbers to Carbon Dioxide

When assigning oxidation numbers, start with the known atoms (usually Group I and II, halides, and oxygen) and use this information to determine the oxidation states of the other atoms. Keep in mind that most transition metals can take on multiple oxidation states. When transition metals are oxidized or reduced, the absorption and emission of light from a metal is altered such that different frequencies are absorbed. For this reason, changes of oxidation state in transition metals usually correspond to a color change.

Balancing Oxidation–Reduction Reactions

By assigning oxidation numbers to the reactants and products, one can determine how many moles of each species are required for conservation of charge and mass, which is necessary to balance the equation. To balance a redox reaction, both the net charge and the number of atoms must be equal on both sides of the equation. The most common method for balancing redox equations is the half-reaction method, also known as the ion–electron method, in which the equation is separated into two half-reactions—the oxidation part and the reduction part. Each half-reaction is balanced separately, and they are then added to give a balanced overall reaction.

Key Concept

Oxidizing agents oxidize other molecules, but are themselves reduced. Reducing agents reduce other molecules, but are themselves oxidized. If you determine one ion to be an oxidizing agent then the other must be a reducing agent.

MCAT Expertise

Methodical, step-by-step approaches like the half-reaction method are great for the MCAT. Usually, you will not have to go through all of these steps before you can narrow down your answer choices and may be able to find the correct answer partway through the problem with a little critical thinking.