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Oxidation–reduction (redox) reactions

What is an oxidation–reduction reaction?

Sunlight shining on bright green plant leaves.
Plants use photosynthesis, a redox process, to derive energy from the sun. Image credit: Eschtar M. on Pixabay, Pixabay Licence.
An oxidation–reduction or redox reaction is a reaction that involves the transfer of electrons between chemical species (the atoms, ions, or molecules involved in the reaction). Redox reactions are all around us: the burning of fuels, the corrosion of metals, and even the processes of photosynthesis and cellular respiration involve oxidation and reduction. Some examples of common redox reactions are shown below.
CHA4(g)+2OA2(g)COA2(g)+2HA2O(g)(combustion of methane)
2Cu(s)+OA2(g)2CuO(s)(oxidation of copper)
6COA2(g)+6HA2O(l)CA6HA12OA6(s)+6OA2(g)(photosynthesis)
During a redox reaction, some species undergo oxidation, or the loss of electrons, while others undergo reduction, or the gain of electrons. For example, consider the reaction between iron and oxygen to form rust:
4Fe(s)+3OA2(g)2FeA2OA3(s)(rusting of iron)
In this reaction, neutral Fe loses electrons to form FeA3+ ions and neutral OA2 gains electrons to form OA2 ions. In other words, iron is oxidized and oxygen is reduced. Importantly, oxidation and reduction don’t occur only between metals and nonmetals. Electrons can also move between nonmetals, as indicated by the combustion and photosynthesis examples above.

Oxidation numbers

How can we determine if a particular reaction is a redox reaction? In some cases, it is possible to tell by visual inspection. For example, we could have determined that the rusting of iron is a redox process by simply noting that it involves the formation of ions (FeA3+ and OA2) from free elements (Fe and OA2). In other cases, however, it is not as obvious, particularly when the reaction in question involves only nonmetal substances.
To help identify these less obvious redox reactions, chemists have developed the concept of oxidation numbers, which provides a way to track electrons before and after a reaction. An atom’s oxidation number (or oxidation state) is the imaginary charge that the atom would have if all of the bonds to the atom were completely ionic. Oxidation numbers can be assigned to the atoms in a reaction using the following guidelines:
  1. An atom of a free element has an oxidation number of 0. For example, each Cl atom in ClA2 has an oxidation number of 0. The same is true for each H atom in HA2, each S atom in SA8, and so on.
  2. A monatomic ion has an oxidation number equal to its charge. For example, the oxidation number of CuA2+ is +2, and the oxidation number of BrA is 1.
  3. When combined with other elements, alkali metals (Group 1A) always have an oxidation number of +1, while alkaline earth metals (Group 2A) always have an oxidation number of +2.
  4. Fluorine has an oxidation number of 1 in all compounds.
  5. Hydrogen has an oxidation number of +1 in most compounds. The major exception is when hydrogen is combined with metals, as in NaH or LiAlHA4. In these cases, the oxidation number of hydrogen is 1.
  6. Oxygen has an oxidation number of 2 in most compounds. The major exception is in peroxides (compounds containing OA2A2), where oxygen has an oxidation number of 1. Examples of common peroxides include HA2OA2 and NaA2OA2.
  7. The other halogens (Cl, Br, and I) have an oxidation number of 1 in compounds, unless combined with oxygen or fluorine. For example, the oxidation number of Cl in the ion ClOA4A is +7 (since O has an oxidation number of 2 and the overall charge on the ion is 1).
  8. The sum of the oxidation numbers for all atoms in a neutral compound is equal to zero, while the sum for all atoms in a polyatomic ion is equal to the charge on the ion. Consider the polyatomic ion NOA3A. Each O atom has an oxidation number of 2 (for a total of 2×3=6). Since the overall charge on the ion is 1, the oxidation number of the N atom must be +5.
One thing to note is that oxidation numbers are written with the sign (+ or ) before the number. This is in contrast to the charges on ions, which are written with the sign after the number. Now, let’s see some examples of assigning oxidation numbers!

Example 1: Assigning oxidation numbers

What is the oxidation number of each atom in (a) SFA6, (b) HA3POA4 and (c) IOA3A?
To assign the oxidation numbers to the atoms in each compound, let’s follow the guidelines outlined above.
(a) We know that the oxidation number of F is 1 (guideline 4). Because the sum of the oxidation numbers of the six F atoms is 6 and SFA6 is a neutral compound, the oxidation number of S must be +6:
SF6+61
(b) The oxidation number of H is +1 (guideline 5) and the oxidation number of O is 2 (guideline 6). The sum of these oxidation numbers is 3(+1)+4(2)=5. Since HA3POA4 has no net charge, the oxidation number of P must be +5:
H3PO4+1+52
(c) The oxidation number of O is 2 (guideline 6), so the sum of the oxidation numbers of the three O atoms is 6. Since the net charge on IOA3A is 1, the oxidation number of I must be +5:
IO3+52
Concept check: What is the oxidation number of the carbon atom in COA3A2?

Recognizing redox reactions

How do we actually use oxidation numbers to identify redox reactions? To find out, let’s revisit the reaction between iron and oxygen, this time assigning oxidation numbers to each atom in the equation:
4Fe(s)+3OA2(g)2FeA2OA3(s)00+32
Notice how iron (which we already know is oxidized in this reaction) changes from an oxidation number of 0 to an oxidation number of +3. Similarly, oxygen (which we know is reduced) changes from an oxidation number of 0 to an oxidation number of 2. From this, we can conclude that oxidation involves an increase in oxidation number, while reduction involves a decrease in oxidation number.
So, we can identify redox reactions by looking for changes in oxidation numbers over the course of a reaction. Let’s explore this idea more in the next example.

Example 2: Using oxidation numbers to identify oxidation and reduction

Consider the following reaction:
4NHA3(g)+5OA2(g)4NO(g)+6HA2O(g)
Is this reaction a redox reaction? If so, which element in the reaction is oxidized and which element is reduced?
Considering this is an article about redox reactions, the reaction probably is a redox reaction! However, let’s prove it by assigning oxidation numbers to the atoms of each element in the equation:
4NHA3(g)+5OA2(g)4NO(g)+6HA2O(g)3+10+22+12
The oxidation numbers of N and O are different on either side of the equation, so this is definitely a redox reaction! The oxidation number of N increases from 3 to +2, which means that N loses electrons and is oxidized during the reaction. The oxidation number of O decreases from 0 to 2, which means that O gains electrons and is reduced during the reaction.

Summary

The image shows four test tubes, each containing a solution of a different color. From left to right, the solution colors are yellow, blue, green, and purple.
The most common oxidation numbers of vanadium are +5 (yellow), +4 (blue), +3 (green), and +2 (purple). Image credit: "Vanadium oxidation states" by W. Oelen on Wikimedia Commons, CC BY-SA 3.0.
Oxidation–reduction reactions, commonly known as redox reactions, are reactions that involve the transfer of electrons from one species to another. The species that loses electrons is said to be oxidized, while the species that gains electrons is said to be reduced. We can identify redox reactions using oxidation numbers, which are assigned to atoms in molecules by assuming that all bonds to the atoms are ionic. An increase in oxidation number during a reaction corresponds to oxidation, while a decreases corresponds to reduction.

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