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Triplet oxygen

physical science Maturity 11-13 Next article →

Triplet oxygen is the most common form of molecular oxygen, also known as dioxygen. It refers to the specific electronic ground state of the molecule. In this state, the molecule is considered a diradical. This means it contains two unpaired electrons. While most stable molecules have electrons that exist in pairs, triplet oxygen is a rare example of a stable molecule with unpaired electrons. This unique arrangement is why oxygen behaves the way it does in our atmosphere and in chemical reactions.

Valence orbitals of oxygen atom and dioxygen molecule (diagram)
Valence orbitals of oxygen atom and dioxygen molecule (diagram)

To understand how triplet oxygen works, we must look at molecular orbital theory. This theory describes how electrons occupy different spaces called orbitals. In triplet oxygen, two electrons occupy two different pi molecular orbitals, or $\pi$ MOs. These two orbitals are degenerate, which means they have the exact same energy level. According to Hund's rules, electrons in these types of orbitals will remain unpaired. They also maintain spin-parallel alignment, meaning they spin in the same direction. This specific configuration is what makes the molecule's ground state a triplet state.

Valence orbitals of oxygen atom and dioxygen molecule (diagram)
Valence orbitals of oxygen atom and dioxygen molecule (diagram)

This electron arrangement affects the strength of the bond between the oxygen atoms. These half-filled orbitals are antibonding in character. Antibonding orbitals actually work to reduce the strength of a chemical bond. Because of this, the bond order of triplet oxygen is 2. For comparison, dinitrogen has a bond order of 3 because its antibonding orbitals are empty. The oxygen-oxygen bond is also described as one full sigma bond plus two pi half-bonds. Each of these half-bonds is a two-center three-electron bond. This specific structure explains why the bond is shorter than a single bond but not as strong as a triple bond.

Scientists have used different models to try and represent this structure. One common method is the Lewis structure, which was used by Linus Pauling.

Ow-Pauling
Ow-Pauling

However, a standard Lewis structure is not perfectly accurate for triplet oxygen. A standard structure usually shows all electrons in pairs, which would not explain the molecule's magnetic properties. Another version might imply a single bond, but experiments show the bond is much shorter. The bond length in triplet oxygen is 121 pm. This is much shorter than the 140 pm bond length found in hydrogen peroxide. Because of these discrepancies, scientists prefer using molecular orbital theory to explain both the magnetism and the bond length.

One of the most famous properties of triplet oxygen is paramagnetism. A substance is paramagnetic if it can be attracted to the poles of a magnet. This happens because of the net magnetic moment created by the total electron spin. You can observe this phenomenon most clearly in a liquid state. If you cool oxygen down until it becomes a liquid, its magnetic nature becomes very obvious. You can pour liquid oxygen between the poles of strong, close magnets and watch it stay suspended in mid-air. A magnet can also visibly pull the stream of liquid oxygen as it is being poured.

Valence orbitals of oxygen atom and dioxygen molecule (diagram)
Valence orbitals of oxygen atom and dioxygen molecule (diagram)

The electron configuration of triplet oxygen also dictates how it reacts with other substances. Most other molecules exist in a singlet state, where their electrons are all paired. Because triplet oxygen has unpaired electrons, it does not react directly with many singlet molecules at room temperature. A reaction would require a triplet transition state to conserve the spin quantum number. This requires a significant amount of extra energy. Because of this energy barrier, triplet oxygen is actually quite stable in our air.

Ow-Pauling
Ow-Pauling

However, triplet oxygen will react readily with molecules that are in a doublet state. This reaction forms a new radical. If you provide enough energy, such as high temperatures or a catalyst, the reaction can happen more easily. For example, white phosphorus is a substance that reacts very quickly with oxygen. Many other flammable substances have an autoignition temperature. This is the temperature at which they will undergo combustion in the air without needing an external spark or flame. This entire process is controlled by the way the spins of the electrons interact during the chemical change.

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