Sigma and Pi Bonds

Sigma and Pi bonds

Sigma and pi bonds are types of covalent bonds that differ in the overlapping of atomic orbitals. Covalent bonds are formed by the overlapping of atomic orbitals. Sigma bonds are a result of the head-to-head overlapping of atomic orbitals whereas pi bonds are formed by the lateral overlap of two atomic orbitals.

Sigma and Pi Bonds

Sigma and Pi Bonds

Various bond parameters such as bond length, bond angle, and bond enthalpy depend on the way the overlapping of atomic orbital takes place. This overlap occurs in two major ways, giving rise to two primary types of covalent bonds, i.e. sigma and pi bonds.

The Sigma (σ) Bond

This type of covalent bond is formed by head-on positive (same phase) overlap of atomic orbitals along the internuclear axis. Sigma bonds are the strongest covalent bonds, owing to the direct overlapping of the participating orbitals. The electrons participating in a σ bond are commonly referred to as σ electrons.

Generally, all single bonds are sigma bonds. They can be formed via the following combinations of atomic orbitals.

S-S Overlapping

In this kind of overlapping, one ‘s’ orbital from each participating atom undergoes head-on overlapping along the internuclear axis. An s orbital must be half-filled before it overlaps with another.

s-s Overlap in Sigma Bonds

s-s Overlap in Sigma Bonds

The overlapping of two s orbitals resulting in a sigma bond is illustrated above. This type of overlap occurs in H2 molecules, where each hydrogen atom has a half-filled s orbital.

S-P Overlapping

Here, one half filed s orbital overlaps with one half-filled p orbital along the internuclear axis, forming a covalent bond. This condition is illustrated below.

s-p Overlap in Sigma Bonds

s-p Overlap in Sigma Bonds

This type of overlapping can be observed in ammonia. An NH3 molecule features 3 sigma bonds, formed by the overlap of the 2px, 2py, and 2pz orbitals belonging to the nitrogen atom and the 1s orbitals of the three hydrogen atoms.

P-P overlapping

In this condition, one half-filled p orbital from each participating atom undergoes head-on overlapping along the internuclear axis. This type of overlapping is illustrated below.

p-p Overlap in Sigma Bonds

p-p Overlap in Sigma Bonds

A Cl2 molecule features a p-p overlap of the 3pz orbitals of two chlorine atoms. It is important to note that the head-to-head overlapping of two p orbitals gives a sigma bond whereas the lateral overlap of these orbitals leads to the formation of pi bonds.

The Pi (π) Bond

Pi bonds are formed by the sidewise positive (same phase) overlap of atomic orbitals along a direction perpendicular to the internuclear axis. During the formation of π bonds, the axes of the atomic orbitals are parallel to each other whereas the overlapping is perpendicular to the internuclear axis. This type of covalent bonding is illustrated below.

Pi Bonds

Pi Bonds

Pi Bonds are generally weaker than sigma bonds, owing to the significantly lower degree of overlapping. Generally, double bonds consist of one sigma and one pi bond, whereas a typical triple bond is made up of two π bonds and one σ bond. It is important to note that a combination of sigma and pi bonds is always stronger than a single sigma bond.

Difference Between Sigma and Pi Bonds

The key differences between sigma and pi bonds are tabulated below.

Sigma Bond Pi Bond
The overlapping orbitals can be pure or hybrid The overlapping orbitals must be unhybridized
These bonds are strong and have high bond energies. These bonds are relatively weak.
Can exist independently Must exist along with a sigma bond.
Has an impact on the shape of molecules Has no role in determining the shape of molecules

Frequently Asked Questions

How Many Pi Bonds Exist in Double and Triple Bonds?

A triple bond consists of two pi bonds and one sigma bond. A double bond contains one sigma and one pi bond. Single bonds are always sigma bonds.

What are the Possible Combinations of Orbitals in Sigma Bonds?

The three most common overlap conditions that result in sigma bonds are:

  1. s-s overlap
  2. s-p overlap
  3. p-p overlap

What is the Number of Sigma and Pi bonds in a Benzene Molecule?

The benzene ring consists of six carbon-carbon single bonds, all of which are sigma bonds. Additionally, there exist six carbon-hydrogen sigma bonds. Therefore, the total number of sigma bonds in a benzene molecule is 12. The aromatic features alternating double bonds between carbon atoms. Therefore, the total number of pi bonds in a benzene molecule is 3.

Further Reading

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