Learn · Organic Chemistry

Sigma and Pi Bonds

Why a single bond rotates freely, a double bond is locked, and π electrons are the reactive part of every alkene.

Quick answer

Every bond has exactly one sigma (σ) bond; a double adds one pi (π) bond, a triple adds two. σ allows free rotation and holds atoms together; π bonds lock rotation and carry the reactive electrons.

Ethane · single · 1 σ, 0 π
Ethene · double · 1 σ, 1 π
Ethyne · triple · 1 σ, 2 π
Single, double, and triple carbon–carbon bonds and the σ/π count each one contains.

1. A Single Bond Is Exactly One Sigma Bond

A σ bond comes from end-on overlap of hybrid orbitals along the internuclear axis, so every single bond in an alkane is one σ.

Methane · 4 C–H σ bonds
Ethane · 1 C–C σ + 6 C–H σ

2. A Double Bond Is One Sigma Bond Plus One Pi Bond

A double bond is one σ plus one π bond, formed by side-on overlap of the leftover p orbitals above and below the plane of the sp²-hybridized carbons.

Ethene · 5 σ + 1 π
Formaldehyde · C=O = 1 σ + 1 π

3. A Triple Bond Is One Sigma Bond Plus Two Pi Bonds

A triple bond is 1 σ + 2 π: each sp-hybridized carbon has two p orbitals that form two perpendicular π bonds — count every "extra" line beyond the first as a π.

Ethyne · C≡C = 1 σ + 2 π
Acetonitrile · C≡N = 1 σ + 2 π
Carbon dioxide · two C=O, so 2 σ + 2 π

4. More Pi Bonds Mean Shorter, Stronger, Less Rotatable Bonds

Each added π shortens the bond and raises total strength (single > double > triple in length), yet a lone π is weaker than a σ — so π breaks first in reactions.

C–C · longest, lowest bond order
C=C · shorter, stronger
C≡C · shortest, strongest

5. Pi Bonds Block Rotation — the Basis of Cis/Trans

Single bonds spin freely, but rotating a double bond would break its side-on p-orbital overlap — that locked C=C is what makes cis/trans (E/Z) isomers possible.

Propene · locked C=C, free C–C
Butadiene · two locked π bonds

6. Pi Electrons Are the Reactive, Nucleophilic Site

Loosely-held π electrons sit exposed outside the bond axis, making the π bond the nucleophilic site that drives most reactions while the σ skeleton stays intact.

Benzene · reactive π system
Acetaldehyde · C=O π is the reactive site

7. Summary

Single = 1 σ · double = 1 σ + 1 π · triple = 1 σ + 2 π · more π → shorter, stronger · σ rotates, π locks (cis/trans) · π electrons react.

Quiz yourself

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One σ bond and two π bonds. The σ forms from end-on overlap of sp hybrid orbitals; the two π bonds come from two pairs of perpendicular unhybridized p orbitals.

A σ bond's end-on overlap is unchanged by rotation, so single bonds spin freely. Twisting a double bond would break the side-on p-orbital overlap of its π bond, which costs too much energy — so double bonds are locked, giving cis/trans isomers.

The C–C single bond is longer and weaker. Adding a π bond (making it C=C) raises the bond order, pulling the atoms closer and increasing total strength; a triple bond is shorter and stronger still.

π electrons lie above and below the bond axis and are held more loosely than σ electrons, so they are exposed and easy to donate. That makes the π bond the nucleophilic, reactive site while the strong σ framework stays intact.

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