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The difference in pi and sigma bonds lies in how the orbitals in a bond are oriented. In a sigma bond, the orbitals of the atoms involved in the bond overlap end to end while in a pi bond, the orbitals overlap in two places side by side. Therefore, pi bonds cannot be rotated without breaking the bond. There can be two pi bonds in a triple bond (two pi and one sigma), however there can never be more than one sigma bond.
I've always thought of sigma bonds as "head on collisions" between two orbitals, while pi bonds are just sideways overlaps between two orbitals. Once orbitals have "collided," they can't collide anymore, i.e. once a sigma bond has been formed between two atoms/molecules, another sigma bond can't form.
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