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The first bond that forms between atoms is always a sigma bond and any other bonds are pie bonds. So if there is a double bond, one of them is sigma bond and the other is pie bond. If it's a triple bond, one of them is a sigma bond and the other two bonds are pie bonds, and so on.
Also: sigma bonds form when two orbitals interact end-to-end, whereas pi bonds form when 2 orbitals overlap side-by-side. Note that pi bonds have electron density on each side of the internuclear axis, whereas sigma bonds have electron density along it. This will change the rotatability of the atoms!
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