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If you determine which atom is more electronegative, you will be able to determine where the electron will most likely be attracted to. So you draw the molecule like a lewis structure, but you will be able to see where the electrons are drawn towards.
The arrows (especially in organic molecules) also denote places where bonds are being broken and electrons are being distributed to another atom(s) as lone pairs. So if a curly arrow is directed from a double bond towards another atom, it means that the bond is being broken and those electrons are being added to the atom that the arrow is pointing to.
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