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Another way to tell is by using delta negative and delta positives. For example, a hydrogen bromide molecule is a great example. Since bromine has a stronger electronegative pull on the atoms being shared it is delta negative making the hydrogen delta positive.
From my understanding, when identifying an atom as a nucleophile, an atom that donates an electron pair to a electrophile due to free electrons or a pi bond, we must pay attention to the electronegativity, therefore we can distinguish the delta negative atom from the delta positive atom. As mentioned earlier, this can be seen in the case of H-Br. H is delta positive while Br is delta negative. The delta negative atom is the nucleophile, while the delta positive atom is the electrophile because it accepts electrons in order to complete it's octet. This is how we can differentiate a nucleophile from an electrophile.
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