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Usually you find out how many unpaired electrons there should be after you determine how many electrons the the entire molecule should have and how many bonds there are between the different atoms. The unpaired electrons are the ones that let you reach the amount of electrons you should have in total.
In order to find the number of unpaired electrons you first have to write the electron configuration. Then, you can either draw the valence orbitals or picture it in your head and see how many electrons are unpaired. For example, if the electron configuration ends with 3p^4 you would have to know that the p subshell has three orbitals for a total of 6 electrons. According to Hund's rule, orbitals of the same energy are each filled with one electron before filling any with a second. Therefore, you'd fill in the three orbitals with one electron then add the fourth electron to the first orbital. This would leave the other two orbitals with one electron each, therefore there would be 2 unpaired electrons.
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