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A simple rule to follow: Filling up of orbitals is dependent on orbital energy while removal of electrons from orbitals is dependent on orbital location.
4s has a lower energy than 3d. So it gets filled up first. But 4s is farther away from the nucleus than 3d. So while removal of electrons, they are first removed from 4s. It is easier to remove electrons that are farther away from the nucleus.
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