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When 4s is not filled, it has lower energy than 3d so it is filled first. But when 3d is filled it is no longer higher in energy, which is why Lavelle wants us to write 4s after 3d. So, when you remove an electron, you would remove it from the closest orbital which would be 4s.
Okay, so when the 3d shell starts to gain electrons, its energy level drops and it ends up having less energy than the 4s energy level. Since the electrons are removed from the orbitals that are farthest away from the nucleus (and that encounter the most shielding), the electron would be removed from the 4s orbital. :) I hope this helps!
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