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According to the Aufbau principle, the 4s sublevel is filled before the 3d sublevel because the 4s is lower in energy. However, when the 3d orbital starts to become filled, the energies of 4s and 3d fluctuate and 4s ends up higher than 3d energy level. so electrons are lost from 4s first.
when there are electrons in the 3d orbital, they automatically are of lower energy than 4s. For this reason, even if there are electrons in the 3d orbital, the electrons will be lost from the 4s orbital.
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