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4d has a greater energy than 5s when the 4d orbitals are empty. However when the 4d orbital starts to fill up with electrons, it has a lower energy than 5s because the electrons in the 4d orbital shield the electrons in the 5s orbital. Therefore when an element in the d-block is ionized, or loses electrons, it will lose electrons from the s-orbital first because electron shielding in the d-orbital causes the s-orbital electrons to be further away from the nucleus, and therefore are more easily lost.
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