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An element has multiple ionization energies in the sense that the first ionization energy is the energy it takes to remove the outermost electron (ex. from Na to Na+). Then the second ionization energy is the energy it takes to remove another electron (Na+ to Na^2+), the third ionization energy is the energy it takes to remove yet another electron (Na^2+ to Na^3+), etc. It takes more and more energy to remove each electron. The charge does matter because it takes more energy to remove an electron from a positively charged ion than from a neutral atom (when Na loses an electron it has a full outer shell). This explains why the second ionization energy of sodium is larger than the first ionization energy.
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