Chemistry Unit I

Ionization Energy D.Hines

Ionization energy

First ionization energy of an element is the energy needed to convert one mole of its gaseous atoms into gaseous ions with a
single positive charge.

M (g) →M+(g) + e- ∆Hi1st = +kJ/mol

Example Cl (g) → Cl+(g) + e- ∆Hi1st = +1260 kJ/mol

 Factors influencing the ionization energies of elements - The distance the outer electron is from the nucleus - The
further the outer electrons are from the nucleus, the less attractive force between the nucleus and the electrons and the
lower the value of the ionization energy.
 Size of the nuclear charge- As the nuclear charge increases, the attraction of the nucleus for the outer electron
increases and the ionization energy increases because It requires more energy to remove the electron.
 The screening or shielding effect of the inner electrons - Apart from electrons bring attracted to the nucleus, they
also experience repulsion by other electrons. Electrons in full inner shells reduce the attractive force between the
nucleus and the outer electrons. The greater the number of inner shells, the greater the shielding effect and the lower
the ionization energy, because it will take less energy to remove electrons.

Evidence for energy levels

Evidence for discrete energy levels come successive ionization energies required to remove all electrons from an atom. When
we remove electrons from an atom one by one, the energies associated with removing these electrons are called the successive
ionisation energies. Successive ionization energies increase since the inner electrons are more strongly attracted to the
positively charged nucleus. Each time an Electron is removed it becomes more difficult to remove the successive electron
therefore larger increases in ionization energy are observed. However unusually large increases occur when all the electrons
are removed from the outer shell and an electron is now being removed from the inner shell.

Successive ionization energies can therefore tell the group the atom is in by the number of electrons in the outer shell of the
atom. It can also tell the number of electrons shells in the atom.

Table showing large increase in ionization of Na and other elements.

Na Mg Al Si P S Cl Ar
st
1 496 738 578 787 1010 1000 1251 1520
2nd 4562 1451 1817 1577 1903 2251 2297 2665
3rd 6912 7733 2745 3231 2912 3361 3822 3931
4th 9543 10540 11575 4356 4956 4564 5158 5770
5th 13353 13630 14830 16091 6273 7013 6542 7238
6th 16610 17995 18376 19784 22233 8495 9458 8781
7th 20114 21703 23293 23783 25397 27106 11020 11995
8th 25496 25661 27465 29287 29872 31719 33604 13842

Plot of successive ionization energies of Na

Evidence for sub-energy levels

The first ionization energy of the elements in a period gives evidence for the presence of sub-levels. Across a period there is a
general increase in first ionisation energy. Since the nuclear charge (number of protons) increases, the atomic radii decreases
as you go across the period. The attractive force between the outer electrons and nucleus will result in a general increase of
ionization energy as you go across the period. However, there are two irregularities in the pattern. The first ionization energy of
boron is smaller than beryllium and the first ionization energy of oxygen is smaller than nitrogen.

1
 Diagram showing first ionization energy across period 2.

These observations can be explained by the presence of sub-shells. It requires less energy to remove the first electron from the
2p orbital in boron that it is to remove one from the filled 2s orbital in beryllium. This is because the 2p sub-shell is slightly further
from the nucleus and the shielding effect also increases.

Be is 1s2 2s2
B is 1s2 2s22p1

In the case of nitrogen, the three electrons in the 2p orbitals all have the same spin, but in oxygen the fourth electron is paired in
one of the 2p orbitals
N is 1s2 2s2 2p2
O is 1s2 2s2 2p4

The electron - electron repulsion in the paired p orbitals makes it easier to remove the paired electrons with opposite spin, thus
the first ionization energy of oxygen is less than that of nitrogen

Exercises
1. State the maximum number of electrons that can be held in an s,p and d sub-shell.
2. a. What is an atomic orbital?
b. Draw a: i. 2s orbital ii. 2p orbital
3. Write the electronic configurations of the following atoms and ions:
a. Ca b. Zn c. Cl- d. Mn2+ e. S2- f. Ca2+
4. Define the term the ‘first ionisation energy’
b. Write an equation showing the first and second ionisation energy of calcium
5. State the three factors that influence the value of the ionisation energy
6. Explain the general trend of an increase in ionisation energy across a period
7. Explain why there is a decrease in the first ionisation energy between:
a. Mg and Al b. P and S
8. The following data show the first seven successive ionisation energies of an element X. Suggest which group of
the Periodic table X belongs to. Give reasons for your answer.
Ionisation energy number Enthalpy/kJmol-1
1st 737.7
2nd 1450.7
3rd 7732.7
4th 10542.5
5th 13630
6th 18020
7th 21711

9.

a. Explain why the 1st ionization energy of fluorine is greater than that of oxygen
b. Why is the 1st ionization energy of oxygen less than that of nitrogen
c. Explain how the data in the graph provide evidence for the existence of sub-shells within the atom