Unit 4B

Ionization Energy
Content
1 Introduction
2.0Learning Outcomes
3.0 Learning Content
3.1Factors affecting ionization energy
3.1 Periodicity in ionization energy
3.2 Trends in ionization energy
3.3 Trends in successive ionization energy
4.0 Conclusion
5.0 Summary
6.0 Tutor Mark Assignments
7.0 References and Further Readings
1.0 Introduction
When elements react, they do so by gaming, losing or sharing of electrons. This process of gaining, losing
or sharing of electrons is usually accompanied by energy changes. You know that the electrons to be shared,
gained or lost are bound to the nucleus of its atom by an electrostatic force of attraction. To remove an
electron from an atom, its force of attraction has to be overcome. This can be done by supplying energy.
The energy required to remove the least strongly bonded electron from an isolated gaseous atom in its ground
state is known as the ionization energy. This process can be represented by the following:

M(g) M+ + e ion

Since more than one electron may be removed from an atom, the energy required for the above process is
called the first ionization energy. The second ionization energy is the energy required to remove an
electron from a univalent cation that process is represented by this reaction.

M+(g) M2+ + e ion

The second ionization energy is much larger than the first ionization energy. This is because in this case an
electron is being removed from a positively charged cation. Similarly, you can define third, fourth and
higher ionization energies. The energy needed to remove an electron completely from an atom of an
element is known as the first ionization energy, the second ionization energy is the energy needed to
remove completely the second electron from a singly charged ion, and so on.
K(g) K+ + e-1 1st ionization energy +418KJmol-1 K(g)
K2+ +e-1 2nd ionization energy +3070KJ mol-1

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Notice the large difference between the two values, due to the fact that it is difficult to ionize an electron
when the atom already bears a positive charge. The SI unit of ionization energy which we will use
throughout this course is KILOJOULE per mole. The ionization energies for the group the Group 2
elements show that the first ionization energy is almost double the value for the corresponding Group 1
element, but in general, the first ionization energy decreases regularly on descending the main groups.
In this unit, you will be studying the factors that affect ionization energy, periodicity in ionization across the
periods, trends in ionization energy, down the groups and trends in successive ionization energy.

2.0 Learning Outcomes

After studying this unit, you should be able to:
1. Define ionization energy
2. Differentiate between first, second, subsequent ionization energies
3. List the factors that affect ionization energies
4. Explain trends in ionization energies across period down the groups

3.0 Learning Content

3.1 Factors Affecting Ionization Energies·

The ionization energyy (I) of an outer valence electron is related to the effective nuclear charge felt by
the electron and its average distance from the nucleus as stated in the equation below

Where Z* is the effective nuclear charge, e is the charge on the electron and(1/r)av is the average value of the
electron from the nucleus, thus the higher the effective charge felt by the electron, the higher will be the ionization
energy. Also the further the electron is from the nucleus, the lower will be the ionization energy and vice versa. In
addition to the above, the ionization energy also depends upon the relative stabilities of the sub shell from which
the electron is removed. As we have seen before, completely filled and half-filled sub shells are comparatively more
sTable, so removal of an electron from them requires more energy. The valence shell electronic configurations of
noble gases are exceptionally stable and therefore their ionization energies are the highest in their respective period.
Factors affecting ionization energies are (i) The size of the atom (2) The charge on the nucleus
(3) How effectively the inner electron shells screen the nuclear charge (4) The type of electron
involved (s, p, d and f).

3.2 Periodicity in Ionization Energy Across Periods

In the previous sub-section, we defined and identified factors which affect ionization energies. In the next sub-
sections, we shall examine the variation in ionization energy across the periods and down, the group in the periodic

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Table, values of ionization energies of elements are given in Table 9
Table 9: Ionization energies of elements in KJmol-1

Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

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The variation in ionization energy in a particular group or period is best shown by a graph showing ionization
energies against atomic number. Figure 9 shows the plot of first ionization energies of the elements of the firstsix
periods against their atomic numbers. As is evident from the figure, the first ionization energy generally increases
from alkali metals to noble gases across any row of the periodic Table. But the increase is not perfectly regular.

Figure 9: The variation in ionization energy

You have seen from an earlier section that across any row of the periodicTable the effective nuclear charge
steadily increases and the atomic radii decrease. These two effects reinforce each other to increase the
ionization energies across a period. Thus the ionization energies of the alkali metals are the lowest and those
of the noble gases are the highest intheir respective periods. However, as pointed out earlier the increase is
notsmooth and some anomalies are observed. For example, in the elements of period 2, despite the increase
in Z* and decrease in r, the first ionizationenergies of B and O are lower than those of Be and N respectively.
However, these anomalies in the trend in ionization energy can be explained by the electronic structures of
these elements. In the case of beryllium, the electron is removed from the filled 2S sub-shell whereas in
boron, the electron is removed from the singly occupied2p subshell. The 2p sub-shell is higher in energy
than the 2S, so the 2p electron of boron is more easily removed than the 2S electron of beryllium. When we
come to nitrogen, we will find out that we have a half-filled 2p subshell (electronic configuration IS22S23P3)
while in oxygen the 2p subshell is occupied by four electrons. The fourth electron in this 2p sub-shell is in
an orbital already occupied by another electron, so it experiences considerable repulsion. As a result, this
electron is more easily removed than one of the electrons from a singly occupied orbital in a nitrogen atom.
Thus the ionization energy of oxygen becomes less than that of nitrogen. Similar anomalies are observed in
elements of period 3 where the first ionization energies of magnesium and phosphorous are higher than
those of aluminium and sulphur respectively. We have earlier seen that across the transition series, the
increase in effective nuclear charge and consequent decrease in atomic radius is small. Therefore, the
increase in the first ionization energies is also small. However, following the transition elements, the first
ionization energy drops abruptly in gallium, indium and thallium. This again is due to the removal of an
electron from a singlyoccupy n p orbitals which are of relatively higher energy than the ns orbital of Zn, Cd
and Hg
In-text Question
Establish why large difference exist in the two ionization energies of thereaction below.

K(g) K+ +e-1 1st ionization energy +418KJmol-1

K(g) K2+ +e-1 2nd ionization energy +3070KJ mol-1

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3.3 Trends in Ionization Energy Down the Groups

We have learned from a previous sub section that on moving down a group of S and p- block elements
effective nuclear charge remains almost steady. But there is a general increase in the atomic radius due to
an increase in the value of the principal quantum number n1, thus the dominant factor in determining the
ionization energies of the elements on moving down the group is their atomic radius rather than the effective
nuclear charge. Therefore, as expected, the first ionization energies decrease down the groups in the case of
the main group elements in the periodic Table. But in the case of transition elements opposite trends are
observed. Thus, the first ionization energies of the corresponding elements of 3d and 4d series are almost
similar but these are smaller than the first ionization energies of the elements of 5d series. Certainly, the
higher values of ionization energies of the 5d transition elements are consistent with the relatively smaller
size of their atoms.
3.4 Trends in Successive Ionization Energies

We have already defined successive ionization energies that is first, second, third etc. Values of eight
successive ionization energies of the first twenty elements are listed in Table 10. It is evident from the values
in the Table that the successive ionization energies of an element inevitably become larger because the
removal of a successive electron leaves a higher charge on the nucleus to hold the remaining electrons. It is
also clear from the Table that the difference between successive ionization energies of the same element is not
constant. Big jumps occur whenever an electron from a subshell of a lower principal quantum number is
removed for the first time. For example, for alkali metals, the second ionization energies are much higher
than the first. For alkaline earth, metal the third ionization energies are much larger than the second and for
the halogen, the eighth ionization energies are much greater than the seventh. These however cannot be
explained based on an increase in nuclear charge alone. The stabilities of closed shell configurations similar
to those of noble gases are more important in these cases. So far in our study, we have seen that ionization
energy generally increases across a period and decreases down the group in the periodic Table. Accordingly,
the tendency to form cation that is metallic character decreases across a period and increases down the group.
For example, inperiod 3 metallic character decreases from Na to Cl whereas in the elements of group 14, C
is a nonmetal, Si and Ge are semimetals or metalloids whereas Sn and Pb are metals.

Discuss why the first ionization energies decrease down the groups in the
case of the main group element.

4.0 Conclusion

We can conclude this unit by observing that chemical reaction inevitably involves either a gain, a loss or
sharing of electrons by atoms. It follows therefore that, whether a reaction takes place or not, the ease with
which it can happen and how regularly it happens, depends very much on the factors that affect the formation
of ions by the element. The valence shell electronic configurations of noble gases are exceptionally

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stable and therefore their ionization energies are highest in their respective periods. Factors affecting
ionization energies are (i) The size of the atom (2) The charge on the nucleus (3) How effectively the inner
electron shells screen the nuclear charge (4) The type of electron involved (s, p, d of f). We have earlier seen
that across the transition series, the increase in effective nuclear charge and consequent decrease in atomic
radius is small. Therefore, the increase in the first ionization energies is also small. However, following the
transition elements, the first ionization energy drops abruptly in gallium, indium and thallium.

5.0 Summary

In this unit we have studied the following:

i. The ability of an element to participate in a chemical reaction is

governed by it stability to give up, gain or share its outer most electrons.
ii. That this ability is measured in form of its ionization energy.
iii. That the ionization energy can be defined as the energy required to
remove the least strongly bond electron from an isolated gaseous atom
in its ground state.
iv. That the ionization energy is affected by such factors as the effective
nuclear charge of the atom and the reactive stabilities ofthe sub-shell
from which the electron is removed.
6.0 Tutor-Marked Assignments
1. Why is the second ionization energy of sodium higher than that of
magnesium?
2. Each member of the class should write an electronic configurationof any
element with atomic number not more than 30.
7.0 References/Further Reading

J. G Wilson, A. B. Newell (1971) General and Inorganic Chemistry (2nd edition) Published by
Cambridge University Pres.
F. A Cotton, G. Wilkinson and P. L. Gayus (1995) Basic Inorganic Chemistry. (3nd edition) John Wiley
and Sons Published.
Gary L. Miessler, Paul J. Fischer and Donald A. Tour (2014) Inorganic Chemistry. 5th edition. Pearson
Publishers. ISBN 10:0-321-81105-4.
J. D Lee (2016) Concise Inorganic Chemistry. (5th edition)WileyPublishers. Factors Affecting
Ionization Energies [Link]

Periodicity in Ionization Energy across Periods [Link]

Trends in Ionization Energy down the Groups [Link]

Trends in Successive Ionization Energies [Link]

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