Ionization Energy

Ionization
Ionization is a process that involves the removal of electron present in an orbit of an atom to the
outside of the atom. Since the electron in each orbit has characteristic energy, ionization energy
is equal to the difference of energy between the energy of the electron in the initial orbit and the
energy of the electron outside the atom (in the infinite orbit from the nucleus).

Ionization Energy
The ionization energy is the energy required to remove the most loosely held electron from one
mole of neutral gaseous atoms or ions resulting in formation of cations.
H(g)→H+(g) +e−
This energy is usually expressed in kJ/mol, or the amount of energy it takes for all the atoms in a
mole to lose one electron each. Also Known as: ionization potential, IE, IP, ΔH°

Factors affecting the size of ionization energy

Bohr’s Atomic Model

Ionization energy is a measure of the energy needed to pull a particular electron away from the
attraction of the nucleus. A high value of ionization energy shows a high attraction between the
electron and the nucleus. The size of that attraction will be governed by:
 The charge on the nucleus: The more protons there are in the nucleus, the more
positively charged the nucleus is, and the more strongly electrons are attracted to it.
 The distance of the electron from the nucleus: Attraction falls off very rapidly with
distance. An electron close to the nucleus will be much more strongly attracted than one
further away.
 The number of electrons between the outer electrons and the nucleus: Consider a
sodium atom, with the electronic structure 2,8,1.
If the outer electron looks in towards the nucleus, it does not see the nucleus sharply. Between it
and the nucleus there are the two layers of electrons in the first and second levels. The 11 protons
in the sodium's nucleus have their effect cut down by the 10 inner electrons. The outer electron
therefore only feels a net pull of approximately 1+ from the center. This lessening of the pull of
the nucleus by inner electrons is known as screening or shielding effect.
 Whether the electron is on its own in an orbital or paired with another
electron: Two electrons in the same orbital experience a bit of repulsion from each other.
This offsets the attraction of the nucleus, so that paired electrons are removed rather more
easily than you might expect.

Types of Ionization Energy

Second, Third, Fourth, and Higher Ionization Energies

The first ionization energy of aluminium, for example, is the energy it takes to remove one
electron from a neutral atom to form a unipositive cation.
Al(g) + energy Al+(g) + e-
The second ionization energy is the energy it takes to remove another electron to form an
Al2+ ion in the gas phase.
Al+(g) + energy Al2+(g) + e-
The third ionization energy can be represented by the following equation.
Al2+(g) + energy Al3+(g) + e-
The energy required to form a Al3+ ion in the gas phase is the sum of the first, second, and third
ionization energies of the element.
First, Second, Third, and Fourth Ionization Energies
of Sodium, Magnesium, and Aluminum (kJ/mol)

Naturally, removing the second electron from an already positive ion will be difficult. Hence, the
second ionization energy will be larger than the first ionization energy. The third ionization
energy will be more than the second ionization energy etc.
∆H1st < ∆H2nd < ∆H3rd < ….
The higher the ionization energy, the more difficult it is to remove an electron. Therefore,
ionization energy is an indicator of reactivity. Ionization energy is important because we can use
it to predict the strength of chemical bonds.

Ionization Energy Trend in the Periodic Table

Ionization, together with atomic and ionic radius, electronegativity, electron affinity, and
metallicity, follows a trend on the periodic table of elements.
 Ionization energy generally increases, moving from left to right across an element
period (row). This is because the atomic radius generally decreases moving across a
 period, so there is a greater effective attraction between the negatively charged electrons
and positively-charged nucleus. Ionization is at its minimum value for the alkali metal on
the left side of the table and at its maximum for the noble gas on the far right side of a
period. The noble gas has a filled valence shell, so it resists electron removal.
 Ionization decreases, moving top to bottom, down an element group (column). This is
because the shell of the outermost electron increases moving down a group. There are
more protons in atoms moving down a group (greater positive charge), yet the effect is to
pull in the electron shells, making them smaller and screening outer electrons from the
attractive force of the nucleus. More electron shells are added moving down a group, so
the outermost electron becomes increasingly distant from the nucleus.
The fall in ionization energy as you go down a group will lead to lower activation
energies and therefore faster reactions. This explains why reactivity of elements increase
down the group.

*The increasing trend of ionization energy in KJ/mol (exception in case of Boron) from
left to right in the periodic table.

Li 520 Be 899 B 800 C 1086 N 1402 O 1314 F 1680

The decreasing trend of ionization energies (Kj/mol) from top to bottom (Cs is the exception in the
first group)

Li 520

Na 496

K 419

Rb 408

Cs 376

Fr 398

He 2372 5250

Li 520 7297 11810

Be 899 1757 14845 21000

B 800 2426 3659 25020 32820

C 1086 2352 4619 6221 37820 47260

N 1402 2855 4576 7473 9442 53250 64340

O 1314 3388 5296 7467 10987 13320 71320 84070

F 1680 3375 6045 8408 11020 15160 17860 92010

Ne 2080 3963 6130 9361 12180 15240

Na 496 4563 6913 9541 13350 16600 20113 25666

Mg 737 1450 7731 10545 13627 17995 21700 25662

Key Points
 Ionization energy is the minimum energy required to remove an electron from an atom or
ion in the gas phase.
 The most common units of ionization energy are kilojoules per mole (kJ/M) or electron
volts (eV).
 Ionization energy exhibits periodicity on the periodic table.
 The general trend is for ionization energy to increase moving from left to right across an
element period. Moving left to right across a period, the atomic radius decreases, so
electrons are more attracted to the (closer) nucleus.
 The general trend is for ionization energy to decrease moving from top to bottom down a
periodic table group. Moving down a group, a valence shell is added. The outermost
electrons are further from the positive-charged nucleus, so they are easier to remove.

Electron Affinity
The electron affinity (Eea) of an atom or molecule is defined as the amount of energy released
when an electron attaches to a neutral atom or molecule in the gaseous state to form an anion.
X(g) + e− → X−(g) + energy

When an electron is added to a neutral atom (i.e., first electron affinity) energy is released; thus,
the first electron affinities are negative. However, more energy is required to add an electron to a
negative ion (i.e., second electron affinity) which overwhelms any the release of energy from the
electron attachment process and hence, second electron affinities are positive.

 First Electron Affinity (negative energy because energy released):

X(g)+e−→X−(g)

 Second Electron Affinity (positive energy because energy needed is more than gained):
X−(g) +e−→X2−(g)
Periodic Trends
The amount of energy released when an electron is added to a neutral atom to form an anion is
called electron affinity. Electron affinities are difficult to measure.
 Electron affinity increases going left to right across a period because of increased
nuclear attraction.
 Going down the group the electron affinity should decrease since the electron is being
added increasingly further away from the nucleus. Electron becomes less tightly bound
and can be easily removed
Note:
Both ionization energy and electron affinity have similar trend in the periodic table. For example,
just as ionization energy increases along the periods, electron affinity also increases. Likewise,
electron affinity decreases from top to bottom due to the same factor, i.e., shielding effect.
Halogens can gain an electron easily as compared to elements in the first and second group. This
tendency to gain an electron in a gaseous state is termed as electronegativity.
The electronegativity determines one of the chemical differences between Non-metallic and
metallic elements.
 Metals: Metals like to lose valence electrons to form cations to have a fully stable octet.
They absorb energy (endothermic) to lose electrons. The tendency to lose electrons is
referred to as electropositivity. The electron affinity of metals is lower than that of
nonmetals.
 Nonmetals: Nonmetals like to gain electrons to form anions to have a fully stable octet.
They release energy (exothermic) to gain electrons to form an anion; thus, electron
affinity of nonmetals is higher than that of metals.

Prediction of Covalent and Ionic Bonds

The difference of electronegativity or ionization energies between two reacting elements
determine the fate of the type of bond. For example, there is a big difference of ionization
energies and electronegativity between Na and Cl. Therefore, sodium completely removes the
electron from its outermost orbital and chlorine completely accepts the electron, and as a result
we have an ionic bond.
However, in cases where there is no difference in electronegativity, the sharing of electrons
produces a covalent bond. For example, electronegativity of Hydrogen is 2.1 and the
combination of two Hydrogen atoms will definitely make a covalent bond (by sharing of
electrons).
The combination of Hydrogen and Fluorine (electronegativity=3.96) will produce
a polar covalent bond because they have small differences between electronegativity.