Lecture - Ionization Energy and Electron Affinity

1. Ionization Energy (IE)

Definition:

Ionization energy is the minimum energy required to remove the most loosely bound
electron from a gaseous atom or ion in its ground state.

• First Ionization Energy (IE1): Energy required to remove the first electron.

• Second Ionization Energy (IE2): Energy required to remove the second electron, and so
on.

Unit:

• The common unit is kilojoules per mole (kJ/mol).

• It can also be expressed in electron volts (eV).

Example:

The first ionization energy of sodium (Na) is 496 kJ/mol:

2. Electron Affinity (EA)

Definition:

Electron affinity is the energy change when an electron is added to a gaseous atom, forming a
negative ion.

• A positive electron affinity indicates that energy is released (exothermic process).

• A negative electron affinity means that energy is absorbed (endothermic process).

Unit:

• Electron affinity is typically measured in kilojoules per mole (kJ/mol) or electron volts
(eV).

Example:

The electron affinity of chlorine (ClClCl) is -349 kJ/mol:

3. Successive Ionization Energies

• Successive ionization energies increase because it becomes harder to remove

additional electrons due to the increasing effective nuclear charge.
 • For example, the ionization energies of magnesium (Mg) are:

• Notice the large jump from IE2 to IE3, indicating that the third electron is removed from a
more stable, noble gas-like configuration.

4. Factors Affecting Ionization Energy and Electron Affinity

Factors Influencing Ionization Energy

The value of IE is influenced by several factors:

1. Atomic Radius

• The atomic radius is the distance from the nucleus to the outermost electron.

• Impact on Ionization Energy:

o Larger Atomic Radius: When the atomic radius is large, the outermost electrons
are farther away from the nucleus. This results in a weaker attraction between
the nucleus and the electron, making it easier to remove the electron.

o Smaller Atomic Radius: In smaller atoms, the electrons are closer to the
nucleus, resulting in a stronger attraction and thus a higher ionization energy.

Example: Ionization energy decreases as you move down a group in the periodic table because
the atomic radius increases. For example, potassium (K) has a lower ionization energy than
lithium (Li).

2. Nuclear Charge

• The nuclear charge is the total positive charge of the nucleus, determined by the
number of protons.

• Impact on Ionization Energy:

o Higher Nuclear Charge: A higher number of protons in the nucleus increases

the positive charge, which pulls the electrons more strongly. This results in a
higher ionization energy.

o Lower Nuclear Charge: Fewer protons mean a weaker attraction, leading to

lower ionization energy.

Example: Across a period, ionization energy increases from left to right due to the increasing
nuclear charge. For instance, carbon (C) has a higher ionization energy than boron (B).

3. Shielding Effect

• The shielding effect refers to the reduction in the effective nuclear charge on the
outermost electrons due to the repulsion by inner-shell (core) electrons.
 • Impact on Ionization Energy:

o Greater Shielding: More inner electrons increase the shielding effect, which
reduces the effective nuclear charge felt by the outermost electrons. This makes
it easier to remove the outer electron, lowering the ionization energy.

o Lesser Shielding: Fewer inner electrons mean less shielding, resulting in a

higher effective nuclear charge and thus higher ionization energy.

Example: The ionization energy of calcium (Ca) is lower than that of magnesium (Mg), even
though they are in the same group, because Ca has more inner electrons that increase the
shielding effect.

4. Electron Configuration

• The arrangement of electrons in the orbitals of an atom.

• Impact on Ionization Energy:

o Stable Configurations: Atoms with full or half-filled orbitals are more stable
and have higher ionization energies. This is due to the extra stability provided
by a full or half-filled subshell, which makes it harder to remove an electron.

o Unstable Configurations: Atoms with an incomplete subshell have lower

ionization energies because the electrons are more easily removed.

Example: The ionization energy of nitrogen (N) is higher than that of oxygen (O), even though
oxygen is to the right of nitrogen in the periodic table. This is because nitrogen has a half-filled
p-orbital, which is relatively stable.

Factors Influencing Electron Affinity

The factors influencing EA are similar to those affecting ionization energy but have some
differences:

1. Atomic Size

• Smaller Atomic Size: In smaller atoms, the incoming electron is closer to the nucleus,
where the nuclear attraction is stronger. This results in a more negative electron
affinity (more energy released).

• Larger Atomic Size: In larger atoms, the added electron is farther from the nucleus and
feels a weaker attraction, resulting in a less negative electron affinity (less energy
released).

Example: The electron affinity of fluorine (F) is higher (more negative) than that of iodine (I)
because fluorine is smaller in size.

2. Nuclear Charge

• Higher Nuclear Charge: A higher nuclear charge results in a stronger attraction for the
incoming electron, leading to a more negative electron affinity.
 • Lower Nuclear Charge: A lower nuclear charge decreases the attraction for the added
electron, resulting in a less negative electron affinity.

Example: The electron affinity of chlorine (Cl) is more negative than that of sulfur (S) because
chlorine has a higher nuclear charge.

3. Electron Repulsion

• High Electron Repulsion: In smaller atoms, adding an electron to an already densely

populated valence shell leads to significant electron-electron repulsion, which can
reduce the electron affinity.

• Low Electron Repulsion: In larger atoms, the added electron experiences less
repulsion, allowing for a higher electron affinity.

Example: The electron affinity of oxygen is less negative than that of sulfur. Despite being
smaller, oxygen experiences greater electron-electron repulsion when an additional electron is
added.

5. Trends in the Periodic Table

Ionization Energy:

1. Across a Period:

o Ionization energy increases from left to right.

o Reason: Increasing nuclear charge and decreasing atomic size.

2. Down a Group:

o Ionization energy decreases.

o Reason: Increasing atomic size and effective shielding of outer electrons by

inner shells.

Electron Affinity:

1. Across a Period:

o Electron affinity generally becomes more negative (higher).

o Elements on the right side of the table (e.g., halogens) have a strong desire to
gain electrons to achieve a noble gas configuration.

2. Down a Group:

o Electron affinity becomes less negative (lower).

o Larger atomic size and increased shielding make it harder for the nucleus to
attract an additional electron.

Exceptions to Trends:

• Noble gases have positive electron affinities because they have a stable, filled
valence shell and do not readily accept electrons.
 • Elements like Be and N also have low or positive electron affinities due to their stable
configurations (filled s-orbitals and half-filled p-orbitals, respectively).

6. Examples and Applications of Ionization Energy and Electron Affinity

Alkali Metals (e.g., Na, K)

• Ionization Energy:

o Alkali metals have low ionization energies because they have a single valence
electron, which is easily removed.

o This makes them highly reactive and good reducing agents.

• Electron Affinity:

o Their electron affinity is generally low because adding an electron results in an

unstable s2 configuration.

Halogens (e.g., Cl, Br)

• Ionization Energy:

o Halogens have high ionization energies due to their small atomic size and high
nuclear charge.

• Electron Affinity:

o They have high electron affinities (more negative values) because they readily
accept an electron to achieve a stable noble gas configuration.

o This makes them strong oxidizing agents.

Transition Metals

• Ionization Energy:

o Transition metals exhibit variable ionization energies due to their partially filled
d-orbitals, which can stabilize different oxidation states.

• Electron Affinity:

o They generally have moderate electron affinities, but the values can vary based
on the specific electron configuration.

7. Practice Problems

1. Why is the first ionization energy of oxygen lower than that of nitrogen, despite
being to the right in the periodic table?

Hint: Consider the stability of a half-filled p-orbital.

2. Explain why the electron affinity of fluorine is less negative than that of chlorine.

Hint: Think about atomic size and electron-electron repulsion.

 5. Predict the ionization energy trend for elements from Li to F and justify your answer
using atomic radius and effective nuclear charge.

6. Compare the electron affinity of S and Se and explain the difference using periodic
trends.

7. Explain why the ionization energy of Na is lower than that of Mg, but the
electron affinity of Cl is higher than that of S.

8. Calculate the energy required to remove two electrons from magnesium, given
that the first ionization energy is 738 kJ/mol and the second ionization energy is
1451 kJ/mol.

Solution:

9. Predict the trend in electron affinity for the elements C, N, and O. Explain any
deviations from the general trend.

Conclusion

• Ionization energy and electron affinity are key indicators of an element’s reactivity.

• Trends in these properties help predict the behavior of elements in chemical reactions.

• The factors affecting these properties, including atomic radius, shielding, and nuclear
charge, provide insight into the underlying atomic structure.