Periodic Trends

Unit Objectives
(1) Explain the trend in ionization energy down the group and factors that influence
ionization energy, e.g shielding effect.
(2) How sizes of atoms and ions vary in a group and period
(3) To apply Slater’s rules and calculate effective nuclear charge.
(4) Identify different scales of electronegativity and their application.
(5) Deduce percentage ionic character of a bond

1. Ionisation Potential
The energy required to remove the most loosely bound electron from an
isolated gaseous atom is called ionization energy. The first ionization energy is the
energy required to remove the first electron and convert the species M to M +. The
second ionization energy is the energy required to remove the second electron and
convert M+ to M2+.
M + I1 → M+ + e
M+ + I2 → M2+ + e
The values of successive ionization potential increase in the order
I1 < I2 < I3 < …… This is because except in the first case, we are removing an electron
from a positively charged species.

Factors that influence ionization potential

(1) Size of the atom: In a small atom the electrons are tightly held, while in a
larger atom the electrons are less tightly held. Thus ionization energy
decrease as the size of the atom increases.
(2) Nuclear Charge: Ionization energy increases with increase in nuclear charge.
Thus it increases from left to right in a period. Example, halogens and
charged ions like Mg+.
(3) Shielding effect: The electron in the inner shell act as a screen between the
nucleus and electrons in the outer most shell. This is shielding effect.
Consequently the electrons in the valence shell experience less attraction from
the nucleus and hence ionization energy is low. Shielding effect offered by an
s electron is greater than a p electron and p orbital offers more shielding than
d and so on.
(4) Penetration effect: Ionisation energy also depends on the type of electron
which is removed. s, p, d, f electrons have orbitals with different shapes. An s
electron from a spherically symmetrical s orbital penetrates nearer to the
nucleus and therefore more tightly held than a p electron. Thus ionization
energy decreases in the order s > p > d > f
 (5) Electronic arrangement: If an atom has fully filled or half filled orbitals, its
ionization energy is higher than expected. This is due to the extra stability of
these orbitals. For example He, Ne, Ar….. have highest ionization energy in
their periods.

Figure 2.1: Periodic trend for ionization energy. Each period begins at a minimum for the alkali metals,
and ends at a maximum for the noble gases.

ACTIVITY: 1
Discuss why the substantial decrease in the first ionization energy observed between Na and
K, and Mg and Ca, not observed between Al and Ga?

SOLUTION:
As we move from Na to K, the extra electron is added in the new shell (3s→4s). So
potassium will be bigger in size and nuclear charge felt by the valence electron will be less,
or the outer electrons are under the influence of nucleus to a lesser extent only. So ionization
energy will be less for K than Na. This happens in Mg and Ca also. In Al, Ga pair, there is the
introduction of d orbitals. As you already know screening offered by d orbitals will be less.
Less shielding draws the valence electrons into the nucleus. This greater force of attraction on
the electrons will be reflected in the ionization energies. So ionisation energies will not be
very less with Ga, even if it is bigger in size.

PRACTICE PROBLEM: 1

Use the trends in the ionization energies of the elements to explain the following
observations.

(a) Elements on the left side of the periodic table are more likely than those on the right to
form positive ions.

(b) The maximum positive charge on an ion is equal to the group number of the element
 2. Electron Affinity

It is the quantity of energy F liberated when an electron is accepted by a neutral atom E,

converting it into a negative ion E-.
E + e → E- ± F (e is an electron)
It is expressed either in kJ/mole or eV/atom. Numerically electron affinity is equal to
ionization energy of a negatively charged ion E - (but with opposite sign). A negative electron
affinity means the process is endothermic or energy is absorbed. Second electron affinity i.e.
(M- (g) + e → M2-(g)) is always negative, due to the difficulty in bringing together negatively
charged ion and a negatively charged electron.
Electron affinity increases across a period in accordance with the increasing effective nuclear
charge. It decreases as we move down a group.

3 Sizes of atoms and ions

Size of atoms decrease from left to right across a period. On moving from Lithium to
Berillium, one extra positive charge is added to the nucleus and an extra electron is added in
the same orbital. Increasing the nuclear charge results in all of the orbital electrons being
pulled closer to the nucleus. On descending a group in the periodic table such as that
containing Li, Na, K, Rb and Cs, the sizes of the atoms increase due to the effect of extra
shells of electron being added, this outweighs the effect of increased nuclear charge.
Positive ions formed are usually smaller than the atoms from which they are formed. In a
cation number of positive charges exceeds the number of orbital electons and this increased
nuclear charge exerts greater attraction on orbital electrons making it small.
Metallic radius of Na is 1.86 Å.
Ionic radius of Na+ is 1.02 Å.
When a negative ion is formed, one or more electrons are added to the atom, the effective
nuclear charge is reduced and hence the electron cloud expands. Negative ions are bigger
than corresponding atom.
Covalent radius of Cl is 0.99 Å.
Ionic radius of Cl- is 1.84 Å.

PRACTICE PROBLEM: 2
Pick out the ion with larger effective radius. Account for your answer.
(a) Sn 2+: Pb2+ (b) Sn2+ : Sn4+

4. Effective Nuclear Charge

It is the ratio of number of charges on the nucleus to the number of electrons. In an atom the
attractive force of the nucleus on the outermost electron will be lessened by the shielding
effect of electrons in between. Thus the net nuclear charge felt by the outermost electron is
called effective nuclear charge. The effective nuclear charge which depends on the extent of
shielding can be estimated using Slater’s Rules. Higher the effective nuclear charge higher
the stability of atom.
According to Slater’s rule, effective nuclear charge Zeff = z-s
z = total nuclear charge
s = shielding constant (extent of shielding)

Slater’s rules for calculating s and Zeff

The value of s for an electron residing in an ns or in one of the np orbitals of nth shell of an
atom or an ion is the sum of the following contributions.
1. Each of the remaining electrons in the nth shell makes a contribution of 0.35 to the
value of s.
2. Each of the electrons in (n-1)th shell makes a contribution of 0.85.

3. Each of the electrons in the next inner shells makes a contribution of 1.0.
4. There will be no contribution to the value of s by electrons residing in orbital’s having
higher value of their principal quantum number than the orbital containing the
electron for which s is being calculated.
5. If s is being calculated for an electron of 1s orbital, there will be a contribution of 0.30
from other single electron in 1s orbital.

The value of s for an electron residing in (n-1)d orbitals, of (n-1) th shell of an atom or an ion
is the sum of the following contributions.
1. There will be no contribution to the value of s by the electrons residing in ns shell.
2. Each of the remaining electrons present in (n-1)d orbitals, makes a contribution of
0.35.
3. Each of the electrons present in the (n-1)s, (n-1)p orbitals and inner shells makes a
contribution of 1.0.
Thus s for a (n-1)d electron = 0.35 x [No: of electrons in (n-1)d orbitals] + 1.0 x
[No: of electrons in (n-1)s, (n-1)p orbitals and inner shells] .
The application of the above rules will be clear for you from the following example.

ACTIVITY: 2
Calculate s and Zeff for 3d electron in Mn (z = 25)
 SOLUTION: Mn = 1s2,2s2p6, 3s2p6d5,4s2
On arranging the various orbitals as per Slater’s rules, we get
{1s2,2s2p6, 3s2p6 } { d5 } { 4s2}
18 e 5e 2e

4s2 electrons will not contribute to the value of s for a 3d electron.

‘s’ for 3d electron in Mn atom = 0.35 x [No: of the remaining electrons in 3d orbitals] +
1.0 x [No: of electrons in 1s, 2s, 2p, 3s and 3p orbitals].
= 0.35 x 4 + 1.0 x 18 = 19.40
Zeff = z – s = 25-19.40 = 5.60
ACTIVITY: 3

The first ionization energy for hydrogen is 1310 kJ·mol–1 while the first ionization energy for
lithium is 520 kJ·mol–1. The IE for lithium is lower for two reasons. Discuss.

SOLUTION:

1) The average distance from the nucleus for a 2s electron is greater than a 1s electron;

2) The 2s1 electron in lithium is repelled by the inner core electrons, so the valence electron is
easily removed.

For reason #2 the inner core electrons shield the valence electron from the nucleus so the
outer most electron only experiences an effective nuclear charge. In the case of the lithium
the bulk of the 1s electron density lies between the nucleus and the 2s1 electron. So the
valence electron `sees' the sum of the charges or approximately +1. In reality the charge the
valence electron experiences is greater than 1 because the radial distribution show there is
some probability of finding the 2s electron close to the nucleus.

PRACTICE PROBLEM: 3
Why is 4s orbital filled earlier than 3d orbital in potassium atom? [Apply Slaters rules].
Comment on the stability of two possible configurations by calculating Zeff.

Hint[Hint] Find the Z on 4s electron with electronic configuration

eff

(1s22s22p6 3s2 3p6 4s1)

Also find the Zeff on 3d electron with electronic configuration

(1s22s22p63s2 3p6 3d1)
 Now compare the Zeff values and find the stable configuration.

5 Electronegativity

It is the ability of an atom in a molecule to attract electron density towards itself. It

increases across a period due to the increase in effective nuclear charge. For main group
elements, electronegativity decreases down a group due to increasing size of atom.
Flourine is having the highest electronegativity. For transition metals the electronegativity
increases down the group. This is the result of very poor shielding ability of d and f
electrons and hence a large increase in effective nuclear charge down the group. There are
various scales to measure electronegativity.

Mulliken scale
According to Mulliken, the electronegativity of an atom χ can be expressed as the half-
sum of its ionization energy and electron affinity.

χ = ½ (I+F)

Conversly, if its ionization energy and electron affinity are both low, then atom will tend
to lose electron and hence be classified as electropositive. e.g. alkali metal.

Pauling Scale
According to Pauling scale, the excess energy Δ of an A-B bond over the average energy
of A-A and B-B bonds can be attributed to the presence of an ionic contribution to the
covalent bonding. He defined difference in electronegativity as
| χA - χB | = 0.102 x √Δ kJ/mol
Where Δ = E(A-B) – ½{E(A-A) + E(B-B)}
Thus if A-B and B-B bond energy differs markedly from the average of nonpolar A-A and
B-B bonds, there is a substantial ionic contribution, hence a large difference in
electronegativity between the two atoms.

Allred -Rochow’s Scale

They defined electronegativity of the atoms as the electrostatic force exerted by the nucleus
on the valence electron.
Electronegativity = 0.359 Zeff / r2 + 0.744
Where Zeff is the effective nuclear charge and r is the radius of the atom.

PRACTICE PROBLEM: 4
In some tabulations of electronegativity, the electronegative atom is listed as Neon. This is
contrary to the usual statement that “the most electronegative atom is fluorine”. Using the
Mulliken definition of electronegativity, explain how Neon has a higher electronegativity
than fluorine.
Fluorine Ionisation energy =17.422 eV
Neon Ionisation energy = 21.56
Flourine Electron affinity = 3.34 eV
Neon Electron affinity = 0.0 eV

ACTIVITY: 4

What happens if two atoms of equal electronegativity bond together?

SOLUTION:

Consider a bond between two atoms, A and B. Each atom may be forming other bonds as
well as the one shown - but these are irrelevant to the argument. If the atoms are equally
electronegative, both have the same tendency to attract the bonding pair of electrons, and so it
will be found on average half way between the two atoms. To get a bond like this, A and B
would usually have to be the same atom. You will find this sort of bond in, for example, H2
or Cl2 molecules.

 No electronegativity difference between two atoms leads to a pure non-polar covalent

bond.

 A small difference in electronegativity leads to a polar covalent bond.

 A large electronegativity difference leads to an ionic bond.

PRACTICE PROBLEM 5
Arrange the following compounds in the order of the increasing polarity of their bonds: 
CO, HF, NaCI, O2

2.2 Percentage Ionic Character

Consider the polar covalent bond A-B, it behaves like a dipole since it has two poles A δ--
δ+
B . These two charges are separated by a definite distance called bond length. If q is the
charge (positive or negative), ℓ is the bond length, then product of q and ℓ is called dipole
moment of A-B molecule.
μ=qxℓ
Here dipole moment measures the degree of polarity or ionic nature of the bond.
Dipole moment of HF molecule = electronic charge (in coulombs) x bond length (in meters)
μHF = (1.602 x 10-19 C) x (0.92 x 10-10 m) = 1.47 x 10-29 Cm.
Dipole moment of a polar molecule arises due to the difference in electronegativity of
values of the two atoms. Greater the electronegativity difference, greater is the percentage
ionic character associated with the bond.
Thus the percentage ionic character in A-B bond can be calculated as
{μexperimental }x 100 %
{μcalculated}
Usually the calculated value of dipole moment is more than its experimental value. This is
because the calculated value of dipole moment is based on the complete transfer of electrons
from electropositive atom to the electronegative atom. But in the actual case the anion will be
polarized by the cation resulting in partial overlap. (See Fajans rules in unit 1.) This flow of
electric charge decreases the dipole moment of the bond.
Dipole moments can be used to predict the shape of the molecules. Homonuclear diatomic
molecules like C2, N2 have zero dipole moment and have symmetrical dumb bell shape. H2O
and SO2 have resultant dipole moment and have angular shape.
PRACTICE PROBLEM: 6
 The electronegativities of the period-3 elements are listed. Calculate the
electronegativity differences for the following pairs of bonded period -3 atoms.
 Na and Cl
 Mg and S

An electronegativity difference greater than 1.7 generally corresponds to a bond

that is considered ionic. For which of the bonded-atoms combinations would
give an ionic bond.

Use the graph to find the approximate percent ionic character for the
pair of bonded atoms (1) Si and S and (2) Al and P
Calculate the percent covalent character for the bonded pair Si and Cl
ACTIVITY: 5
In NaCl ionic crystal, bond length is 2.36 Å and the experimental dipole moment of this
molecule is 8.5 D.Calculate the percentage of ionic character in Na-Cl bond in the given
molecule.
SOLUTION: (μcal)Na+Cl- = Bond length in NaCl crystal (in cm) X Electronic charge (in e.s.u)
= (2.36 x10-8cm) X (4.8 x10-10 esu)=11.32 x10-18 cm.esu =11.32 D
We know that (10-18 cm.esu =1D)
Observed dipole moment, (μexp)NaCl =8.5 D
Thus the % of ionic character in Na-Cl bond in NaCl molecule =
8.5
100 %=75.03 %
11.32