Module 5: Periodic Properties and Related Concepts —-PYQ-based Notes

1. s, p, d, f Orbitals & Electronic Configuration

Q1: What is the shielding constant value for 1s orbital electron?
The shielding constant for a 1s orbital electron is zero because there are no inner electrons to reduce
the nuclear attraction. Since shielding is caused by repulsion from other electrons, and the 1s
electron is the closest to the nucleus with no electrons inside it, there is no shielding effect. Thus,
using Slater’s rule, S = 0 and Z* = Z.

Q2: Which of the following has larger size and why? (i) Mg²⁺ (ii) N³⁻
N³⁻ has a larger size than Mg²⁺ because although both ions have the same number of electrons (10),
their nuclear charges are different. Mg²⁺ has 12 protons attracting 10 electrons, resulting in a
stronger nuclear pull and a smaller ionic radius. In contrast, N³⁻ has only 7 protons attracting 10
electrons, leading to weaker nuclear attraction and increased electron-electron repulsion, causing
the electron cloud to expand. Therefore, N³⁻ is larger due to its lower effective nuclear charge and
greater repulsion among electrons. Ionic size is governed by the balance between nuclear attraction
and electron repulsion, which varies with the ion’s charge and atomic number.

Q3: Why is there only one electron in the 4s subshell of chromium?

Chromium has the electron configuration [Ar] 3d⁵ 4s¹ instead of the expected [Ar] 3d⁴ 4s² due to the
special stability associated with a half-filled d-subshell. A half-filled 3d subshell (3d⁵) provides extra
stability because of symmetrical distribution of electrons and maximized exchange energy, which
reduces repulsion among electrons of parallel spins. To attain this stable arrangement, one electron
from the 4s orbital is promoted to the 3d orbital, resulting in a 3d⁵ 4s¹ configuration. Such deviations
from the Aufbau principle are common in transition metals due to the close energy levels of 3d and
4s orbitals.

Q4: Write the electronic configuration of Fe (Z = 26).

The electronic configuration of iron (Fe), which has atomic number 26, is [Ar] 3d⁶ 4s². This is derived
by first filling the orbitals in the order of increasing energy according to the Aufbau principle. After
completing the configuration of argon (18 electrons), the next two electrons go into the 4s orbital,
and the remaining six occupy the 3d orbital. This configuration also follows Hund’s rule, which states
that electrons fill degenerate orbitals singly before pairing, and Pauli’s exclusion principle, which
restricts two electrons from having the same quantum numbers within an orbital.

Q5: Calculate the effective nuclear charge for a 4s electron of Fe (Z = 26) using Slater’s
Rule.
To calculate the effective nuclear charge (Z*) for a 4s electron in Fe using Slater’s rule, we group the
electron configuration as [Ar] 3d⁶ 4s². According to Slater’s rule, the 4s electron is shielded by: (i) 1
other 4s electron contributing 0.35, (ii) 6 electrons in 3d contributing 0.85 each, and (iii) 18 core
electrons in [Ar] contributing 1.00 each. So, shielding constant S = (1 × 0.35) + (6 × 0.85) + (18 × 1.00)
= 0.35 + 5.10 + 18 = 23.45. Hence, Z* = Z – S = 26 – 23.45 = 2.55. Therefore, the 4s electron feels an
effective nuclear charge of approximately 2.55, which explains its ease of ionization compared to
core electrons.

2. Ionisation Energy
Q1: Write the increasing order of effective nuclear charge: Na, Al, Mg, Si
The increasing order of effective nuclear charge (Z*) among Na, Mg, Al, and Si is: Na < Mg < Al < Si.
As we move across a period from left to right, the atomic number (Z) increases while the shielding
effect increases only slightly, because electrons are added to the same shell. This results in a gradual
increase in effective nuclear charge. Therefore, the outer electrons feel a stronger attraction to the
nucleus, and Z* increases across the period.

Q2: Why is the first ionisation energy of carbon greater than boron?
The first ionisation energy of carbon is greater than that of boron because carbon has a higher
nuclear charge and a smaller atomic radius, which results in a stronger attraction between the
nucleus and the outer electrons. As we move across a period from boron (Z = 5) to carbon (Z = 6),
the number of protons increases, but the added electron enters the same shell, so shielding remains
nearly constant. This leads to an increase in effective nuclear charge, making it harder to remove an
electron from carbon than from boron. Hence, carbon has a higher first ionisation energy.

Q3: Why is the second ionisation energy of Cr and Cu very high?

The second ionisation energy of chromium and copper is very high because after losing one electron,
both Cr⁺ and Cu⁺ attain stable electronic configurations. Cr⁺ has the configuration [Ar] 3d⁵, which is a
half-filled d-subshell, and Cu⁺ has the configuration [Ar] 3d¹⁰, a fully-filled d-subshell. These
configurations are especially stable due to symmetrical electron distribution and maximum exchange
energy. Removing a second electron from such stable states requires significantly more energy, as it
disrupts the stability. Therefore, the second ionisation energy of both Cr and Cu is unusually high.

Q4: Why is the first ionisation energy of Cu higher than alkali metals, but second and third
are lower?
The first ionisation energy of copper is higher than that of alkali metals because copper has a filled
3d¹⁰ subshell, which provides extra stability, making it harder to remove the first electron. In
contrast, alkali metals have a single loosely held valence electron, so their first ionisation energies
are lower. However, after removing the first electron from copper, the remaining electrons
experience increased electron-electron repulsion and reduced stability, so the second and third
ionisation energies are lower compared to the alkali metals’ successive ionisations. This difference
arises from copper’s stable electron configuration and how ionization affects electron repulsions.

3. Electronegativity
Q1: Define Pauling’s scale of electronegativity.
Pauling’s scale of electronegativity is a numerical system that quantifies an atom’s ability to attract
shared electrons in a covalent bond. Developed by Linus Pauling, this scale assigns fluorine—the
most electronegative element—a value of 4.0, and other elements are rated relative to it. Higher
values indicate stronger attraction for bonding electrons, influencing bond polarity and chemical
reactivity. This scale helps predict molecular behavior by comparing the tendency of different atoms
to attract electrons within bonds.

Q2: Why is the electron affinity of Cl greater than that of F?

The electron affinity of chlorine is greater than that of fluorine because chlorine’s larger atomic size
reduces electron-electron repulsion when an extra electron is added. Although fluorine has a higher
nuclear charge, its smaller size causes the added electron to experience strong repulsion from
existing electrons in the compact 2p orbital, lowering its electron affinity. In contrast, chlorine’s
larger 3p orbitals provide more space for the added electron, resulting in less repulsion and a higher
electron affinity. Thus, electron affinity depends on the balance between nuclear attraction and
electron-electron repulsion.

4. Electronic Configuration of Ions

Q1: Why is Mn(II) written as 3d⁵?
Mn(II) is written as 3d⁵ because when manganese loses two electrons to form the Mn²⁺ ion, it loses
the two 4s electrons first, leaving the 3d subshell with five electrons. This 3d⁵ configuration is half-
filled, which is particularly stable due to symmetrical electron distribution and exchange energy.
Therefore, the electron configuration of Mn²⁺ is [Ar] 3d⁵, reflecting the loss of 4s electrons before 3d
in transition metal ions.

Q2: Is Zn a transition element?

Zinc (Zn) is not considered a transition element because its common ion, Zn²⁺, has a completely filled
3d¹⁰ subshell and does not exhibit variable oxidation states or form colored compounds typically
seen in transition metals. Transition elements are defined as elements that have an incomplete d-
subshell in one or more of their common oxidation states, which zinc lacks. Hence, despite being in
the d-block, zinc is classified as a post-transition metal rather than a true transition element.

5. Coordination Number & Geometry

Q1: What is the geometry and CFSE of [Fe²⁺(H₂O)₆]²⁺ and [Fe³⁺(H₂O)₆]³⁺?

Both [Fe2+(H2O)6]2+and [Fe3+(H2O)6]3 have octahedral geometry, as six water molecules

coordinate symmetrically around the central metal ion. Water is a weak field ligand and
forms high-spin complexes with both Fe²⁺ and Fe³⁺. In [Fe2+] the oxidation state is +2, so the
electronic configuration is 3d⁶. In an octahedral field, the five d-orbitals split into lower-
energy t₂g and higher-energy eg orbitals. For high-spin d⁶, the electron configuration is
t2g4eg2, leading to a Crystal Field Stabilization Energy (CFSE) of

CFSE=(4×−0.4Δ0)+(2×0.6Δ0)=−1.6Δ0+1.2Δ0=−0.4Δ0

For [Fe3+], the oxidation state is +3, giving a 3d⁵ configuration. In a high-spin octahedral
field, the electrons are arranged as t2g3eg2 , with one electron in each orbital, resulting in a
CFSE of 0. This is because the stabilizing and destabilizing contributions cancel out. Crystal
Field Theory explains this splitting of d-orbitals and provides insight into the relative
stabilities and magnetic behavior of transition metal complexes.
Q2: What are the postulates of Crystal Field Theory?

Postulates of Crystal Field Theory (CFT):

1. Electrostatic Interaction
The bond between the central metal ion and the ligands is purely electrostatic in
nature. The metal ion is treated as a positive point charge, and the ligands are
considered as negative point charges (anions) or neutral molecules with lone pairs
modeled as point charges or dipoles.
2. Ligands as Point Charges or Dipoles
Ligands act as point charges or dipoles that generate an electric field affecting the
metal ion’s d-orbitals. The negative end of a ligand’s dipole interacts with the
positively charged metal ion.
3. No Orbital Overlap (No Covalent Bonding)
The theory assumes no overlap or sharing of electrons between metal d-orbitals and
ligand orbitals, so no covalent bonding is considered in CFT. It treats bonding as
purely ionic.
4. Degeneracy of d-Orbitals in Free Metal Ion
In an isolated metal ion (without ligands), all five d-orbitals have the same energy,
i.e., they are degenerate.
5. Splitting of d-Orbitals in Presence of Ligands
When ligands approach the metal ion, the degeneracy is lifted due to electrostatic
repulsions. The d-orbitals split into different energy levels depending on the geometry
of the complex:
o In an octahedral field: d-orbitals split into two sets - lower-energy t₂g (dxy,
dxz, dyz) and higher-energy e_g (dz², dx²−y²).
o In tetrahedral and square planar geometries, different splitting patterns occur.
6. Magnitude of Splitting Depends on Ligand and Geometry
The extent of splitting (called crystal field splitting energy, Δ) varies with the nature
of the ligand (weak or strong field) and the geometry of the complex.
7. Crystal Field Stabilization Energy (CFSE)
The splitting of d-orbitals leads to stabilization of the complex when electrons occupy
the lower-energy orbitals preferentially. This stabilization energy influences the
magnetic properties, color, and stability of the complex.

6. Hard and Soft Acids and Bases (HSAB)

Q1: Give one example of a soft acid.
A: Ag⁺ is a soft acid. Soft acids prefer to bind with soft bases due to polarizability and bond
character. HSAB concept categorizes acids and bases based on polarizability and hardness,
predicting stability of complexes.

Q2: Write short notes on HSAB theory.

he Hard and Soft Acids and Bases (HSAB) theory classifies acids and bases based on their
polarizability and charge density. Hard acids and bases are small, have high charge density, and are
less polarizable, whereas soft acids and bases are larger, have lower charge density, and are more
easily polarizable. According to the HSAB principle, hard acids prefer to bind with hard bases, and
soft acids prefer to bind with soft bases, leading to more stable and favorable interactions. This
concept helps predict the stability of complexes, reaction pathways, and selectivity in chemical
reactions by matching acids and bases of similar hardness or softness.

7. Polarizability
Q1: What is Fajan’s rule?
Fajan’s rule explains the covalent character in ionic compounds caused by polarization, where a
small, highly charged cation distorts the electron cloud of a large, highly charged anion. This
distortion increases covalent bonding due to electron sharing. Fajan’s rule can also be explained
using ionic potential, which is defined as the ratio of the ion’s charge (Z) to its radius (r), i.e., ionic
potential = Z/r. A cation with high ionic potential (high charge and small size) has a strong polarizing
power, meaning it can strongly distort the electron cloud of the anion. This distortion increases the
covalent character of the bond. Conversely, cations with low ionic potential cause less polarization
and maintain more ionic character. Therefore, the greater the ionic potential of the cation, the more
covalent the bond becomes according to Fajan’s rule.

8. Molecular Geometry & Shape

Q1: What is the shape of XeF₄?
The shape of xenon tetrafluoride (XeF₄) is square planar. Xenon is the central atom and has 8
valence electrons. It forms four single bonds with four fluorine atoms, using 4 electron pairs. In
addition, xenon has two lone pairs of electrons, making a total of six electron pairs around it.
According to VSEPR (Valence Shell Electron Pair Repulsion) theory, six electron pairs arrange
themselves in an octahedral electron geometry to minimize repulsion. The two lone pairs occupy
positions opposite to each other, leaving the four fluorine atoms in a single plane. This results in a
square planar molecular geometry for XeF₄.

Q2: What is the hybridization in [Fe(H₂O)₆]²⁺?

In the complex ion [Fe(H2O)6]2+ the oxidation state of Fe is +2. The electronic configuration of Fe is
[Ar] 3d⁶ 4s², so Fe²⁺ becomes [Ar] 3d⁶. Water is a weak field ligand and does not cause pairing of 3d
electrons. Therefore, the 3d orbitals remain singly and doubly occupied. The complex forms six
coordinate bonds with six water molecules, which means six vacant orbitals are required for
hybridization. Since no pairing occurs in the 3d orbitals, Fe²⁺ uses 4s, 4p, and 4d orbitals for bonding,
leading to sp³d² hybridization. The geometry of the complex is octahedral, consistent with this type
of hybridization.