Unit –IV

Periodic properties

1. Define electron affinity.

The electron affinity of an element may be defined as amount of energy
which is released when an extra electron enters the valence orbital of an
isolated neutral atom to form a negative ion.
Cl + 1e- → Cl-

2. What is an atomic radius?

Atomic radius is the distance from the centre of the nucleus to the
outermost shell containing electrons.
3. What is polarizability?
Polarizability is the ability to form instantaneous dipoles. It is a property
of matter. Polarizabilitiesdetermine the dynamical response of a bound
system to external fields, and provide insight into a molecule's internal
structure.
4. Define Ionization Energy.
Ionisation energy of an element is defined as the amount of energy
required to remove the most loosely bound electron from isolated neutral
gaseous atom in its lowest energy state.
Mg → Mg+ + 1e-

5. Write the electronic configuration of Mn2+ and Cr.

Mn 2+ = 1S2, 2S2, 2P6, 3S2, 3P6, 3d5, 4S0
Cr = 1S2, 2S2, 2P6, 3S2, 3P6, 3d5, 4S1

6. Write the rules of periodic table.

i) Aufbau principle:
Electrons occupy energy levels with lowest energy first.
ii) Pauli exclusion principle:
If 2 electrons occupy the same energy level they must have opposite
spins.
iii) Hund’s rule:
 Electrons that occupy orbitals of the same energy will have the maximum
number of electrons with the same spin.

7. What is HSAB Principle?

This led to the hard and soft acid and base (HSAB) concept. Other things
being approximately equal:
i. Hard acids react faster with hard bases and form stronger bonds with
them
ii. Soft acids react faster with soft bases and form stronger bonds with
them

8. What is Chelate? Give an example.

A chelating agent is a multidentate ligand. An example of a
simplechelating agent is ethylenediamine. A single molecule of
ethylenediamine can form two bonds to a transition-metal ion such as
nickel(II), Ni2+.
9. Define Electronegativity.
Electronegativity is a measure of how strongly atoms attract bonding
electrons to themselves.

10.How coordination compound is formed?

A coordination complex is the product of a Lewis acid-base reaction in
which neutral molecules or anions (called ligands) bond to a central
metal atom (or ion) by coordinate covalent bonds.

11.What is meant by co-ordination number?

A coordination number is the number of ions and atoms around a central
neutron, or the total number of attachment locations to the central
element in a molecule.
Ex: [Cu (H2O)6]2+

Here, the co-ordination number is 6.

 12.Draw the Cis and Trans isomer of any one of the co-ordination complex.

Part -B
1. Explain the variation of IE along the group and period.
Ionisation energy of an element is defined as the amount of energy
required to remove the most loosely bound electron from isolated neutral
gaseous atom in its lowest energy state.
Mg → Mg+ + 1e-
Factors governing ionization energy. The ionization energy depends upon
the following factors:
(a) Size of atom or ion.
lesser energy is required for removal of electrons from larger atoms
than the smaller one. Hence ionization energy is lower for larger
atoms and higher for smaller atoms.
Ionization Potential ∝ 1/ Size of atom
(b) Magnitude of nuclear charge.
The higher the nuclear charge of protons in the nucleus, the higher is
the ionization energy. Because of the higher nuclear charge, the
electrons are bound with more force and hence higher energy will be
required for their removal.
Ionization Potential ∝ Nuclear charge

(c) shielding effect.

The attractive force exerted by the nucleus on the most loosely bound
electron is atleast partially counterbalanced by the repulsive forces
 exerted by the electrons present in the inner shells. The electron to be
removed is thus shielded from the nucleus by the electrons in the
inner shell.
Ionization Potential ∝ 1/ Shielding Effect

(d) Effect of shape of orbital.

The shape of orbital also influences the ionization potential. As s-
electrons remain closer to the nucleus than p-,d-, and f-electrons of
the same valence shell, the ionization energy decreases in the order
given below:
s>p>d>f

(e) Effect of arrangement of electrons

The more stable the electronic arrangement, the greater is the
ionization energy. As the noble gases have the stablest electronic
arrangements, they show maximum ionization energy.

2. Explain the various factors affecting the electron affinity.

The electron affinity of an element may be defined as amount of energy
which is released when an extra electron enters the valence orbital of an
isolated neutral atom to form a negative ion.
Cl + 1e- → Cl-

Change of Electron Affinity along a Group.

On moving down a group, the size of atom increases significantly and
hence, the effective nuclear attraction for the electron decreases.
Consequently the atom will possess less tendency to attract additional
electrons towards itself.
Factors affecting electron affinity
(1) Atomic size
Smaller the size of an atom, greater is its electron affinity. As the size
of atom increases, the effective nuclear charge decreases or the
nuclear attraction for adding electron decreases.
electron affinity ∝ 1/ Size of atom
(2) Shielding or Screening Effect
 Electronic energy state, lying between nucleus and outermost state
hinder the nuclear attraction for incoming electron. Therefore, greater
the number of inner lying state, less will be the electron affinity.
electron affinity ∝ 1/ Shielding Effect
(3) Electronic Configuration
The electronic configurations of elements influence their electron
affinities to a considerable extent.
Electron affinities of inert gases are zero. This is because their atoms
have stable ns2 np6 configuration in their valence shell and there is
no possibility for addition of an extra electron.
Half filled – nS2, nP3
full filled – nS2, nP6

3. Explain all the possible periodic trends of orbital.

The periodicity is mostly due to similar outermost electronic
configuration of the elements. Some of the properties are briefly
reviewed.
i. Atomic and Ionic radii
Atomic or Ionic radius is generally defined as the distance between
the centre of the nucleus and the outermost shell of electrons in an atom
or ion.
As we move from left to right across a period, there is regular decrease in
atomic and ionic radii of the elements. This is due to the increase in the
nuclear charge and the additive electrons are added to the same electronic
level.
ii. Ionisation Energy (Ionisation Potential)
The energy required to remove the most loosely bound electron from
an isolated atom in the gaseous state in known as Ionisation Energy.
In a period, the value of ionisation potential increases from left to right
with breaks where the atoms have somewhat stable configurations. In a
group, the ionisation potential decreases from top to bottom.
iii. Electron affinity
Electron affinity or electron gain enthalpy is the amount of energy
released when an isolated gaseous atom accepts an electron to form a
monovalent gaseous anion
 Electron gain enthalpies generally increase on moving from left to right
in a period. Electron gain enthalpies generally decrease on moving down
the group.
iv. Electronegativity
Electronegativity may be defined as the relative tendency of an atom
in a molecule to attract the shared pair of electrons towards itself.
In a period, electronegativity increases on moving from left to right. This
is due to the reason that the nuclear charge increases whereas atomic
radius decreases. In a group, electronegativity decreases on moving down
the group. This is due to the effect of the increased atomic radius.

4. Explain the trends of polarizability.

Polarizability is the ability to form instantaneous dipoles. It is a property of

matter. Polarizabilities determine the dynamical response of a bound system
to external fields, and provide insight into a molecule's internal structure.

Factors that Influence Polarizability

The relationship between polarizability and the factors of electron density,

atomic radii, and molecular orientation is as follows:

i. The greater the number of electrons, the less control the nuclear charge has
on charge distribution, and thus the increased polarizability of the atom.

ii. The greater the distance of electrons from nuclear charge, the less control the
nuclear charge has on the charge distribution, and thus the increased
polarizability of the atom.

iii. Molecular orientation with respect to an electric field can affect

polarizibility (labeled Orientation-dependent), except for molecules that are:
tetrahedral, octahedral or icosahedral (labeled Orientation-independent).
This factor is more important for unsaturated molecules that contain areas of
electron dense regions, such as 2,4-hexadiene. Greatest polarizability in
these molecules is achieved when the electric field is applied parallel to the
molecule rather than perpendicular to the molecule.
 Homogenous diatomic molecules have no polarizing ability due to the zero
electro negativity of these molecules. But in the case of hetero generous
molecules polarizing character is there.

In periodic table, the polarizing character decreased when we move from left
to right but its increased when it is move from top to bottom.

Fajans' Rules

If two oppositely charged ions are brought together, the nature of the
bond between them depends upon the effect of one ion on the other.

5. Predict the various coordination numbers and geometries of metal complexes,

with an example.
The total number of points of attachment to the central element is termed
the coordination number and this can vary from 2 to as many as 16, but is
usually 6. In simple terms, the coordination number of a complex is
influenced by the relative sizes of the metal ion and the ligands and by
electronic factors, such as charge which is dependent on the electronic
configuration of the metal ion.
Coordination Number 2
This arrangement is not very common for first row transition metal ion complexes
and some of the best known examples are for Silver(I). In this case we have a low
charge and an ion at the right hand side of the d-block indicating smaller size
Ex: The linear [Ag(NH3)2]+ ion
Coordination Number 3

• Once again, this is not very common for first row transition metal ions. Examples
with three different geometries have been identified: Trigonal planar Geometry:
Well known for main group species like CO32- etc., this geometry has the four
atoms in a plane with the bond angles between the ligands at 120 degrees.

EX: The Trigonal planar [Cu(CN)3]2- system

Coordination Number 4
Two different geometries are possible.
Tetrahedral Geometry: The chemistry of molecules centered around a tetrahedral C
atom is covered in organic courses. To be politically correct, please change all
 occurrences of C to Co. There are large numbers of tetrahedral Cobalt(II) complexes
known.
Square Planar Geometry: This is fairly rare and is included only because some
extremely important molecules exist with this shape.
cisplatin - cis-PtCl2(NH3)2
Coordination Number 5

• Trigonal Bipyramid Geometry: The structure of [Cr(en)3][Ni(CN)5] 1.5 H2O was

reported in 1968 to be a remarkable example of a complex exhibiting both types
of geometry in the same crystal. The reaction of cyanide ion with Ni 2+ proceeds
via several steps:

EX: [Ni(CN)5]3-
Coordination Number 6
Octahedral (Oh): The most common geometry found for first row transition
metal ions, including all aqua ions. In some cases distortions are observed
and these can sometimes be explained in terms of the Jahn-Teller
EX: [Co(en)3]Cl3
6. Explain about hard soft acids and bases Concepts.

This led to the hard and soft acid and base (HSAB) concept. Other things being
approximately equal:

• hard acids react faster with hard bases and form stronger bonds with them
• soft acids react faster with soft bases and form stronger bonds with them

• Hard Acids and Bases

Hard acids consist of small highly charged cations and molecules in which a
high positive charge can be induced on the central atom.
Examples of Hard Acids: H+, Li+, K+, Ca2+, Al3+, Sn4+, BF3
Hard bases are highly electronegative and of low polarizability.
Examples of Hard Bases: F-, OH-, NH3, N2H4, ROH, H2O, SO42-, PO43

Hard bases react more readily to form stable compounds and complexes with
hard acids

Soft Acids and Bases

 Soft acids consist of large low charge cations and molecules with
relatively high energy occupied molecular orbitals. Soft acids are readily
polarizable.

Examples of Soft Acids: Cs+, Cu+, Au+, Pt2+, Hg+, BH3, Br2, I2

Hard bases have low electronegative and low polarizability.

Examples of Soft Bases: H-, R-, CO, PR3, C6H6, SCN-

Soft bases react more readily and form stable compounds and
complexes with soft acids.