Modern Inorganic Chemistry

R. D. Madan

Modern Periodic Table and

Electronic Configuration of Atoms

Chapter 3
 Periodic Table

Mendeleef's Periodic Law

(1869, 63 elements)

The properties of elements are a periodic function of their

atomic weights, i.e., if the elements are arranged in the
increasing order of their atomic weights, the properties of
the elements are repeated after definite regular intervals.

2
 Periodic Table

Defects of Mendeleef's Periodic Law

(1) Position of hydrogen: The position of hydrogen is

anomalous.

(2) Position of lanthanides and actinides (anomalous?): A

group of 15 elements (57-71) known as rare earth or
lanthanides and another group of 15 (89-103) elements
known as actinides do not find their proper place. They
have been placed at one place in group III and period
6.

3
 Periodic Table
Defects of Mendeleef's Periodic Law

(3) Similar elements are separated (e. g., Cu and Hg, Ag

and Tl, Ba and Pb) while dissimilar elements (e.g., Cu, Ag
and Au) are paced in the same place.

(4) Anomalous pairs of elements: The order of increasing

atomic weight has been ignored in some cases. e. g.,
(a) Ar (40) precedes K (39)
(b) Co (59.9) precedes Ni (58.6)

(5) Position of isotops: It is not possible to accommodate in

the periodic table.
(6) Group does not represent valency. 4
 Periodic Table
Mosley's Modern Periodic Law (1911)

The properties of elements are a periodic function of their

atomic numbers, i.e. if the elements are arranged in the
increasing order of their atomic numbers, the properties of
the elements are repeated after definite regular.

With the replacement of atomic weight by atomic number,

many of the irregularities in the Mendeleef's Periodic table
are despaired.

5
 Periodic Table

Disapreance of Mendeleef's Periodic Irregularities

(1) Position of hydrogen: The dual role of hydrogen is

explained.

(2) Position of rare earths: The rare earth elements can be

represented as 2, 8, 18, (18+x), 8,2, where x varies 0
(La) to 14 (Lu). With this arrangements of electrons, all
of them possess the same valancy and similar chemical
properties.
(3) Justification for dissimilar elements being placed
together:
6
 Periodic Table
Defects of Mendeleef's Periodic Law

(4) Anomalous pairs of elements:

The anomaly of the pairs Ar-K (18-19), Co-Ni (27-28), Te-I

(52-53) and Th-Pa(90-91) are despaired.

(5) Position of isotops: Since isotops possess the same

atomic number, all of them should occupy the same place in
the periodic table

7
 Periodic Table
Extended or Long Form of Periodic Table : Modern
Periodic Table

In order to remove the defects of Mendeleef's periodic

table, a number of tables have been suggested Out of the
various tables, the Extended or Long Form of Periodic
Table is the most widely accepted. This table is also called
Bohr's Periodic Table.

This table was proposed by Rang (1893), modified by

Werner (1905) and extended by Bury (1921).

8
Periodic Table
Bohr’s Classification

10 10
 Periodic Table
Groups
The vertical columns shown in the periodic table are called groups.

(a) There are nine groups in all. Groups I to VII are sub-divided into sub-groups
A and B.
(b) Elements of groups IA – VIIA and VIII have their outermost shells incomplete
while each of their inner shells is complete. These elements are called
representative elements. These elements consist of some metals, all non-
metals and metalloids.
(c) Elements of groups IB, IIB, IIIB (only Sc, Y, La and Ac) IVB, VB, VIB, VIIB
and VIII have their two outermost shells incomplete. These are called
transition elements. All these elements are metals.
(d) Elements of group zero have all their shells completely filled. These elements
are called noble gases.
(e) Two groups of 14 elements lying in group III B [Ce-Lu and Th -Lw (103) have
their three outermost shells incomplete. These are called lanthanides and
actinides respectively. 11
 Periodic Table
Periods
The horizontal rows shown in the periodic table are called
periods.

There are seven periods in the table.

a) 1st period consists of 2 elements.

b) 2nd and 3rd periods have 8 elements each. Both these
periods are called short periods. The elements of 3rd
period are called typical elements.
c) 4th and 5th periods have 18 elements each while 6th
period has 32 elements. These three periods are called long
periods.
d) 7th period is an incomplete period and at present it consists
of 19 elements.
12
 Periodic Table
General characteristics of groups

1) Number of valence electrons: On moving down a given

group the number of valence electrons does not change.
2) Valency: The valencies of all the elements of the same
group are the same.
3) Properties: All the elements of a given group possess very
similar physical and chemical properties.
4) Size of atoms: Size of atoms increases on descending a
group (Li<Na<K<Rb<Cs).
5) Metallic character: The metallic character of the elements
increases in moving from top to bottom in a group.
6) Number of electron shells: In going down a group the
number of electron shells increases by one at each step.
13
 Periodic Table
General Characteristics of Periods

1) Number of valence electrons: Number of valence electrons

increases from 1 to 8 when we proceed from left to right in a
period.
2) Valency: The valency of the elements with respect to hydrogen
in each short period increases from 1 to 4 and then falls to one
while the same with respect to oxygen increases from 1 to 7.
 Periodic Table
General Characteristics of Periods

3) Size of atoms: Size of atoms decreases from left to right in a

period.
4) Properties of elements: The properties of the elements of a
given period differ considerably.
5) Metallic character: On moving from left to right in a period the
metallic character of the elements decreases.

6) Number of shells: In going from left to right in a period the

number of electron shells remains the same
15
 Periodic Table
Diagonal relationship: Diagonal relationship is the
resemblance of the properties of the elements of 2nd period
with their diagonally opposite members lying in 3rd period.

The two elements of a diagonal pair are called bridge

elements, since each diagonal pair forms a sort of bridge
between the periods. The following are the important
examples of diagonal relationship.

16
 Periodic Table
Merits of long form of Periodic table

1. It relates the position of an element to its electronic

configuration. Each group contains elements with
similar valence-shell electronic configuration and hence
similar properties.

2. It explains the similarities and dissimilarities in the

properties of the elements. 17
 Periodic Table

Defects of long form of Periodic table

1. Position of hydrogen still remain unsolved.

2. Fails to accommodate the lanthanides and actinides in
the main body.
3. Unable to reflect the electronic configuration of many
elements.

18
 Periodic Table

Electronic configuration of atoms

What is electronic configuration of an atom?

The distribution of electrons in various shells, sub-shell and

orbitals of an atom is called electronic configuration.

What is valance-shell electronic configuration of an

atom?

The distribution of electrons in various sub-shell and

orbitals of the valence-shell of an atom is called valence-
shell electronic configuration. 19
 Periodic Table
Representation of Electronic configuration
The electronic configuration of an atom is written in terms
of nlx where l indicates sub-shell.

20
 Periodic Table
Rules for writing electronic configuration

1. Maximum number of electrons in a shell of an atom

The maximum number of electrons in a shell is equal to 2n2

where n is the number of the shell (principal quantum
number).

The maximum number of electrons in 1st shell (n = 1) = 2 x 12 = 2

The maximum number of electrons in 2nd shell (n = 2) = 2 x 22 = 8
The maximum number of electrons in 3rd shell (n = 3) = 2 x 32 = 18
The maximum number of electrons in 4th shell (n = 4) = 2 x 42 = 32
21
 Periodic Table
2. Maximum number of electrons in a sub-shell of an
atom

The maximum number of electrons in a sub-shell is equal

to 2(2l+1) where I = 0, 1, 2 or 3 for s, p, d or f sub-shells
respectively..

22
 Periodic Table

3. Aufbau principle (building up principle or

construction principle)

This principle states as:

The orbitals are filled up with electrons in the increasing
order of their energy (The orbitals of minimum energy are
filled up first with electrons and then the orbitals of higher
energy start to fill.)

The energy of various orbitals of an atom increases as

1s <2s<2p<3s<3p <4s<3d<4p <5s <4d<5p<6s<4f< 5d < 6p
<7s <5f< 6d < 7p <8s ..... 23
 Periodic Table
Limitations (Deviations) of Aufbau principle

Some elements does not obey Aufbau principle.

(i) Configuration of La (57) atom

According to Aufbau principle, the configuration of Ba (57)
atom is [Xe]544f15d06s2. But observed configuration is
[Xe]544f05d16s2.
Why does the extra electron go to 5d orbital instead of 4f
orbital in La atom?
Explanation: It is explained on the basis that at La, 5d and
4f orbitals are supposed to have almost the same energy
and hence the extra electron is free to occupy any of these
two orbitals. 24
 Periodic Table

(n+l) Rule

The relative order of energy of different orbitals can be

determined with the help of (n + l) value for a given
orbital (n = principal quantum number, l = azimuthal
quantum number). According to this rule:

The orbital having the lowest value of (n + l) has the

lowest energy and hence is filled up first with electrons.

When two or more orbitals have the same value of (n + 1),

the orbital with lower value of n is lower in energy and
hence is filled up first with electrons.
25
 Periodic Table

(n+l) Rule

Example:

3d orbital: 3+2=5
4p orbital: 4+1=5
5s orbital: 5+0=5
We see that n+l for orbitals is 5. Thus orbitals will be filled
up with electrons in the following sequence:

26
 Periodic Table
4. Pauli's Exclusion Principle:

The maximum number of identical quantum numbers

which two electrons in an orbital can have is only three
but never four.

Example: For He(2)

27
 Periodic Table

5. Hund's rule of maximum multiplicity

The orbitals of a given sub-shell are first filled singly and

then the pairing of electrons in each orbital begins.

Example: For O(8)

28
Periodic Table

29
 Periodic Table

6. Rule of half-filled or completely-filled orbitals

According to this rule:

The orbitals tend to become half-filled or completely-
filled, since such orbitals are more stable than other
orbitals and hence give more stable configuration to the
atom.
Example:

Cr (24), Cu (29)
In case of these elements one or both the electrons from ns
orbital get shifted to (n-1)d orbitals to make (n-1)d orbitals
half-filled or completely- filled. 30
 Periodic Table

6. Rule of half-filled or completely-filled orbitals

According to this rule:

The orbitals tend to become half-filled or completely-
filled, since such orbitals are more stable than other
orbitals and hence give more stable configuration to the
atom.
Example:
(i) Electronic configuration of Cr (Z = 24), Cu (Z = 29),
Mo (Z = 42), Pd (Z = 46), Ag (Z = 47) and Au (Z = 79). In
case of these elements one or both the electrons from ns
orbital get shifted to (n-1)d orbitals to make (n-1)d orbitals
half-filled or completely- filled, since such half-filled 31or
Periodic Table

32
 Periodic Table
Divivision of the Elements into s-, p-, d- and f-Block
Elements

Elements may be divided into four blocks on the basis

whether the last electron goes to s, p, d or f orbital.

(i) s-Block elements

(ii) p-Block elements
(iii) d-Block elements and
(iv) f-Block elements

33
 Periodic Table
(i) s-Block elements:

In the atoms of these elements the last electron enters the s-

orbital of the outermost shell, i.e., the last electron goes to ns
orbital where n denotes the number of the outermost shell.

In the atom of these elements, ns-orbital is being progressively

filled. Hence the name s-block elements. Consequently, the
valence shell electronic configuration of these elements varies
from ns1 to ns2.

The elements of group IA (H to Fr : Alkali metals), group II A

(Be to Ra Alkaline earth metals) and He (zero group) belong to
this block.
34
 Periodic Table
(ii) p-Block elements:

In the atoms of these elements, the last electron enters the p-orbital
of the outermost shell, i.e. the last electron goes to np orbital.

In the atom of these elements, np-orbital is being progressively

filled. Hence the name p-block elements.

In the atoms of these elements the ns-orbital is completely filled and

hence the valence-shell configuration of these elements varies from
ns2p1 to ns2p6.

The elements of groups IIIA, IVA, VA, VIA, VIIA, and zero (Ne to
Rn) belong to this block.

35
 Periodic Table
(iii) d-Block elements:

In these elements, the last electron enters the d-orbital of

the penultimate shell, i.e. the last electron goes to (n-1)d
orbital.

In other words, in the atom of these elements, (n - 1)d

orbitals are being progressively filled. Hence the name d-
block elements.

The elements of groups IIIB, IVB, VB, VIB. VIIB, VIII,

IB and IIB belong to this block. d-block elements are
called transition elements, since their properties are
intermediate between those of s and p-block elements.
36
 Periodic Table

(iv) f-Block elements:

In these elements, the last electron enters the f-orbital of

ante-penultimate (Inner to the penultimate) shell i.e. the
last electron goes to (n-2) f-orbital.

In the atoms of these elements, (n-2)f orbitals are being

progressively filled. Hence the name f-block elements. The
valence shell electronic configuration of the atoms of these
elements is represented as:

f-block elements are called inner transition elements. 37

Thank you

38
Modern Inorganic Chemistry

R. D. Madan

Periodic Properties

Chapter 4

39
 Periodic Properties
Periodicity of Properties and Magic Number

The periodicity of properties means the elements with similar

properties reappear at certain regular intervals of atomic number
in the periodic table.

The examination of the properties of these elements will show that

the elements belonging to the same group have similar properties40
 Periodic Properties
1. What is the cause of periodicity of properties?

An examination of the valence-shell electronic configurations

of the elements shows that

the elements belonging to the same group have the same

valence-shell electronic configuration. In any group, similar
valence-shell electronic configurations of the elements
reoccur after certain regular intervals of atomic number
which becomes the cause of periodicity of properties.

Magic numbers: The atomic number intervals at which the

elements with similar properties reappear are 2, 8, 8, 18, 18, 32
and 32. The numbers 2, 8, 18 and 32 are called magic
numbers. 41
 Periodic Properties

Same group have the same valence-shell electronic configuration

42
 Periodic Properties

The properties of the elements are periodic functions of

their atomic number. These properties depend on the
electronic configuration (particularly valence-shell
configuration) of the atoms of the elements. Some of such
properties are :

(1) Atomic volume

(2) Size of the atoms and ions (atomic and ionic radii)
(3) Ionisation potential
(4) Electron affinity
(5) Electronegativity
(6) Bond energy or bond strength
(7) Polarisation of ions. 43
 Periodic Properties

In order to clear understand of periodic properties, we

should have knowledge of two concepts. These concepts
are :

a) Shielding or screening effect of the inner-shell electrons

on the valence shell electron and

b) Effective nuclear charge

44
 Periodic Properties
a) Shielding or screening effect of inner-shell electron
on the valence shell electron

In a multi-electron atom, the valence-shell electrons are

attracted by the nucleus and also at the same time repelled
by the electrons present between the nucleus and the
valence-shell electrons (i.e. inner shell electrons). The
combined effect of these two forces is that the actual force
exerted by the nucleus on the valence-shell electron is
partially decreased by the presence of repulsive force
exerted by the inner-shell electrons.

45
 Periodic Properties
The decrease in the attractive force exerted by the nucleus
on the valence shell electron, which is obviously due to the
presence of the electrons lying between the nucleus and
valence-shell electrons, (called intervening electrons) is
called shielding effect or screening effect.

Actually, the intervening electrons screen or shield the

valence-shell electrons from the nucleus.

46
 Periodic Properties
Factors Affecting the Magnitude of Shielding Effect

i. No. of inner-shell electrons or inner shells

Greater is the number of inner-shell electrons or inner

shells, greater is the magnitude of shielding effect.

47
 Periodic Properties
ii. Type of the orbital occupied by the electrons

s-electrons spend most of their time nearer the nucleus

while p-electrons belonging to the same shell spend most
of their time farther away from the nucleus. Thus for a
given shell the penetration power ns electron is greater
than that of an np electron. The penetration power of an np
electron is greater than that of an nd electron and so on.

48
 Periodic Properties
b) Effective nuclear charge (Zeff): consequence of
shielding effect
Effective nuclear charge (Zeff) is defined as the actual
nuclear charge (Z) minus the screening effect caused by
the electrons intervening between the nucleus and the
outer electrons. It is represented by

Here  is a constant which is called screening constant.

This constant is a measure of the extent to which the other

electrons in an atom are able to screen the nucleus from the
chosen electron. 49
 Periodic Properties
Greater is the number of intervening electrons between the nucleus
and the outer electrons, more will be the magnitude of  and hence
the magnitude of effective nuclear charge, Zeff will decrease.

Calculation of  and Zeff by Slater's Rules.

According to Slater's rules, the value of  for a given electron is

estimated as follows:
(1)Write down the complete electronic configuration of the element
and divide the electrons into the following orbital groups starting
from the inside of the atom. (1s); (2s, 2p); (3s, 3p); (3d); (4s, 4p);
(4d); (4f); (5s, 5p); (6s, 6p) etc.

(2) Now select the electron for which the value of  is to be

calculated. For this calculation add up the contributions to  for the
other electrons according to the following rules: 50
 Periodic Properties

Type of electron Contribution to 

for each
electron of this type
(a) All electrons in groups outside the 0
electron chosen
(b) All other electrons in the same group 0.35 (or 0.30 for 1s
electron)
(c) All electrons in shell immediately inside 0.85
(d) All electrons further inside 1.00

Problem 1: Calculate the effective nuclear charge

experienced by the 4s electron in potassium atom.
51
 Periodic Properties

What is the shielding

constant experienced
by a valence d-electron
in the copper atom?

What is the shielding

constant experienced
by a 3d electron in the
bromine atom?

Graphical depiction of Slater's rules 52

 Periodic Properties
Solution: The electronic configuration of K atom (Z = 19) is 1s2,
2s2p6,3s2p6,4s1 and this atom has 4 shells in all. Evidently the
magnitude of Zeff experienced by 4s1 electron is given by

Zeff = Z-
= 19—[(0.85  No. of electrons in 3rd shell) + (1.00 
total number of electrons in the inner shells)]
= 19 - [0.85  8 + 1.00  (2 + 8)]
= 2.20

This is the effective nuclear charge experienced by 4s electron in

potassium atom.

Problem 2: Calculate the effective nuclear charge of the last electron

in an atom whose configuration is 1s2,2s2p6,3s2p5.
53
 Periodic Properties
Atomic volume is defined as the volume in c.c, occupied by one
gram atom of the element in the solid state and hence is
commonly called gram atomic volume.

It is obtained by dividing the atomic weight of the element by

its density; i.e.

Atomic volume = Atomic weight / Density

In other words, atomic volume is the volume in c.c. occupied

by 6.023 x 1023 atoms of an element (Avogadro's number).

The volume occupied by a single atom may be obtained by

dividing gram atomic volume with Avogadro's number of
atoms. 54
 Periodic Properties
Variation of atomic volume in a group and a period

(a) In a group
Atomic volume increases more or less regularly in going
down a group. The increase in atomic volume in going
down a group is due to the increase in the number of shells.
The larger the number of shells, the bigger is the volume of
the atom.

(b) In a period
In going from left to right in a period, it varies cyclically,
i.e., it decreases at first for some elements, becomes
minimum in the middle and then increases.
55
Periodic Properties

56
 Periodic Properties
Size of atoms and ions
An atom is composed of a compact nucleus surrounded
by electron cloud which does not have a sharply defined
boundary because of its diffused nature. The diffused
nature of the electron cloud makes it difficult for us to give
an exact definition of atomic size or atomic radius.

Thus, the atomic radius is an arbitrary concept and is

influenced by the nature of neighboring atoms. However,
atomic radius is usually considered as the distance from
the centre of the nucleus to the point where the electron
density is effectively zero (i.e. negligible).
57
 Periodic Properties
Size of atoms and ions
Types of radii
Because of the vagueness of the concept of atomic radius, a
number of radii have been defined for an.

Some of these radii are

1) Covalent radius
2) Crystal radius (atomic or metallic radius)
3) van der Waal's radius (collision radius) and
4) Ionic radius
58
 Periodic Properties
The distance between the nuclei of two bonded atoms is called bond
length (or bond distance or inter-nuclear distance).

In case of homonuclear diatomic molecules of A2 type the bond

length d(A—A) is given by

Equation (i) shows that in case of molecule of A2 type, the covalent

radius of an atom can be obtained by dividing the inter-nuclear
distance by two. Example –

The value of Cl-Cl bond distance as found experimentally is 1.98 A°.

Thus
59
 Periodic Properties
Size of atoms and ions
In case of hetero-nuclear diatomic molecule of AB type,
bond length, d(A—B) is given by:

Here r (A) and r (B) are the covalent radii of A and B

atoms. Equation (ii) shows that the magnitude of r(A) can
be calculated if d(A-B) and r (B) are known.

The covalent radii obtained by equation (i) and (ii) are

called single bond covalent radii. The single bond
covalent radii are additive in nature. This principle is
called the principle of additivity of covalent radii. 60
 Periodic Properties

61
Single bond covalent radii (in A°)
 Periodic Properties
Size of atoms and ions

Characteristics of covalent radii

(i) single bond covalent radii are additive in nature.

(ii) The values of covalent radii change with the multiplicity

of the bonds between the atoms.

(iii) Covalent radius of an element is less than its van der

Waals radius.

(iv) The magnitude of covalent radius undergoes a change

depending on the nature of the space model of the atoms
linked such as tetrahedral, square planar, octahedral etc.
62
 Periodic Properties

Double and triple bond covalent radii (in A°) of some common elements 63
 Periodic Properties
Factors affecting the magnitude of bond length

1) Electronegativity of the bonded atoms

The increase in ionic character decreases the bond length.
Again the amount of ionic character depends on the difference
in electronegativity of the bonded atoms. The decrease in
bond length ultimately is due to the difference in
electronegativity of the bonded atoms.

Taking into account the ionic character in A-B bond,

Schomaker and Stevenson (1941) gave the following
empirical equation by which the bond distance can be
calculated.
d (A-B) = r (A) + r (B) – 0.09 (XA – XB)
Here XA and XB are the electronegativities of the elements A and B. 64
Calculated and experimental values of some bond lengths (A°) of A-B bonds in AB molecules

Bond Calculated value Experimental value

r (A) + r (B) =d (A-B)

65
 Periodic Properties
2) Bond order or bond multiplicity

Bond order or bond multiplicity is defined as the number

of covalent bonds between the two bonded atoms.

The bond length between the two atoms decreases with the
increase of multiplicity of the bond between the atoms.

66
Periodic Properties

67
 Periodic Properties
3) Hybridisation
The change in hybridization affects the shape of the
molecule and hence the bond length is also changed. With
the increase of the percentage of s-character in a hybrid
orbital, the bond length decreases.

68
 Periodic Properties
Size of atoms and ions
4) Resonance
Sometimes bond order increases due to resonance and bond
shortening is observed. For example, in benzene molecule
the bond distance between two carbon atoms is 1.39Å
which is intermediate between the C-C (C-C=1.54A°) )
and C=C (C-C=1.34A°) ) bond lengths. In other words the
bond order between the two carbon atoms is more than 1
and less than 2.

69
 Periodic Properties
The crystal radius or metallic radius is defined as one-half of the
distance between the nuclei of two adjacent metal atoms in the
metallic close-packed crystal lattice. Metallic radii are higher than
single bond covalent radii and smaller than the van der Walls radii.
Metallic (or atomic) radii of some common elements (in A°)

70
 Periodic Properties
van der Waals radius:
The distance between two non-bonded atoms belonging to
two adjacent molecules of an element in the solid state is
called van der Waals distance while the half of this
distance is called van der Waals radius.

Two Cl atoms are

just in contact with
each other (No bond
formation condition)
71
Illustration of van der Waals radius
 Periodic Properties
Comparison of van der waals radius with covalent radius
van der Waals radius of an element is higher than its covalent
radius.

This is because of the fact that in the formation of covalent

bond, atoms have to overlap each other while in van der Waals
forces the atoms/molecules simply come closer to each other
and do not enter into overlapping (No bond formation).

72
 Periodic Properties
Ionic radius
The ionic radius is based on
the distance between the
nuclei of ions joined by an
ionic bond. Ionic radii have
an additive character. Thus,
r(C+ + r(A-) = d(C+ —A-)

Problem: Ionic radius of Na

ion is 0.95 A° and the inter-
nuclear distance between the
ion-pairs in NaCl ionic
crystal is equal to 2.76 A°.
Calculate the radius of Cl-
ion.
73
 Periodic Properties
Variation of atomic and ionic radii in a period and a group

In a period
We know that the number of shells in all the elements of a
given period remains the same but the value of effective
nuclear charge increases from left to right. The increased
effective nuclear charge pulls the electron cloud of the
atom nearer to the nucleus and thus the size of the atoms
and ions goes on decreasing from left to right.

74
Periodic Properties

75
 Periodic Properties
In a group
In going down a group of s-and p-block elements the
atomic and ionic radii both increase with the increase of
atomic number.

76
Periodic Properties

77
Atomic Radius:

Figure: Metallic, covalent and ionic radii compared. 78

78
 Figure: Atomic radii (in picometers) of representative
elements according to their positions in the periodic
table. Note that there is no general agreement on the
7979

size of atomic radii.

Ionization potential or Ionization energy:

Ionisation energy of an element is defined as the amount of

energy required to remove the most loosely bound
electron (i.e. outermost shell electron) from isolated
neutral gaseous atom in its lowest energy state (i.e.
ground state) to convert it into a unipositive gaseous
cation.

The ionization energy of an atom can be represented by the

following equation:
M(g) + Energy supplied → M+(g) + e-
Isolated Gaseous
Gaseous cation
Ionization
atom
Potential (I1) 80
Ionization potential or Ionization energy:

Ionization potential is an atomic property which is shown

by the atoms of all the elements. This property gives us an
idea of the tendency of the elements to lose the outer-most
shell electron to form a cation.

With the help of this property a number of other properties

of the elements like reducing power, metallic character etc.
can be explained.

Ionization energy defined as above is strictly called first

ionisation energy.

81
Successive Ionization Potentials (I1, I2, I3 ...)

In addition to first ionization potential (I1), second, third. etc.

ionization potentials are also known.

Second ionization potential (I2) is the energy required to remove

one more electron from the gaseous cation to get the doubly
positively charged gaseous cation.

M+(g) + Energy supplied → M2+(g) + e-

Similarly, third ionisation potential (I3) is the energy required to

remove still one more electron from M+2(g) cation to get M+3(g)
cation.

Similarly ionization potentials of higher and higher grades are also

known.
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Factors affecting the magnitude of ionization potential

1) Effective nuclear charge

2) Size of the atom
3) Principal quantum number (n)
4) Shielding effect.
5) Half-filled and completely filled orbitals

83
1) Effective nuclear charge: With the increase of the magnitude of
effective nuclear charge, the magnitude of ionization potential
increases.

2) Size of the atom: Higher is the value of radius (r) of an atom,

lower will be its ionization energy.

3) Principal quantum number: With the increase of the principal

quantum number (n) of the orbital from which the electron is to
be removed, the magnitude of ionization potential decreases.

4) Shielding effect : With the increase of shielding effect, ionization

potential decreases.

5) Half-filled or completely-filled orbitals: The ionization

potential of an atom having half-filled or completely-filled
orbitals in its electronic configuration is relatively higher than
that expected normally from its position in the periodic table. 84
85
Electron affinity
Electron affinity of an element is defined as the amount of
energy released in adding an extra electron from outside
to an isolated neutral gaseous atom in its lowest energy
state (i.e. ground state) to convert it into a gaseous anion.

Thus, electron affinity of an atom can be defined by the

following process:

M (g) + e- → M-(g) + Energy released (E1)

Isolated Gaseous
Gaseous anion
Electron
atom
affinity (E1)
Electron affinity defined above is strictly called first
electron affinity. 86
Second electron affinity

Second electron affinity of an element is defined as the

amount of energy required to add one more electron to its
mono-negative anion to convert it into di-negative anion.
Thus
M- (g) + e- → M2- (g) + Energy requied (E2)

Factors Affecting the Magnitude of Electron Affinity

1) Effective nuclear charge

2) Size of the atom
3) Electronic configuration
87
1) Effective nuclear charge
Higher the effective nuclear charge
greater the tendency of the atom to attract the additional electron towards
itself
greater the force of attraction exerted by the nucleus on the extra electron
greater the amount of energy released when the extra electron is added to
the atom.

Thus, the atoms with higher effective nuclear charge have higher electron
affinities.

2) Atomic radius
Larger the atomic radius -
lesser the tendency of the atom to attract the additional electron towards
itself
lesser the force of attraction exerted by the nucleus on the extra electron
lesser the amount of energy released when the extra electron is added to the
atom.

Thus, smaller atoms have higher electron affinities. 88

89
 Electronegativity
Electronegativity: When two different atoms in a
molecule are bonded together by a covalent bond, the
electron pair forming the covalent bond is not shared
equally by both the atoms. Rather, the electron pair lies
nearer to one atom than the other.

The relative tendency (or ability or power) of a bonded

atom in a molecule to attract the shared electron pair
towards itself is termed as its electronegativity.

The electronegativity (EN) of an element is a measure of

the relative tendency of an atom to attract electrons to itself
when it is chemically combined with another atom.
90
 Electronegativity
Electronegativities of the elements are expressed on a
somewhat arbitrary scale, called the Pauling scale. The
electronegativity of fluorine (4.0) is higher than that of
any other element.
Difference between electron affinity and electronegativity

Electron affinity Electronegativity

Electron affinity represents Electronegativity represents
the tendency of an isolated the tendency of a bonded
gaseous atom to attract the atom in a molecule to attract
electrons the shared electron pair

91
 Electronegativity

Factors affecting the magnitude of electronegativity

1) Size of the atom

2) Number of inner shells
3) Charge on the ion
4) Number and nature of atoms to which the atom is
bonded
5) Ionization energy and electron affinity
6) Type of hybridization
 Electronegativity
1) Size of atom: Smaller atoms have greater
electronegativity values than the larger atoms.

93
 Electronegativity
2) Number of inner shells : Atom with greater number of
inner shells has less value of electronegativity than the
atom with smaller number of inner shells.

94
 Electronegativity
3) Charge on the ion:
(i) A cation has higher electronegativity than its parent
atom.
(ii) Element in higher oxidation state has more value of
electronegativity than that in the lower oxidation state

95
 Electronegativity
4) Number and nature of atoms to which the atom is
bonded: Electronegativity of an atom depends on the
number and nature of the atoms to which the atom is
bonded. For example, electronegativity value of P atom
in PC13 molecule is different from that in PF5 molecule.

5) Ionisation energy and electron affinity: atoms of the

elements which have higher values of ionization energy
and electron affinity also have higher values of
electronegativity. For example, the elements of group
VIIA (halogens) which have the highest ionization
energies and electron affinities also have the highest
values of electronegativity.
96
6) Type of hybridisation: The magnitude of
electronegativity increases as the s-character in hybrid
orbitals increases.

97
98
Electronegativity

99
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