Unit III: Classification of Elements and Periodicity

in Properties

The Need for Classification of Elements:

Various attempts to classify the elements arose from the necessity to develop a simple
method that would facilitate the study of the properties of various elements and their
compounds. After numerous attempts scientists were ultimately successful in arranging the
elements in such a way so that similar elements were grouped together and different elements
were separated.

The arrangement of elements in such a way that similar elements fall within the same vertical
group and dissimilar elements are separated is known as classification of elements.

The classification of elements led to the formation of periodic table.

Periodic table: Periodic table may be defined as the table that classifies all the known
elements according to their properties so that similar elements fall within the same vertical
column and dissimilar elements remain separated.

Earlier Attempts of Classification of Elements:

Dobereiner’s Triads:

He arranged the elements in a group of three such that atomic weight of the middle element is
the average of the atomic weights of the other two.

Table 3.1 Dobereiner’s Triads

Triad Atomic weight Average of the atomic

weights of the first and the
third elements
Li 7
7 + 39
Na 23 = 𝟐𝟑
2
K 39

1
 S 32
32 + 128
Se 79 = 𝟖𝟎
2
Te 128
Cl 35.5
35.5 + 127
Br 80 = 𝟖𝟏. 𝟐𝟓
2
I 127
Ca 40
40 + 137
Sr 88 = 𝟖𝟖. 𝟓
2
Ba 137

The Telluric Helix:

In 1862, A. E. B. de Chancourtois, a French geologist, indicated a relation between the

properties of the elements and their atomic weights in the form of his telluric helix. He used a
vertical cylinder with 16 equidistant lines on its surface, the lines being parallel to the axis of
the cylinder. He drew a helix at 45° to the axis and arranged the elements on the helix in
order of their increasing atomic weights. In this way the elements that differed from each
other in atomic weight by 16 or multiples of 16 fell very nearly on the same vertical line. The
concept failed to garner much attention.

Newland’s Law of Octaves:

Newland arranged the elements in increasing order of their atomic weights and found that any
given element has similar properties to the eighth element that followed it.

Table 3.2 Newland’s Octaves

Element Li Be B C N O F
Atomic
7 9 11 12 14 16 19
weight
Element Na Mg Al Si P S Cl
Atomic
23 24 27 29 31 32 35.5
weight
Element K Ca
Atomic
39 40
weight

2
He named this generalization, the law of octaves due to its similarity to the musical scale.

Limitations:

1. The law of octaves could not be applied beyond calcium.

2. With the discovery of noble gases, the eighth element no longer remains a similar
element.

Lothar Meyer Arrangement:

Figure 3.1 Lothar Meyer’s Atomic Volume Curves

In 1869, Lothar Meyer, a German chemist, studied the physical properties such as atomic
volume, melting point and boiling point of various elements.

He plotted a graph between atomic volumes and atomic weights of the elements and observed
that the elements with similar properties occupied similar positions on the curve. For
instance, he made the following observations:

3
1. The most strongly electropositive alkali metals occupy the peaks on the curve.

2. The less strongly electropositive alkaline earth metals occupy the descending positions on
the curve.

3. The most electronegative elements, i.e., the halogens, occupy the ascending positions on
the curve.

4. The transition elements occupy minima of the curve.

He, therefore, proposed that the physical properties of the elements are a periodic function of
their atomic weights. He arranged the elements in a tabular form in order of their increasing
atomic weights.

Mendeleev’s Periodic Table:

The Russian scientist, Dmitri I. Mendeleev put forward a scheme of classification in 1869.
He gave a periodic law known as Mendeleev’s periodic law. The law states that, the
properties of elements are a periodic function of their atomic weights.

On the basis of this periodic law, Mendeleev constructed a periodic table in such a way that
the elements were arranged horizontally in the order of their increasing atomic weights. He
also kept in mind the similarities in their chemical properties. The main criterion of the
judgment of similarities in the properties was valency of the elements.

Mendeleev observed that some of the elements did not fit in his scheme of classification if the
order of atomic weights were strictly followed. He ignored the order of atomic weights and
placed the elements with similar properties together. For example, iodine having atomic
weight 127 was placed after tellurium with atomic weight of 128, together with fluorine,
chlorine and bromine due to similarities in properties.

The modified Mendeleev’s periodic table consists of:

i. Nine vertical columns, called groups. These are numbered from I to VIII and zero. Each
group, from I to VII, is further divided into two subgroups- A and B. Group VIII has
three sets each one containing three elements. Group zero consists of inert gases (and
was later added to the table when they came to be discovered).

4
ii. Seven horizontal rows, called series or periods. These are numbered from 1 to 7. First
period contains two elements. Second and third periods have eight elements each. These
periods are called short periods. Fourth and fifth periods have eighteen elements each.
These periods are called long periods. Sixth period has 32 elements and is called the
longest period. Seventh period is incomplete.

Table 3.3 Modified form of Mendeleev’s Periodic Table

Significance of Mendeleev’s Periodic Table:

1. Classification of elements: In this periodic table, elements are classified into groups with
similar properties, thus facilitating the study of properties of elements.

2. Prediction of new elements: Mendeleev left certain vacant places in his table which
provided a clue for the discovery of new elements. The properties of these unknown
elements could be predicted on the basis of periodic law. These predicted properties aided
the discovery of these unknown elements. For example, gallium and germanium were
unknown when Mendeleev presented the periodic table. These elements were named eka-

5
 aluminium and eka-silicon respectively. The predicted properties of these elements
actually matched those found experimentally when the elements were later discovered.

3. Determination of correct atomic weights: With the help of this table, doubtful atomic
weights of certain elements were corrected. For example, Be was assigned an atomic
weight of 13.5 on the basis of its equivalent weight (4.5) and valency (wrongly calculated
as 3). Be should, therefore, have been placed between C (atomic weight 12) and N
(atomic weight 14). But no place was left vacant between them. Besides, the properties of
Be did not justify this position. Hence, valency 2 was assigned to Be which gave it an
atomic weight of 4.5 × 2 = 9 and it was placed at its proper place between Li (atomic
weight 7) and B (atomic weight 11).

Defects in the Mendeleev’s Periodic Table:

Following are the defects in the Mendeleev’s periodic table:

1. Position of hydrogen: The position of hydrogen in the table was not fixed because it can
be placed in group I as well as group VII as it resembles both the alkali metals and
halogens.

2. Four anomalous pairs of elements: Elements of higher atomic weight precede those
with lower atomic weight. For example, Te (atomic weight 128) preceded I (atomic
weight 127). [Likewise, Ar (atomic weight 40) preceded K (atomic weight 39), Co
(atomic weight 58.93) preceded Ni (atomic weight 58.69) and Th (atomic weight 232)
preceded Pa (atomic weight 231).]

3. Lanthanides and Actinides: A group of 14 elements (atomic number 58 to 71) called

rare earths or lanthanides are placed together with 57La at one place in group III of 6th
period. Likewise, another group of 14 elements (atomic number 90 to 103) called
actinides are placed together with 89Ac at one place in group III of 7th period.

4. Position of isotopes: Isotopes of elements are placed in the same position in the table
although according to atomic weights they should have occupied different positions.

5. Separation of similar but grouping of dissimilar elements. For example, alkali metals
such as Li, Na, K, etc. (group IA) are grouped together with coinage metals such as Cu,

6
 Ag and Au (group IB) though their properties are different. On the other hand, certain
chemically similar elements like, Cu and Hg are placed in different groups.

6. Position of elements of group VIII: No proper place has been allotted to nine elements
of group VIII which have been arranged in three triads in 4th, 5th and 6th periods without
justification.

Modern Periodic Law:

Henry Moseley studied the X-ray spectra of many elements. He observed that a plot of √ν
(where ν is the frequency of the X-rays emitted) against atomic number (Z) gave a straight
line and not the plot of √ν against atomic weight. He proposed that the basis of classification
of elements should be atomic number rather than atomic weight. Moseley, therefore,
proposed the Modern Periodic Law which states that:

The properties of elements are periodic functions of their atomic numbers.

Cause of Periodicity:

The periodic repetition of elements with similar properties after certain regular intervals when
the elements are arranged in order of increasing atomic number is called periodicity.

Periodicity is due to the recurrence of similar valence shell configurations after certain
regular intervals.

Moreover, such similarity in properties is repeated after the intervals of 2, 8, 18 or 32 in their

atomic numbers. These numbers of 2, 8, 18 or 32 after either of which elements of similar
properties start recurring frequently are called magic numbers.

Long Form of Periodic Table:

It is also referred to as Bohr’s table as it follows the Bohr’s classification of elements based
on the outermost electronic configuration governed by the Aufbau’s principle. Since it results
from the extension of Mendeleev’s periodic table, it is also referred to as the extended form
of periodic table.

7
8
Structural Features of Long Form of Periodic Table:

Description of Periods:

A horizontal row of a periodic table is called a period. A period consists of a series of

elements having same valence shell. There are seven periods in all, which are numbered as 1,
2, 3, 4, 5, 6 and 7.

Each period begins with the filling of new energy shell. In fact, the number of the period also
represents the highest principal quantum number of the elements present in it. The number of
elements in each period is equal to the number of electrons which can accommodate in the
orbitals belonging to that electron shell.

The first period corresponds to the filling of electrons in the first energy shell (i.e., n = 1).
Since this shell has one orbital (i.e., 1s) to fill up with two electrons, the first period has two
elements.

The second period corresponds to the filling of electrons in the second energy shell (i.e., n =
2). Since this shell has four orbitals (one 2s and three 2p orbitals) to fill up with eight
electrons, the second period has eight elements.

The third period corresponds to the filling of electrons in the third energy shell (i.e., n = 3).
However, although this shell has 9 orbitals (one 3s, three 3p and five 3d orbitals), the 3d
orbitals being of higher energy is filled up only after 4s has been occupied. Thus, along the
period only 3s and 3p orbitals are filled up and hence, the third period also has eight
elements.

The fourth period corresponds to the filling of electrons in the fourth energy shell (i.e., n =
4). Along the period, nine orbitals (one 4s, five 3d and three 4p orbitals) are filled up and
hence, the fourth period has eighteen elements. The filling of 3d orbitals starts from Sc (Z =
21) and continues till Zn (Z = 30). These ten elements are called 3d-transition series.

The fifth period corresponds to the filling of electrons in the fifth energy shell (i.e., n = 5).
There are nine orbitals (one 5s, five 4d and three 5p orbitals) to be filled and hence, the fifth
period also has eighteen elements. The filling of 4d orbitals starts at Y (Z = 39) and
continues till Cd (Z = 48). These ten elements are called 4d-transition series.

9
The sixth period corresponds to the filling of electrons in the sixth energy shell (i.e., n = 6).
Sixteen orbitals (one 6s, seven 4f, five 5d and three 6p orbitals) are filled up and hence, the
sixth period has thirty two elements. The filling of 4f orbitals begins with cerium (Z = 58)
and ends at lutetium (Z = 71). These fourteen elements constitute the first (or 4f-) inner
transition series and are called lanthanides or preferably lanthanoids.

The seventh period corresponds to the filling of electrons in the seventh energy shell (i.e.,
n = 7). It also has thirty two elements corresponding to the filling of 7s, 5f, 6d and 7p
orbitals. The filling up of 5f orbitals begins with thorium (Z = 90) and ends at lawrencium
(Z = 103). These fourteen elements constitute the second (or 5f-) inner transition series and
are called actinides or preferably actinoids. They are mostly man-made radioactive elements.

In order to avoid undue expansion of the periodic table, the 4f- and 5f- transition elements
have been placed separately.

The first period is the shortest period in the periodic table. Periods 2 and 3 are referred to as
short periods. Periods 4 and 5 are called long periods. Period 6 is the longest period in the
periodic table. Period 7 has just attained completion in the recent years with mostly artificial
elements.

Description of Groups:

A vertical column of the periodic table is called a group. A group consists of a series of
elements having similar configurations of the outer energy shell. They are numbered from 1
to 18. Elements belonging to the same group are said to constitute a family. For example,
elements of group 16 constitute chalcogen family or oxygen family. Likewise, elements of
group 16 constitute halogen family.

Nomenclature of Elements with Atomic Number > 100:

IUPAC suggested a system of nomenclature for naming elements with atomic number > 100
till their names are officially announced. The Latin words for various digits of the atomic
number are written together in order of which makes the atomic number and ‘ium’ is added at
the end. The Latin words for various digits are given in the following table:

10
 Table 3.4 Latin Word Roots for Various Digits

Digit Latin word Abbreviation

0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 oct o
9 enn e

Table 3.5 Recommended and Official Names of Elements with Z > 100

Atomic Number Recommended Name Symbol IUPAC IUPAC

Official Name Symbol

101 Unnilunium Unu Mendelevium Md

102 Unnnilbium Unb Nobelium No

103 Unniltrium Unt Lawrencium Lr

104 Unnilquadium Unq Rutherfordium Rf

105 Unnilpentium Unp Dubnium Db

106 Unnilhexium Unh Seaborgium Sg

107 Unnilseptium Uns Bohrium Bh

108 Unniloctium Uno Hassium Hs

109 Unnilennium Une Meitnerium Mt

110 Ununnilium Uun Darmstadtium Ds

111 Unununium Uuu Roentgenium Rg

112 Ununbium Uub Copernicium Cn

11
 113 Ununtrium Uut Nihonium Nh

114 Ununquadium Uuq Flerovium Fl

115 Ununpentium Uup Moscovium Mc

116 Ununhexium Uuh Livermorium Lv

117 Ununseptium Uus Tennessine Ts

118 Ununoctium Uuo Oganesson Og

119 Ununennium Uue - -

120 Unbinilium Ubn - -

Division of Periodic Table into s-, p-, d- and f-Blocks:

The long form of periodic table can be divided into four main blocks. These are s-, p-, d- and
f-blocks. The division of elements into blocks is primarily based upon their electronic
configuration.

1. s-Block Elements:

The elements in which the last electron enters the s-subshell of their outermost energy level
are called s-block elements. This block is situated at the extreme left of the periodic table. It
contains elements of groups 1 and 2. Their general configuration is 𝐧𝐬𝟏−𝟐 . The elements of
group 1 have the general configuration 𝐧𝐬𝟏 and are called alkali metals while those of group
2 with general configuration 𝐧𝐬𝟐 are called alkaline earth metals.

General Characteristics of s-Block Elements:

i. They are soft metals with low melting and boiling points.

ii. They have low ionization enthalpies and hence are highly electropositive.

iii. They are very reactive and do not occur in native state in nature.

iv. They show oxidation states of +1 (in case of alkali metals) or +2 (in case of alkaline
earth metals).

v. They are strong reducing agents.

12
 vi. They mostly form ionic compounds except Li and Be.

vii. Most of them except Be and Mg impart characteristic colours to the flame.

viii. They are good conductors of heat and electricity.

2. p-Block Elements:

The elements in which the last electron enters the p-subshell of their outermost energy level
are called p-block elements. Their general configuration is 𝐧𝐬𝟐 𝐧𝐩𝟏−𝟔 . This block is situated
at the extreme right of the periodic table and contains elements of groups 13, 14, 15, 16, 17
and 18. Most of these elements are non-metals, some are metalloids and a few others are
heavy elements which exhibit metallic character. The metallic character declines across a
period from left to right while it increases down the group.

General Characteristics of p-Block Elements:

i. They show variable oxidation states.

ii. They mostly form covalent compounds.

iii. They have relatively high ionization energies.

iv. Most of them are non-metals.

v. Most of them are highly electronegative.

vi. Most of them form acidic oxides.

3. d-Block Elements:

The elements in which the last electron enters the d-subshell of the penultimate shell are
called d-block elements. Their general configuration is (𝐧 − 𝟏)𝐝𝟏−𝟏𝟎 𝐧𝐬𝟏−𝟐 . The d-block
contains three complete rows of ten elements each. The three rows are called first, second and
third transition series. They involve the filling of 3d, 4d and 5d orbitals respectively. The d-
block contains elements of groups 3 to 12. The properties of d-block elements, being
intermediate between s-block and p-block properties, mark a transition of character from s- to
p-block. Hence, the d-block elements are called transition elements.

13
 General Characteristics of d-Block Elements:

i. They are hard metals with high melting and boiling points.

ii. They show variable oxidation states.

iii. They form coloured complexes.

iv. They form ionic as well as covalent compounds.

v. Most of them exhibit paramagnetism.

vi. Most of them have catalytic properties.

vii. They form alloys. (For example, brass is an alloy of Cu and Zn.)

viii. They are good conductors of heat and electricity.

The elements Zn, Cd and Hg do not exhibit most of the characteristics of transition elements
because they have fully filled d-subshell.

4. f-Block Elements:

The elements in which the last electron enters the f-subshell of the anti-penultimate shell are
called d-block elements. Their general configuration is (𝐧 − 𝟐)𝐟 𝟏−𝟏𝟒 (𝐧 − 𝟏)𝐝𝟎−𝟏 𝐧𝐬𝟐 .
They consist of two series of elements placed at the bottom of the periodic table. The
elements of first series follow lanthanum ( 57La) with general configuration
𝟒𝐟 𝟏−𝟏𝟒 5𝐝𝟎−𝟏 𝟔𝐬𝟐 and are called lanthanoids. The elements of second series follow actinium
( 89Ac) with general configuration 𝟓𝐟 𝟏−𝟏𝟒 6𝐝𝟎−𝟏 𝟕𝐬𝟐 and are called actinoids.

General Characteristics of f-Block Elements:

i. They are heavy metals.

ii. They have high melting and boiling points.

iii. They show variable oxidation states.

iv. They usually form coloured compounds.

14
v. They have high tendency to form complexes.

vi. Most of the actinoids are radioactive.

Some Important Points:

1. Elements of group 18 are called inert gases or noble gases or aerogens.

2. The elements of s- and p-blocks are called representative elements. They are also called
main group elements.

3. The elements of d-block are called d-transition elements.

4. The elements of f-block are called f-transition elements or inner transition elements.

5. The f-block elements after uranium are called transuranium elements.

Metal, Non-metals and Metalloids:

More than 78 % of the elements are metals. They appear on the left hand side of the periodic
table. All s-block, d-block and f-block elements are metals. Non-metals are located at the top
right hand side of the periodic table. In a period, the non-metallic character increases on
moving from left to right. In a group, the non-metallic character decreases and metallic
character increases on going down a group. The change from metallic to non-metallic
character is not abrupt but is represented by a zigzag line in the periodic table. The elements
Si, Ge, As, Sb and Te bordering this line show properties of metals as well as non-metals.
These elements are called semi-metals or metalloids.

Advantages of the Long Form of the Periodic Table:

The important advantages of the long form of the periodic table are given below:

1. This classification is based on the atomic number which is a more fundamental property
of the elements.

2. Since isotopes of the same element have the same atomic number, the placing of isotopes
at the same place in the periodic table is justified.

15
3. The position of elements in the periodic table is governed by the electronic configurations
which determine their properties.

4. The marked similarities of elements in the same group are attributed to similar outer
electronic configurations.

5. The elements are classified into normal elements belonging to 1, 2, 13-17 groups and
transition elements belonging to 3-12 groups on the basis of their outer electronic
configurations.

6. The elements are also classified as active metals placed in groups 1 and 2, heavy metals
placed in groups 3-12 and non-metals placed in the upper right corner (groups 13-17) of
the periodic table.

7. The grouping of elements into s-, p-, d- and f-blocks on the basis electronic configuration
has made the study of elements more simple.

8. The positions of some element which were misfits on the basis of atomic weight is now
justified on the basis of atomic number. For example, Ar proceeds K because Ar has
atomic number 18 and K has 19.

9. A satisfactory position has been provided to the elements of groups 8-10 consisting of
nine elements in three triads previously placed in group VIII of the Mendeleev’s periodic
table.

10. It is easy to remember and reproduce.

Defects of the Long Form of the Periodic Table:

1. The position of hydrogen is not settled. Although it resembles alkali metals as well as
halogens, it has been placed with alkali metals.
2. Lanthanoids and actinoids have not been accommodated in the main body of the periodic
table.

16
Prediction of Period, Group and Block of a given Element:

The period, group and block of an element can be predicted as follows:

1. The period of an element corresponds to the principal quantum number of the valence
shell.

2. The block of an element corresponds to the type of orbital which receives the last
electron.

3. The group of an element is predicted from the number of electrons in the valence shell
or/and penultimate shell as follows:

a) For s-block elements, group number is equal to the number of valence electrons.

b) For p-block elements, group number is equal to 10 + number of valence electrons.

c) For d-block elements, group number is equal to number of electrons in (n − 1) d-

subshell and n s-subshell.

[1] Eka-aluminium and eka-silicon were the names given by Mendeleev for the then
unknown elements gallium and germanium respectively. A recently discovered element
was first named eka-mercury. What is its atomic number? Write its group number,
electronic configuration, IUPAC and official names.

Ans: The element which comes after mercury in the same group of the periodic table is called
eka-mercury. Its various parameters are:

Z = 80 + 32 = 112. ⸫ IUPAC name is Ununbium (Uub). Official name is Copernicium (Cn).

112Cn ∶ [Rn] 7s2 5f 14 6d10

⸪ it is a d-block element, ⸫ Group = Number of ns electrons + Number of (n – 1) d electrons

= 2 + 10 = 12.

17
[2] Elements have been classified as s-, p-, d- and f-block elements on the basis of the type of
orbital which receives the last electron. Are there any exceptions to this generalization?
Comment.

Ans. There are some exceptions as listed below:

i. Zn, Cd, Hg and Cn all receive the last electron in their respective s orbitals but are
called d-block elements.

ii. Th receives the last electron in the d orbital but is called f-block elements.

[3] On the basis of symmetry, ns 2 (n – 1)d4 and ns2 (n – 1)d9 configurations are less stable
and immediately change over to the corresponding more stable ns1 (n – 1)d5 and
ns1 (n – 1)d10 configurations. Are there any exceptions to this generalization?
Comment.

Ans: There are a few exceptions which are as follows:

Name of the element Atomic number Expected electronic Actual electronic

configuration configuration

1. Tungsten (W) 74 [Xe] 6s1 4f 14 5d5 [Xe] 6s2 4f 14 5d4

2. Platinum (Pt) 78 [Xe] 6s0 4f 14 5d10 [Xe] 6s1 4f 14 5d9

3. Seaborgium (Sg) 106 [Rn] 7s1 5f 14 6d5 [Rn] 7s 2 5f 14 6d4

[4] Write the electronic configurations of the following elements: A (Z = 9), B (Z = 12), C (Z
= 29), D (Z = 54) and E (Z = 58). Also predict the period, group and block to which they
belong. Classify them as representative elements, noble gases, transition and inner
transition elements.

Soln:

The electronic configurations of the elements are as follows:

9A ∶ 1s 2 2s2 2p5

12B ∶ 1s2 2s 2 2p6 3s 2

18
29C ∶ 1s2 2s 2 2p6 3s 2 3p6 4s1 3d10

54D ∶ 1s2 2s 2 2p6 3s 2 3p6 4s1 3d10 4p6 5s2 4d10 5p6

58E ∶ 1s2 2s 2 2p6 3s 2 3p6 4s1 3d10 4p6 5s2 4d10 5p6 6s2 4f 1 5d1

9A receives the last electron in a 2p orbital. ⸫ its

Period = 2nd

Block = p

Group = 10 + Number of valence electrons = 10 + 7 = 17.

12B receives the last electron in a 3s orbital. ⸫ its

Period = 3rd

Block = s

Group = Number of valence electrons = 2.

29C receives the last electron in a 3d orbital. ⸫ its

Block = d

Since its valence shell is 4th. Therefore,

Period = 4th

Group = Number of ns electrons + Number of (n – 1) d electrons = 1 + 10 = 11.

54D receives the last electron in a 5p orbital. ⸫ its

Period = 5th

Block = p

Group = 10 + Number of valence electrons = 10 + 8 = 18.

58E receives the last electron in a 4f orbital. ⸫ its

19
Block = f

Since its valence shell is 6th. Therefore,

Period = 6th

Further, since it belongs to lanthanide series, it does not have any group number of its own
but is usually considered to lie in group 3.

[5] Predict the position of the element in the periodic table satisfying the electronic
configuration ns2 (n – 1)d1 for n = 4.

Ans: For n = 4, electronic configuration is 4s 2 3d1 . The element is scandium (Sc).

⸫ period = 4th; block = d and group = Number of ns electrons + Number of (n – 1) d electrons

= 2 + 1 = 3.

[6] Elements A, B, C, D and E have the following electronic configurations.

A ∶ 1s2 2s2 2p1 B ∶ 1s2 2s 2 2p6 3s2 3p1 C ∶ 1s2 2s 2 2p6 3s2 3p3

D ∶ 1s2 2s2 2p6 3s2 3p5 E ∶ 1s 2 2s2 2p6 3s 2 3p6 4s2

Which among these will belong to the same group in the periodic table?

Ans: Since A and B have similar valence electronic configuration of ns 2 np1, ⸫ A and B
belong to the same group (i.e., 10 + 3 =13) of the periodic table.

[7] Arrange the following elements in increasing order of metallic character: (a) B, Al, Mg,
K; (b) Si, Be, Mg, Na, P; (c) B, C, Si, N, F.

Ans: (a) B < Al < Mg < K; (b) P < Si < Be < Mg < Na; (c) F < N < Si < C < B.

[8] On the basis of quantum numbers, justify that the sixth period of the periodic table should
have 32 elements.

Ans: The sixth period of the periodic table begins with n = 6. Sixteen orbitals (one 6s,
seven 4f, five 5d and three 6p orbitals) are filled up progressively and a maximum of 32
electrons can be accommodated in them, hence, the sixth period has thirty two elements.

20
[9] In terms of period and group where would you locate the element with Z = 114?

Soln:

Electronic configuration is [Rn] 7s 2 5f 14 6d10 7p2 . Since the last electron enters a 7p orbital,
it belongs to 7th period and p=block. Thus, its group is = 10 + number of valence electrons =
10 + 4 = 14.

[10] The elements Z = 117 and 118 have been recently discovered and named. In which
family or group would you place these elements and also give electronic configuration in
each case. Name these elements.

Soln:

Electronic configuration with Z = 117 is [Rn] 7s2 5f 14 6d10 7p5 . Since it has outermost
configuration of ns2 np5 , it belongs to halogen family or group 17. Its IUPAC official name
is Tennessine (Ts).

Electronic configuration with Z = 118 is [Rn] 7s2 5f 14 6d10 7p6 . Since it has outermost
configuration of ns2 np6 , it belongs to the family of noble gases or group 18. Its IUPAC
official name is Oganesson (Og).

[11] Write the atomic number of the element present in the third period and sixteenth
group of the periodic table. Give its name.

Ans: Since it belongs to 3rd period, ⸫ its outermost shell would be n = 3. Its configuration
would be [Ne] 3s 2 3p4 . So, Z = 16. ⸫ the element is sulphur (S).

[12] The element 119 has not been discovered so far. What would be the IUPAC name and
the symbol for this element? On the basis of the periodic table, predict the electronic
configuration of this element and the formula of its most stable chloride and oxide.

Ans: IUPAC name is Ununennium. Symbol is Uue.

Electronic configuration: [Rn] 7s 2 5f 14 6d10 7p6 8s1 .

Formula: Chloride: ECl

Oxide: E2 O

21
Periodic Trends in Physical Properties:

Most of the properties of elements such as atomic volume, atomic size, ionization enthalpy,
electron gain enthalpy and electronegativity are directly related to the electronic
configuration of the atoms. These properties undergo periodic variation with the change in
the atomic number with a period or a group. These properties indirectly control physical
properties such as melting point, boiling point, density, etc.

Atomic Radius:

Atomic radius is defined as the distance from the center of nucleus of the atom to the
outermost shell of electrons. However, its exact measure is not possible due to the following
reasons:

a) Atom is too small to be isolated.

b) The atom does not have well-defined boundary. The probability of finding the electrons is
never zero even at a large distance from the nucleus.

c) The probability distribution of an atom is affected by neighbouring atoms.

d) Size of an atom also changes from one bonding state to another.

Therefore, atomic size is expressed in different types of radii. Some of these are discussed
below:

1. Covalent Radius:

It is defined as one-half of the distance between the nuclei of two similar atoms bonded by a
single covalent bond. This is generally used for non-metals.

For homonuclear diatomic molecule,

1
rcovalent = [Internuclear distance between two bonded atoms]
2

1
i.e., rcovalent = [bond length]
2

22
For example, bond length (dH−H ) in H2
molecule is 74 pm. Therefore, the covalent
radius of hydrogen atom is 37 pm. Likewise
bond length (dCl−Cl )in Cl2 molecule is 198
pm. Therefore, the covalent radius of
chlorine atom is 99 pm. For heteronuclear
diatomic molecule, the covalent radius is
taken as the distance between the nucleus of
the atom and the mean position of the shared
pair of electrons. Figure 3.2 Covalent radius of H-atom

2. van der Waal’s Radius:

It is defined as one-half of the distance between the nuclei of two non-bonded neighbouring
atoms of two adjacent molecules in solid state.

van der Waal’s radius of an element is longer than its covalent radius because while van der
Waal’s forces are weak, a covalent bond results from the overlap of atomic orbitals.

Thus, 𝐫𝐯𝐚𝐧 𝐝𝐞𝐫 𝐖𝐚𝐚𝐥 > 𝐫𝐜𝐨𝐯𝐚𝐥𝐞𝐧𝐭

Figure 3.3 Comparison of covalent radius and van der Waal’s radius

23
3. Metallic or Crystal Radius:

It is defined as half of the internuclear distance between two adjacent atoms in the metallic
lattice.

The metallic radius of an atom is always larger than it covalent radius because metallic bond
is weaker than covalent bond.

Thus, 𝐫𝐦𝐞𝐭𝐚𝐥𝐥𝐢𝐜 > 𝐫𝐜𝐨𝐯𝐚𝐥𝐞𝐧𝐭

For instance, metallic radius of Na is 186 pm, whereas its covalent radius as determined from
its vapours which exist as Na2 molecules is 154 pm. Likewise, metallic radius of K is 231 pm,
whereas its covalent radius is 203 pm.

In fact, 𝐫𝐯𝐚𝐧 𝐝𝐞𝐫 𝐖𝐚𝐚𝐥 > 𝐫𝐦𝐞𝐭𝐚𝐥𝐥𝐢𝐜 > 𝐫𝐜𝐨𝐯𝐚𝐥𝐞𝐧𝐭

Variation of Atomic Radii in the Periodic Table:

a) Variation in a Period:

Atomic radii decrease with increase in atomic number in a period. This is because on moving
from left to right across a period, effective nuclear charge increases gradually as electrons are
being added to the same principal shell thereby leading to contraction in atomic size.

Thus, orders of covalent radii are:

Ne (van der Waal′ s radius) > Li > Be > B > C > N > O > F

Ar (van der Waal′ s radius) > Na > Mg > Al > Si > P > S > Cl

The size of the atoms of inert gases are however larger than those of the preceding elements
of a period. This is because while for other elements covalent radii are considered, for atoms
of inert gases van der Waal’s radii are used as they do not form covalent bonds.

However, orders of van der Waal’s radii are:

Li > Be > B > C > N > O > F > Ne

Na > Mg > Al > Si > P > S > Cl > Ar

24
b) Variation in a Group:

Atomic radii increase on moving down a group. This is due to progressive increase in the
number of energy shells that outweighs the effect of increased effective nuclear charge.

Thus, orders of covalent radii are:

Li < Na < K < Rb < Cs

F < Cl < Br < I < At

The covalent radii of d-block or transition elements in a period first show substantial
decrease, then gradually become constant and finally increase again. Initially, the poor
screening by d orbitals is not enough to counterbalance the rise in nuclear charge; hence an
obvious contraction in size occurs. But as d orbitals are progressively filled, they are able to
better screen the nuclear charge. This results in a decreased contraction in size until the two
opposite effects cancel out each other resulting in the constancy of size. Finally, as more
electrons are added, the interelectronic repulsions increase to push away the outer electrons
thereby causing a slight increase in atomic radii.

Figure 3.4 Trends in atomic (metallic) radii of transition elements.

25
Atoms of the transition elements are smaller than those of the group 1 or 2 elements in the
same period. This is partly because of the usual contraction due to poor screening of d
electrons and partly because additional electrons enter the penultimate d shell rather than the
outermost shell of the atom.

The atomic radii increase down a group in transition elements. But the atomic radii of the
second and third transition series are almost the same due to lanthanoid contraction.

Lanthanoid contraction: The regular decrease in the atomic and ionic radii of lanthanoids
with increasing atomic number is known as lanthanoid contraction.

Thus,

Ce > Pr > Nd > Pm > Sm > Gd > Tb > Dy > Ho > Er > Tm > Lu

In the lanthanoids, differentiating electrons enter the 4f orbitals. The screening by electrons in
f orbitals is smaller than those in d orbitals. Thus the effective nuclear charge increases with
increase in atomic number on moving across the series leading to a considerable contraction
of size initially. However, as 4f orbitals are progressively filled, the screening effect enhances
to somewhat counterbalance the increase in nuclear charge. Thus, the contraction gradually
decreases towards the end. However, the trend of decrease in atomic radii of lanthanoids is
not followed by Eu and Yb.

Actinoids too show actinoids contraction which is more pronounced than lanthanoid
contraction due to poorer shielding by 5f electrons.

Ionic Radius:

Ionic radius is the distance between the nucleus and the outermost shell of an ion (or it is the
distance between the nucleus and the point where the nucleus exerts its influence on the
electron cloud).

[13] Explain why cations are smaller and anions are larger in radii than their parent atoms.

Ans: A cation is formed by the removal of one or more electrons from an atom. The nuclear
charge acting on a lesser number of electrons pulls them closer. Thus an increase in the
effective nuclear charge of a cation causes the electron cloud to contract thereby resulting in a

26
decrease of the ionic radius. However, an anion is formed by the addition of one or more
electrons to an atom. The effective nuclear charge decreases and with electrons being less
tightly held, there happens an expansion of the electron cloud. Thus, the ion radius increases
in an anion.

N.B. Sometimes the formation of cation (such as the formation of Na+ from Na) also involves
the removal of the valence shell (3rd shell) completely. This also results in the decrease in the
size of the ion.

Na → Na+ + e−

1s 2 2s2 2p6 3s1 1s 2 2s2 2p6

[14] Consider the following species: C4-, N3-, O2-, F-, Na+, Mg2+ and Al3+. (a) What is
common in them? (b) Arrange them in order of increasing ionic radii.

Ans: (a) Each one of these ions contains 10 electrons and hence they are isoelectronic ions.

(b) The ionic radii of isoelectronic ions decrease with the increase in the magnitude of
nuclear charge. Magnitude of nuclear charge increases in the order of C4- < N3- < O2- < F- <
Na+ < Mg2+ < Al3+. ⸫ ionic radii decrease in the order of C4- > N3- > O2- > F- > Na+ > Mg2+ >
Al3+.

Z Z
N.B. Also larger the value of , smaller the size of the ions. increases in the order: C4-
e e
6 7 8 9 11 12 13
( ) < N3- ( ) < O2- ( ) < F- ( ) < Na+ ( ) < Mg2+ ( ) < Al3+ ( ). ⸫ ionic radii
10 10 10 10 10 10 10
decrease in the order of C4- > N3- > O2- > F- > Na+ > Mg2+ > Al3+.

27
The ions (cations or anions) increase in size on moving down a group. This is due to increase
in the number of shells. Thus,

H + < Li+ < Na+ < K + < Rb+ < Cs+

Be2+ < Mg 2+ < Ca2+ < Sr 2+ < Ba2+ < Ra2+

F − < Cl− < Br − < I −

O2− < S 2− < Se2− < Te2−

The size of the cations of the same element decreases with the increase in positive charge.
This is due to increase in the value of effective nuclear charge (and also due to increase in the
Z
value of ). Thus, (a) Pb2+ > Pb4+; (b) Fe2+ > Fe3+ ; (c) Cu+ > Cu2+ ; (d) Co2+ >
e
Co3+ ; (e) Cr 2+ > Cr 3+ ; (f) Ti2+ > Ti3+ ; (g) Mn2+ > Mn4+ > Cr 7+ . The smallest cation
is H + .

The size of the anions of the same element increases with the increase in negative charge.
This is due to decrease in the value of effective nuclear charge

(a) O2− > O− ; (b) S 2− > S −

N.B. The smallest anion is F − and not H − . The radius order of anions is F − < Cl− <
Z
Br − < H − < I− . This is because H − is the only anion with = 2.
e

[15] Which one among P or As has a larger size? Explain.

Ans: As has four shells while P has three. Therefore, As has a larger atomic size than P.

[16] Select from each group, the species with the smallest radius stating appropriate
reason. (a) O, O-, O2-; (b) K+, Sr2+, Ar; (c) Si, P, Cl.

Ans: (a) Among different species of the same element, size increases with the increase in
negative charge. Therefore, among O, O- and O2-, O has the smallest radius.

(b) In K+ and Ar, the outermost shell is the third shell while in Sr2+ it is the fourth. Among K+
and Ar, both being isoelectronic, K+ has smaller size due to greater nuclear charge. Hence, K+
has the smallest radius.

28
(c) Si, P and Cl belong to the 3rd period. Since in a period atomic size decreases due to
increase in effective nuclear charge, Cl has the smallest radius.

[17] Arrange the following in order of increasing radii. (i) I, I+, I-; (ii) C, N, Si, P; (iii) O2-,
N3-, S2-, F-.

Ans: (i) Size of a cation is smaller than an atom while that of an anion is bigger than an atom.
So, the order of increasing radii is I+ < I < I-.

(ii) C and N are in the 2nd period while Si and P are in the 3rd period. Along a period atomic
size decreases and down a group it increases. So, the order of increasing radii is N < C < P <
Si.

(iii) O2-, N3- and F- are isoelectronic ions from the second period elements. Therefore with
increase in nuclear charge, their size decreases in the order of N3- > O2- > F-. However, S
belongs to the 3rd period and therefore S2- has to be bigger than O2-, N3- and F-. So, the order
of increasing radii is F- < O2- < N3- < S2-.

[18] Give examples of three cations and three anions which are isoelectronic with Ar.

Ans: Cations are K+, Ca2+ and Sc3+. Anions are Cl-, S2- and P3-.

Ionization Enthalpy:

Ionization enthalpy of an element may be defined as the amount of energy required to remove
the most loosely bound electron from its isolated gaseous atom in the ground state.

A(g) → A + (g) + e− ; ΔH = Δi H; where, Δi H = ionization enthapy = +ve

Units: Ionization enthalpy is expressed in terms of eV atom−1 or kcal mol−1 or kJ mol−1.

1 eV atom−1 = 1.6 × 10−19 J atom−1 ≈ 1.6 × 10−19 × 6.023 × 1023 J mol−1 =

96.49 kJ mol−1
96.49 kJ mol−1 = = 23.06 kcal mol−1
4.184 J cal−1

The amounts of energies required to remove the most loosely bound electron from
unipositive, dipostive, tripositive… ions of the element in gaseous state are called second,

29
third, fourth… ionization enthalpies respectively. These are collectively called successive
ionization enthalpies.

A(g) → A + (g) + e− ; ΔH = Δi H1

A+ (g) → A 2+ (g) + e− ; ΔH = Δi H2

A2+ (g) → A 3+ (g) + e− ; ΔH = Δi H3

A3+ (g) → A 4+ (g) + e− ; ΔH = Δi H4

Successive ionization enthalpy always increases for any species. This is due to the increase in
Z
the effective nuclear charge (and also due to increase in in the value of ).
e

Thus, Δi H1 < Δi H2 < Δi H3 < Δi H4 <...

Factors on which Ionization Enthalpy depends:

1. Size of the Atom: As the size of the atom increases, the outermost electrons are less
tightly held by the nucleus. As a result, it becomes easier to remove the electron.
Therefore, ionization enthalpy decreases with increase in atomic size.

2. Magnitude of the Nuclear Charge: With increase in nuclear charge, it becomes difficult
to remove an electron. Therefore, ionization enthalpy increases.

3. Screening Effect of the Inner Electrons: As the shielding or screening effect of the
inner electrons increases, the effective nuclear charge felt by the valence shell electrons
decreases. Therefore, ionization enthalpy decreases. Thus, an increase in the number of
electrons in the inner shells tends to decrease the ionization enthalpy.

4. Penetration Effect of the Electrons: Ionization enthalpy increases as the penetration

effect of the electron increases because electrons with greater penetration effect remain
closer to the nucleus. Within the same shell, the penetration effect decreases in the order
of s > p > d > f. Thus, ionization enthalpy will be more to knock out an s electron than a p
electron of the same shell, which in turn, will be more than that required to remove a d
electron and so on.

30
5. Electronic Configuration: An atom having a more stable half-filled or completely filled
configuration has less tendency to lose electron and so, has high value of ionization
enthalpy.

Variation of Ionization Enthalpy in the Periodic Table:

Variation across a Period: Across a period, ionization enthalpy increases due to an increase
in the effective nuclear charge. The following orders are observed for the first ionization
energy:

Li < B < Be < C < O < N < F ≪ Ne

Na < Al < Mg < Si < S < P < Cl ≪ Ar

K < Ga < Ca < Ge < Se < As < Br ≪ Kr

Rb < Sr < In < Sn < Sb < Te < I ≪ Xe

Cs < Ba < Tl < Pb < Bi < Po < At ≪ Rn

Some exceptions to the trend are:

1. 𝐁𝐞 > 𝐁; 𝐌𝐠 > 𝐀𝐥; 𝐂𝐚 > 𝐆𝐚: This is because in Be, Mg and Ca the effect of
increased effective nuclear charge is outweighed by (a) greater penetration of s electron
than p electron, (b) better shielding of p electrons by the inner electrons, and (c)
relatively stable configuration of Be, Mg and Ca due to fully filled ns2 orbitals. Thus, np
electrons in B, Al and Ga are less tightly held by ns electrons in Be, Mg and Ca.

2. 𝐍 > 𝐎; 𝐏 > 𝐒; 𝐀𝐬 > 𝐒𝐞: N, P and As have relatively stable configuration due to half-
filled np3 orbitals while O, S and Se achieve half-filled configuration on losing one
electron. Thus the ionization energies follow the observed trend of N > O; P >S; As > Se.

N.B. Inert gases have abnormally high Δi H1 values due to fully filled configuration of np6.

Variation in a Group: Down a group, ionization enthalpy decreases. This is because the
combined effect of the increase in atomic size and the screening effect of inner electrons
more than compensate the effect of increased nuclear charge. Consequently, the valence
electrons become less and less firmly held by the nucleus.

31
[19] Explain why Be has higher Δi H1 than B.

Ans:

4Be ∶ 1s 2 2s 2

5B ∶ 1s2 2s 2 2p1

Since electron to be removed from Be lies in a more penetrating, relative stable fully filled 2s
orbital while the one to be removed from B lies in a less penetrating, partially filled 2p
orbital, the Δi H1 of Be is higher than that of B.

[20] Explain why O has lower Δi H1 than N and F.

Ans:

7N ∶ 1s2 2s 2 2p1x 2p1y 2p1Z

8O ∶ 1s2 2s 2 2p2x 2p1y 2p1Z

9F ∶ 1s2 2s2 2p2x 2p2y 2p1Z

O has lower Δi H1 than N and F. This is because in case of O, loss of an electron gives O+
with stable exactly half-filled electronic configuration while, in case of N, an electron has to
be lost from a half-filled electronic configuration.

[21] How would you explain the fact that Δi H1 of Na is lower than that of Mg but its Δi H2
is higher than that of Mg?

Ans:
Δi H1
Na → Na+ + e−

1s 2 2s2 2p6 3s1 1s 2 2s2 2p6

Δi H1
Mg → Mg + + e−

1s 2 2s2 2p6 3s 2 1s 2 2s2 2p6 3s1

32
The Δi H1 of Mg is higher than that of Na because it has greater nuclear charge, smaller
atomic size and stable electronic configuration. However, Δi H2 of Na is higher than that of
Mg because Na+ has stable noble gas configuration. Besides, in Na+ the valence shell is
second while in Mg + it is third.

[22] Out of Na+ and Ne which has higher ionization enthalpy? Explain why.

Ans: Na+ and Ne are isoelectronic species. But the nuclear charge is more in Na+ than in Ne.
Therefore, electrons are more tightly held in Na+ and it has higher ionization enthalpy than
Ne.

[23] The first ionization enthalpy values (in kJ mol-1) of group 13 elements are:

B Al Ga In Tl

801 577 579 558 589

How will you explain this deviation from the general trend?

Ans: On moving down a group a decrease in ionization enthalpy values of elements is

expected. However, Δi H1 increases on moving from Al to Ga. This is due to firstly the low
penetrating effect of the 3d electrons and also the failure of the effect of increased inner
electrons to counterbalance the effect of the increased nuclear charge in Ga resulting in the
predominance of nuclear charge. Thus Ga has higher Δi H1 than that of Al. On further moving
down to In, the increased shielding effect of additional 4d and other inner electrons
outweighs the effect of the increased nuclear charge. Thus, the Δi H1 of In is expectedly less
than that of Ga. Thereafter, the effect of nuclear charge predominates and hence the Δi H1 of
Tl is higher than that of In. Further an increase in atomic size down the group also opposes
the increase in nuclear charge.

[24] The Δi H1 and Δi H2 in kJ mol-1 of four elements I, II, III and IV are given below:

I II III IV

Δi H1 2372 520 900 1680

Δ i H2 5251 7300 1760 3380

33
Identify the element which is likely to be (a) a reactive metal (an alkali metal) (b) a reactive
non-metal (c) a noble gas (d) a metal that forms a stable binary halide of the formula
AX2 where X = halogen (i.e., an alkaline earth metal).

Ans: (a) Since element II has a very low Δi H1 but a very high Δi H2, therefore, it has only one
electron in the valence shell and hence is likely to be a reactive metal.

(b) Since element IV has a very high Δi H1 but comparatively not so high Δi H2, therefore, is
likely to be a reactive metal.

(c) Since Δi H1 for element I is the highest but its Δi H2 is comparatively not so high, therefore
it must be a noble gas.

(d) Since Δi H1 for element III is higher than that of element I, but unlike element I, its Δi H2
is comparatively not so high, it is likely to have two electrons in the valence shell (i.e., an
alkaline earth metal) and hence is likely to form a stable binary halide of the formula AX2
where X = halogen.

[25] Arrange the following in the order of increasing ionization enthalpy:

(a) 1s2 2s 2 2p6 3s 2 (b) 1s2 2s 2 2p6 3s1 (c) 1s 2 2s2 2p6 (d) 1s2 2s 2 2p4
(e) 1s2 2s 2 2p3 (f) 1s2 2s 2 2p2 (g) 1s 2 2s 2 2p5

Ans: (b) < (a) < (f) < (d) < (e) < (g) < (c) which is Na < Mg < C < O < N < F < Ne.

In the second period elements, the trend takes into account the effects of increase in effective
nuclear charge and stability due to half-filled and fully-filled p orbitals at N and Ne
respectively. But Na and Mg belonging to s-block have bigger atomic size and so have lower
Δi H1 than second period elements of p-block. Out of Na and Mg, Mg has higher Δi H1 due to
greater nuclear charge, smaller atomic size and stable electronic configuration.

[26] For each of the following pairs of elements would you expect to have lower first
ionization enthalpy? Explain.

(a) Cl or F (b) Cl or S (c) K or Ar (d) Kr or Xe (e) Na or Na+ (f) Be+ or Mg 2+

(g) B or C (h) I or I − .

34
Ans: (a) Due to bigger atomic size and strong shielding effect, Cl has lower Δi H1 than F.

(b) Due to bigger atomic size and lower nuclear charge, S has lower Δi H1 than Cl.

(c) K has lower Δi H1 than Ar because K has an electron more than Ar and so, can easily lose
it to acquire stable Ar-like configuration.

(d) Due to bigger atomic size and strong shielding effect, Xe has lower Δi H1 than Kr.

(e) In case of Na+ , an electron has to lost from a stable inert gas configuration while in case
of Na, loss of an electron gives stable inert gas configuration. Besides, while Na is neutral,
Na+ is positively charged. So, Na has lower Δi H1 than Na+ .

(f) In case of Mg 2+ , an electron has to lost from a stable inert gas configuration while in case
of Be+ , loss of an electron gives stable inert gas configuration. Besides, Be+ is unipositive
while Mg 2+ is dipositive. So, Be+ has lower Δi H1 than Mg 2+ .

(g) B has lower Δi H1 than C due to its lower effective nuclear charge.

(h) I has lower Δi H1 than I − because in case of I − , an electron has to be removed from a
stable inert gas configuration.

[27] Calculate the energy required to convert all the atoms of Mg to magnesium ions
present in 24 mg of Mg vapours. Δi H1 and Δi H2 of Mg are 737.76 and 1450.73 kJ mol−1 .

Soln:
Δi H1 Δ i H2
Mg(g) → Mg + (g) → Mg 2+ (g)
e− e−
⸫ total amount of energy needed to convert Mg(g) atom to Mg 2+ (g) ion = Δi H1 + Δi H2 =
(737.76 + 1450.73) kJ mol−1 = 2188.49 kJ mol−1

24 × 10−3 g
nMg = = 10−3 mol
24 g mol−1

⸫ amount of energy needed to ionize 10−3 mol Mg vapours = 10−3 mol ×

2188.49 kJ mol−1 = 2.188 kJ

35
[28] Δi H1 and Δi H2 of Mg(g) are 740 and 1450 kJ mol−1. Calculate the percentage of
Mg + (g) and Mg 2+ (g) if 1 g of Mg(g) absorbs 50 kJ of energy.

Soln:

1g
nMg = = 0.0417 mol
24 g mol−1

Energy absorbed for the ionization of 0.0417 mol of Mg(g) to Mg + (g) = 0.0417 mol ×
740 kJ mol−1 = 30.86 kJ

Energy left unused = (50 − 30.86)kJ = 19.14 kJ.

Hence, 19.14 kJ will be used to ionize Mg + (g) to Mg 2+ (g).

19.14 kJ
⸫ number of moles of Mg + (g) converted into Mg 2+ (g) = = 0.0132 mol
1450 kJ mol−1

0.0132
⸫ % of Mg 2+ (g) = × 100 = 31.65 %
0.0417

⸫ % of Mg + (g) = (100 − 31.65) % = 68.35 %

[29] The ionization potential of hydrogen is 13.6 eV. Calculate the energy required to
produce H + ions from 0.5 g of hydrogen atoms.

Soln:

⸪ 1 eV = 96.49 kJ mol−1

∴ 13.6 eV = 13.6 × 96.49 kJ mol−1 = 1312.264 kJ mol−1

0.5 g
Now, nH = = 0.5 mol
1 g mol−1

⸫ amount of energy needed to ionize 0.5 mol H-atoms = 0.5 mol × 1312.264 kJ mol−1 =
656.132 kJ

36
Electron Gain Enthalpy:

Electron gain enthalpy of an element may be defined as the enthalpy change taking place
when an isolated gaseous atom of the element accepts an electron to form a monovalent
gaseous anion.

X(g) → X − (g) + e− ; ΔH = Δeg H; where, Δeg H = electron gain enthalpy

N.B. Large negative value of electron gain enthalpy reflects greater tendency of an atom to
accept the electron.

Units: Electron gain enthalpy is expressed in terms of eV atom−1 or kJ mol−1.

Electron affinity (Ae) is a term often used interchangeably with electron gain enthalpy. The
two terms are related to each other as:

5
Δeg H = − Ae − RT
2

5
Since has RT a small value of 2.477 kJ mol−1, it is ignored so that electron affinity can be
2
taken to be equal to the negative of electron gain enthalpy.

Factors Affecting Electron Gain Enthalpy:

1. Nuclear Charge: Greater the nuclear charge greater will be the attraction for incoming
electron, and hence, larger will be the negative value of electron gain enthalpy.

2. Atomic Size: Larger the atomic size more will be distance between the nucleus and the
additional electron, and smaller will be the negative value of electron gain enthalpy.

3. Electronic Configuration: Elements with exactly half-filled or completely filled subshells

are very stable. Hence, energy has to be supplied to add an electron. They have lower
tendency to accept an electron. Thus, electron gain enthalpy is positive for inert gases,
alkaline earth metals and nitrogen.

Successive electron gain enthalpy is always positive. This is because the addition of an
electron to an atom renders it negatively charged and thereafter, the addition of the second
electron is opposed by repulsive force from the anion and to overcome it, energy has to be

37
supplied. Thus second, third, fourth… electron gain enthalpies have positive values. For
instance,

O(g) + e− → O − (g); ΔH = Δeg H1 = −141 kJ mol−1

O − (g) + e− → O 2− (g); Δeg H2 = +780 kJ mol−1

Variation across a Period: Across a period electron gain enthalpies become more negative
due to decrease in atomic size and an increase in nuclear charge (that together lead to greater
attraction for the incoming electron).

Exception: Group 2 elements have filled ns subshell, group 15 elements have half-filled np
subshell and group 18 elements have all subshell filled. These electronic configurations are
relative stable and hence these elements have positive or very low negative enthalpies.

Variation in a Group: On moving down a group electron gain enthalpies become less
negative due to the effect of increasing atomic size that subdues the effect of increasing
nuclear charge (resulting in smaller attraction for the incoming electron).

Exception: p-block elements of the second period have less negative values of electron gain
enthalpy than the third period elements.

Second Period Third Period

B < Al
C < Si
N < P
O < S
F < Cl

[30] The electron gain enthalpy of F is less negative than that of Cl. Why?

Ans: In F, the additional electron enters a relatively compact 2p subshell resulting in strong
interelectronic repulsion to overcome which energy has to be supplied. However, In Cl, the
additional electron enters a relatively spacious 3p subshell. Thus lesser amount of energy is
released in case of F than in case of Cl. Hence, electron gain enthalpy of F is less negative
than that of Cl.

38
[31] Out of oxygen and sulphur, which has greater negative electron gain enthalpy and
why?

Ans: In O, the additional electron enters a relatively compact 2p subshell resulting in strong
interelectronic repulsion to overcome which energy has to be supplied. However, In S, the
additional electron enters a relatively spacious 3p subshell. Thus lesser amount of energy is
released in case of O than in case of S. Hence, electron gain enthalpy of S is more negative
than that of O.

[32] The electron gain enthalpy of chlorine is −349 kJ mol−1 . How much energy is
released when 3.55 g of chlorine is converted completely into Cl− ion in the gaseous
state?

Soln:

3.55 g
nCl = = 0.1 mol
35.5 g mol−1

⸫ energy released when 0.1 mol Cl is ionized = 0.1 mol × 349 kJ mol−1 = 34.9 kJ.

[33] The amount of energy released when 1 × 1010 atoms of chlorine in vapour state is
converted to Cl− ions according to the equation, Cl(g) + e− → Cl − (g) is 57.86 ×
10−10 J. Calculate the electron gain enthalpy of chlorine atom in terms of kJ mol−1 and
eV atom−1 .

Soln:

6.023 × 1023 mol−1

Electron gain enthalpy of chlorine atom = −57.86 × 10−10 J × =
1 × 1010
−348.49 kJ mol−1

⸪ 1 eV = 96.49 kJ mol−1

−348.49
⸫ Electron gain enthalpy = eV = −3.61 eV
96.49

39
[34] Why halogens have the highest negative electron gain enthalpies in their respective
periods?

Ans: This because they require one more electron to acquire the nearest stable inert gas
configuration of ns2 np6 and hence, have the strongest tendency in their respective periods to
accept an additional electron.

[35] Why noble gases have the largest positive electron gain enthalpies in their respective
periods?

Ans: This is due to their stable electronic configuration comprising of subshells all of which
are fully-filled.

[36] Which of the following has the most negative electron gain enthalpy? Give reasons.

(i) [Ne]3s2 3p3 (ii) [Ne]3s2 3p4 (iii) [Ne]3s2 3p5

Ans: The element Cl corresponding to configuration (iii) will have the most negative electron
gain enthalpy. This because it requires one more electron to acquire the stable inert gas
configuration of [Ne]3s 2 3p6 and hence, has the strongest tendency to accept an additional
electron.

[37] In each of the following sets, arrange the elements in increasing order of their
negative electron gain enthalpies: (i) C, N, O (ii) O, N, S (iii) S, Cl, Ar
(iv)F, Cl, Br.

Ans: (i) N < O < F (⸪ N has stable half-filled p subshell, it has positive Δeg H1 while F with
an electron short of nearest stable inert gas configuration has the most negative Δeg H1 in the
2nd period.)

(ii) N < O < S (⸪ N has stable half-filled p subshell, it has positive Δeg H1 while O due to
relatively compact 2p subshell has less negative Δeg H1 than S with relatively spacious 3p
subshell.)

(iii) Ar < S < Cl (⸪ Ar has stable configuration with all subshells fully-filled, it has positive
Δeg H1 while Cl with an electron short of nearest stable inert gas configuration has the most
negative Δeg H1 in the 3rd period.)

40
[38] Which of the following will have the most negative electron gain enthalpy and which
has the least negative? P, S, Cl, F. Explain your answer.

Ans: Within a period electron gain enthalpy gets more negative on moving from left to right.
Hence, the order among P, S, Cl, is P < S < Cl. Among Cl and F, F due to relatively compact
2p subshell has less negative Δeg H1 than Cl with relatively spacious 3p subshell. Thus, Cl
will have the most negative electron gain enthalpy and P will have the least negative electron
gain enthalpy.

Electronegativity:

Electronegativity may be defined as the tendency of an atom in a molecule to attract towards

itself the shared pair of electrons.

Electronegativity depends upon the following factors:

1. It decreases when atomic size increase.

2. It increases when effective nuclear charge increases.

3. It decreases when screening constant (S) increases.

4. It increases when the oxidation state of an element increases.

5. It increases as much the percentage of s character in hybrid orbital increases. For

example,

Carbon compound Hybridization Electronegativity

sp3 2.5

sp2 2.75

sp 3.25

41
Methods of Estimating Electronegativity:

1. Pauling Scale: This scale is based upon energy calculation and the expression is

χA − χB = 0.102 √∆A−B (where energies are expressed in kJ mol−1 )

χA − χB = 0.208 √∆A−B (where energies are expressed in kcal mol−1 )

where χA and χB are the respective electronegativities of A and B;

∆A−B is the resonance energy of the bond A − B = |EA−B (observed) − EA−B (theoretical)|
and EA−B (theoretical) = √EA−A × EB−B

2. Mulliken Scale: In the Mulliken scale, electronegativity is given by the relation:

IE + EA
χM = (where IE and EA are expressed in eV atom−1 )
2

Since the values of electronegativity are about 2.8 times larger than the Pauling scale values,

χM
∴ χP =
2.8

More accurately, χP = 0.336 χM − 0.2

3. Allred Rochow Scale: In this scale, electronegativity is given by

0.359 Z∗
∴ χAR =
r2

Where r is the covalent radius in Å and Z ∗ is the effective nuclear charge on the incoming
electron. The following equation gives the correlation of χAR and χP :

χP = χAR + 0.744

Periodic Variations of Electronegativity:

Variation across a Period: Across a period from left to right electronegativity increases due
to increased effective nuclear charge.

42
Variation in a Group: Down a group, electronegativity decreases due to increased atomic
size and increased screening effect.

Table 3.6 Electronegativity Values of the Main Group Elements in Pauling scale

Group 1 Group 2 Group 13 Group 14 Group 15 Group 16 Group 17

2.1

Li Be B C N O F

1.0 1.5 2.0 2.5 3.0 3.5 4.0

Na Mg Al Si P S Cl

0.9 1.3 1.6 1.9 2.2 2.6 3.1

K Ca Ga Ge As Se Br

0.8 1.0 1.8 2.0 2.2 2.5 2.9

Rb Sr In Sn Sb Te I

0.8 1.0 1.8 1.8 2.0 2.1 2.6

Cs Ba Tl Pb Bi Po At

0.7 0.9 1.6 1.8 2.0 2.0 2.2

Some Important Points:

1. F has the highest electronegativity.

2. Cs has the lowest electronegativity.

3. Alkali metals have the lowest electronegativity in their respective periods.

4. Halogens have the highest electronegativity in their respective periods.

5. Electronegativity of inert gases is zero.

43
Applications of Electronegativity:

Metallic and non-metallic character: Non-metals have strong tendency to gain electron. Thus,
electronegativity is directly related to non-metallic character. Hence, it is inversely related to
metallic character. Across a period, as electronegativity increases non-metallic character also
increases. Down a group, as electronegativity decreases metallic character increases.

Polar and non-polar bonds: A bond between two atoms of the same element is said to be non-
polar since the shared pair of electrons is equally attracted by the two atoms. For example,
bonds in H2, Cl2, O2 and N2 are non-polar. However, when two different elements form a
bond, their electronegativities being different, the shared pair of electrons is attracted more
towards the more electronegative element. The atom of the more electronegative element
acquires a partial negative charge and that of the less electronegative element acquires a
partial positive charge. As a result, two poles are developed and the bond is said to be polar.
For example, bonds in
𝛿+ 𝛿− 𝛿+ 𝛿− 𝛿+ 𝛿− 𝛿+ 𝛿−

H − F, H − Cl, H − Br, H − I, etc. are polar.

Thus,

[1] If χA − χB = 0, the bond is non-polar and is said to be purely covalent.

[2] If χA − χB > 0, the bond is polar covalent.

a) If χA − χB = 1.9, the bond is 50 % ionic and 50 % covalent.

b) If χA − χB < 1.9, the bond is predominantly covalent.

[3] If χA − χB > 1.9, the bond is predominantly ionic and is represented by A− B+ .

N.B. Electropositivity is the tendency of an atom to lose electrons to form a positive ion. A
more electropositive element has more metallic character. Across a period, ionization
enthalpy increases and so electropositivity falls. Down a group, ionization enthalpy decreases
and so electropositivity increases.

44
Differences between Electron Gain Enthalpy and Electronegativity:

Electron Gain Enthalpy Electronegativity

1. It is the tendency of an isolated atom to 1. It is the tendency of an atom in a molecule

attract an electron. to attract the shared pair of electrons.

2. It can be measured experimentally and is 2. It cannot be measured experimentally and

expressed in eV atom−1 or kJ mol−1. is only a relative number w.r.t. fluorine taken
as 4.0.

3. It is the property of an isolated atom. 3. It is the property of a bonded atom.

4. For an atom, it is constant. 4. It is not constant. It depends upon the

hybridization of the atom.

[39] Among alkali metals which element do you expect to be the least electronegative and
why?

Ans: Electronegativity decreases down a group. Hence, Cs can be expected to be the least
electronegative among alkali metals.

Valence:

Valence of an element may be defined as its combining capacity.

It is expressed in terms of the number of H atoms or the number of Cl atoms or twice the
number of O atoms that combine with an atom of the element.

The number of valence electrons in the atom of an element often determines the valance of an
element. In case of representative elements, valence equals the number of valence electrons
or eight minus the number of valence electrons. However, transitional elements exhibit
variable valence due to involvement of not just the valence electrons but also d- or f-
electrons. However, their most common valences are 2 and 3.

45
Group 1 2 13 14 15 16 17 18

Number of valence electrons 1 2 3 4 5 6 7 8

Valence 1 2 3 4 3, 5 2, 6 1, 7 0, 8

Variation of Valence in the Periodic Table:

Variation across a Period: On hydrogen scale, valence first increases from 1 to 4 and then
decreases to zero. On oxygen scale, particularly observed in the 3rd period, valence increases
from 1 to 7 on moving from Na to Cl.

Variation in a Group: In a group, the number of valence electrons remains the same, hence,
all elements in a group show same valence. For instance, valence of all group 1 elements is 1
and valence of all group 2 elements is 2.

[40] Predict the formulas of the stable binary compounds that would be formed by the
following pairs of elements:

(i) Silicon and oxygen (ii) Aluminium and (iii) Calcium and iodine
bromine

(iv) Lithium and oxygen (v) Phosphorous and (vi) Magnesium and nitrogen
fluorine

(vii) Silicon and bromine (viii) Aluminum and (ix) Aluminium and nitrogen
sulphur

(x) Element 71 and fluorine (xi) Element 114 and (xii) Element 120 and oxygen
fluorine

46
Soln:

(i) Si: group = 14; valence = 4. The valence of O is 2. Thus, the formula of the binary
compound is SiO2.

(ii) Al: group = 13; valence = 3. The valence of Br is 1. Thus, the formula of the binary
compound is AlBr3.

(iii) Ca: group = 2; valence = 2. The valence of I is 1. Thus, the formula of the binary
compound is CaI2.

(iv) Li: group = 1; valence = 1. The valence of O is 2. Thus, the formula of the binary
compound is Li2O.

(v) P: group = 15. Its valence is either 3 or 5. The valence of F is 1. Thus, the formula of the
binary compound is PF3 or PF5.

(vi) Mg: group = 2; valence = 2. The valence of N is 3. Thus, the formula of the binary
compound is Mg3N2.

(vii) Si: group = 14; valence = 4. The valence of Br is 1. Thus, the formula of the binary
compound is SiBr4.

(viii) Al: group = 13; valence = 3. S: group = 16; valence = 2. Thus, the formula of the binary
compound is Al2S3.

(ix) Al: group = 13; valence = 3. N: group = 15; valence = 3. Thus, the formula of the binary
compound is AlN.

(x) Element with Z = 71 is a lanthanoid called Lu. Its common valence is 3. The valence of F
is 1. Thus, the formula of the binary compound is LuF3.

(xi) The element (M) with Z = 114 belongs to group 14. It will exhibit a valence of 2 (due to
inert pair effect) and 4. The valence of F is 1. Thus, the formula of the binary compound is
MF2.

(xi) The element (M) with Z = 120 belongs to group 2. Its valence is 2. The valence of O is
2. Thus, the formula of the binary compound is XO.

47
Differences between Metals and Non-metals:

Metals Non-metals

1. They have usually 1 to 3 valence electrons. 1. They have usually 4 to 8 valence electrons.

2. They have low ionization enthalpy. 2. They have high ionization enthalpy.

3. They have low electron affinities. 3. They have high electron affinities.

4. They are electropositive. 4. They are electronegative.

5. Form basic oxides. 5. Form acidic oxides.

6. Good reducing agent. 6. Good oxidizing agent.

Periodic Trends and Chemical Reactivity:

Chemical reactivity is maximum at the two extremes and lowest in the center of the periodic
table. The chemical reactivity of alkali metals on the extreme left is due to their ability to lose
an electron to form the corresponding cations. In contrast, the chemical reactivity of halogens
on the extreme right is due to their ability to gain an electron to form the corresponding
anions. In other words, alkali metals are good reducing agents while halogens are good
oxidizing agents.

Nature of Oxides:

In general, on moving across a period from left to right, the basic character of the oxides
decreases while acidic character increases.

Na2 O < MgO < Al2 O3 < SiO2 < P2 O5 < SO3 < Cl2 O7 (increasing order of acidity of oxides)

The oxide formed by element on the extreme left (most metallic) is most basic (Na2 O)
whereas, that formed by element on the extreme right (most non-metallic) is most acidic (e.g.,
Cl2 O7 ). Oxides of the elements in the center are amphoteric (e.g., Al2 O3 ) or neutral (e.g., CO,
NO, N2 O, etc.) The amphoteric oxides behave acidic with bases and basic with acids. Neutral
oxides, however, have no acidic or basic properties.

48
[41] Show by a chemical reaction with water that Na2O is basic oxide and Cl2O7 is an
acidic oxide.

Ans: The following reactions show that Na2O is basic oxide and Cl2O7 is an acidic oxide:

Na2O(s) + H2O(l) → 2NaOH(aq)

Basic oxide Base

Cl2O7(l) + H2O(l) → 2HClO4(aq)

Acidic Acid
oxide

[42] Show by chemical reactions that Al2O3 is an amphoteric oxide.

Ans: The following reactions show that Al2O3 is an amphoteric oxide:

Al2O3(s) + 6HCl(aq) → 2AlCl3(aq) + 3H2O(l)

Al2O3(s) + 2NaOH(aq) + 3H2O(l) → 2Na[Al(OH)4](aq)

Sodium aluminate

[43] Show by a chemical reaction that MgO is basic oxide and P4O10 is acidic.

Ans: The following reactions show that MgO is basic oxide and P4O10 is an acidic oxide:

MgO(s) + 2HCl(aq) → MgCl2(aq) + H2O(l)

Basic Acid Salt
oxide

P4O10(l) + 6H2O(l) → 4H3PO4(aq)

Acidic Acid
oxide

N.B. Thus, it is obvious that oxides of metals are usually basic while those of non-metals are
mostly acidic.

49
 Anomalous Properties of the Second Period Elements and Diagonal
Relationship:

The second period elements differ in many respects from other members of their respective
groups.

(For instance, Li forms compounds with predominantly covalent character while other alkali
metals form compounds with predominantly ionic character. Likewise, Be forms compounds
having predominantly covalent character while other alkaline earth metals form compounds
with predominantly ionic character.)

The anomalous behaviour of second period elements is due to:

i. Small size of their atoms and ions.

ii. Large charge/radius ratio.

iii. High electronegativity.

iv. Absence of d orbitals in their valence shells.

v. Ability to form pπ − pπ multiple bonds.

Diagonal Relationship:

The similarity in the properties of definite pairs of diagonally adjacent elements in the second
and third periods of the periodic table is called diagonal relationship.

Li Be B C

Na Mg Al Si

Across a period from left to right, electronegativity increases while down a group,
electronegativity decreases. These two effects partly cancel each other in moving diagonally
from top left to bottom right accounting for the occurrence of diagonal relationship.

50
[44] Use the periodic table to answer the following questions:

a) Identify an element with five electrons in the outer subshell.

b) Identify an element that would tend to lose two electrons.

c) Identify an element that would tend to gain two electrons.

d) Identify the group having metal, non-metal, liquid as well as gas at the room
temperature.

Ans: (a) N, P, As, Sb or Bi; (b) Mg, Ca, Sr or Ba; (c) O, S, Se or Te; (d) Group 13.

[45] What is the significance of the terms- isolated gaseous atom and ground state while
defining the ionization enthalpy and electron gain enthalpy?

Ans: The force with which an electron is attracted by the nucleus of an atom is affected by
the presence of other atoms within its molecule or in the neighbourhood. In the gaseous state,
the atoms are widely separated; hence, interatomic forces are minimum. This makes possible
precise measurement of ionization enthalpy and electron gain enthalpy and so, the term
‘isolated gaseous atom’ has been included in their definitions.

Further, in an excited gaseous atom, the removal of the outermost electron or the addition of
an incoming electron involves lesser amount of energy changes. Therefore, ionization
enthalpy and electron gain enthalpy of an atom must be determined in its ground state which
refers to its most stable state.

[46] Among the elements B, Al, C and Si:

a) Which has the highest first ionization enthalpy?

b) Which has the most negative electron gain enthalpy?

c) Which has the largest atomic radius?

d) Which has the most metallic character?

Ans: (a) C (⸪ Al < Si < B < C; third shell < second shell); (b) C (⸪ Al < Si < B < C); (c) Al
(⸪ Al > Si > B > C); (d) Al (⸪ Al > Si > B > C, *see electronegativity values)

51
[47] Answer the following:

a) Which is largest in size: Ca+, Ca2+, Ca and why?

b) Which element in the periodic table has the highest ionization enthalpy?

c) Which element is more metallic, Mg or Al, and why?

Ans: (a) Ca has the largest nuclear size. This because with loss of every electron in Ca,
effective nuclear charge increases leading to a contraction in size.

(b) He has the highest ionization enthalpy.

(c) Due to lower electronegativity, Mg has greater tendency to lose electrons. Therefore, Mg
is more metallic than Al.

[48] Why do noble gases tend to be less reactive?

Ans: This is because they have stable electronic configuration comprising of subshells, all of
which are fully filled.

[49] Why are f-block elements placed in a separate row at the bottom of the periodic table?

Ans: This is because they resemble each other but do not resemble any other group elements.

[50] How many elements can be accommodated in the present set up of the long form of
periodic table? Explain.

Ans: In the present set up of the long form of periodic table, there are seven periods and four
blocks, namely s-, p-, d- and f-blocks. Thus the maximum number of electrons that can be
accommodated in an element following Aufbau principle is

1s 2 2s2 2p6 3s 2 3p6 4s 2 3d10 4p6 5s 2 4d10 5p6 6s2 4f 14 5d10 6p6 7s 2 5f 14 6d10 7p6

118. Thus, 118 elements can be accommodated in the periodic table.

[51] Give the name and atomic number of the inert gas atom in which the total number of
d electrons is equal to the difference in the number of total p and s electrons.

Soln: The first inert gas which contains d electrons is krypton (Kr) with Z = 36.

52
36Kr ∶ 1s2 2s 2 2p6 3s 2 3p6 4s 2 3d10 4p6

Total number of d electrons = 10

Total number of p electrons = 6 + 6 + 6 = 18

Total number of s electrons = 2 + 2 + 2 + 2 = 8

⸫ difference in the total number of p and s electrons = 18 − 8 = 10

⸫ the inert gas is krypton.

[52] Consider the elements F, Cl, O and N, the correct order of their chemical reactivity in
terms of oxidizing property is:

(a) F > Cl > O > N (b) F > O > Cl > N

(c) Cl > F > O > N (d) O > F > N > Cl

Ans: Across a period from left to right, reactivity and hence oxidizing power increases for p-
block elements. Hence, among the 2nd period elements, the order of reactivity is F > O > N.
However, oxidizing power decreases down a group. Hence, F > Cl in terms of oxidizing
power. Also, due to higher electronegativity of O, it has greater tendency to gain electrons
than Cl. Hence O > Cl in terms of oxidizing power. So, the order of oxidizing power is (a) F
> O > Cl > N.

N.B. Best indicator to judge metallic or non-metallic character is electronegativity.

Higher electronegativity implies higher non-metallic character. Lower electronegativity
suggests higher metallic character. Electronegativity is also a good parameter to judge
the oxidizing power (nature) and reducing power (nature) of an element. Higher
electronegativity means higher oxidizing power and therefore, lower reducing power;
and lower electronegativity means higher reducing power and therefore, lower
oxidizing power.

N has stable half-filled compact 2p subshell, it has positive Δeg H1. In case of P, although
it has stable half-filled 3p subshell, the 3p subshell is spacious and hence incoming
electron causes lesser electronic repulsions and so, lesser energy is spent to overcome
it. Thus, there is net release of energy and so Δeg H1 has a small negative value.

53