 AND PERIODICITY IN PROPERTIES

CLASSIFICATION OF ELEMENTS

1 NEED FOR CLASSSIFICATION


It is very difficult to study individually the chemistry of more than one hundred elements known
and their innumerable compounds. This practical problem was felt by scientists and after numerous
attempts the scientists were ultimately successful in arranging the elements. This arrangement of elements
provided a proper classification of elements, which led to the formation of a periodic table.
Periodic table may be defined as the table, which classifies all the known elements in accordance
with their properties in such a way that the elements with similar properties are grouped together in the
same vertical column and dissimilar elements are separated from one another.
The periodic table provides a systematic framework for organizing the large available information
on the chemical behavior of the elements into simple logical patterns. Using the position of an element in
the periodic table, it is possible to predict its chemical behavior.

2 HISTORICAL DEVELOPMENT OF CLASSIFICATION F ELEMENTS

Several scientists for long have tried to classify the elements and to find patterns in their properties.
Some of them are as:
DOBEREINER’S TRIADS
He arranged similar elements in groups of three and showed that atomic weights are either nearly
the same or the atomic weight of the middle element is approximately the arithmetic mean of the other two.
e.g.
Element Atomic weight Element Atomic weight Element Atomic weight
Li 7 Ca 40 Cl 35.5
Na 23 Sr 88 Br 80
K 39 Ba 137 I 127

Drawback: This applies only to limited number of elements.

NEWLAND LAW OF OCTAVE

When lighter elements are arranged in order of their increasing atomic weight, the properties of
every eighth element is similar to the first, like eighth node of a musical scale.
Element Li Be B C N O F
Atomic weight 7 9 11 12 14 16 19

Element Na Mg Al Si P S Cl
Atomic weight 23 24 27 29 31 32 35.5

Element K Ca
Atomic weight 39 40

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Drawbacks: (a) It could not be applied for the element of atomic mass greater than 40.
(b) With the discovery of noble gases, the above sequence was disturbed and the arrangement
was no longer valid.

LOTHER MEYER ARRANGEMENT

By plotting graph between atomic volume and atomic mass of element it was observed that
elements having similar properties occupy similar positions on the curve e.g. alkali metals occupy maxima
of the curve. Most electronegative elements found ascending portions of the curve and it was found that
physical properties are the periodic function of their atomic weights.
By 1868, Lother Meyer had developed a table of the elements that closely resembles with the
Modern Periodic Table. However, his work was not published until after the work of Dimitri Mendeleev,
the scientist who is generally credited with the development of the Modern Periodic Table.

MENDELEEV’S PERIODIC TABLE

While Dobereiner initiated the study of periodic relationship, it was Mendeleev who was
responsible for publishing the Periodic law for the first time.
Thus, in the development of the periodic table the work of Dmitri Mendeleev was a breakthrough.
To explain his scheme of classification, he gave a periodic law which is known as Mendeleev’s periodic
law. This law states as follows, the physical and chemical properties of elements are periodic function of
their atomic masses i.e. when the elements are arranged in order of their increasing atomic masses,
elements with similar properties are repeated after certain regular intervals.
On the basis of this periodic law, he constructed a periodic table in such a way that elements were
arranged horizontally in the order of their increasing atomic masses.
Mendeleev’s system of classifying elements was more elaborated than that of Lother Meyer’s. He
fully recognized the significance of periodicity and used broader range of physical and chemical properties
to classify the elements.

Characteristics of Mendeleev’s Periodic Table

1. It has 9 vertical columns called groups I, II, III, IV, V, VI, VII, VIII and zero group. Except
VIII and zero groups, each group is subdivided into two groups designated as
A and B.
2. It has seven horizontal rows called periods. The I, II and, III periods are short periods, IV and
V periods are long periods and VI period is the longest period.

Importance of Periodic Table

1. Classification based on atomic mass facilitates systematic study of the elements.
2. It helped in prediction of new element e.g. Ga, Ge. Keeping his primary aim of arranging the
elements of similar properties in the same group, he proposed that some of the elements were
still undiscovered and, therefore, left several gaps in the table. For example, both gallium and
germanium were unknown at the time when Mendeleev published his Periodic Table. He left
the gap under aluminium and a gap under silicon, and called these elements Ekaaluminium
and Ekasilicon. Mendeleev predicted not only the existence of gallium and germanium, but
also described some of their general physical properties.
3. Correction of doubtful atomic mass. The atomic mass of Be was taken as 13.5 but periodic
classification helped in arriving at its correct atomic mass i.e. 9.

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Drawbacks of Mendeleev’s Periodic Table

1. Position of H: H is placed along with alkali metals in group I(A). It can also be placed along
with halogens in group VIIA.
2. Anomalous positions of some elements: Although most of the elements have been
arranged in the increasing order of their atomic masses, but in some cases, the element
having higher atomic mass precedes the element with lower atomic mass. For example, Ar
(Atomic mass = 39.9) precedes K (Atomic mass = 39.1) and similarly, Co (Atomic mass =
58.9) precedes Ni (Atomic mass = 58.7).
3. Position of isotopes: Different isotopes of the same element are not given separate position
in periodic table.
4. No corelation of elements in subgroups: Some dissimilar elements are grouped
together while some similar elements are placed in different groups. Alkali metals
(Li, Na) and coinage metals (Cu, Ag, Au) are placed in the same group although they have
different properties. Copper and mercury have been placed in different groups although they
have similar chemical properties.
5. Position of lanthanides and actinides: These elements could not be accommodated in
the main periodic table. Instead they have been placed in two separate rows at the bottom of
the periodic table.
6. Cause of Periodicity: No proper explanation has been offered as to why the elements
placed in a group show resemblance in their properties.

3 MODERN PERIODIC LAW AND LONG FORM OF PERIODIC TABLE

When Mendeleev developed his Periodic Table, chemists knew nothing about the internal structure
of atom. However, the beginning of the 20 th century witnessed profound developments in theories about
sub-atomic particles. In 1913, the English physicist, Henry Moseley observed regularities in the
characteristic X–ray spectra of the elements. A plot of  (where  is frequency of X–rays emitted)
against atomic number (Z) gave a straight line and not by the plot of  vs. atomic mass. Thus, Moseley
observed that atomic number is a more fundamental property of an element than its atomic mass, and
physical and chemical properties of the elements are determined by their atomic numbers. Based on this,
modern periodic law was given which states that physical and chemical properties of the elements are
periodic functions of their atomic numbers. i.e. if the elements are arranged in increasing order of their
atomic numbers, the elements with similar properties are repeated after certain regular intervals.

CAUSE OF PERIODICITY
When the elements are arranged in an order of increasing atomic number, the periodic repetition of
elements with similar properties is observed after certain regular intervals. This is called periodicity.
The cause of periodicity in properties is due to repetition of similar outer electronic configuration
after certain regular intervals as shown below:
Li (3)  1s2, 2s1
Na (11)  1s2, 2s2, 2p6, 3s1
K (19)  1s2, 2s2, 2p6, 3s2, 3p6, 4s1
FEATURES OF LONG FORM OF PERIODIC TABLE

Periods

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A horizontal row of a periodic table is known as a period. Entire table is divided into
7 periods. The first period contains 2 elements. The subsequent periods consists of 8, 8, 18, 18 and 32
elements, respectively. The seventh period is incomplete and like the sixth period would have a theoretical
maximum (on the basis of quantum numbers) of 32 elements. In this form of the Periodic Table, 14
elements of both sixth and seventh periods (lanthanoids and actinoids, respectively) are placed in separate
panels at the bottom. Thus, 1 st, 2nd and 3rd period are short periods, 4 th and 5th periods are long and 6 th
period is the longest and 7 th period is incomplete.

Groups
A vertical column of the periodic table is called a group. It is divided into 18 groups. According to
IUPAC, these groups are numbered from 1 to 18. replacing the older notation of groups I A … VII A, VIII, I
B …. VII B and O.
ADVANTAGES OF LONG FORM OF PERIODIC TABLE
Long form of periodic table has the following advantages:
1. Same group elements have similar electronic configuration, hence they have similar chemical
properties.
2. Elements are properly divided into reactive metals, heavy metals and non metals.
3. Since same group elements have similar electronic configuration, the study of elements
become very simple.
4. Since, classification is based on the atomic number and not on the atomic mass, the idea of
placing isotopes at one place is fully justified.

DRAWBACKS OF THE LONG FORM OF PERIODIC TABLE

The main defects of this table are as follows:
1. Position of H: H is still placed along with alkali metals as well as halogens.
2. Separate position of lanthanides and actinides: Like Mendeleev’s periodic table lanthanides and
actinides are placed separately at the bottom of the periodic table.

PRACTICE PROBLEMS
PP1. What is the modern periodic law?
PP2. What is the difference between Mendeleev’s and modern periodic table?

4 DIVISION OF PERIODIC TABLE

The entire periodic table can be divided into two broad categories as indicated below:

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 Classification of Elements and Periodicity in Properties

Periodic Table Classification

On the basis of distribution of On the basis of properties of

electrons into orbitals of an atom. the elements.

s-Block elements p-Block elements d-Block elements f-Block elements

Metals Non-Metals Metalloids

CLASSIFICATION ON THE BASIS OF ELECTRONIC DISTRIBUTION OF ELECTRONS INTO

ORBITALS OF AN ATOM
Entire periodic table is divided into four blocks known as s, p, d and f based on the orbital in which
last electron enters.

sBLOCK ELEMENTS
The elements of group 1 (alkali metals) and Group 2 (alkaline earth metals) which have ns1 and ns 2
outermost electronic configuration belong to the s-Block Elements. The general features of these
elements are:
1. The general outer shell electronic configuration of s-block elements is ns12.
2. They are soft metals with low melting and boiling points.
3. They have low ionization potential and are very reactive.
4. Alkali metals show +1 oxidation state while alkaline earth metals show +2 oxidation state.
5. Most of the elements of this block impart characteristic colour to the flame.
6. They are strong reducing agents.
7. All of them are good conductors of heat and electricity.

p-BLOCK ELEMENTS

The pBlock elements comprise those belonging to group 13 to 18 and these together with the sBlock
elements are called the Representative Elements or Main Group Elements.

The general features of these elements are:

1. The general outer shell electronic configuration of p-block elements is ns2, np16.
2. This block has metals, non-metals and metalloids.
3. Some of the elements show more than one oxidation states.
4. They form mostly covalent compounds.
5. No member of p-block or the salt of it imparts a characteristic color to the flame because the
energy released by excited elements does not appear in the visible region of the spectrum.

Note: Group–18 elements are known as noble gases; Group–17 elements are known as halogens and the
group-16 elements are known as chalcogens.

d-BLOCK ELEMENTS

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These are the elements of group 3 to 12 in the centre of the periodic table. These are characterized
by the filling of inner d orbitals by electrons and are therefore referred to as d–block elements. The
general features of these elements are:
1. The general outer shell electronic configuration is (n  1)d110 ns02.
2. They are also known as transition elements because their properties show a gradual transition
from the properties of sblock to the pblock elements.
3. They are hard, malleable and ductile metals.
4. They form both ionic and covalent compounds.
5. Their compounds are generally coloured and paramagnetic.
6. Most of the elements or their compounds find their use as catalyst due to their tendency to
show variable oxidation states.
7. Most of the transition elements form alloys.

fBLOCK ELEMENTS
The two rows (series) of the elements at the bottom of the periodic table, called the Lanthanides
and Actinides are classified into the f-block elements. The general features of these elements are:
1. The general outer shell electronic configuration is (n  2)f 114 (n  1)d01ns2 .
2. They are known as inner transition elements since they form transition series within the
transition elements of d-block.
3. 58Ce to 71Lu constitutes the 4f inner transition series and are called Lanthanides because they
follow lanthanum in the 5d transition series. They closely resemble lanthanum in their
properties. They are also called rare earth elements since they occur rarely in earth crust.
4. 90Th – 103Lr constitutes the 5f inner transition series and are known as actinides since they
follow actinium in the 6d transition series.
5. All actinides are radioactive elements. Three elements namely Thorium, Protoactinium and
Uranium occur in nature but the remaining 11 elements i.e. from neptunium to Lawrencium
(93Np – 103Lr) have been prepared artificially. These 11 elements are called Transuranium
elements since they follow uranium in periodic table and also have been derived from it
through nuclear reactions.
6. They show variable oxidation states.
7. Their compounds are generally coloured.
8. They have strong tendency to form complexes.

CLASSIFICATION ON THE BASIS OF PROPERTIES OF THE ELEMENTS

I. Metals:
Metals comprise more than 78% of all known elements and appear on the left side of the Periodic
Table. The general properties of metals are listed below:
(a) Metals are usually solids at room temperature. Mercury is an exception.
(b) Metals usually have high melting and boiling points.
(c) They are good conductors of heat and electricity.
(d) They are malleable (can be flattened into thin sheets by hammering) and ductile (can be
drawn into wires)
II. Non-metals:
In contrast to metals, non-metals are located at the top right hand side of the periodic table.
Infact, in a horizontal row, the property of elements changes from metallic on the left to non-
metallic on the right and the elements become more metallic as we go down a group. The
characteristics of the non-metals are as follows:

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(i) Non-metals are usually solids or gases at room temperature with low melting and boiling
points (boron and carbon are exceptions).
(ii) They are poor conductors of heat and electricity.
(iii) Most non-metallic solids are brittle and are neither malleable nor ductile.
III. Metalloids
Certain elements (Si, Ge, As, Sb, Te, Po and At) show properties that are characteristic of both
metals and non-metals. These elements are called semi-metals or metalloids.

Question: Which of the following elements given below belong to the same period?
Al, Ca, O, Cs, Si
Solution: Al and Si both belong to the same period.

PRACTICE PROBLEMS
PP3. An element having atomic mass 37 contains 20 neutrons. Write the electronic configuration of this
element and locate the position of this element in periodic table.
PP4. Two elements X and Y having atomic number 15 and 17 respectively. To which group these
elements belong?

5. EFFECTIVE NUCLEAR CHARGE

The effective nuclear charge is the actual charge felt by the valence electrons. Between the outer
most valence electrons and the nucleus of an atom, there exists finite number of shells containing electrons.
Due to the presence of these intervening electrons, the valence electrons are unable to experience the
attractive pull of the actual number of protons in the nucleus. These intervening electrons act as shield
between the valence electrons and protons in the nucleus. Thus, the presence of intervening (shielding)
electrons reduces the electrostatic attraction between the protons in the nucleus and the valence electrons
because intervening electrons repel the valence electrons. The concept of effective nuclear charge allows
us to account for the effects of shielding on periodic properties.

6 THE PERIODICITY OF ATOMIC PROPERTIES

The electronic configuration of the elements shows a periodic variation with increasing atomic
number. Consequently, there are also periodic variations in physical and chemical behaviour of the
elements. Let us now study the variation of some of the atomic properties in the periodic table. These
properties are classified as follows:
(i) Atomic radius
(ii) Ionisation energy
(iii)Electron gain enthalpy
(iv) Electronegativity

7 TRENDS IN PHYSICAL PROPERTIES

ATOMIC RADIUS
It is defined as the distance from the centre of the nucleus to the outer most shell containing
electrons.
Difficulties in determining radius
(a) Exact size of electron cloud can not be determined as the probability of finding
an electron even at large distance from the nucleus never becomes zero.
(b) It is not possible to isolate a single atom.
(c) The probability of finding an electron in an atom is appreciably affected by the presence of the
other atoms within its molecule or its neighbourhood.

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(d) The atomic radius also changes when the atom is present in different bonding state.

Type of Radius
Covalent Radius
Bond length
It is defined as one-half of the distance between the
nucleus of two covalently bonded atoms of the same
element in a molecule. A A

d
rcovalent = where ‘d’ is the internuclear distance between
2
two bonded atoms. d
Overlapping of atomic orbitals
to form a covalent bond.

Question: The internuclear distance of a given molecule A2 (dA–A) is 1.4Å. Calculate the atomic (covalent)
radius of an atom A.
d A A
Solution: rA   1.4 / 2  0.7 Å.
2
Vander Waal’s radius (collision radius)
It is defined as one half of the distance between two non
bonded isolated atoms or two adjacent atoms of the same
element belonging to the two neighbouring molecules of the
dAB
same substance in the solid state. vander Waal’s radius
increases with increasing shell. vander Waal’s radius is
greater than covalent radius. Radius of inert gas is large due
to exactly fully filled configuration and also due to maximum vander Waal bond
atomic repulsion between the two atoms. Moreover, in case length= d AB
v.w. radius
of inert gas the atomic size is defined in terms of vander
Waal’s radius instead of covalent radius.
2

Question: Arrange the given atoms in order of decreasing vander Waal’s radii: Cl, H, O, N.
Solution:
The vander Waal’s radii increase as the number of energy shells increases and decreases as the
nuclear charge increases. Hence the order is Cl > N > O > H.

Question: Vander Waal’s radius is greater than the covalent radii of the atoms. Explain.
Solution: vander Waal’s radius is measured between two non bonded atoms whereas covalent radii is measured
between two bonded atoms. Hence, the vander Waal’s radius is greater than the covalent radius of the
atoms.

Metallic Radius

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

Ionic radius
Ionic radii may be defined as the effective distance from the Radius of Radius of
nucleus of the ion to the point upto which it exerts its cation anion

influence on its electron cloud. Radius of cation is always

smaller than that of the parent atom because it has fewer
electrons while its nuclear charge remains the same. e.g. the
radius of Na+ is lesser than Na. Similarly the radius of anion
A B
is larger than that of the parent atom because the addition of
one or more electrons would result in increased repulsion
among the electrons and a decrease in effective nuclear Cation Anion
charge. e.g. the radius of I  is greater than I. For
isoelectronic species greater the nuclear charge lesser will be Internuclear
distance
the ionic radius. e.g.
d AB  rcation  ranion
N3 > O2 > F > Na+ > Mg2+

Variation of Atomic Radii in the Periodic Table

In general, the atomic radii decreases with increase in the atomic number in a period. It is because
of increase in the effective nuclear charge along the period.
In general, the atomic radii increases from top to bottom within a group. As we move down the
group there is progressive increase in the principal energy level, which increase the distance between
nucleus and outermost electron and the size increases.

PRACTICE PROBLEMS
PP5. Which one of the element or ion in the following pairs would have a large size? Explain.
(b) Br or Br
+ + +
(a) K or K (c) Li or Na
PP6. Why the atomic radius of an inert gas element is higher than the atomic radius of any of the
remaining elements belonging to the same period?

IONIZATION ENERGY
Ionization energy is defined as the minimum energy (in kJ/mole) required to remove the most
loosely bound electron from an isolated gaseous atom in its ground state. Alternatively, ionization energy
is the amount of energy required in kilojoules needed to knock out one mole of electrons from one mole of
isolated gaseous atoms. In this definition, gaseous atoms are specifically used because an atom in the gas
phase is virtually uninfluenced by its neighbours and so, there are no intermolecular forces to take into
account while measuring ionization energy.
The magnitude of ionization energy is a measure of how “tightly” the electron is held in the atom.
Higher is the ionization energy, more difficult it is to remove the electron.

Successive Ionization Energies

For a multielectron atom, the amount of energy required to remove the first electron from the
atom in its ground state is called the first ionization energy (IE1).
X(g) + energy  X+(g) + e
The second ionization energy (IE2) and the third ionization energy (IE3) are shown in the following
equations:
X+(g) + energy  X2+(g) + e (IE2)

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X2+(g) + energy  X3+(g) + e (IE3)
The pattern continues for the removal of subsequent electrons. Theoretically, an atom can have as
many ionization energy values as the number of electrons present in that atom.
The ionization enthalpies required to remove first, second, third etc. electrons from an isolated
gaseous atom are called successive ionization energies. It may be seen that, IE2 is always greater than IE1
and IE3 is always greater than IE2 and so on IE3 > IE2> IE1. After removing first electron, the resultant
force of attraction on the remaining outermost electrons increases and hence, more energy is required to
remove the next electron.
Factors affecting the Ionization Energy
Ionization energy depends upon the following factors:
(a) Penetration effect of the electrons. i.e. ionization energy of ns  np  nd  nf , because sorbital
is closest to the nucleus.
(b) Greater the nuclear charge greater will be the ionization energy.
(c) Greater the atomic size lesser will be the ionization energy as the distance of the outermost
electron from the nucleus increases.
(d) Greater the screening effect of inner electrons, lesser will be the ionization enthalpy.
(e) Exactly half filled or completely filled orbitals have higher ionization enthalpy because half
filled and fully filled configuration are more stable than partially filled configuration.
Variation of Ionisation Energy in the Periodic Table
In general the value of ionisation energy increases with the increase in atomic number across
the period. This is due to gradual increase in effective nuclear charge and simultaneous decrease in atomic
size. As a result, the attractive force between the nucleus and the electron cloud increases. Consequently,
the electron is more and more tightly bound to the nucleus.
As we move down the group, there is a gradual increase in the atomic size due to progressive
addition of new energy shells. As a result the nuclear hold on the valence electrons decreases gradually and
the ionisation energy also decreases.
Ne

H N O
Be C
Li
B
Atomic number (Z)
First ionization enthalpies of the second period as a function of atomic number (Z).

Li
Na

H K

Rb
Cs
Atomic number (Z)
First ionization enthalpies of the first group as a function of atomic number (Z)
From the above graphs, it is clear that the first ionization enthalpy of boron (Z = 5) is slightly less
than that of beryllium (Z = 4) even though the former has a greater nuclear charge. When we consider the
same principal quantum level, an s-electron is attracted to the nucleus more than a p–electron. In beryllium,
the electron removed during the ionisation is a s–electron whereas the electron removed during ionization
of boron is a p–electron. The penetration of a

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2s–electron to the nucleus is more than that of a 2p–electron; hence the 2p–electron of boron is more
shielded from the nucleus by the inner core of electrons than the 2s–electrons of beryllium. Therefore, it is
easier to remove the 2p–electron from boron compared to the removal of a
2s–electron from beryllium. Thus, boron has a smaller first ionization enthalpy than beryllium.
The first ionization enthalpy of oxygen is smaller as compared to nitrogen. This can be attributed
due to stability of half filled orbitals of 2p–subshell of nitrogen.

Question: The first ionization energy of Al is lower than that of Mg. Explain.
Solution: The electronic configuration of the given elements are:

12 Mg  1s 2 2s 2 2p 6 3s 2

13 Al  1s 2 2s 2 2p 6 3s 2 3p1
In the case of Al, the electron is removed from ‘3p’ orbital, whereas in case of Mg, the electron is
removed from the ‘3s’ orbital.
The ‘3s’ orbital has two electrons which are paired whereas ‘3p’ orbital has only one unpaired
electron. Even though Al atom is smaller than Mg atom, in order to remove an electron from ‘3s’
orbital of Mg, energy has to be spent to unpair the two electrons and to remove one of them from the
nuclear force of attractions. Therefore, 1st ionization energy of Mg is higher than that of Al.

Question: Ionisation energy of one H atom is 2.18 × 10–18 J. Calculate the ionization energy of H atom in
kJ mole–1.
Solution:
2.18  10 18 J 6.02  10 23 atom
I.E.=   1.31  10 6 J mole –1  1310 kJ mole –1.
1 atom mole

Question: The I, II and III ionization energies of Al are 578, 1817 and 2745 kJ mol1 respectively.
Calculate the energy required to convert all the atoms of Al to Al+3 present in 270 mg of Al
vapours.
Solution:
Total amount of energy required to convert
Al ( g ) to Al 3 ( g )  578  1817  2745  5140 kJ mole 1
270 1
Number of moles of Al in 270 mg    10 2 mole
1000 27
1 mole of Al need for ionization = 5140 kJ of energy
10–2 mole of Al need for ionization = 5140 × 10–2 = 51.40 kJ.

PRACTICE PROBLEMS
PP7. The ground state electronic configurations of some of the neutral atoms are given below.
2 2 3 2 2 5 2 2 6 1 2 2 6
(a) 1s , 2s , 2p (b) 1s , 2s , 2p (c) 1s , 2s , 2p , 3s (d) 1s , 2s , 2p
Arrange them in the increasing order of their ionization energies.
PP8. First and second ionization enthalpies of few elements are given below:
IE1 (kJ mol1) IE2 (kJ mol1)
(1) 520 7300
(2) 1680 3380
(3) 2370 5250
(a) Which one of them is an alkali metal?
(b) Which one of them is a reactive nonmetal?
(c) Which one of them is a noble gas?

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ELECTRON GAIN ENTHALPY

Electron gain enthalpy of an element may be defined as the energy released when a neutral
isolated gaseous atom accepts an extra electron to form the gaseous negative ion, i.e., anion. It is denoted
by Heg. Higher is the amount of energy released, more is the electron affinity value.

This process may be represented as:

X(g)  e   X  (g) ; H  Heg
neutral gaseous atom anion

After the addition of one electron, the atom becomes negatively charged and the second electron is
to be added to a negatively charged ion. But the addition of second electron is opposed by electrostatic
repulsion and hence the energy has to be supplied for the addition of a second electron. Thus, the second
electron gain enthalpy of an element is positive.
O(g)  e   O  (g) ; Heg   141 kJ mol 1 (First electron gain enthalpy)
(Energy is released)

O  (g)  e   O 2 (g); Heg   780 kJ mol 1 (Second electron gain enthalpy)
(Energy is absorbed)
Similarly, the second electron gain enthalpy of S is also positive as can be seen from the data given
below:
S(g)  e   S  (g) ; Heg   200 kJ mol 1 (First electron gain enthalpy)
(Energy is released)

  2
S (g)  e  S (g) ; Heg   590 kJ mol 1 (Second electron gain enthalpy)
(Energy is absorbed)

The elements which have stable configuration have positive first electron gain enthalpy.

Factors on which the Electron Gain Enthalpy Depends

Some important factors on which electron gain enthalpy depends are discussed below:
1. Atomic size
As the size of an atom increases, distance between the nucleus and the last shell which receives
the incoming electron increases. As a result, the force of attraction between the nucleus and the
incoming electron decreases and hence the electron gain enthalpy becomes less negative.
2. Nuclear charge
As the nuclear charge increases, the force of attraction between the nucleus and the incoming
electron increases and hence, the electron gain enthalpy becomes more negative.
3. Electronic configuration
Elements having exactly half-filled or completely filled orbitals are very stable. As a result,
energy has to be supplied to add an extra electron. Hence their electron gain enthalpies have
large positive values since they do not accept additional electron so easily.

Variation of Electron Gain Enthalpy in the Periodic Table

On moving across the period, the atomic size decreases and effective nuclear charge increases.
Both these factors result into greater attraction for the incoming electron. Therefore, electron gain
enthalpies tend to become more negative as we go from left to right across a period. On moving down a
group, the atomic size as well as nuclear charge increases. But the effect of increase in atomic size is much
more pronounced than that of the nuclear charge and thus, the additional electron feels less attraction.
Consequently, electron gain enthalpy becomes less negative on going down the group.
The electron gain enthalpy of second period element is lower than that of third period elements.
This is probably due to small size of the atom of second period element. The addition of an extra electron

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 Classification of Elements and Periodicity in Properties
produces high electron charge density in a relatively compact 2p–subshell resulting in strong electron–
electron repulsion. The repulsive forces between electrons imply low electron gain enthalpy. Electron gain
enthalpy of Cl is maximum in periodic table.

Question: Explain, why the formation of F (g) from F(g) is exothermic whereas that of O2 (g) from O(g) is
endothermic?
Solution: The addition of an electron to a neutral atom is an exothermic process.
F  e   F   energy
O  e   O   energy …(i)
The addition of second electron to a monovalent anion O, to make it O2 is difficult because both
electron and anion have the same charge and experience repulsive forces. Thus, the addition of an
electron to O requires energy to overcome the force of repulsion.
O   e   energy  O2– …(ii)
The energy absorbed in (ii) step is more than the energy released in the (i) step. Hence, the formation
of O2(g) from O(g) is endothermic in nature.

Question: The electron affinity values of halogens decrease in the order: F > Cl > Br > I. Comment on the
statement.
Solution:
This statement is wrong because the actual order of electron affinity of halogens is
Cl > F > Br > I
In general, electron affinity decreases down the group but F abnormally shows lower electron affinity
than Cl because of its small size.

PRACTICE PROBLEM
PP 9. The amount of energy released when one million atoms of iodine in vapour state are converted to I
ion is 4.9 × 1013 J according to the following reaction I(g) + e  I(g).
Express the electron gain enthalpy in terms of kJ mol1.

ELECTRONEGATIVITY
The ability of an atom to attract the shared pair of electrons towards itself is known as
electronegativity. It is a unitless quantity because it is relative with respect to F for which the
electronegativity value is fixed as 4. (i) Electronegativity of inert gases is 0. (ii) It is not a property of an
isolated atom but rather property of an atom in a molecule. (iii) Because of electronegativity covalent
molecule acquire some ionic character. (iv) Fluorine is the most electronegative element of the periodic
table.

Factors affecting Electronegativity

1. Size of atom: As the size increases, electronegativity decreases because the distance of
electrons from nucleus increases.
2. Oxidation state of element: Electronegativity increases with higher positive oxidation state
because it has more effective nuclear charge. As for example electronegativity of Fe3+ ion is
greater than that of Fe2+ ion.
3. Effective nuclear charge: Electronegativity increases with increase in nuclear charge because
the attraction on shared pair of electrons increases.

Application of Electronegativity

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 Classification of Elements and Periodicity in Properties
1. To predict the nature of bond.
2. To calculate the percentage ionic character.
3. To explain the variation in bond angle.
4. To explain the bond length variation.
Variation of Electronegativity in the Periodic Table
In a period, electronegativity increases on moving from left to right. This is because the effective
nuclear charge increases whereas atomic radius decreases as we move from left to right in a period. In a
group, electronegativity decreases as we move down the group. This is due to the effect of increased
atomic radius.

Question: Give the correct order of electronegativity of central atom in following compounds:
CH3CH3, CH2=CH2, CHCH
Solution: Greater the scharacter, greater will be the electronegativity therefore the order is
CHCH > CH2=CH2 > CH3CH3
Question: What is the factor on which the polarity of a bond depends?
Solution: The polarity of bond depends upon electronegativity difference of two atoms involved in covalency.

PRACTICE PROBLEMS
PP10. Electronegativity increases as the s-character increases in the hybrid orbitals. Why?
PP11. Why does the change in electronegativity occur on increasing atomic number?

6 PERIODIC TRENDS IN CHEMICAL PROPERTIES

Periodicity of Valency or Oxidation States

Valency of representative elements is usually equal to the number of electrons in the outermost orbit
and or equal to eight minus the number of outermost electrons as shown below:

Group 1 2 13 14 15 16 17 18
Number of valence electrons 1 2 3 4 5 6 7 8
Valency 1 2 3 4 3,5 2,6 1,7 0,8

Now a days the term oxidation state is frequently used for valency. The oxidation state of
an element in a particular compound can be defined as the charge acquired by its atom on the basis of
electronegative consideration from other atoms in the molecule.
Anomalous Properties Of Second Period Elements-Diagonal Relationship
A diagonal relationship is a similarity in properties between diagonal neighbours in the main
groups of the periodic table. Because these properties lie in a diagonal pattern, it is not surprising to find
that the elements within a diagonal band show similar chemical properties. Diagonal relationship helps in
making predictions about the properties of elements and their compounds.
Diagonal relationship is exhibited by lithium and magnesium; beryllium and aluminium.
For example, lithium and magnesium react directly with nitrogen to form nitrides. Beryllium and
aluminum, both are amphoteric i.e. reacts with acids as well as bases.
Reasons for different chemical behavior of the first member of a group of elements in the
s– and p–blocks compared to that of the subsequent members in the same group:
(i) The anomalous behaviour is attributed to their small size, large charge / radius ratio and high
electronegativity of the elements.
(ii) The first member of the group don’t have d orbitals.

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 Classification of Elements and Periodicity in Properties

(iii) The first member of p-block elements display greater ability to form p -p multiple bonds to
itself (e.g. C=C, CC, N=N, NN) and to other second period elements (e.g. C=O, C=N, CN,
N=O) compared to subsequent members of the same group.

EXERCISE
CBSE PROBLEMS

1. Which of the following element has a + 1 valency?

(a) Mg (b) Na (c) B (d) C

2. In which of the following ions chromium shows maximum radius?

(a) Cr+6 (b) Cr+4 (c) Cr+3 (d) Cr+2

3. Ionization potential of Na would be numerically the same as

(a) Electron affinity of Na+ (b) Electronegativity of Na+
(c) Electron affinity of He (d) Ionization potential of Mg

4. Which one of the following statements is correct?

(a) Radius of Cl atom is 0.99 Å, while that of Cl + ion is 1.54 Å.
(b) Radius of Cl atom is 0.99 Å, while that of Na atom is 1.54 Å.
(c) Radius of Cl atom is 0.95Å, while that of Cl– ion is 0.81 Å.
(d) Radius of Na atom is 0.95 Å, while that of Na + ion is 1.54 Å.

5. Why the elements having ns2np6 configuration are called inert?

6. There are only 14 lanthanides and only 14 actinides. Why?

7. Which of the following species are isoelectronic?

(a) Al3+ (b) Cl– (c) O2– (d) Mg2+
Arrange the isoelectronic species in the decreasing order of their size.

8. Arrange the following isoelectronic species in decreasing order of their size.

O 2 , N3 , Ne, F  , Mg 2 , Na 

9. Calculate the amount of energy required to convert 5 mole of sodium atom in the gaseous state to
sodium ion. Ionisation enthalpy of Na = 5.1 eV/atom.
(use 1 eV = 1.602 × 10–19J)

10. The C–Cl bond length in CCl4 is 1.76Å. If atomic (covalent) radius of C is 0.77 Å, determine the
atomic (covalent) radius of Cl.

11. Write the electronic configuration of the following elements whose atomic numbers are given
below –
A (Atomic number = 35) B (Atomic number = 18)
C (Atomic number = 29) D (Atomic number = 37)
Also predict the period, group and block to which they belong.

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12. Write five iso-electronic species for each of the following atoms or ions taking the help of periodic
table in such a manner that two of them are cations, two of them are anions and the remaining
specie is a neutral atom.
(a) O2 (b) Ca2+ (c) Ar

13. Predict the formulae of the stable binary compounds that would be formed by the following pairs
of elements:
(a) silicon and oxygen
(b) aluminium and bromine

14. Elements A, B, C and D have their respective electronic configurations as:

A: 1s2 2s2 2p1
B: 1s2 2s2 2p6 3s2 3p1
C: 1s2 2s2 2p6 3s2 3p3
D: 1s2 2s2 2p6 3s2 3p5
Which among them will belong to the same group of the periodic table?

15. 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 total number of p and s–electrons.

ANSWERS
CBSE PROBLEMS

1. (b) Na (Alkali metals are always univalent).

2. (d) In Cr+2 oxidation state of chromium is +2 (minimum). Thus, it will have maximum radius.
3. (a) Na  Na   e  IE of Na  ve
Na   e   Na; Heg of Na   ve
4. (b) The atomic radius decreases along the period. More over cations are always smaller than their
parent atom and anions are always larger than their parent atom.
5. The elements having ns 2 np 6 configuration have complete octet and thus they neither possess the
tendency to donate electron nor to accept electron and are thus stable.
6. Lanthanides and Actinides are the elements in which differentiating electron enters into (n  2)f
sub-shell. Since ' f ' sub shell can accommodate a maximum of 14 electrons and thus, the number
of Lanthanides and Actinides is 14 each only.
7. The number of electrons in these ions are –
Ion Al3+ Cl– O2– Mg2+
Number of Electrons 10 18 10 10
3+ 2– 2+
Thus, Al , O and Mg are isoelectronic ions because all the three ions have ten electrons. Now
nuclear charge in Al3+ is + 13, in O2– is 8 and in Mg2+ is 12. In isoelectronic species with increase
in nuclear charge while the electrons remaining the same, size will decrease. Consequently, the
size follows the order
O2– > Mg2+ > Al3+
8. Since isoelectronic species have the same number of electrons and the same number of shells,
therefore, greater the nuclear charge smaller will be the size.
Isoelectronic species O2– N3– Ne F– Mg2+ Na+
Number of electrons 8 + 2 7 + 3 10 9+1 12 – 2 11 – 1

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 Classification of Elements and Periodicity in Properties

Number of protons 8 7 10 9 12 11
 decreasing order of size for isoelectronic species is
N3  O 2  F   Ne  Na   Mg 2

9. IE of Na  5.1 eV / atom  5.1 6.023  10 23 eV / mol

 5.1 6.023  10 23  1.602  10 19 J / mol
 492 .091  10 3 J / mol
 Energy required to convert 5 mole Na to Na +
 5  492 .091  10 3 J
 2.46  10 6 J
10. Bond length of CCl = distance between the nuclei of two atoms
= rC  rCl
Given rC  0.77 Å and rC  rCl  1.76Å
 rCl  1.76  0.77  0.99Å
11. A = 1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s 2 4p 5
Period = 4, Group = 17 and block = p-block
B = 1s 2 2s 2 2p 6 3s 2 3p 6
Period = 3, Group = 18 and block = p-block
C = 1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s1
Period = 4, Group = 11 and block = d-block
D = 1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s 2 4p 6 5s1
Period = 5, Group = 1 and block = s-block.
12. (a) O2– has 10 electrons. Therefore, its isoelectronic species are:
Na  , Mg 2 , N3 , F  , Ne
(b) Ca2+ has 18 electrons. Therefore its isoelectronic species are: K+, Sc3+, S2, Cl, Ar
(c) Ar has 18 electrons. Therefore its isoelectronic species are:
K  , Ca2 , S 2 , Cl (Its neutral isoelectronic species is not possible)
13. (a) Silicon belongs to group 14. Its valency is thus 4. Oxygen, on the other hand has a valency of 2.
Therefore, the formula of the binary compound is SiO2
(b) Aluminium and bromine belong to group 13 and group 17 respectively. In order to acquire stable
configuration aluminum shares three of its valence electrons with one electron each of the three
bromine atoms. Thus the formula of binary compound is AlBr3.
14. Elements (A) and (B) belong to the same group of the periodic table because they have the same
valence shell electronic configuration.
15. The first inert gas which contains d–electrons is krypton. Its atomic number is 36 and its electronic
configuration is:
1s 2 2s 2 2p 6 3s 2 3p 6 3d10 4s 2 4p 6
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 total number of p-and s-electrons = 18 – 8 = 10.
Thus, the inert gas is krypton.

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