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Introduction
We have more than 109 elements. To study each element, its isolation, physical and their
chemical properties would be an arduous task. Systematic arrangement of the element
according to their electronic configuration and thereafter to study their properties both
physical and chemical forms the hallmark of this chapter. Elements are classified according
to groups and periods for the better understanding of the properties of the elements.
Significance and Brief History of the Development of Periodic Table
The elements are the basic units of all types of matter. Only 31 elements were known in
1800. Now more than 105 elements are known. It is impossible to remember the
properties of each element and its compounds. Therefore, many attempts have been made
to classify elements into fewer groups. The purpose of the classification has been to make
the study of the chemistry of elements and their compounds easier. Dmitri I. Mendeleev
(1834-1907) developed the periodic table. From the relationships embodied in the table,
he predicted the existence as well as properties of elements then unknown. These
predictions came out to be amazingly accurate. During the course of time, the basis of
classification changed from atomic mass to atomic number.
The study of chemistry has become simple on the basis of the modern classification of
elements. Now, by knowing the properties of one element of a group, it is possible to
predict the properties of the other members. One need not remember all the properties of
elements or their compounds. All one has to do is to know the trends of properties in a
group and in a period of the periodic table.
Brief History of the Development of Periodic Table
In 1829, Döbereiner suggested that elements could be arranged in groups of three i.e.
triads, in which the atomic weight of the middle element was nearly the mean of the atomic
weights of the other two. However, only a limited number of electrons could be grouped
into these traids.

Dobereiner's Triads of Elements

Triads Mean atomic weight
Lithium (7) Sodium(23) Potassium(39) (7+ 39)/2 = 23
(Li) (Na) (K)
Calcium (40) Strontium (87.5) Barium (137.5) (40 +137.5)/2 = 88.75
(Ca) (Sr) (Ba)
Phosphorus (31) Arsenic (76) Antimony (120) (31 + 120)/2 = 75.5
(P) (As) (Sb)
Sulphur (32) Selenium (79) Tellurium (127.5) (32+ 137.5)/2 = 79.25
(S) (Se) (Te)
Chlorine (35.5) Bromine (80) Iodine (127) (35.5 + 127)/2 = 81.25
(Cl) (Br) (I)
John A.R. Newlands, in 1865-1866, reported that if the elements were arranged in order
of their increasing atomic weights, the eighth element starting from a given one, possessed
properties similar to the first, like the eighth note in an octave of music. He called it the
law of octaves. It worked well for the lighter elements but failed when applied to heavier
elements. In 1869, J. Lothar Meyer in Germany and Dmitri I. Mendeleev in Russia, working
independently, gave a more detailed and accurate relationship among the elements.
Lother plotted atomic volumes (=atomic mass/volume) versus atomic weights of elements
and obtained a curve. He pointed out that, elements occupying similar positions in the
curve possessed similar properties.

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Mendeleev's Periodic Table

In March 1869, Mendeleev gave his famous scheme of the periodic classification of
elements. "It states that the properties of the elements are the periodic functions of their
atomic weights.
Mendeleev arranged all the elements known at that time in horizontal rows in order of
increasing atomic weights. He left some gaps in the table for undiscovered elements and
also predicted their properties. Eventually, when these elements were discovered, it was
amazing to find that they fitted correctly in the table. For example, as can be seen in
Mendeleev's original periodic table there are two gaps between zinc (group II) and arsenic
(group V). As these undiscovered elements were to follow aluminium and silicon,
Mendeleev named them eka-aluminium and eka-silicon. When these elements, now known
as gallium (eka-aluminium) and germanium (eka-silicon), were discovered, their
properties were agreed very well with those given by Mendeleev.

Mendeleev's prediction for eka-aluminium (Gallium)

Eka-aluminium Gallium (Ga)

Property (Ea) predicted in Currently
1871 by Mendeleev Reported in 1875
accepted

Atomic
68 69.9 69.72
mass/amu

Density, r/ /g
5.9 5.94 5.904
cm-2

Melting point,
Low 303.15 302.78
T/K

Solubility in Ea will dissolve slowly Ga dissolves slowly

Ga dissolves slowly in both
acid and in both acid and in both acid and
acid and alkali
alkali alkali alkali

Formula of Ga2O3 ((a and b

Ea2O3 Ga2O3
oxide forms)

Density of
6.44 ((a form) and
oxide r /g 5.5 -
5.883 (b form)
cm-2

Gallium forms
Reactions of Ea2(SO4)3 will form alums, e.g.
Gallium forms alums
sulphate alum (NH4)2SO.Ga
(SO).24HO

Ea2S3 will be Ga2S3 is

Preparation Ga2S3 is precipitated by H2S
precipitated by H2S precipitated by H2S
of Sulphide or (NH4)2S
or (NH4)2S or (NH4)2S

Properties of EaCl3 will be more GaCl3 is more volatile than GaCl3 is more
chloride volatile than ZnCl2 ZnCl2 volatile than ZnCl2

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Mendeleev's prediction for eka-silicon (Germanium)

Eka-silicon (Es) Germanium (Ge)

Property predicted in 1871 Reported in 1886
by Mendeleev currently accepted
by Bioshaudran
Atomic mass/ amu 72 72.32 72.59
Density, /g cm-3 5.5 5.47 5.35
Melting point, T/K High - 1220
Specific heat
0.3051 0.3177 0.3903
capacity, c/J g-1
Molar Volume, Vm/
13 13.22 13.5
cm3
Colour Dark grey Greyish white Greyish white
Valence 4 4 4
ES will be slightly Ge is dissolved by Ge is dissolved by
Reaction with acids attacked by acids neither HCl nor neither HCl nor NaOH,
and alkalis but will resist NaOH, but dissolved but dissolved by conc.
attack by alkalis by conc. NaOH NaOH
Boiling point of
tetraethyl 433 433 458-460
derivative, T/K
Density of the
4.7 4.7 4.2
dioxide, /g cm-3
Density of the
tetrachloride, /g cm- 1.9 1.887 1.844
3

Boiling point of the

373 359 357
tetrachloride, T/K

Modern Periodic Law and Present Form of Periodic Table

According to the modern periodic law, the properties of the elements and their compounds
are a periodic function of their atomic numbers. Thus, in the modern periodic table, atomic
number (which is equal to the nuclear charge) forms the basis of the classification of
elements.
Present Form of Periodic Table
There are several forms of the periodic table. The most popular version is the long form.
In that table, there are seven horizontal rows called periods. Each period starts with a new
principal quantum number, n, and the electrons are filled up in orbitals according to the
Aufbau principle. The first period has two elements, hydrogen (1s1), and helium (1s2), and
the first shell (K) is completed. The second period starts with n = 2 and has eight elements.
Starting with lithium (2s1), it ends with neon (2s2 2p6) and thus completes the second
shell (L). In the third period, shell M starts getting filled, (n=3), and also contains eight
elements. It starts with sodium (3s1) and completes at argon (3s2 3p6).

Long form of the periodic table of the elements with their atomic numbers and
ground state electronic configurations (according to the latest 1984 IUPAC
recommendation)

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In contrast to the second period, the outer shell is not completely filled in with elements
of the third period, and the orbitals of the 3d subshell remain vacant. Elements in which
the s subshell is filled are called s-block elements and those in which the p subshell is filled
are known as p-block elements.
In the fourth period, the N shell (n = 4) starts filling with potassium (4s1) and is completed
with krypton (4s24p6). It has 18 elements, i.e. ten more than in the third period. This is
because of the elements in which the filling up of electrons in the 3d orbitals takes place
after 4s orbital but before 4p orbitals:
21Sc 1s 2s 2p 3s 3p 3d 4s
2 2 6 2 6 1 2

22Ti 1s 2s 2p 3s 3p 3d 4s
2 2 6 2 6 2 2

.
.
.
.
.
.
30Zn 1s 2s 2p 3s 3p 3d 4s2
2 2 6 2 6 10

Elements whose d orbitals are filled are called d-block elements. In d-block elements of
the fourth period, the M shell is filled until it contains 18 electrons. Similarly, the fifth
period (n = 5) has 18 elements. It starts with rubidium (5s1) and ends with xenon (5s2
5p6). The sixth period (n = 6) contains 32 elements in which the electrons enter in 6s, 4f,
5d and 6p orbitals, in that order. It begins with two s elements (Cs and Ba) followed by
lanthanum (La) in which the d orbitals of the penultimate shell begin to be filled. But
immediately after this, we have 14 elements (58Ce to 71Lu) in which 4f orbitals are in the
process of getting filled. Then, the 5d orbitals are filled (from 72Hf to 80Hg) and finally, the
period ends with six p block elements (81Tl to 86Rn). The seventh period (n = 7) contains
two s block elements (87Fr and 88Ra), followed by a d block elements actinium (89Ac), and
14f block elements (90Th to 103Lr) and again ends with d block elements (Z = 104 to 107).
This is an incomplete period.
The vertical columns in the periodic table are called groups or families of elements.
According to the latest IUPAC (International Union of Pure and Applied Chemistry)
recommendation, the groups are numbered from 1 to 18.
Types of Elements
The elements can be classified into four types depending on their electronic
configurations (Table 5.4). Thus, we have:
1. Noble gases
2. Representative elements (s-and p-block elements)
3. Transition elements (d-block elements)
4. Inner transition elements (f-block elements)
Noble Gases
Noble gases constitute group 18 of the periodic table. Except for the first element of the
group, helium (which has 1s2 configuration) all other elements, namely neon, argon,
krypton, xenon and radon have ns2 np6 electronic configuration in the outermost shell.
Because of the stable arrangement of electrons in these elements, they exhibit a very low
chemical reactivity.
Representative Elements
Elements belonging to group 1 (alkali metals; Li ... Fr) with outermost electronic
configuration ns1 and those belonging to group 2 (alkaline earth metals; Be... Ra) with
outermost electronic configuration ns2 are placed in the s block. Elements of groups 13 to
17 (outermost electronic configuration varying from ns2 np1 to ns2 np5) belong to the p
block of the periodic table. The elements of s and p blocks are collectively called
representative elements.

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Noble gases are at the end of each period of the representative elements; these are also
grouped with representative elements. The chemistry of these elements depends on the
number of electrons in the valence shell (outermost shell). For groups 1 and 2, the group
number indicates the number of valence electrons. Subtracting 10 gives the number of
valence electrons for groups 13 to 17 from the group number.
Transition Elements
Elements belonging to groups 3 to 12 (in the middle of the periodic table) with an outer
electronic configuration (n - 1) d1-10 ns1-2 constitute the d block of the periodic table and
are called transition elements. In these elements, n is 4, 5 or 6 with the corresponding
filling of 3d, 4d or 5d orbitals. They are all metals and are characterized by variable
oxidation states, the formation of coloured ions and complexes.
Inner Transition Elements
At the bottom of the periodic table, there are two rows-one of lanthanides or lanthanide
series (z = 58 to 71) and the other of actinides or actinide series (Z = 90 to 107) containing
incomplete 4f and 5f orbitals respectively. They also have incomplete (n - 1) d orbitals and
are characterized by the outer electronic configuration (n - 2) f1-14 (n - 1) d0-1 ns2. As in
each of these series, an inner f electron is added to each element, the two series of
elements are called f-block elements or inner transition elements. Among themselves,
lanthanides and actinides show similar properties. All the elements of the two series are
metals.
Through this periodic classification, we can organize and systematize the study of elements
and their compounds. It is seen that the electronic configurations of elements are directly
or indirectly related to their physical as well as chemical properties. From this classification,
we can understand the cause of periodicity in properties and general trends in the
behaviour of elements.
Periodic Trends in Properties of Elements
According to the modern periodic law, properties of elements are repeated at certain
intervals or periods when the elements are arranged in the order of increasing atomic
number. In a period, the number of valence electrons increases with an increase in atomic
number. There is a repetition of similar electronic configurations in the outermost shells in
a group. Therefore, in a group, properties are similar. In the long form of the periodic
table, elements with the same number of outer electrons are in the same group. Moreover,
there is a gradation in the properties of elements in a group. For example, all members of
group 1 have one electron in the outermost shell. Properties of these elements are similar
to each other. Similarly, F, Cl, Br and I have seven electrons in their outermost shells.
They are chemically alike. Members of group 18 have similar electronic configurations with
8 electrons in their outermost shell (except He). All noble gases have similar properties.
We shall now discuss periodic trends in some of the properties of elements.
Density, Melting Point and Boiling Point
The properties like density, melting point and boiling point also show gradation, though
not very regular, in a group of the periodic table. In a period of representative elements,
density increases across a period and reaches a maximum value somewhere in the middle.
Melting points and boiling points increase, attain maximum values in the middle,
thereafter, and begin to decline.
Ionization Energy
First ionization energy is the energy required to remove an electron from an isolated,
neutral gaseous atom of an element resulting in the formation of a positive ion.
M(g) + Energy ------> M+(g) + e-
For example, Li(g) + 520 kJ mol-1 ------> Li+(g) + e-
Thus, the first ionization energy of lithium is 520 kJ mol-1. If another electron is to be
removed, much more energy (called second ionization energy) will be needed.
Li+ + 7297 kJ mol-1 -------> Li2+ + e-

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This is because of the fact that it is more difficult to remove an electron if the atom already
possesses a positive charge. Thus, the successive values of the ionization energy of an
element will show an increasing trend.
The below figure shows a plot of first ionization energies of some elements against their
respective atomic numbers. Certain trends are quite evident from the plot:
1. Noble gases occupy peaks because of their extremely stable configurations.
2. Alkali metals possess the lowest values of ionization energy showing thereby that
they are highly reactive.

3. In general, the values increase across a period (e.g. Li to Ne). This is due to the
increasing nuclear charge and the electrons are more strongly held by the attractive
force of the nucleus.
4. Within a group (e.g. Li to Cs), ionization energies become progressively smaller as
we move down the column. This is because of the fact that the outer electron,
which is being removed lies farther from the nucleus and thus it becomes easier to
pull it out.
General trends in ionization energies in relation to the periodic table may be depicted as
shown in the figure. Ionization energy is either determined by means of a discharge tube
method or by the spectroscopic method
Electron Affinity
Electron affinity is energy released when an electron is added to an isolated atom in the
gaseous state. For example,
X(g) + e- ------> X-(g) + Energy
(where X = F, energy 322 kJ mol; X = Cl, energy = 349 kJ mol; X = Br, energy = 324 kJ
mol; X = I, energy = 295 kJ mol).
Halogens (elements of group 17) can take up an electron to acquire the stable noble gas
configuration. Their values for electron affinity are thus very high. As we move across a
period, electron affinity usually increases, and while going down a group it decreases. The
electron affinity of an element is generally determined indirectly from thermodynamic
data.
Although electron affinities of all the elements have not been determined, the following
trends in electron affinities of some elements in the periodic table are evident.
Electron affinities generally decrease in moving down the group. This is expected on
account of the increase in the size of the atom on moving down the group. Due to an
increase in the size of atoms, the effective nuclear attraction for electrons decreases. As
a result, there are fewer tendencies to attract additional electrons with an increase in
atomic number.

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In the figure electron affinities of halogens are plotted against their atomic numbers. It
may be noted that contrary to expectation, the electron affinity of fluorine is lower than
that of chlorine. This is because the fluorine atom has a very compact electronic shell due
to its small size. The compactness of the fluorine shell results in electron-electron repulsion
whenever an electron is introduced into its 2p shell. This is why its electron affinity is less
than expected. In the chlorine atom, the 3p orbitals are not as compact as the 2p orbitals
in fluorine atom. The chlorine atom, because of weaker electron-electron repulsion, more
readily accepts the incoming electron. The electron affinity of chlorine is, therefore, higher
than that of fluorine.
In the case of noble gases, the outer s and p orbitals are completely filled. No more
electrons can be accommodated in these orbitals. Noble gases, therefore, show no
tendency to accept electrons. Their electron affinities are zero.
Electron affinities generally increase as we move across a period from left to right. This is
due to the increase in the nuclear charge, which results in greater attraction for electrons.
In the second period, for example, the electron affinity has a maximum value for fluorine.
The second electron affinity refers to a process in which an electron is added to a negative
ion. For example
O-(g) + e- -----> O2-(g)
Since a negative ion (O-) and electron repel each other, energy is required and not released
by the process. All second affinities are thus negative.

Electronegativity
Electronegativity is the tendency of an atom to attract the shared pair of electrons in a
chemical bond towards itself. It is, thus, a measure of the ability of an atom in a molecule
to attract electrons. In general, electronegativity increases from left to right across any
period and from bottom to top in any group of the periodic table. The most highly
electronegative elements (Fluorine) are found in the upper right corner of the periodic
table (ignoring the noble gases.) The least electronegative elements (Caesium) are found
in the lower left corner of the table.
When two elements of widely different electronegativities combine, an ionic compound
results. The electronegativity values of the non-metals do not differ much. The bonds
formed between non-metals are essentially covalent with some polar character. The
electronegativity difference gives an indication of the degree of polarity of the covalent
bonds. If the difference is zero or very small, an essentially non-polar bond with equal or
almost equal sharing of electrons can be assumed. The larger the electronegativity
difference, the more polar the covalent bond is. The bond is polarized in the direction of
the atom with larger electronegativity.
Atomic radii: The distance between the nucleus and the outermost shell containing the
electron cloud is known as the atomic radius.

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In general, the atomic radius decreases while going across a period in the periodic table
Figure. This is because of the increasing nuclear charge while the electrons are added to
the same shell. On the other hand, the atomic radius increases as we move from top to
bottom in a group of the periodic table Figure. This happens because of the increasing
number of shells. Though the nuclear charge also increases, the effect of adding a new
shell is very large and overcomes the effect of increased nuclear charge.
Variation of the atomic radius with an atomic number for alkali metals (group 1) and
halogens (group 17).
Ionic radii: It is defined as the distance between the nucleus and the point upto which
the element has influence over its electron cloud. Generally, the cationic radius is smaller
than its neutral atom, whereas the anionic radius is larger. An important point to
remember here is ions which are having same no. of electrons are called isoelectronic
species ( eg. S2- K+ Ca2+Cl-).
Valency
From the position of an element in a particular group of the periodic table, one can infer
its valency. The valency of a representative element is usually given by the number of
electrons in the outermost orbital and /or equal to eight minus the number of outermost
electrons. For example, alkali metals (group 1) having one outermost electron are
monovalent and alkali earth metals (group 2) having two outermost electrons are bivalent.
Halogens (group 17) with seven outermost electrons are monovalent (eight minus number
of outermost electrons). There are, however, some exceptions to this rule.

Periodic Trends in Valence of Elements as shown by the Formulas of Their Compounds.

The first element of each of the groups namely lithium, beryllium, boron differs in many
respects from the other members of their respective group. For example behaviour of
lithium is more similar to that of magnesium. This kind of similarity in properties of certain
elements which are placed diagonally across in the periodic table is known as diagonal
relationship. Diagonal relationships occur because of the directions in the trends of various
properties as you move across or down the periodic table.

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Many of the chemical properties of an element are related to the size of the atom.

The anomalous behaviour is attributed to their small size, large charge/ radius ratio and
high electronegativity of the elements.
Summary
Mendeleev's periodic law is based on atomic masses of the elements. The modern periodic
law proposed by Moslay recognizes the properties of the elements as the periodic functions
of their atomic numbers. Elements are classified into s,p(Representative), d(transition)
and f (inner transition) on the basis of the modern periodic table. Elements following
uranium are called trans uranic elements. Ionisation enthalpy, electron gain enthalpy,
electronegativity are some of the periodic properties which regularly decreases down the
group and increases along the period. Atomic and ionic radii are the periodic properties
which increase down the group and decreases along the period. According to the modern
periodic table, elements on the extreme left form basic oxides, those at the right forms
acidic oxides and amphoteric or neutral oxides are formed by the elements in the middle.

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Section Question
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Total 100

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• The total duration of CBT will be 90 minutes.
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