Chapter 5 - Periodic Classification of Elements

Introduction
Initially scientists had classified elements into metal and non-metals. However, some
elements possessed properties which could neither be classified as metals nor non-metals
called metalloids. This classification was found to be insufficient for scientific study. Later on,
a number of chemists attempted to make a rational and systematic classification of the
physical and chemical properties of elements and tabulate the results in the form of a table.
Periodic table – The table giving the arrangement of the known elements according to their
properties so that similar elements fall within the same vertical column and dissimilar
elements are separated.
Dobereiner's Triads
In the year 1829, Johann Wolfgang Dobereiner, a German scientist, was the first to classify
elements into groups based on John Dalton's assertions. He grouped the elements with
similar chemical properties into clusters of three called 'Triads'. The distinctive feature of a
triad was the atomic mass of the middle element. When elements were arranged in order of
their increasing atomic mass, the atomic mass of the middle element was approximately
the arithmetic mean of the other two elements of the triad.

Defects of Triad Classification

• It was possible that quite dissimilar elements could be grouped into triads.
• Dobereiner could only classify 3 triads successfully (highlighted in the table). Since he failed
to arrange the then known elements in the form of triads his attempt at classification was not
very successful.
Newlands' Law of Octaves
Newland arranged many of the known elements in the increasing order of their atomic
masses. He started with the element having the lowest atomic mass (hydrogen) and ended
at thorium which was the 56th element. He arranged many of the known elements in the
increasing order of their atomic masses. It was noticed that the eighth element was similar in
properties to the first element, just like the eighth note in music - Western as well as Indian.
Newland stated his law of octaves thus 'when elements are arranged in increasing order of
their atomic mass, the eighth element resembles the first in physical and chemical
properties just like the eighth note on a musical scale resembles the first note'. This gave
rise to a new term called 'periodicity' which signifies the recurrence of characteristic
properties of elements arranged in a table, at regular intervals of a period.
Achievements of the Law of Octaves
1. The law of octaves was the first logical attempt to classify elements on the basis of atomic
weights.
2. Periodicity of elements was recognized for the first time.
Defects of Law of Octaves
1. This law could be best applied, only up to the element calcium.
2. Newly discovered elements could not fit into the octave structure.
3. The feature of resemblance of the 8th element when arranged in increasing order of their
atomic mass was not successful with heavier elements.
Mendeleev's Periodic Table
In 1869, Mendeleev classified the then known 56 elements on the basis of their physical and
chemical properties in the increasing order of the atomic masses, in the form of a table.
Mendeleev had observed that properties of the elements orderly recur in a cyclic fashion. He
found that the elements with similar properties recur at regular intervals when the elements
are arranged in the order of their increasing atomic masses. He concluded that 'the physical
and chemical properties of the elements are periodic functions of their atomic masses'. This
came to be known as the law of chemical periodicity and stated: that the physical and
chemical properties of elements are periodic function of their atomic weights. Based on this
law all the known elements were arranged in the form of a table called the 'Periodic Table'.
Mendeleev's periodic table contains eight vertical columns of elements called 'groups' and
seven horizontal rows called 'periods'. Each group has two sub-groups A and B. The
properties of elements of a sub- group resemble each other more markedly than the
properties of those between the elements of the two sub-groups.
Achievements of Mendeleev's Periodic Table
Mendeleev's periodic table was one of the greatest achievements in chemistry with some of
its important contributions as follows:
Systematic Study of Elements
Mendeleev's Periodic table simplified the study of elements. As the arrangements of
elements showing similar properties were classified into groups, it was very useful in studying
and remembering the properties of a large number of elements in a systematic way.
Prediction of New Elements
Based on the positions in the periodic table, Mendeleev could predict the properties of some
undiscovered elements. He left three blanks for elements that were not discovered at that
time. He was able to predict the properties of these unknown elements more or less
accurately. He named them eka-boron, eka-aluminium and eka-silicon. He named them so,
as they were just below boron, aluminium and silicon in the respective sub-groups. Eka-boron
was later named as scandium, eka-aluminium as gallium and eka-silicon as germanium.
Correction of Atomic Masses
Mendeleev's periodic table helped in correcting the atomic masses of some of the elements,
based on their positions in the periodic table. For example, atomic mass of beryllium was
corrected from 13.5 to 9.0. Atomic masses of indium, gold and platinum were also corrected.
Limitations of Mendeleev's Classification
Position of Hydrogen
The position of hydrogen was not correctly defined. It was placed in Group I although its
properties resembled both the Group I elements (the alkali metals) and the group VII
elements (the halogens).
Grouping of Some Elements
In some cases, Mendeleev placed elements according to their similarities in properties and
not in increasing order of their atomic masses, while some dissimilar elements were grouped
together. Thus, the position of these elements was not justified. For example, cobalt (at. mass
58.9) was placed before nickel (at. mass 58.6); copper and mercury are similar in their
properties but were placed separately. Copper was placed in group I although it did not
resemble the elements of this group.
Anomalous Pair
In certain pairs of elements like, Ar (40) and K (39); Co (58.9) and Ni (58.6); Te (127.6) and I
(126.9) the arrangement was not justified. For example, argon was placed before potassium
whereas its atomic mass is more than potassium.
Isotopes
Isotopes are atoms of the same element having different atomic mass but same atomic
number. For e.g., there are three isotopes of hydrogen with atomic mass 1, 2, and 3.
According to Mendeleev's periodic table these should be placed at three separate places.
However, isotopes have not been given separate places in the periodic table.
Lanthanides and Actinides
Fourteen elements that follow lanthanum called lanthanides and fourteen elements following
actinium called actinides were not given proper places in Mendeleev's periodic table.
Long Form of the Periodic Table or Modern Periodic Table
Modern Periodic Law
The modern periodic law states that "the physical and chemical properties of the elements
are periodic function of their atomic numbers". Thus, when the elements were arranged in
the order of their increasing atomic numbers, the elements of similar properties recur at
regular intervals.
Cause of Periodicity of Elements
The modern periodic table is based on the electronic configuration of the elements. The
properties of an element are determined largely by the electrons in its outermost or valence
shell. Valence electrons interact with other atoms and take part in all chemical reactions,
while inner shell electrons have little influence on the properties of elements. When elements
are placed in the order of their increasing atomic number, the elements having the same
number of valence shell electrons is repeated in such a way, so as to fall under the same
group. Since, the electronic configuration of the valence shell electrons is same they show
similar properties. Members of the same group have similar electronic configuration of the
valence shell and thus show same valency.
Magic Numbers – When the elements are arranged in the order of increasing atomic number,
it is observed that the elements with similar properties recur after intervals of either 2 or 8 or
18 or 32 elements. These numbers (2,8,18,32) are called magic numbers.
The Modern Periodic Table - It is based on modern periodic law.
Structural Features of the Modern Periodic Table - This table consists of horizontal rows
called as 'periods' and vertical columns called as 'groups'. There are seven periods in the
modern periodic table. The first three periods are called short periods while the other three
periods are called long periods. There are 18 groups in the long form of the periodic table and
they are numbered from 1 to 18 in the IUPAC system. In the old system of naming they are
numbered as I to VIII with A and B groups. This convention is followed in many places.
The number of elements in these periods is based on the way electrons are filled into various
shells. The maximum number of electrons that can be accommodated in a shell depends on
the formula 2n2 where 'n' is the number of the given shell from the nucleus. For example, K
Shell - 2 x (1)2 = 2, 1st period = 2 elements. L Shell - 2 x (2)2 = 8, 2nd period = 8 elements. The
position of an element in the Periodic table tells us about its chemical reactivity.
Position of Elements in the Modern Periodic Table
Types of Elements On the basis of electronic configuration, the elements of the periodic table
are classified into: • Noble gases • Normal elements • Transition elements • Inner-transition
elements • Alkali metals • Halogens
Position of an Element
In a period, the number of valence shell remains the same for all elements. However, the
number of electrons in the valence shell increases from left to right. The position of an
element in the periodic table is determined by its electronic configuration e.g. electronic
configuration of sodium is 2, 8, 1 i.e., it has three shells and one electron in the outermost
shell. Hence, it is placed in period number 3 and group number 1. However, in the case of
transition elements this pattern is not followed.
Merits of the Long Form of the Periodic Table
• This classification is based on the most fundamental property of the
• Elements - the atomic number, so it is more accurate.
• With the atomic number as the basis of this classification, the position of isotopes in one
place is justified.
• The electronic configuration determines the properties of the elements. The position of
elements governed by this feature is useful in studying the properties of elements.
• The position of the elements, which were misfit on the basis of atomic mass is now justified
on the basis of atomic number.
• The lanthanides and actinides have been placed separately due to their properties being
different from other groups.
• The whole table is easy to remember and reproduce in terms of electronic configuration
and properties of the elements.
Demerits of the Long Form of the Periodic Table
Although the long form of the period table has been able to help in systematic studying the
elements to a great extent, it has some minor defects:

• Hydrogen resembles both the alkali metals and halogens. But it has been placed with the
alkalis and with the halogens.

• The lanthanides and actinides have not been placed in the main body of the table.
Periodic Properties
1. Valency- Valency is the combining capacity of an element. For metals it is the number of
electrons lost during chemical combination while for non-metals it is the number of electrons
gained during chemical combination. When metals combine with hydrogen, they show a
valency corresponding to group number, & non-metals show a valency equal to (8 – group
number). Thus, valency of an element with respect to hydrogen increases from 1 to 4 and
then falls from 4 to 1 across a period.
2. Atomic Size and Atomic Radius –
Atomic Radius – The distance between the centre of the nucleus and the outermost shell of
an isolated atom. Atomic radii increases down the group and decreases across the period.
3. Ionisation Energy - The minimum energy needed to remove the outermost electron from
the neutral atom in the gaseous state. It increases across a period in general and decreases
down the group. Factors affecting ionization Energy 1. Size of the atom 2. Magnitude of
Nuclear Charge 3. Screening Effect of the inner electrons 4. Electronic Configuration
4. Electron Affinity - Electron affinity is the ability of an atom to hold an additional electron. If the
atom has more tendency to accept an electron then the energy released will be large and
consequently the electron affinity will be high. Electron affinities can be positive or negative. It is
taken as positive when an electron is added to an atom. It is expressed as electron volts per atom
(eVper atom) or kilo joules per mole.
In the case of halogens, all the elements have a high electron affinity, as they need one
electron to complete the octet of their outermost shell.
Electron affinity increases from left to right across the period because of increase in nuclear
charge and decrease in atomic size. This causes the incoming electron to experience a greater
pull of the nucleus thus giving a higher electron affinity. • Electron affinity decreases down
the group because the number of shells increases i.e., the atomic size increases and the
effective nuclear charge decreases. • The electron affinity of completely filled atoms is
almost zero. An atom does not accept an electron in its outermost shell if it already has a
stable configuration i.e. a duplet or octet, as in the case of inert gases.
5. Electronegativity - Electronegativity is the tendency of an atom to attract electrons towards
itself in a molecule of a compound. The value of electronegativity of an element describes the
ability of its atom to compete for electrons with the other atom to which it is bonded.
Electronegativity is however not the property of an isolated atom. Electronegativity increases
from left to right in each period ending at group 17. In the 3rd period, electronegativity
increases from sodium to chlorine i.e., chlorine can accept electrons most easily in that period
followed backwards by sulphur, phosphorus, silicon, aluminium, magnesium and sodium. All
the atoms of the above mentioned elements have three shells but chlorine has the smallest
atomic radii. Hence chlorine experiences more positive charge from the nucleus than all other
atoms in that period. So, if one electron is available, chlorine can attract it most easily.
6. Metallic and Non-metallic Character - The tendency of an element to lose electrons and
form positive ions (cations) is called electropositive or metallic character. For example, alkali
metals are the most electropositive elements. "The tendency of an element to accept
electrons to form an anion is called its non-metallic or electronegative character." For
example, chlorine, oxygen and phosphorous show greater electronegative or non-metallic
character. In each period, metallic character of elements decreases as we move to the right.
Elements to the left of the periodic table have a pronounced metallic character while those
to the right have a non-metallic character. Conversely, non-metallic character increases from
left to right. The elements to the left of the periodic table have a tendency of losing
electrons easily as compared to those to the right. As we move from left to right of the
period, the electrons of the outer shell experience greater pull of the nucleus. This greater
force of attraction is because the nuclear charge increases and the size of the atom
decreases from left to right. Thus, electrons of the elements to the right of the table do not
lose electrons easily so are non-metallic in nature.