Ch – 3
Classification of Elements and periodicity in properties
➢ Significance of classification of elements:-
1. Classification helps us to analyze and understand the properties of the
elements and their compounds more systematically and orderly.
2. Classification helps us to predict the properties of the elements and their
compounds based on their positions in the Periodic Table, and vice versa.
3. It becomes easier to study, understand, compare and contrast the related
properties among the elements and their compounds from different groups.
➢ Brief history of the development of periodic table:-
1. Dobereiner’s Triads
Dobereiner defined triads as groups of three elements in 1829.The atomic
weight of the middle element was found to be approximately equal to the
arithmetic mean of the other two elements when the elements in a trio were
ordered in order of increasing atomic weights.
Limitations of Dobereiner’s Triads
The triads given by Dobereiner were helpful in grouping some elements with
similar characteristics together, but he could not arrange all the elements
known at that time into triads.
2. Newlands’ Law of Octaves
John Newlands proposed the law of octaves by stating that when elements are
arranged in order of increasing atomic masses, every eighth element has
properties similar to the first. Newlands called it law of octaves because
similar relationship exists in the musical notes also.
Limitations of Newlands’ Law of Octaves
(i) This classification was successful only up to the element calcium. After that,
every eighth element did not possess the same properties as the element
lying above it in the same group.
(ii) When noble gas elements were discovered at a later stage, their inclusion in
the table disturbed the entire arrangement.
3. Lothar Meyer’s Curve
Meyer presented the classification of elements in the form of a curve
between atomic volume and atomic masses and state that the properties of
the elements are the periodic functions of their atomic volumes.
(atomic volume = molecular mass / density)
He concluded that the elements with similar properties occupy similar
position in the curve.
4. Mendeleev’s Periodic Table
Mendeleev’s Periodic Table is based upon Mendeleev’s periodic law which
states ‘‘The physical and chemical properties of the elements are a periodic
function of their atomic masses.”
• At the time of Mendeleev, only 63 elements were known.This Periodic
Table is divided into seven horizontal rows (periods) and eight vertical
columns (groups).
• He left space for the elements yet to be discovered. e.g., he left spaces for Ga
and Ge and named these elements as Eka-aluminium (Ga) and Eka-silicon
(Ge) respectively.
• Atomic mass correction of doubtful elements on the basis of their expected
positions and properties.
Limitations in the Mendeleev’s Periodic Table
• Position of hydrogen, isotopes, lanthanoids and actinoids were not placed in
the main Periodic Table.
• Anomalous positions of some elements, without any proper justification
some element with higher atomic mass precedes the element with lower
atomic mass. For example, Al (atomic weight = 39.9) precedes K (atomic
weight = 39.1) and similarly Co (atomic weight. = 58.9) has been placed
ahead of Ni (atomic weight = 58.7).
5. Modern Periodic Table
Moseley modified Mendeleev’s periodic law. He stated “Physical and
chemical properties of elements are the periodic function of their atomic
numbers.” It is known as modern periodic law and modern periodic table.
• Long form of Periodic Table is called Bohr’s Periodic Table. There are 18
groups and seven periods in this Periodic Table.
• When the elements were arranged in increasing order of atomic numbers, it
was observed that the properties of elements were repeated after certain
regular intervals 01 2, 8, 8, 18, 18 and 32.
• These numbers are called magic numbers and cause of periodicity in
properties due to repetition of similar electronic configuration.
• Anomalous behaviour of the first element of a group differs from the rest
of the elements of its group.
• This is due to (i) small size (ii) high electronegativity and (iii) unavailability
of d - orbitals for bonding. Anomalous behaviour is observed among the
second row elements (i.e., Li to F).
• The position of hydrogen still remains uncertain.
• The inner-transition elements do not find a place in the main body of the
table, hence placed separately.
• Diagonal Relationship is a diagonal link between adjacent elements in the
second and third periods of the periodic table.
Cause of diagonal relationship is due to the similarity in atomic or ionic
size, electronegativity and polarising power. In moving along the period
from left to right electronegativity increases while in descending a group
electropositivity of the element increases. These two effects tend to cancel
each other in moving diagonally from top left to bottom right. Therefore,
diagonal elements show similarity in properties.
➢ Division of modern periodic table:-
The Periodic Table is divided into four main blocks (s, p, d and n depending
upon the subshell to which the valence electron enters into.
(a) s-block elements includes Ist and IInd group elements belong to this block
and the last electron enters in s-subshell.
General electronic configuration is ns1-2.
(b) p-block elements includes Group 13th to 18th belong to this block in which
last electron enters in p-orbital.
General electronic configuration is ns2 np1-6.
This is the only block which contains metal, non-metal and metalloids.
Examples of metalloids are B, Si, Ge, As, Sb, Te and At.
The elements of s-and p-block elements are collectively called
representative elements.
(c) d-block elements includes Group 3rd to 12th belong to this block, in which
last electron enters in d-orbital. They have inner incomplete shell known as
transition elements.
General electronic configuration is (n – 1)d1-10 ns1-2
d-block elements are generally coloured, paramagnetic and show variable
valency.
(d) f-block elements They constitute two series 4f (lanthanoids) and 5f
(actinides) in which last electron is in 4f and 5f subshell.
General electronic configuration is (n – 2)f 1-14 (n – 1)d0-1 ns2.
The f-block elements are also called as inner-transition elements.
➢ Predicting the Position of an Element in the Periodic Table:-
1. First of all write the complete electronic configuration.
2. The principle quantum number of the valence shell represents the period of
the element.
3. The subshell in which the last electron is filled corresponds to the block of
the element.
4. Group of the element is predicted from the electrons present in the
outermost (n) or penultimate (n -1) shell as follows:
• For s-block elements: group number = number of ns-electrons
• For p-block elements: group number = 10 + (ns + np) electrons
• For d-block elements: group number = (n -1) d + ns electrons
• For f-block elements: group number is 3.
➢ Properties of an element:-
The properties which are directly or indirectly related to their electronic
configuration and show gradual change when we move from left to right in a
period or from top to bottom in a group are called periodic properties.
1. Atomic Radius
We can't measure an isolated atom's exact size, so depending on the atoms
surroundings, multiple forms of atomic radius can be utilised, such as covalent
radius, van der Waals' radius, and metallic radius.
• Covalent Radius
The covalent radius of a molecule is half the distance between the nuclei
of two identical atoms linked by a single covalent bond.
Covalent radius for A−A is rcovalent = dA-A/2
If covalent bond is formed between two different elements then
dA – B = rA+ rB − 0.09(χA−χB)
Where, χA and χB are electronegativities of A and B.
• Vander Waals Radius
In the solid state, it is half of the internuclear distance between adjacent
atoms of two neighbouring molecules.
rvander waal = dA-A/2
• Metallic Radius
In the metallic crystal lattice, it is half the distance between the nuclei of
two neighbouring metal atoms.
Metallic radius for A−A is d = rA + rA and rmetallic = d/2
Hence, overall increasing order of atomic radius is as follows:-
rcovalent < rmetallic < rvander waal
➢ Periodic trends in properties of elements:-
• Atomic Radii and Ionic radii
(a) Variation along a Period:-
Because the electrons are added in the same valence shell throughout
the period as we move from left to right, the effective nuclear charge
increases as the atomic number grows which increases the attraction of
electrons to the nucleus. Hence, atomic radii decrease.
(b) Variation along with a Group:-
Because as the atomic number increases, more number of shells are
added due to which the inner electrons shield the valence electrons from
the effective nuclear charge. The effect of the greater shielding effect
outweighs the increase in nuclear charge hence atomic radius increases.
(c) In case of cations, element ionic radii follow the same pattern as atomic
radii because it has fewer electrons than its parent atom, a cation is
smaller, but its nuclear charge remains the same. Hence, ionic radii
decrease.
(d) In case of anions, the addition of one or more electrons causes
enhanced electron repulsion and a decrease in effective nuclear charge,
the size of an anion will be bigger than that of the parent atom. Hence,
ionic radii increases.
(e) Isoelectronic Species:-
Isoelectronic species have the same number of electrons as each other.
for e.g., O2-, F- , Na+ and Mg2+, have the same number of electrons (10).
Because the electrons are more attracted to the nucleus, the cation with
the higher positive charge will have a smaller radius. The radius of an
anion with a higher negative charge will be larger. The net repulsion of
the electrons will outweigh the nuclear charge in this situation, causing
the ion to expand in size.
Order of Atomic radii is: Mg2+ < Na+ < F- < O2-
• Valency
Valency is the combining capacity of an atom. If number of valence
electrons ≤ 4, valency is equal to valence electrons and if number of
valence electrons ≥ 4, valency is equal to 8 – valence electrons.
(a) On moving left to right across a period in the periodic table, initially
valency increases then starts decreasing.
(b) On moving in a group from top to bottom, periodic trend is constant i.e.
there is no change in valency, elements of the same groups show same
valency.
• Electronegativity
It is a measure of the ability of an atom in a chemical compound to
attract shared electrons to itself is called electronegativity.
(a) Across a Period, electronegativity increases from left to right
because the effective nuclear charge increases and the atomic size
decreases. Therefore, the tendency of nucleus to attract shared pairs of
electrons increases, hence electronegativity increases.
(b) Down the Group, electronegativity decreases from top to bottom
because atomic size increases and the effective nuclear charge decreases.
Therefore, the tendency of nucleus to attract shared pairs of electrons
decreases, hence electronegativity decreases.
• Ionization Enthalpy
It is the energy required to remove an electron from an isolated gaseous
atom in its ground state. The unit of ionization enthalpy is kJ mol-1.
M (g) + I.E. → M+ (g) + e−
(a) Along a period, ionization enthalpies of the elements increase in moving
across from left to the right, because the nuclear charge increases and the
atomic size decreases.
(b) Down the group, ionization enthalpies of the elements decrease on
moving from top to the bottom because there is an increase in number of
main energy shells (n) in moving from one element to the other as well
as an increase in the magnitude of the shielding effect due to the gradual
increase in the number of inner electrons.
Decreasing order of I.E. are as follows: I.E.3 > I.E.2 > I.E.1
• Electron Gain Enthalpy
It is the energy released when an electron is added to an isolated gaseous
atom so as to convert it into a negative ion.
(a) The electron gain enthalpy for halogens is highly negative because they
acquire nearest noble gas configuration by accepting an extra electron.
(b) Noble gases have large positive electron gain enthalpies because the extra
electron has to be placed in the next higher principal quantum energy
level thereby producing highly unstable electronic configuration.
(c) On moving from left to right across a period, the atomic size of elements
decreases and the effective nuclear charge increases. Thus, the force of
attraction between the nucleus and added electrons increases. Hence,
electron gain enthalpy becomes more negative.
(d) As we go down the group, both the atomic size and nuclear charge
increase, but the effect of atomic size is more prominent than that of
nuclear charge. Hence, the force of attraction between the nucleus and
added electron decreases and thus enthalpy becomes less negative.
