Genesis of Periodic Classification Dobereiner’s Triads
In 1829, Dobereiner arranged certain elements with similar properties in groups of three in such a way
that the atomic mass of the middle element was nearly the same as the average atomic masses of the
first and the third elements.
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.
Mendeleev’s Periodic Table
Mendeleev’s Periodic Law: The physical and chemical properties of the elements are a periodic
function of their atomic masses.
Mendeleev arranged the elements known at that time in order of increasing atomic masses
and this arrangement was called periodic table.
Modern Periodic Law
Physical and chemical properties of the elements are the periodic function of their atomic numbers.
• Present Form of the Periodic Table (Long form of Periodic Table)
The long form of periodic table, also called Modem Periodic Table, is based on Modern periodic law. In
this table, the elements have been arranged in order of increasing atomic numbers. There are 18 vertical
groups and 7 horizontal periods.
There are 4 blocks in periodic table
S block elements (Group 1and 2)
General electronic configuration: ns1-2
Group 1 elements are called Alkali metals and group 2 are Alkaline earth metals.
p-Block Elements(Group 13-18)
The elements of s and p block collectively are called representative elements.
General electronic configuration: ns2np1-6
d – block elements (Group 3-12)
Also called transition elements
General electronic configuration
(n -1) d1-10 ns0-2
f-block elements (lanthanides and actinides)
Also called rare earths elements or inner transition elements.
The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids Ce (Z = 58) – Lu (Z
= 71) and ActinoidsTh (Z = 90) – Lr (Z = 103).
General electronic configuration: (n – 2) f1-14 (n -1) d0-1 ns2
Periodic Trends in Properties of Elements
Trends in Physical Properties
Atomic Radii: It is defined as the distance from the centre of the nucleus to the outermost shell
containing the electrons. Depending upon whether an element is a non-metal or a metal, three different
types of atomic radii are used. These are:
(a) Covalent radius (b) Ionic Radius (c) van der Waals radius (d) Metallic radius.
Variation of Atomic Radius in the Periodic Table
Variation in a Period: Along a period, the atomic radii of the elements generally decreases from left to
right because nuclear charge increases and nucleus pull electrons towards itself resulting decrease in
atomic radii.(exception noble gases)
Variation in a group: The atomic radii of the elements in every group of the periodic table increases as
we move downwards as the number of shells increase which outweigh the effect of increased nuclear
charge.
Ionic Radius
The ionic radii can be estimated by measuring the distances between cations and anions in ionic crystals.
In general, the ionic radii of elements exhibit the same trend as the atomic radii.
Cation: The removal of an electron from an atom results in the formation of a cation. The radius of
cation is always smaller than that of the atom.
Anion: Gain of an electron leads to an anion. The radius of the anion is always larger than that ‘ of the
atom.
Isoelectronic Species: Some atoms and ions which contain the same number of electrons, we call them
isoelectronic species. For example, O2-, F–, Na+ and Mg2+ have the same number of electrons (10). Their
radii would be different because of their different nuclear charges.
Screening effect:
The screening effect or shielding effect is the phenomenon of the reduction of the force of attraction
of the nucleus on the outermost valence electrons due to the presence of the inner shell electrons.
The outermost electrons experience attraction force from the nucleus and repulsion from the inner
shell electrons.
It can also be said as the shielding effect is the reduction in the nuclear charge on the outermost
electron cloud.
The order of screening effect in the shells is s>p>d>f.
Ionization Enthalpy
It is the energy required to remove an electron from an isolated gaseous atom in its ground state.
M (g) + I.E ——->M+ (g) + e–
The unit of ionization enthalpy is kJ mol-1 and the unit of ionization potential is electron volt per atom.
In each period, alkali metals show lowest first ionisationenthalpy. Caesium has the minimum value.
.Successive Ionization Enthalpies
If a gaseous atom is to lose more than one electron, they can be removed one after the other i.e., in
succession and not simultaneously. This is known as successive ionization enthalpy (or potential).
Variation of Ionization Ethalpy in a Group
The ionization enthalpies of the elements decrease on moving from top to the bottom in any group.
The decrease in ionization enthalpies down any group is because of the following factors.
(i) There is an increase in the number of the main energy shells (n) in moving from one element to the
other.
(ii) There is also an increase in the magnitude of the screening effect due to the gradual increase in the
number of inner electrons.
Exceptions:
In second period, first ionisation energy of Be is higher than B and first ionisation energy of N is higher
than O. Similarly, in third period, the first ionisation energy of Mg is higher than Al and first ionisation
energy of P is higher than S. This is due to high stability of fully filled orbitals in Be and Mg and high
stability of half filled orbitals in N and P.
An irregular trend in the values of first ionition energyis observed in group 13. The values of Al and Ga
are which almost same. The reason is that Ga comes after ten itself elements of first transition series
(where 3d-shell is Fore gradually filled) which makes Ga smaller than it would otherwise. It is responsible
for abnormal ionisation energy.
Electron Gain Enthalpy
The electron gain enthalpy is the energy change that occurs for the process of adding an electron to a
gaseous isolated atom to convert it into a negative ion, i.e., to form a monovalent anion/It is denoted by
∆H or E. It can be positive or negative.
The magnitude of electron gain enthalpy depends on a number of factors such as:
(i) Size of the atom: Smaller the size of the atom, stronger is the attraction for the added electron
towards nucleus. Thus, smaller the size of atom, greater is the electron gain enthalpy.E
(ii) Nuclear charge: Greater the nuclear charge, stronger is the attraction for the added electron towards
nucleus. Thus,electron gain enthalpy increases as nuclear charge increases.
(iii) Electronic configuration: The elements having stable configuration (half filled or fully filled valence
subshells) have very little or no tendency to accept additional electron; hence, electron gain enthalpies
are low or zero in these cases.
For few elements, such as the noble gases, the electron gain enthalpy has a positive value, meaning that
the anion is higher in energy than the isolated atom and electron. In a noble gas electron has to be
accommodated in the next higher principal shell which is somewhat difficult i. e., the extra electron will
not attach itself to the noble gas atom or the anion formed is very unstable
Variation:
In general, the electron gain enthalpy becomes less negative in going from top to bottom in a group and
more negative in going from left to right in a period. The electron gain enthalpies, in general, become
less negative in going down from top to bottom in a group. This is due to increase in size on moving down
a group. This factor is predominant in comparison to other factor, i.e., increase in nuclear chargeThe
elements having high negative values of electron gain enthalpy are capable of accepting electron easily.
Exceptions:
The electron gain enthalpy of flourine is less negative than clorine and that of oxygen is less
negative than sulphur. Give reason
The electron gain enthalpies of oxygen and fluorine, the members of the second period, have less
negative values than the elements sulphur and chlorine of the third period.
This is due to small size of the atoms of oxygen and chlorine. As a result, there is a strong inter-
electronic repulsion when extra electron is added to these atoms, i. e., electron density is high and the
addition of electron is not easy. Thus, the electron gain enthalpies of third period elements, sulphur and
chlorine, have more negative values than corresponding elements oxygen and fluorine.
Electron gain enthalpies of some of the members of alkaline earth metals, noble gases and nitrogen are
positive. This is because they have stable configurations. Alkaline earth metals have stable
configurations due to completely filled ns orbital while nitrogen has extra stability due to half filled p
orbital .
Electronegativity
The relative tendency of an atom to attract the shared electron pair towards itself is called
electronegativity.
In a period from left to right, the value of electronegativity increases while in a group from top to
bottom, the value of electronegativity decreases. The electronegativity of any given element is not
constant but is dependent on the following factors:
I)State of hybridization: For example, in the case of carbon, electronegativity decreases from state to
state.
More s character, more stability.
(ii) Oxidation state of the element: With increase of Oxidation state, electronegativity increasesFe^ 3+
(EN = 1.96) has higher electronegativity than F e^ 2+ (EN = 1.83) .
Other Periodic Trends in Chemical Properties along a Period
(i) Metallic character: Decrease across a period maximum on the extreme left (alkali metals).
(ii) Non-metallic character: Increasess along a period. (From left to right).
(iii) Basic nature of oxides: Decreases from left to right in a period.
(iv) Acidic nature of oxides: Increases from left to right in a period.
• Variation from Top to Bottom on Moving Down a Group
(i) Metallic character. Generally increases because increase in atomic size and hence decrease in the
ionizatiort energy of the elements in a group from top to bottom.
(ii) Non-metallic character. Generally decreases down a group. As electronegativity of elements
decreases from top to bottom in a group.
(iii) Basic nature of oxides. Since metallic character or electropositivity of elements increases in going
from top to bottom in a group basic nature of oxidise naturally increases.
(iv) Acidic character of oxides. Generally decreases as non-metallic character of elements decreases in
going from top to bottom in a group.
(v) Reactivity of metals. Generally increases down a group. Since tendency to lose electron increases.
(vi) Reactivity of non-metals. Generally decreases down the group, Higher the electro-negativity of non-
metals, greater is their reactivity. Since electronegativity of non-metals in a group decreases from top to
bottom, their reactivity also decreases.