Periodicity of the Elements

Md. Didarul Islam

 Periodicity of the Elements > Mendeleev’s Periodic Law
Mendeleev’s Periodic Table
Russian chemist Dmitri Ivanovich Mendeleev put forth his periodic table in 1869. He observed that the
properties of elements, both physical and chemical, were periodically related to the atomic mass of the
elements, which is known as Mendeleev’s periodic law
Mendeleev’s Periodic Law states that the physical and chemical properties of elements are a periodic
function of their atomic weights.

The advantages of Mendeleev’s Periodic table are:

• The inclusion of these newly discovered elements did not disturb the periodic table. Examples include
germanium, gallium, and scandium.
• It was used to correct the wrong atomic weights in use at that time.
• A variance from the atomic weight order was provided by Mendeleev’s table.
The limitations of Mendeleev’s Periodic table are:
• Hydrogen’s position was in the group of alkali metals but hydrogen also exhibited halogen-like
qualities.
• Isotopes were positioned differently since this type of classification of elements was done by
considering the atomic weight of the element. An anomalous positioning of a few elements showed
that the atomic masses did not increase regularly from one element to the next. An example of this
would be the placement of cobalt (atomic mass of 58.9) before nickel (atomic mass of 58.7).
 Periodicity of the Elements > Modern periodic table

In the year 1913, English physicist Henry Moseley studied the wavelength of the characteristic x-rays By
using different metals as anti-cathode and showed that the square root of the frequency of the line is
related to the atomic number.
On the basis of the above observations Moseley gave the modern periodic law which states that:
“Physical and chemical properties of the elements are the periodic function of their atomic
numbers”.

Periodicity
Repetitions of the similar properties of the elements placed in a group and separated by a certain definite
gap of atomic number are known as Periodicity.
 Periodicity of the Elements > Modern periodic table
Classification of elements in the modern periodic table
✓ The modern periodic table consists of 18 vertical columns, called the groups (1-18) and 7 Horizontal rows,
called periods.
✓ The first period contains two elements, Hydrogen and Helium.
✓ The second period contains eight elements, from Lithium to Neon.
✓ The third period contains eight elements, from Sodium to Argon.
✓ The fourth period contains eighteen elements, from Potassium to Krypton.
✓ The fifth period contains eighteen elements, from Rubidium to Xenon.
✓ The sixth period contains thirty-two elements.
✓ The seventh period is incomplete.
✓ On the basis of electronic configuration, elements are classified into four Blocks known as s, p, d and f-
blocks.
✓ 1st and 2nd group elements are called s-block elements. The general electronic configuration is ns1-2.
✓ 13th to 18th group elements are called p-block elements. The general electronic configuration is ns2 np1-6.
✓ 3rd to 12th group elements are called d-block elements. The general electronic configuration is (n-1)d1-
10 ns1-2.

✓ Lanthanides and actinides elements are called f-block elements. The general electronic configuration is (n-
2)f1-14 (n-1)d0-1 ns2.
 Periodicity of the Elements > Periodic Properties
Periodic properties and their trends
The periodic properties may be defined as:
The properties of the elements are directly or indirectly related to the electronic configuration of their atoms
and show gradation (increases or decreases) in moving down a group or a longer period.
The common physical properties of the elements are melting points, boiling points, density, enthalpy of fusion
and vaporization etc. But we shall focus our attention mainly on the properties which are based on electronic
configuration these are:
✓ Atomic radii and ionic radii
✓ Electron affinity
✓ Ionization enthalpy
✓ Electronegativity
 Periodicity of the Elements > Periodic Properties
1. Atomic Radii and ionic radii
An atom does not have a definite size, because the statistical distribution of electrons does not abruptly end but
merely decreases to very small values as the distance from the nucleus increases. The atomic size must be
defined in a somewhat arbitrary manner, so various measures of atomic size exist.

✓ Within each period (horizontal row), the atomic radius tends to decrease with increasing atomic number
(nuclear charge). The largest atom in a period is a Group IA atom and the smallest is a noble-gas atom.
✓ Within each group (vertical column), the atomic radius tends to increase with the period number.
✓ Cations are smaller than their parent atoms. The outermost electron is removed and repulsions are
reduced.
✓ Anions are larger than their parent atoms. Electrons are added and repulsions are increased.
2. Ionization enthalpy
The first ionization energy (or first ionization potential) of an atom is the minimum energy needed to remove the
highest-energy (that is, the outermost) electron from the neutral atom in the gaseous state.

✓ From left to right in the period, IE increases whereas on moving down the group it decreases but half-
filled orbital and fully filled orbitals are highly stable and thus have high IE.
✓ Within each group (vertical column), IE increases whereas on moving down the group it decreases but
half-filled orbital and fully-filled orbitals are highly stable and thus have high IE.
 Periodicity of the Elements > Periodic Properties
3. Electron affinity
The amount of energy liberated when an electron is added to a neutral atom to form a negatively charged ion.

✓ Electron affinity increases going left to right across a period because of increased nuclear attraction.
✓ Going down the group the electron affinity should decrease since the electron is being added increasingly
further away from the nucleus. Electron becomes less tightly bound and can be easily removed.

4. Electronegativity
The tendency of an atom in a molecule to attract the shared pair of electrons toward itself is known
as electronegativity.
As we move across a period from left to right the nuclear charge increases and the atomic size decreases,
therefore the value of electronegativity increases across a period in the modern periodic table.
There is an increase in the atomic number as we move down the group in the modern periodic table. The nuclear
charge also increases but the effect of the increase in nuclear charge is overcome by the addition of one shell.
Hence, the value of electronegativity decreases as we move down the group.
Periodicity of the Elements > Quantum Number
Periodicity of the Elements > Quantum Number
Periodicity of the Elements > Quantum Number
Periodicity of the Elements > Quantum Number
 Periodicity of the Elements > Aufbau Principle
Aufbau principle
It states that electrons are filled into atomic orbitals in the increasing order
of orbital energy level. According to the Aufbau principle, the available
atomic orbitals with the lowest energy levels are occupied before those with
higher energy levels.

✓ According to the Aufbau principle, electrons first occupy those

orbitals whose energy is the lowest. This implies that the electrons
enter the orbitals having higher energies only when orbitals with
lower energies have been completely filled.
✓ The order in which the energy of orbitals increases can be
determined with the help of the (n+l) rule, where the sum of the
principal and azimuthal quantum numbers determines the energy
level of the orbital.
✓ Lower (n+l) values correspond to lower orbital energies. If two
orbitals share equal (n+l) values, the orbital with the lower n value
is said to have lower energy associated with it.
✓ The order in which the orbitals are filled with electrons is: 1s, 2s,
2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, and so
on.
 Periodicity of the Elements > Hund's rule
Hund's rule
Hund's rule states that:
✓ Every orbital in a sublevel is singly occupied before any orbital is doubly occupied.
✓ All of the electrons in singly occupied orbitals have the same spin (to maximize total spin).
 Periodicity of the Elements > Pauli Exclusion Principle
Pauli Exclusion Principle
The Pauli exclusion principle states that in a single atom no two electrons will have an identical set or the same
quantum numbers (n, l, ml, and ms). To put it in simple terms, every electron should have or be in its own unique
state (singlet state). There are two salient rules that the Pauli Exclusion Principle follows:
✓ Only two electrons can occupy the same orbital.
✓ The two electrons that are present in the same orbital must have opposite spins or they should be
antiparallel.
However, Pauli’s Exclusion Principle does not only apply to electrons. It applies to other particles of half-integer
spin such as fermions. It is not relevant for particles with an integer spin such as bosons which have symmetric
wave functions. Moreover, bosons can share or have the same quantum states, unlike fermions. As far as the
nomenclature goes, fermions are named after the Fermi–Dirac statistical distribution that they follow. Bosons, on
the other hand, get their name from the Bose-Einstein distribution function.
 Periodicity of the Elements > Electron Configuration
GROUND-STATE ELECTRON CONFIGURATION OF ELEMENTS
So far we have considered the electron configuration of simple atoms. For complicated atoms which may contain
many electrons and have many energy levels or orbitals, the ‘building up’ process for the electrons is governed by
the following rules:
Rule 1. Each electron shell can hold a maximum of 2n2 electrons where n is the shell number.
Rule 2. These electrons are accommodated in s, p, d and f orbitals, the maximum number of electrons in each type
of orbitals being determined by its electron-holding capacity (for s = 2, p = 6, d = 10, and f = 14).
Rule 3. In the ground state of an atom, the electrons tend to occupy the available orbitals in the increasing order of
energies, the orbitals of lower energy being filled first. This is called the ‘building up principle’ or Aufbau Principle
(Aufbau is a German expression meaning building up or construction). Lower energy orbitals are, therefore, better
seats for electrons and better seats are occupied first.
The increasing order of energy of various orbitals is as follows:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s ......
The energy of an orbital is determined by the sum of the principal quantum number (n) and the azimuthal quantum
number (l). This rule is called the (n + l) rule. There are two parts to this rule :
(a) The orbitals with the lower value of (n + l) has lower energy than the orbitals of higher (n + l) value.
(b) When two orbitals have same (n + l) value, the orbital with lower value of n has lower energy.
 Periodicity of the Elements > Electron Configuration
Rule 4. Any orbital may have one or two electrons at the most. Two electrons can occupy the same orbital only if
they have opposite spins (Pauli’s exclusion principle).
Rule 5. When several orbitals of equal energy (degenerate orbitals) are available, electrons prefer to occupy
separate orbitals rather than getting paired in the same orbital. Such electrons tend to have same spins (Hund’s
rule).
Periodicity of the Elements > Electron Configuration
Reference Book
❖ Essential Physical Chemistry, B.S. Bahl, G.D Tuli, A. Bahl

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