Periodicity of Properties

Periodic classification of elements : periodicity of proprerties USDB 2023/2024
Introduction :
From the electronic structure of the atoms, it is understood that the similar
properties of the elements arose from their similar peripheral (external)
electronic configurations. The following study describes the relationships
between these and their chemical and physical properties.
1) The effective nuclear charge and the shielding effect :
The effective nuclear charge, or nucleus charge, is the positive charge

experienced by a peripheral electron in a polyelectron atom. The term
"effective" is used because of the "screen effect" exerted by the inner electrons
on the peripheral electrons that are both "attracted to the positive nucleus"
and "repelled by the negative charges of the other electrons."
2) Atomic radius :
It is the half-distance between the centers of the 2 nuclei of a homonuclear

diatomic molecule.
The atomic radius is a fundamental parameter of atoms.

« The atomic radii of representative elements increase in a group and decrease

in a period. » This trend reflects two important effects :
• The size of an atom is determined by its peripheral electrons. In a group, the

values of the principal quantum number "n" increase, the orbitals become
larger and larger, the inner electrons occupy more and more space, and the
peripheral electrons have to move further and further away from the nucleus :
the size of the atoms increases.
• In a period, the principal quantum number "n" of the peripheral electrons is

the same for each element. From one element to another, a proton is added to
the nucleus as a peripheral electron is added. At each step, the effective
nuclear charge (Z eff) increases a little because the effect of an extra proton is
greater than the effect due to the added electron. As the positive charge
experienced by all the elements increases, the attractive forces between the
nucleus and the electrons also increase (Coulomb's law) : the electron clouds
contract and the radius of the atoms decreases.
3) Physicochemical properties :
a) Ionization energy :
It is the energy required to tear off, extract, or eject an electron from
a gaseous atom, in its fundamental state.
E (g) E+ (g) + 1 e- (1st ionization)
E+ (g) E2+ (g) + 1 e- (2nd ionization)
It is always positive because energy must be provided to remove an

electron from its atom, i.e. to overcome the forces of attraction between
the nucleus and the electron. Note that removing a 2nd electron requires
more energy than removing the 1st because it must be expelled not from
a neutral atom, but from a positively charged ion.
• The 1st ionization energies of the representative elements (s and p
blocks) decrease in a group and generally increase in a period.
• In a group, the Ei decreases, as the electron is farther and farther away
from the nucleus, and the nucleus-electron attraction weakens as a
result. The trend in one period can be explained by the increase in the
effective nuclear charge (Z eff), which is also responsible for the decrease
in the size of the atoms.
b) Electron affinity :
The electron affinity of an element is the change in energy that
accompanies the addition of an electron in a gaseous state.
E (g) + 1 e- E- (g)
Electron affinity and ionization energy are respectively the energy involved
when an atom gains or loses an electron.
c) Electronegativity:
It is the ability of an atom to attract the covalent bond pair
established between it and another atom.
Initially, it was proposed to evaluate ϰ of elements by arithmetic
average of their ionization energy (Ei) and electron affinity (Ae).
This is the principle of the simple Mulliken scale :
ϰ= (Ei + Ae)/2
The Allred-Rochow scale is based on the measurement of the
effective nuclear charge Zeff, i.e. ϰ= 0.359 (Zeff2/R2) + 0.744
with Zeff = Z- shielding effect
In the 1930s, Linus Pauling proposed a formula for measuring
electronegativity.
Fluorine is the most electronegative element, the one with the lowest
electronegativity is the alkali metal Fr.
• Electronegativity usually increases in a period and decreases in a group.

It varies in the opposite direction to the metallic character of the
elements. The electronegativity of metals is low, ranging from just under
1 to about 2, that of metalloids is around 2, while that of nonmetals is
greater than 2. Since the electronegativity of the elements on the right of
the periodic table is significantly higher than that of the elements on the
left of the table, the compounds they form are ionic.
4) Metallic & Electrical Properties :

The ease with which an element loses an electron and becomes a cation
with a low ionization energy is an expression of the metallic character of
this element : a metal is nothing more than an assembly of cations
bathed in a sea of electrons, which makes them electrically conductive.

Metals are also good thermal conductors. They have a so-called
"metallic" sheen and are ductile and malleable. From a chemical point of
view, their oxides (Na2O) are transformed by the action of water into
bases (NaOH).
As for the elements to the right of the periodic table, characterized by
high electronegativities, they do not tend to lose an electron but rather
to gain it. They are non-metals, which are very poor conductors of
electricity and heat. Nonmetals give oxides (SO3) which, in water,
become acids (H2SO4).
5) Classification of oxides :
Oxides are a chemical compound with one or more oxygen atoms combined
with other elements. (MxOY)
This combination, is a combustion reaction, is often exothermic

(releases heat).
Oxygen has a very high electronegativity (χ = 3.5 second highest after fluorine).
It reacts with most element of periodic table.
The oxides can be classified according to :

 The nature of the bond between O and M into ionic, covalent and
polymeric oxides
 acid-basic character : acidic, basic, amphoteric and neutral oxides
The nature of the bond depends on :
 the cation charge
 the ionic radius of the cation
 Difference between electronegativities ΔE = (χo - χM).
 An oxide is said to be acidic if :
It reacts with water and forms protons H+
Ex. : SO3 + H2O → SO42- + 2 H+
In reaction of neutralization it reacts with base (hydroxyde ions):

Ex. : SiO2 + 2 OH- → SiO32- + H2O
The covalent oxides are acidics.
 An oxyde is said to be basic if :
It reacts with water and forms OH−
Ex. : CaO + H2O → Ca2+ + 2 OH-
In reaction of neutralization it reacts with acids
Ex. : CuO + 4 HCl → (CuCl42-, 2H+) + H2O
The ionic oxides are basics.
 An amphoteric oxide behaves like an acid when it reacts with a base and
behaves like a base when it reacts with an acid,
Example : ZnO, Cr2O3, Al2O3
It doesn’t dissolve in, or react with water.
 An oxide is neutral when it doesn’t react with acid or base. Example : CO,
NO, H2O.

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Periodic classification of elements : periodicity of proprerties USDB 2023/2024

1) The effective nuclear charge and the shielding effect :

The effective nuclear charge, or nucleus charge, is the positive charge

It is the half-distance between the centers of the 2 nuclei of a homonuclear

The atomic radius is a fundamental parameter of atoms.

« The atomic radii of representative elements increase in a group and decrease

• The size of an atom is determined by its peripheral electrons. In a group, the

• In a period, the principal quantum number "n" of the peripheral electrons is

It is always positive because energy must be provided to remove an

• Electronegativity usually increases in a period and decreases in a group.

4) Metallic & Electrical Properties :

bathed in a sea of electrons, which makes them electrically conductive.

This combination, is a combustion reaction, is often exothermic

The oxides can be classified according to :

 An oxide is said to be acidic if :

It reacts with water and forms protons H+

Ex. : SO3 + H2O → SO42- + 2 H+

In reaction of neutralization it reacts with base (hydroxyde ions):

Ex. : SiO2 + 2 OH- → SiO32- + H2O

The covalent oxides are acidics.

 An oxyde is said to be basic if :

It reacts with water and forms OH−

Ex. : CaO + H2O → Ca2+ + 2 OH-

In reaction of neutralization it reacts with acids

Ex. : CuO + 4 HCl → (CuCl42-, 2H+) + H2O

The ionic oxides are basics.

It doesn’t dissolve in, or react with water.

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