Faculty of Electrical Engineering

Department of Telecommunications
1st year Common core Engineers
Structure of Matter IST 1.4

Chapter IV: Periodic classification of the elements

1. Mendeleev's classification:
The periodic classification, the most elaborate and complete, was proposed in 1869 by Dimitri Mendeleev,
Russian chemist. At the time, only 66 chemical elements were known. He left empty boxes, which will be
filled later, as the corresponding elements are discovered.

2. Principle of Construction:
Mendeleev classified the elements in ascending order of their atomic number Z, based on the structure
electronics of atoms.
The periodic table is made up of 7 rows called "periods" and 18 columns called "groups and subgroups".
The 18 columns are divided into 9 groups. 8 of them are noted in Roman numerals I, II, III,…., VIII
and the 9th group is denoted O (zero).
The Roman numeral represents the number of valence electrons.

 The elements of the same period have the same value of the maximum principal quantum number n.

 Elements belonging to the same column generally have the same external electronic structure (valence),
therefore often similar chemical or physical properties.

 In the table, there are 118 natural and artificial elements:

 6th period: 57 ≤ Z ≤ 71: lanthanides (from Lanthanum: 57La)

 7th period: 89 ≤ Z ≤ 118: actinides (from Actinium: 89Ac)

 87 ≤ Z ≤ 92: natural radioactive

 Z >92: artificial radioactive, most unstable.

 The periodic table is divided into 4 blocks based on the external electronic structure of the
elements: s2, p6, d10, f14

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 Figure 1: The different blocks of the periodic table

Block s: ns1or ns2; columns 1 and 2.

Block p: ns2, npx (with: 1  x  6); columns 13 to 18.

Noticed : 2He (configuration: 1s2) is classified in column 18, due to the similarity of its properties

with those of the elements in this column (inert gases).

Block d: (n-1) dx, nsy (with: 1  x  10 and 0  y  2); columns 3 to 12: “metals of transition".

Block f: (n-2)fx, (n-1)dy, ns2 (with n = 6 or 7, 0  x  14 ; y = 0 or 1 or exceptionally 2 for 90Th).

Elements for which n = 6 are called "Lanthanides"; those for which n = 7 are called "Actinides"

(the latter are all radioactive).

3. Description of the families of the periodic table:

The elements of the same column are classified by families (or group), they have properties
related physical and chemical properties. We distinguish :
Column 1: alkalis
The external electronic structure is: ns1 =˃ they give monovalent cations: Na+, K+…
Column 2: alkaline earths
The external electronic structure is: ns2 =˃ they give bivalent cations: Mg2+, Ca2+
Columns 3 to 12: transition metals
Their external electronic structure is: (n-1)dx, ns2 (ns1 or ns0) with 1  x  10. .
=˃ they give cations with multiple valences: Fe2+, Fe3+, Cu+, Cu2+ ...
Column 13: the boron family
The external electronic structure of these elements is: ns2, np1

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Column 14: the carbon family
The external electronic structure is: ns2 , np2 =˃ They mainly form bonds of covalence.
Column 15: the nitrogen family
The external electronic structure is: ns2, np3 =˃ they mainly give bonds of covalence
Column 16: the oxygen family or chalcogens
Their external electronic structure is: ns2, np4 =˃ they give bivalent anions: O2- , S2-
Column 17: halogens
Their external electronic structure is: ns2, np5 =˃ they give monovalent anions: F-, Cl-, Br- ...
Column 18: rare gases (group 0)
The external electronic structure is: ns2, np6, except for He (1s2) The configuration of rare gases
corresponds to the saturation of the external electronic layer: =˃ they have a high
chemical inertia: this usually means 8 electrons in the valence layer =˃ Octet Rule.

Figure 2: The different families of the periodic table

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4. Physical properties of elements:

We have three categories:

 Metals :

- They are located on the left and in the center of the periodic table: block s (except H), d, f
And half of the p block: (eg: Al, Sn, Pb, Bi, Po ...).

- They are all solid at room temperature (25°C), except mercury (80Hg) which is liquid.

- They are good conductors of heat and electricity.

 Non-metals:
- They are located on the right in the periodic table: second half of block p (e.g. F, O, N, C, P..).
- They are solid or gaseous at 25°C, exceptionally liquid (dibromine, Br2).
- They are poor conductors of heat and are electrical insulators.
(except carbon which is insulating (diamond) or conductive (graphite)).

 Semi-metals:
They behave like semiconductors (compounds whose conductivity increases with temperature,
for example Silicon (14Si) and Germanium (32Ge) used in electronics).
Note: Hydrogen is a special case: it is a molecular gas (H2) at 25°C. He can give
a positive ion (H+), but also the hydride ion (H-).

5. Atomic characteristics and periodicity:

The reactivity of an atom depends on:

 Its size, that is to say its atomic radius,

 Its electronic structure of the peripheral layer.

The atom always tends to reach the configuration of the nearest rare gas by attaching or losing electrons.

5.1. Atomic and Ionic radius:

a. Atomic radius ra:

We can define the atomic radius as being half the distance between the centers of the two atoms
linked by a single bond.
• On a period: if Z increases then ra decreases
• On a column: if Z increases then ra increases

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 b. Ionic radius ri :
In a general way :

 Cations are smaller than their parent atoms: ri (cation) < ra

Examples: rLi: 0.123 nm rLi+: 0.060 nm

rAl: 0.125 nm rAl3+: 0.005 nm

 Anions are larger than their parent atoms: ri (anion) > ra

Examples: rS: 0.104 nm rS2-: 0.184 nm

 For ions having the same electronic configuration (S2- , Cl-, K+, Ca2+, Ti4+,…). if Z increases;
ri decreases.

 For equal charges, the ionic radius varies in the same direction as the atomic radius: if Z
increases then ri decreases.

5.2. Melting and boiling points:

The melting temperature decreases along the group. The elements in the last column (Group 0) have the
lowest melting and boiling points.

5.3. Ionization energy:

This is the minimum energy required to extract a valence electron from a gaseous atom X(g) in its ground
state. This is the energy required for :
1) 1st ionization: Ei1 (the energy necessary to remove an electron least retained by the nucleus)
Ei1= E(A+) – E(A)
K(g) K+ (g) + 1 é + Ei1 with Ei1 = 4.31 eV
Ei1= E(K+) – E(K)
2) 2nd ionization: Ei2 energy necessary to remove the 2nd electron
Ei2= E(A++) – E(A+)
K+ (g) K+2 (g) + 1 é + Ei2 with Ei2 = 31.7 eV
Ei2= E(K++) – E(K+)

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3) of nth ionization:
Thus: Ei1 < Ei2< Ei3< …….< Ein: the further the electron is from the nucleus, the easier it is to extract it.
The internal electrons have a higher ionization energy than the valence electrons.
Ein= E(A+n) – E(A+(n-1))
 In a period, the ionization energy increases with Z and in a group (column), it decreases as Z increases.

 Noble gases are very stable: highest ionization energies (electrons are difficult to extract).

Calculation of Ionization Energy:

The energy of an electron in an orbital is given by the relation:
𝟐
−𝟏𝟑,𝟔 𝒁∗
E𝑛𝑖=
𝒏𝟐𝒊

ni: characteristic of electron i

Z*: Effective Z.
The total energy is equal to the sum of the energies:
E=∑𝒊 𝑬𝒏𝒊
With: E1𝑠 < E2𝑠 < E2𝑃 < E3𝑠 < E3𝑝 … … … ..

Example of calculation:
7N : 1s2 2s2 2p3
E(N) = 2E1𝑠 + (2+3) E2𝑠2𝑝 So E(N) = 2E1𝑠 + (5) E2𝑠2𝑝
+
7N : 1s2 2s2 2p2
E(N+) = 2E1𝑠 +(2+2) E2𝑠2𝑝 + So E(N+ ) = 2E1𝑠 +(4) E2𝑠2𝑝 +
-
7N : 1s2 2s2 2p4
E(N-) = 2E1𝑠 + (2+4) E2𝑠2𝑝 − So E(N-) = 2E1𝑠 + (6) E2𝑠2p−

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Application example:
Calculate the first ionization energy of the carbon atom
6C : 1s2 2s2 2p2
+
6C : 1s2 2s2 2p1

Calculation of the screen constant:

The first ionization energy of the carbon atom E1i (C)= 11.456 eV.
The experimental value of the first ionization energy of the carbon atom E1i =11.2 eV.

5.4. Electronic affinity:

It is the energy released by an atom when it captures an electron (it is energy provided to oxidize)

Ae = E(x) – E(x-)

X + 1é X- + A (affinity)

Example:

AH: (H + 1é H-) AH = 0.75 eV

The electron affinity increases when crossing a period from left to right, on the other hand the electron

affinity varies very little going down a group

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5.5. Electronegativity:

Is the tendency of an atom to attract towards itself the electrons of the bonding doublet in a covalent bond

=˃ appearance of partial charges.

If B is more electronegative than A, the bonding doublet will be closer to B than to A.

 Electronegativity is measured on the Mullikan or Pauling scale which is much more

extent (from 0 to 4). It can be used as a measure of the metallic character of an element.

 It increases along a period because the radius decreases, and decreases along a family because the

radius increases.

 The three most electronegative elements are F, fluorine, N, nitrogen and O, oxygen

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6. Electronic configuration and position in the periodic table:
How to find an element based on its configuration?
Example : Locate the following element in the periodic table.
An element has the following electronic configuration:
1s2 2s2 2 p6 3s2 3p6 4s2 3d10 4 p2
What is this element?
This element has an atomic number Z = 32 because the sum of the electrons is equal to 32.
The electronic configuration of the peripheral layer is 4s2 4p2 so this element is found:
 in the 4th period because n = 4,
 in a column A because the sublayer p is not yet saturated.

 IVA because the number of valence electrons is 4 (2 on s and 2 on p).

 2nd column in block p: 2 (columns of block s) + 10 (columns of block d) + 2 (columns of
block p) = 14 =˃ 14th column in the periodic table.
 In summary, this element is placed in the periodic table in the 14th column IVA and in the 4th period.
It corresponds to Germanium.

Dr CA BERREKHCHI BERRAHMA