I.3.

Periodicity in Physicochemical Properties

I.3.1. Covalent Atomic Radius
The atomic radius (ra) of an element is defined as half of the observed distance between the
nuclei of two neighboring atoms.

(I-1)

Example:
Element R(a) Å Element R(a) Å
H 0.37 K 2.03
Li 1.23 Rb 2.16
Na 1.57 Cs 2.34

In general, the atomic radius exhibits a consistent trend within the periodic table.
The covalent radius increases from top to bottom within a group (Z , r(a) ).
In a period, the principal quantum number remains constant (n= cst) as Z , r(a) .

I.3.2. Ionic Radius (ri)

In general:
Cations are smaller than their parent atoms: ri (A+) < r (A)
Anions are larger than their parent atoms: ri (A-) > r (A)
I.3.3. Ionization Energy
The first ionization energy of X is the energy required to remove the first electron from the
electron cloud of atom X in the gaseous state.
We can thus define:

 The first ionization energy Ei1: it is the energy required to remove the least tightly
bound electron from the atom.
 The second ionization energy Ei2: it is the energy required for the ionization of the
resulting cation and so on
Example:

6C: 1s22s22p2
N (Ionization order) 1 2 3 4 5 6
Ei (eV) 11.26 24.38 47.89 64.49 392.07 489.98

As with each ionization, the atomic radius decreases (Attraction force ), therefore: Ei1 < Ei2 <
Ei3 < Ei4 < Ei5 < Ei6.
In the periodic table, ionization energy (Ei) varies systematically. We observe that the first
ionization energy generally increases from left to right within a period and increases from
bottom to top within a group.
Within a group, if Z , Ei
Within a period, if Z Ei

Fgiure I.1. Variation of Ionization Energy in the Periodic Table

According to the figure, it is evident that from left to right within a row of the periodic table,
valence electrons become increasingly tightly bound to the nucleus and are more challenging
to remove, leading to the formation of a cation.
I.3.4. Electron Affinity
Electron affinity (Ae) corresponds to the energy released by an atom when capturing an
electron in the gaseous phase.

I.3.5. Electronegativity
The tendency of atoms to gain or lose electrons can be characterized by a single parameter:
electronegativity (χ). The higher χ is, the more the element tends to retain its electrons and
potentially capture additional ones.
Example:

I.3.5.1. Electronegativity According to Mulliken

It is defined as the arithmetic mean of ionization energy (Ei) and electron affinity:

(I-2)

With
I.3.5.2. Electronegativity According to Pauling
Pauling's definition is based on the values of bond dissociation energies:

| | √ (I-3)

Where are the bond dissociation energies of the molecules AB, A2, B2,
respectively, in kJ/mol.
 Electronegativity is expressed as a value between 0.7 and 4, with fluorine being the most
electronegative element on the periodic table.
 Electronegativity increases from left to right and from bottom to top (except for noble
gases, which do not have χ values on this scale).
  It is important to note that hydrogen deviates from this trend and possesses
electronegativity close to that of carbon. This result holds significance in organic
chemistry.

I.3.6. Metallic Properties

Metals have a tendency to readily lose their valence electrons to achieve the configuration of
noble gases. Nonmetals, on the other hand, tend to gain electrons to attain the noble gas
configuration.
Metals are characterized by:

 Good electrical and thermal conductivity.

 Metallic luster.
 Malleability and ductility.
I.3.7. Magnetic Properties
 An element is termed diamagnetic if the atom has only paired electrons.
 An element is termed paramagnetic if its atom has unpaired electrons.
I.4. Chemical Bond
A chemical bond is a force that holds atoms together to form a molecule.
I.4.1. Lewis Theory
To form a molecule, atoms don't randomly come together; instead, they follow specific rules
aimed at achieving maximum stability.
I.4.1.1. Lewis Diagram
This is a two-dimensional schematic that allows the visualization of the atoms in a molecule
or ion, along with the presence of bonding or non-bonding electron pairs. To create it, it is
advisable to follow the systematic steps outlined below:
1. Determine the number of valence electrons.
2. Represent a lone pair with a dot (•).
3. Represent a doublet pair with a dash (-) on the atom.
4. Represent a bond with a dash between the atoms.
Example
The Lewis diagrams of select atoms

6C 1s22s22p2 4 valence electron

8O 1s22s22p4 6 valence electron

9F 1s22s22p5 6 valence electron

I.4.1.2. Octet Rule
Atoms tend to receive, donate, or share electrons until their outer electron configuration
matches eight electrons (noble gas configuration). To represent a given molecule using the
Lewis diagram, follow the steps outlined below:
Example: The Lewis diagram of the molecule CH3O-
There is always a central atom in the molecule or ion under consideration, with the other
atoms being the external atoms. Create a diagram with the central atom in the center and the
external atoms surrounding it.
We know that Nv (C) = 4, Nv (O) = 6, and Nv (H) = 1. Therefore, we calculate:
Nt = 4 + (3 × 1) + 6 + 1 = 14. Thus, there are 7 available electron pairs (14/2 = 7).
Next, form single bonds between atoms using the available electron pairs.
Complete the octet of each external atom by adding the necessary number of non-bonding
electron pairs.
Conclude the Lewis representation by enclosing the structure with brackets and indicating its
overall electric charge.
I.4.2. Various Types of Chemical Bond
a) Covalent Bond
A covalent bond is established through the sharing of an electron pair between two identical
atoms or atoms with similar electronegativities.
Example
H2: H + H → H2

1H: 1s1

H atom H atom
 Molecule of H2
Figure I.2. Covalent bond formation in the H2 molecule.
In this type of bond, there is a symmetric distribution of the electron cloud, ensuring the
connection between the two atoms.
b) Dative (coordinate) bond
This bond is established between two atoms with the following properties: one atom has a
lone pair in its outermost electron shell, and the other atom has an empty orbital. Example:

7N: 1s22s22p3
+
1H : 1s0

Ammonia NH3 ammonium ion

Figure I.3. Coordination bond in the ammonium ion.
c) Ionic bond
It occurs between two atoms with a significant difference in electronegativity, typically
involving a highly electronegative atom and a significantly less electronegative atom. In
general, ionic bonds form between electron-donating metallic atoms from the IA, IIA, and IIIA
groups and electron-accepting non-metallic atoms from the VIA and VIIA groups.

Example:
NaCl 11Na : 1s22s22p63s1
17Cl : 1s22s22p63s23p5

Figure I.4. Ionic bond in the NaCl molecule

The ionic bond is maintained by an electrostatic attraction force.
d) Metallic bond
In the case of the metallic bond, a large number of atoms lose their valence electrons located
on the outermost electron shell and occupy the typical positions within a crystalline lattice. As
they move through this crystalline structure framework, the liberated valence electrons are
shared among all the atoms. They create a kind of constantly moving and disordered "electron
gas."

Figure I.5. An electron cloud

e) Weak bonds
Van der Waals bond: This is a low-intensity electrical interaction between two atoms or
molecules.
Hydrogen bond (hydrogen bridges): It corresponds to a generally attractive interaction
between a hydrogen atom carrying a strong partial positive charge from a polar group like O-
H, N-H, and another highly electronegative atom carrying a lone pair.
 Figure I.6. A hydrogen bond between two water molecules
I.4.3. Polar Covalent Bond and Dipole Moment
When a covalent bond forms between two atoms with a significant difference in
electronegativity, the bonding electron pair is not equally shared between the two atoms. It is
located very close to the more electronegative atom.
Between the two atoms, the distribution of the two bonding electrons is not symmetrical, and
in this case, an electric dipole arises. The electric dipole is characterized by a dipole moment
(µ).

The μ is oriented from the less electronegative atom to the more electronegative atom.
(1.4)
Where:
d: the bond length between A and B
q: the effective charge with | | (1.5)
The unit of μ is the Debye, where 1 D (Debye) = 3.33 × 10 C.m
Exemple
HCl

A molecule with μ = 0 is a nonpolar molecule.

A molecule with μ ≠ 0 is a polar molecule.
I.4.4. Partial Ionic Character (PIC)
When a covalent bond is polarized, it is said to possess partial ionic character (PIC).
 Consider the non-polar covalent bond
 Consider the polar covalent bond
 Consider the ionic bond
The partial ionic character is defined as:

(1.6)

 If: PIC=0 purely covalent bond.

 0<PIC<100 covalent bond with PIC.
 PIC=100% purely ionic bond.
Example
The HF molecule is characterized by d=0.92 Å and μ=1.98 D. Calculate its PIC.
We can directly apply the PIC formula:

I.5. Molecular Orbitals

A molecular orbital represents the spatial region where an electron is likely to be found and is
obtained through an approximate solution to the Schrödinger equation. A molecular orbital
results from the overlap of two atomic orbitals (AOs).
It's important to recall that there are various types of atomic orbitals, including:
 Spherical ns orbitals:

AO ns
The np orbitals take the shape of two touching spheres (dumbbells).
The d orbitals form two crossed dumbbells.

Two atomic orbitals can overlap only when their energies are close, and only valence
electrons participate in the formation of molecular orbitals.
I.5.1. Different Types of Molecular Orbitals
I.5.1.1. Bonding and Antibonding MOs
Bonding MOs result from the combination of AOs with the same sign in the overlapping
region (positive overlap). Bonding MOs provide cohesion between the two nuclei and
facilitate bond formation.
Antibonding MOs involve AOs with opposite signs in the overlapping region (negative
overlap). Antibonding MOs counteract bond formation.
Example
The H2 molecule represents the overlap of two s-type AOs.

 An occupied bonding orbital lowers the molecule's energy.

 An occupied antibonding orbital increases the molecule's energy.
I.5.1.2. Criteria for the Combination of Atomic Orbitals
There is no overlap (null overlap) between AOs of different symmetry types, and their
combination does not lead to any bonding.
 An AOs from one atom and an AOpx or AOpy from the other atom.
 An OApz from one atom and an AOpx or AOpy from the other atom.
 An AOpy from one atom and an AOpx or OApz from the other atom.
I.5.1.3. σ and π Molecular Orbitals
a) σ MOs: Formed by the axial overlap of two AOs, they possess symmetry around the
molecular axis. These orbitals are formed in the following cases:
 Overlap of 2 s-type AOs.
  Overlap of 2 s-type and pz-type AOs.

 Overlap of two pz-type AOs.

b) π MOs: Formed by the lateral overlap of AOs, they exhibit symmetry with respect to a
nodal plane containing the molecular axis. They are created by combining two AOpx or two
AOpy.
I.5.2. Energy Diagram of Molecular Orbitals
I.5.2.1. Energy Diagram for Homonuclear Diatomic Molecules
a) Model with Interaction (Atoms with Z 7)
When the atomic orbitals S-P have similar energies, the s and pz interaction occurs, affecting
the energy level of the σz MO. As a result, σz becomes less stable compared to the (πx; πy)
orbitals (inversion of the σz and (πx; πy) levels). The diagram takes the following shape:

Figure I.7. Energy Diagram of Diatomic Molecules (Z<7)

Filling Rules
The filling of MOs is done considering:
 The principle of stability: Start by populating the lowest-energy MOs.
 Pauli's exclusion principle: Up to a maximum of 2 electrons per MO.
 Hund's rule: Populate the maximum number of MOs with the same energy.
Example: The N2 molecule

7N: 1s2 2s22p3, with 5 valence electrons for N. Thus, 10 valence electrons are involved in the
formation of the N2 molecule (the valence electrons contributing to the bond).
b) Non-interaction Model (Atoms with Z>7)
Theoretical data have shown that if the energy difference between S-P orbitals is relatively
large, there will only be interactions between 2S-2S and 2P-2P. In this case, we observe the
stabilization of the σz orbitals compared to the πx and πy orbitals. In the periodic table, the s-p
distance increases from Li to F, as shown in the following figure:

Figure I.8. The energy difference between the 2S and 2P orbitals from Li to F.
It is generally accepted that for atoms with Z > 7, as is the case for O2 and F2, the energy
diagrams have the following shape:

Figure I.9. Energy diagram of homonuclear diatomic molecules with Z > 7.

Example: The O2 molecule

8O: 1s22s22p4, with 6 valence electrons for O. Thus, O2 has a total of 12 valence electrons.
I.5.2.2. Energy Diagram of Heteronuclear Diatomic Molecules (A-B)
In this model, the electronegativity difference between the two atoms is not zero. The more
electronegative atom has lower energy levels for its atomic orbitals. In these diagrams, it's
also necessary to consider the energy difference between s and p orbitals to determine
whether the s and pz orbitals interact or not.

I.5.2.3. Magnetic Properties

A molecule is paramagnetic if it has unpaired electrons (meaning it's attracted to a magnetic
field). However, a compound is diamagnetic if all its electrons are paired.
I.5.3. Bond Order
Bond order indicates the number of bonds in a molecule. It also provides information about
the strength of a bond (higher bond order stronger bond ).
∑ ∑
( )

 Bonding Electrons: The number of electrons in bonding orbitals.

 Antibonding Electrons: The number of electrons in antibonding orbitals.
Example: Based on the energy diagram of N2

Hence, there are 3 bonds present in the N2 molecule.

I.6. Hybridization
Hybridization involves the combination of different atomic orbitals of an atom during the
formation of a molecule.
I.6.1. Different Types of Hybridization
Each type of hybridization corresponds to a specific molecular geometry in space.
I.6.1.1. sp Hybridization
It involves an s-type orbital and a p-type orbital. Around the central atom, there are two sp
hybrid orbitals positioned 180 degrees apart from each other. The uninvolved p y and pz
orbitals in this hybridization result in π overlaps.
Example
C2H2
6C : 1s22s22p2 The molecule is thus linear,

Forming 3 sigma (σ) bonds and 2 pi (π)

bonds.

So, around each carbon atom, there are 2 sp hybrid orbitals with the following shape:

I.6.1.2. sp2 Hybridization

It arises from the combination of one s orbital and two p orbitals from the same atom.
Minimal repulsions occur between these orbitals at an angle of 120 degrees.
Example: The molecule BH3
5B: 1s22s22p1 3 valence electrons

Hence, atom B is surrounded by three equivalent sp2 hybrid orbitals. The BH3 molecule is
trigonal with a 120-degree angle between the axes.

I.6.1.3. sp3 Hybridization

This hybridization arises from the combination of one s orbital and three p orbitals from the
same atom. The angle between the axes is 109.5 degrees.
Example: CH4
6C : 1s22s22p2

Hence, the CH4 molecule is tetrahedral, with a 109.5-degree angle between the axes.
I.6.1.4. sp3d Hybridization
This is a combination of one s orbital, three p orbitals, and one d orbital to yield five sp3d
hybrid orbitals as follows:

Example: PF5

15P: 1s22s22p63s23p3
The valence shell of P is as follows:

Therefore, P forms 5 single bonds with the F atoms. As a result, the molecule takes on the
shape of a trigonal bipyramid.
I.6.1.5. sp3d2 Hybridization
This hybridization results from the combination of one s orbital, three p orbitals, and two d
orbitals to produce six sp3d2 hybrid orbitals as follows:

Example:
16S: 1s22s22p63s23p4
The valence shell of S is as follows:

S forms 6 bonds with the F atoms. The sulfur hexafluoride molecule adopts an octahedral
shape.
I.6.2. Gillespie's Theory (VSEPR) and Molecular Geometry
This theory was established in 1957 by the chemist R.J. Gillespie and is also known as the
VSEPR method (Valence Shell Electron Pair Repulsion) or (Distribution of valence electron
pairs around the central atom). In this technique, a molecule is symbolized as follows:
AXnEm
Where: A is the central atom
n represents the number of atoms X bonded to A
m is the number of nonbonding electron pairs E in the valence shell of A.
The geometry of a given molecule is the one in which electron pair repulsions are minimized,
meaning they are positioned as far apart from each other as possible.
The various VSEPR shapes are illustrated in the following table:

Type of Total number Designation Angle Examples Hybridization

molecule of electron
pairs
AX2 2 Linear BeCl2 ; CO2 sp
AX3 3 Trigonal BF3 ; AlCl3 sp2
AX2E Bent or V- SO2 ; SnCl2
shaped
AX4 4 Tetrahedral CH4; SiCl4 sp3
AX3E Trigonal NH3; H3O+
pyramid
AX2E2 Bent H2O ; H2S
AX5 5 Trigonal PCl5 sp3d
bipyramid
AX4E Distorted SF4
triangular
bipyramidal
molecule
AX3E2 T-shaped ICl3 ; ClF3
molecule
AX2E3 Linear XeF2
molecule
 AX6 6 Octahedral SF6 Sp3d2

AX5E Square IF5 ; BrF5

pyramid
AX4E2 Square XeF4
planar

I.7. Molecular Moments

In a polyatomic molecule, each bond is characterized by a dipole moment known as a bond
moment. The total moment of a polyatomic molecule (μ total) is equal to the geometric sum
of the bond moments. As an example, the water molecule (Figure I.10) has a moment equal to
1.85 D.

Figure I.10. Polarity of the Water Molecule

The H2O molecule is electrically equivalent to a dipole, with the negative charge located on
the oxygen atom and the positive charge at a virtual point equidistant from the two hydrogen
atoms. In this geometry, the angle is 120 degrees.
Note: It can occur that a molecule with polarized bonds is not overall polar. This happens
when the molecule's geometry is such that the sum of bond moments is zero. For instance, the
CCl4 molecule is tetrahedral, and its total dipole moment is zero.