CHAPTER I: STRUCTURE OF THE MATTER

I.1. Constitution of the atom

I.1.1. Introduction.

The matter that surrounds us consists of atoms. Atom’ comes from the Greek ‘atomos’ meaning
indivisible.
We currently believe that the atom is the basic unit of matter, which consists of a dense nucleus
surrounded by a cloud of negatively charged electrons. The nucleus contains a mix of positively
charged protons and electrically neutral neutrons. The atom is indivisible, unbreakable; quantity of
infinitely small matter.
The atom consists of elementary particles: the nucleus (the atom’s central core) and electronic cloud
(electrons). Electron, proton and the neutron are called fundamental subatomic particles).

The atom is a very small quantity of matter whose dimensions are of the order 10-10 m (Angstrom) and
its mass is of the order of 10-26 kg
We have:
1A0 = 10-10 m

1nm= 10-9m

A. The nucleus:

The nucleus is composed of neutrons and protons, which are nucleons. Protons (noted p) and neutrons
(noted n) have substantially the same mass. The nucleus is composed of neutrons (mn=1,6749.10-27kg)
and protons (mp = 1.6726.10-27kg), so it is positively charged. The electric charge of a proton is
called elementary charge, it is noted e. With: e = 1.6 10-19 Coulomb. The proton and the neutron are
called nucleons.
The charge of the nucleus is equal to the number of protons «Z» multiplied by the charge of the proton,
(Q nucleus= Z* e)

B. The electronic cloud:

The electronic cloud is composed of electrons, noted e. The electron has a negative charge equal

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e = - 1.6 10-19 C.
The mass of the electron is me = 9.109 10-31 kg, about 2000 times lower than that of protons and
neutrons, it will often be negligible.
The charge of an electronic cloud is equal to the number of electrons «Z» multiplied by the charge of
the electron (-e ). Q cloud= Z * (-e). .

I.2. Characteristics of the atom: The atom is characterized by:

A. Number of charge or atomic number Z: The number of charge of an atom, the number Z of
protons or electron.

The atomic number (Z): number of protons contained in the nucleus of each atom of an element.
This number Z determines the nature of an element.

 In an atom (neutral entity), the number of protons is equals the number of electrons.

Example: Nitrogen Z=7 each N atom has 7 protons and 7 electrons.

 It is the nucleus of the atom, which determines the belonging of the given element.

B. Mass number (atomic mass) A

The mass number (atomic number) A, represents the number of nucleons (total number of protons and
neutrons). We have A = Z+N avec A: mass number, Z (number of protons or electrons),
N: number of neutrons.

The difference A - Z = N gives the number of neutrons in the nucleus of the atom. Z give also the
number of electrons in the atom.

Example: The carbon atom is represented by:

Z = 6 So this carbon atom has 6 protons in the nucleus and also 6 electrons around the
nucleus.
A = 12 this means

The nucleus of the carbon atom contains 12 nucleons 6 protons and 6 neutrons.

C. Symbolic representation of the atom

A
An atom is represented symbolically by ZX but this symbol more precisely designates the nucleus of
the chemical element “X” because:
The number of nucleons present in the nucleus is the sum of protons and neutrons.
Z : is called the atomic number and represents the number of protons in the nucleus of the atom.
Definition of the Nuclide: It is an atom type, which characterized by Z (protons or electrons) and N
(neutrons), a couple of these two values define a nuclide.

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Remarks:

 The mass of the electron is about 2000 times weaker than that of a nucleon.
 The mass of the atom concentrated at the nucleus because 𝑚𝑒 − negligible in front 𝑚𝑝 or 𝑚𝑛 .
 Nucleons form almost all the mass of the atom.
 The mass of an atomic nucleus is always slightly less than the sum of the masses of its nucleons.
The difference Δm between the mass of nucleons and that of the nucleus is called «mass defect».
The amount of ΔE corresponding energy (ΔE= Δm.C2 , is called the energy that would be released
if the nucleus is formed from its nucleons.

D. The atomic molar mass

The atomic molar mass of an element or the mass of one mole of atoms is the relative atomic mass
(Ar) expressed in grams per mole.
 The symbol is M
 Unit is gram per mole = g.mol -1

E. Molar mass of a molecule

This molar mass is equal to the sum of the molar masses of the atoms constituting the molecule.
Example: Mm H2SO4= 2×MmH+ MmS + MmO = (2×1)+32+4×(16) = 98 g/mole

 AVOGADRO constant (Number of AVOGADRO)

The number of Avogadro is the number of elementary entities (atoms, ions or molecules) contained in
a mole of these same entities. In other words, it corresponds to the number of carbon atoms contained
in 12 grams of carbon 12, approximately N= 6.022 x 1023.

 The unit of atomic mass

It is a standard unit of measurement, used to express the mass of elementary particles (very small), it
is the unit of measurement most suitable for small particles. Atomic mass units are often used to
describe an element’s atomic weight . We have 1 u.m.a = 1.66.10-27Kg.
 Isotopes:
Isotopes are defined as nuclides that have the same Z but a different atomic mass (number of masses)
“A” so different number of neutrons.
Natural elements are usually mixtures of isotopes.
Only a small fraction of the isotopes is known to be stable indefinitely. All the others disintegrate
spontaneously with the release of energy by processes. There are about 3000 nuclides either stable or
radioactive.

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 Average atomic mass of an element:
It is the mass of this element in U.m.a taking into account its isotopes, it is given by the following
formula 𝑴 = 𝜮 𝑿𝒊 × 𝑴𝒊⁄𝑿𝒊
With X1, X2, X3, … (Abundance of different isotopes of the element)
M1, M2, M3, … (atomic mass of different isotopes)

1.3. Binding and cohesion energies of the nucleus

I.3.1: Nucleus binding energy. It is the energy necessary for the formation of any nucleus from
particles. We consider the following reaction Z + N → Z AX+E
If E is negative, then the nucleus is stable.
Mass balance
Δm = m2-m1 with m1 masses of proton+ neutron
m2 nucleus mass = atom mass – electron mass

Formation of the nucleus, Δm < 0 ‘mass defect”

Example 1 Formation enrgy of deuterium nucleus

ΔE <0 loss mass, so the nucleus of the Deuterium is more stable than the nucleons together.
The reaction of Deuterium nucleus formation is occur with energy release according to EINSTEIN
formula:

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I.3.2: Energy of cohesion in the nucleus: This is the energy necessary for the destruction of a
nucleus.

Let the reaction: With : Positive energy ( =-E)

Mass balance:

The destruction of a nucleus requires positive energy. This energy is used (in part) during a nuclear
reaction that transforms the nucleus.

I.3.3: Binding energy per nucleon:

The binding energy per nucleon refers to the amount of energy needed to completely separate
the nucleus of an atom into its individual nucleons. It can be thought of as the average energy
“binding” each nucleon within the nucleus. The binding energy per nucleon is an important concept
in nuclear physics because it helps to determine the stability of an atomic nucleus. Nucleus with
higher binding energies by nucleon are generally more stable, while those with lower binding energies
per nucleon are less stable. ΔE = ΔE/A Mev/nucleon)

I.4. Atomic models:

The atomic models developed in classical mechanics are:
A. RUTHERFORD Model (1910)
The mass electron me revolves around the nucleus by describing a circular orbit of radius r with a
uniform speed v. But this model is not acceptable since it cannot justify the stability of the atoms,
because according to RUTHERFORD the electron must emit an electromagnetic wave (radiation)
whose frequency is a function of its speed. So by radiating energy continuously and moving in a spiral
trajectory, the electron should have approached the nucleus and once the energy was exhausted the
electron would have fallen on the nucleus from where the end of the existence of the atom.

B. Bohr model
This model combines the nuclear model of the atom with the quantum theory of light, based on three
postulates:
- Mechanical postulate: electrons can only move on circular and privileged orbits around the
nucleus. During its movement (rotation) on an orbit the electron does not radiate energy.

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- Optical postulate: There is no emission or absorption of energy only when the electron passes from
one energy level to another. We have ∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = ℎ𝜐 = ℎ/𝜆
Or ∆𝐸: 𝑉𝑎𝑟𝑖𝑎𝑡𝑖𝑜𝑛 𝑑𝑒 𝑙′𝑒𝑛𝑒𝑟𝑔𝑖𝑒, 𝐸𝑓: 𝑒𝑛𝑒𝑟𝑔𝑖𝑒 𝑓𝑖𝑛𝑎𝑙𝑒 , 𝐸𝑖: 𝑒𝑛𝑒𝑟𝑔𝑖𝑒 𝑖𝑛𝑖𝑡𝑖𝑖𝑎𝑙𝑒
h: Planck constant = 6.62. 10-34J.S, γ: Frequency Hz (S-1). λ: wavelength
- Assumption of the kinetic moment: The kinetic moment of the electron is quantified at a whole
number of times the quantity h/2π, m.v.r = n.h/2π
From these assumptions, Bohr was able to calculate the radius of the circular orbits and the possible
energies of the electron of the hydrogen atom:

Bohr’s calculation
For calculation of permissible orbits r = ? , Bohr took as model the hydrogen atom (the simplest atom)
z = 1. The electron makes a circular trajectory around a fixed nucleus.
The electron is under the action of two forces⃗⃗⃗⃗⃗⃗ ⃗⃗⃗⃗
𝐹𝑎 and.𝐹𝑐
𝐾∗𝑍∗(𝑞1∗𝑞2) 𝐾∗𝑍∗(−𝑒)∗(+𝑒)
Fa: force of attraction, 𝐹𝑎 = =
𝑟2 𝑟2
− 𝐾∗𝑍∗𝑒 2
𝐹𝑎 = ………………………(1)
𝑟2
𝑚𝑒 ∗v2
Cf: Centrifugal force𝐹𝑐 = ……………….(2)
𝑟
The mass electron moves me with a velocity v is subjected to two equal and opposite forces.
𝐾∗𝑍∗𝑒 2 𝑚𝑒 ∗v2 𝐾∗𝑍∗𝑒 2
At equilibrium, Fa = Fc, i.e.: = = ……………..(3) 𝑚𝑒 ∗ 𝑣 2
𝑟2 𝑟 𝑟
𝑛∗ℎ 𝒏∗𝒉
We know that, 𝑚 ∗ 𝑣 ∗ 𝑟 = 2𝜋 …….. 4 𝒗=
𝟐𝝅∗𝒎𝒆∗𝒓
𝐾∗𝑍∗𝑒 2 𝒏∗𝒉
Replace (4) in (3), = me* ( )𝟐
𝑟 𝟐𝝅∗𝒎𝒆∗𝒓
𝒏𝟐 ∗𝒉𝟐
𝑟= ………………………….(*)
𝟒𝝅𝟐 ∗𝑲∗𝒁∗𝒆𝟐 ∗ 𝒎𝒆

𝑛2 ∗ℎ2
For the ground state n =1, we determine the Bohr radius, (Z =1, n =1), 𝑟 =
4𝜋 2 ∗𝐾∗𝑍∗𝑒 2 ∗ 𝑚𝑒

r = r0= 0,53 A° with : h : Planck constant = 6,62*10-34 J.S, K = 9*109 N.m2/C, e = 1,6*10-19 C, me =
9,1 *10-31 kg, we have also 1ev = 1,6*10-19 J
𝟏𝟐 ∗(6,62∗10−34 )2
A.N r= = 0.53A°
𝟒∗𝟑,𝟏𝟒𝟐 ∗(9∗109 )∗𝟏∗1,6∗10−19 ∗ 9,1 ∗10−31

𝒏𝟐
r = 𝒓𝟎 ∗ with n = 1, 2, 3, 4, 5, ……………..∞
𝒁

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 Calculation of the energy of electronic states

ET : Total Energy Ec= 1/2 (m v2)…….(1’)

ET = EC+EP
EC: Kinetic energy EP= - (K e2 Z)/r…….(2’)

Ep : potential Energy

𝐾∗𝑍∗𝑒 2
ET = 1/2 (m v2 ) - (K e2 Z)/r ......(3’), From equation (3), we have = 𝑚𝑒 ∗ 𝑣 2
𝑟
𝐾∗𝑍∗𝑒 2 1∗𝐾∗𝑍∗𝑒 2
So equation (3’) becomes, ET = 1/2 ( ) - (K e2 Z)/r = -
𝑟 2∗ 𝑟
𝟏∗𝑲∗𝒁∗𝒆𝟐 𝑛 2 ∗ℎ 2 − 𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐
ET = - , as known 𝑟 = donc ET =
𝟐∗ 𝒓 4𝜋2 ∗𝐾∗𝑍∗𝑒 2 ∗ 𝑚 𝑒 𝒏𝟐 × 𝒉𝟐
𝟒
− 𝟐×𝝅𝟐 ×(𝟗,𝟏×𝟏𝟎 −𝟑𝟏 )×(𝟏,𝟔×𝟏𝟎−𝟏𝟗 ) ×(𝟗×𝟏𝟎𝟗 )𝟐×𝒁𝟐
For hydrogen Z = 1, ET = En = 𝒏𝟐 × (𝟔,𝟔𝟐.𝟏𝟎−𝟑𝟒)𝟐

so En= -13.6×Z2/n2 with n = 1,2, 3,……

 Transition energy calculation

ΔE is the transition energy between two levels:

− 𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐
We have ET =
𝒏𝟐 × 𝒉𝟐
− 𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐 𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐
And ΔE = Ef-Ei, so ΔE = +
𝟐 𝟐
𝒏 × 𝒉𝟐 𝒏 × 𝒉𝟐
𝒇 𝒊

𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐 𝟏 𝟏

𝚫𝐄 = 𝟐 × (𝒏𝟐 − 𝒏𝟐 )……….1
𝒉 𝒊 𝒇

ΔE=(𝒉 × 𝑪)/𝝀…………….2
𝟐×𝝅𝟐 ×𝒎𝒆×𝒆𝟒 ×𝑲𝟐 ×𝒁𝟐 𝟏 𝟏
1=2 ×( − ) = (𝒉 × 𝑪)/𝝀 this formula become:
𝒉𝟐 𝒏𝟐𝒊 𝒏𝟐𝒇

𝟏 𝟏 𝟏
= 𝑹𝑯 × 𝒁𝟐 × ( − ) It is RITZ FORMULA and RH is RHYDBERG constant
𝝀 𝒏𝟐𝒊 𝒏𝟐𝒇

RH = 109737 cm-1

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I.5. Theory of light
I.5.1. Definition:
Light is an electromagnetic vibration that propagates by wave in a way analogous to sound waves but
outside any material support.
The speed of electromagnetic radiation in voids is a universal constant C=3.108 m/s

This wave is characterized by λ = Wavelength.

The light is both wavy and corpuscular.
 Undulatory because it results from the propagation of a vibration frequency wave.
 Corpuscular because the energy of this wave is concentrated in particles called photons.
We have :
Planck relationship E=hv ……… 1
ℎ𝑐 ℎ
Relation d’EINSTEIN E=mc²…...2 1=2 hv=mc², = 𝑚𝑐 2, 𝜆 = ……….. 3
𝜆 𝑚.𝑐

Equation 3 translates the double aspect (wave and corpuscular)

The period T of vibration is the necessary time to achieve this vibration (wave).
The frequency of light determines the color.
Example:
 Blue light oscillates with a frequency of 6.4.1014 Hz
 Red light oscillates with a frequency of 4.3.1014 Hz
 Green light oscillates with a frequency of 5.7.1014 Hz
The spectrum domains are:

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 UV =Ultra-violet 10 nm 400 nm
Visible 400nm 700 nm
IR (Infrared): 700 nm 50 µm

The light is studied by a spectroscope, which consists of:

Light is a mixture of colors separated by a prism that are photographed as a spectrum

I.5.2. Hydrogen Atom Spectrum:
The hydrogen emission spectrum is emitted when an electric shock is performed in a tube containing
hydrogen at low pressure:
The emission spectrum of hydrogen extends over;
 UV(Lyman)
 Visible (Balmer)
 Infra red (Paschen)

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 All lines constitute the spectrum.

E1−𝟏𝟑,𝟔
=
En= 𝒁²
𝒏²

I.5.3. Extension of the Bohr model to hydrogenoids:

(Z-1)+
A hydrogen is a single-electron, monoatomic building. For the element , the ion is the
hydrogen ion .
2He 3Li2+, Be+3…
+, 4

1 1 1
Remark: For Hydrogenoid ion, we have : v= =RHe+( − ) , RHe =RH x Z²
𝜆 𝑛1 ² 𝑛2 ²

Remark:
 The atom is the ground state when n=1, it corresponds to the lowest energy level so the highest
stability, then the electron occupies the orbit closest to the nucleus and the energy has a value of -
13.6 ev
 When n 2 the atom is in an excited state and has an energy E>E1
Conclusion:
Bohr’s theory, despite its remarkable success on hydrogen and hydrogenoid, could not explain the
spectra of multi-electron atoms because Bohr did not take into account the new electron-electron,
electron-nucleus repulsion forces. This theory gave way in the 1920 to the theory of quantum
mechanics.

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I.6.Quantum models developed in quantum mechanics
I.6.1. Broglie 1924 Hypothesis:
By analogy with light, Broglie postulated the wave-corpuscle duality, which does not apply only to
light, but it can be generalized to any movement of a corpuscle of mass m and speed v:
ℎ𝑐
For light, E = hδ= = ……. 1
𝜆

According to Einstein E=mc²………2

ℎ ℎ𝑐 ℎ
1=2 = 𝑚𝑐² = 𝑚𝑐 𝜆 = 𝑚𝑐
𝜆 𝜆

For an electron in motion comparable to a wave

ℎ ℎ
𝜆 = 𝑚𝑣 , mv= amount of movement, p=mv so 𝜆 = 𝑝

I.5.2. Heisenberg uncertainty principle:

It is not possible to know with absolute precision the position and the speed of an electron at a given
moment, their determination always supposes an uncertainty Δx × Δp > ћ
ℎ
ћ = 2𝜋 ћ: mean Planck constant
ℎ
Δx × Δp > …..(1) , p = mv …..(2)
2𝜋
ℎ
Replace (2) in (1) Δx . Δ(mv), Δx [m Δv + v Δm] , Δm = 0 (no mass exchange, system
2𝜋
ℎ
preserved) 2𝜋
ℎ 𝒉
Δx. m.Δv ⩾ 2𝜋 Δx ⩾ 𝟐𝝅𝒎𝚫𝐯

With:
 Δv error about speed
 Δx: error on the position

I.6.3. Wave function and Schrödinger equation:

Quantum mechanics no longer takes into account the precise position of the particle but the probability
of its presence at a point in space. In 1926 Schrödinger put the fundamental relationship of quantum
mechanics in the form of a differential equation:

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 𝟖𝝅²𝒎
𝚫Ѱ + [𝑬 − 𝑽]Ѱ = 𝟎
𝒉²

Ѱ : Wave function It is written in reduced form:

Δ: Laplacian operator,
m the mass of the particle,
V (r) the potential energy of the
particle at point r.
E: Total energy of the particle
h: Planck constant
The resolution of the Schrödinger equation reveals 4 quantum numbers which are n,l,m,s
I.7. Quantum numbers
Quantum numbers:
1. Main quantum number «n»
It characterizes the layer (orbit and quantifies the energy of this layer, n= 1, 2, 3, 4, 6, 7….
En= -13.6 Z2/n2 Each level corresponds to a value of n
2. Secondary quantum number «l »
It determines the geometric shape of the atomic orbital and it defines an electronic sublayer, for n
given, l can take n values so, 0 ≤ l ≤ n-1.
l = 0 S orbital

2 electrons

l = 1 p orbital

6 electrons

l = 2 d orbital

10 electrons

l = 3 f orbital

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3. Quantum magnetic number «m»
This number refers to the orientation in space of the atomic orbital in a magnetic field, for the values,
m can take 2l+1 value. -l ≤ m ≤ +l

4. Quantum number of spin «s»:

It means the direction of rotation of the electron with respect to its axis, by convention an electron is
represented by an arrow, an arrow directed upwards, s =+1/2, an arrow directed upwards, s =-1/2.

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 layer n l m Distribution cases spin Nb(é)max
K 1 0 0 1S 2
L 2 0 0 2S 8
1 -1, 0,+1 2p
M 3 0 0 3S 18
1 -1, 0,+1 3P
2 -2, -1,0,1,2 3d +-1/2

N 4 0 0 4S 32
1 -1, 0,+1 4P
2 -2, -1,0,1,2 4d
3 -3, -2, - 4f
1,0,1,2,3

Note:
- For each value of n we have a layer
- For each value of n we have a value of n2 boxes.
- Each layer contains 2 more cells than the previous one
- In the hydrogen atom and hydrogen ions, the orbitals of a given layer have the same energy since
the energy depends only on n and not on other quantum numbers. Energy levels are called
degenerate.

I.8. Orbital filling rules and representation of the electronic structure:

The distribution of electrons of the ground state (electronic configuration) in atomic orbitals (OA) is
done according to three rules:
- Klechkwsky rule
- Pauli rule
- Hund rule

I.8.1. principle of stability: Klechkwsky rule :

The electrons of an atom occupy at the ground state the most stable OA, so that of lower energy.
Generally, the filling is done in ascending order (n+1) with some exceptions.

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Klechwsky’s graphic rule allows us to easily remember the order of energy levels.

Ascending energy order: 1S<2S<2P<3S<3P<4S<3d<4P<5S<4d<5P<6S<4f<5d

X: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p6…

I.8.1. Pauli exclusion principle

The Pauli principle states that in the same atom 2 electrons can never have their 4 identical quantum
numbers.
I.8.2. Filling Principle: Hund rule
The electrons that can be distributed according to OA of the same energetic level (same quantum
number l) the electrons will occupy a maximum number of orbital before saturating each orbital, and
we start with the spin electron s=+1/2 and s= -1/2
Remarks :
An underlay d has a high stability state if it is either filled or fully filled.
ns1 (n-1)d5 is most stable than ns2 (n-1)d4
ns1 (n-1)d10 is most stable than ns2(n-1)d9

I.8.3. Representation of the electronic structure (electronic configuration)

This is the distribution of electrons in the different atomic orbitals. The valence layer is the outer layer.

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