MECH 227

Engineering Materials

Lecture 2
Atomic structure and interatomic bonding

Dr. Reza Mohammadi

Why study atomic structure and interatomic bonding?

Properties of Atomic structure

materials and bonding

o The carbon atoms in

o Each carbon atom forms
graphite are arranged in
four strong covalent
flat, hexagonal layers.
bonds with neighboring
o Each layer is made up of a
carbon atoms in a three-
2D lattice of carbon
dimensional tetrahedral
atoms where each carbon
structure.
is bonded to three others
o There are no free
by covalent bonds.
electrons available for
o The bonding within each
electrical conduction. All
layer is strong covalent
the electrons are involved
bonding, but the layers
in the covalent bonding,
are held together by
making diamond an
weak van der Waals
insulator.
forces.
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hardest known natural material soft and slippery
Atomic structure

Atomic number (Z) Atomic mass (A)

The sum of the masses of
Number of protons in the protons (Z) and neutrons
nucleus (N) within the nucleus
For a complete atom:
Z= number of electrons Unit: atomic mass unit
(amu)

Atomic weight Isotopes

The average of the atomic
masses of the atom’s Atoms of some elements
naturally occurring have two or more
isotopes different atomic masses as
Unit: amu/atom (or the number of neutrons
molecule) = g/mol (N) may be variable

In one mole of a substance, there are 6.022×1023 (Avogadro’s number) atoms or molecules
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The periodic table

o Elements are situated in seven

horizontal rows called periods,
with increasing atomic number.
o All elements arrayed in a given
column (group) have similar
valence electron structures,
chemical and physical properties.
o Electropositive elements are
capable of giving up their few
valence electrons to become
positively charged ions
o Electronegative elements accept
electrons to form negatively
charged ions, or sometimes they
share electrons with other atoms
o Electronegativity increases in
moving from left to right and from
Electronegativity is a measure of the ability of an atom in a chemical compound to bottom to top
attract electrons toward itself.
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Electron structure Electrons...
Valence electrons (that occupy the o have discrete energy levels
outermost shell) determine all of the o tend to occupy lowest available energy level.
following properties o Maximum number of electrons for each energy level = 2n2
1) Chemical quantum
number
2) Electrical
4d
3) Thermal
4) Optical N-shell n = 4
4p
3d
4s

Energy 3p M-shell n = 3
3s

2p
L-shell n = 2
2s

1s K-shell n = 1
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Orbitals Orbitals can hold up to 2 electrons
Electron configuration of some elements
We can determine the stability of elements by electron configuration
Most elements: Electron configuration not stable.

Element Atomic # Electron configuration

Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
o Filled shells more stable
Lithium 3 1s22s1 o Valence electrons – those in
Beryllium 4 1s22s2 unfilled shells
Boron 5 1s22s22p1 o Valence electrons are most
Carbon 6 1s22s22p2 available for bonding and tend to
... ...
control the chemical properties
Neon 10 1s22s22p6 (stable)
Sodium 11 1s22s22p63s1
Magnesium 12 1s22s22p63s2 example: C (atomic number = 6)
Aluminum 13 1s22s22p63s23p1 1s2 2s2 2p2
... ...
Argon 18 1s22s22p63s23p6 (stable)
... ... ... valence electrons
Krypton 36 1s22s22p63s23p63d10 4s24p6 (stable)

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Atomic bonds

Primary or Secondary or
Chemical bonds Physical bonds

Ionic
Van der Waals
Covalent
Hydrogen
Metallic

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Ionic bond

metal + nonmetal

donates electrons accepts electrons

e.g.: MgO Mg12 1s2 2s2 2p6 3s2 O8 1s2 2s2 2p4

Oxygen (O) is more electronegative than magnesium (Mg)

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

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Ionic bonding (cont.)
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
Example: NaCl (Sodium Chloride)

Na (metal) Cl (nonmetal) Na11 1s2 2s2 2p6 3s1

unstable unstable
electron Cl17 1s2 2s2 2p6 3s2 3p5

Na (cation)
stable
+ - Cl (anion) Na+ 1s2 2s2 2p6 3s1
Coulombic stable
attraction Cl- 1s2 2s2 2p6 3s2 3p6

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Ionic bonding (cont.)

The ionic bond is the result of the Coulombic Attraction between the
oppositely charged species.
FA=-K/a2 (Eq. 1)
FA : Coulombic force of attraction between two oppositely charged ions
a : Seperation distance between the centers of the ions
K=ko(Z1q)(Z2q) (Eq. 2)
Z : valence of the charged ion
q :charge of a single electron (0.16×10-18 C)
Ko:proportionality constant (9×109 Vm/C)

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Type of forces in ionic bonding
In ionic bonding two forces are appeared:
o Attractive forces between the oppositely charged species.
o Repulsive forces between electrons of the charged species.
This is similar to forces between two atoms in solids, including attractive force between electrons and
nucleus and repulsive force between electrons and nucleus

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Ionic bonding forces
When
the centers of the two atoms remain separated by
the equilibrium spacing r0

EN, EA, and ER are, respectively, the net, attractive,

and repulsive energies for two isolated and adjacent
atoms
bonding energy (E0): potential energy at r0

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Ionic bonding energies
Attractive energy of two isolated ions

EA= -A/r

r is interatomic distance,
ɛ0 is the permittivity of a vacuum (8.85 × 1012 F/m),
|Z1| and |Z2| are absolute values of the valences for the two ion types, and
e is the electronic charge (1.602 × 1019 C).

Repulsive energy of two isolated ions

ER= B/rn

B and n are constants for the particular ionic system. n ~ 8.

Ionic bonding energy is high in the range 600 -1500 kJ/mol.

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Covalent bonding
o In covalent bonding two atoms share one or more pairs of electrons to achieve a more stable electron
configuration, typically to fill their outer electron shells.
o This type of bond occurs mostly between nonmetals.
o It occurs between atoms with similar electronegativity  share electrons
o The strength of a covalent bond depends on how many electron pairs are shared. They are strong
(diamond) or weak (Bi).
o Their materials are electrical insulators or semiconductors.
o Covalent bonding is central to the structure and function of most organic compounds

•Example: CH4 (methane) shared electrons

H
C: has 4 valence e-, from carbon atoms
CH4
needs 4 more

H: has 1 valence e-, H C H

needs 1 more
shared electrons
Each carbon atom has 4 covalent
Electronegativities H from hydrogen atoms bonds to four other carbon atoms.
are comparable. 14
Metallic bonding

o Metallic bond occurs between metal atoms.

o The outermost electrons of metal atoms are not tightly bound to any one atom. Instead, these electrons
are free to move throughout the entire structure, forming what is often referred to as an electron sea.
o There is an electrostatic attractive force between clouds of valence electrons and positively charged
metal ions.
o They can be weak or strong with energy in the range of 62 -850 kJ/mol.
o Examples of metals with metallic bonding include copper, aluminum, and iron
o The free movement of electrons allows metals to have
several key properties:
• Electrical conductivity
• Thermal conductivity
• Luster: The free electrons are responsible for
metals' shiny appearance.

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Secondary bond
o Van der Waals force includes attraction and repulsion between atoms, molecules, and surfaces.
o Van der Waals bonding are weak intermolecular forces between molecules or atoms due to temporary
or induced dipoles.
o Bonding energies low (4-30 kJ/mol).
o Hydrogen bonding is one type of Van der Waals interactions.
o It occurs when hydrogen is bonded to highly electronegative atoms like fluorine (F), oxygen (O), or
nitrogen (N). The hydrogen atom develops a significant partial positive charge, and it is strongly
attracted to the lone pairs of electrons on electronegative atoms in neighboring molecules.

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Mixed bonding
o Bonding tetrahedron: Each of the four extreme bonding types (i.e., ionic, covalent,
metallic, and van der Waals) is located at one corner of the tetrahedron
o Mixed bonds: for many real materials, the atomic bonds are
mixtures of two or more of these extremes:
covalent–ionic, covalent–metallic, and metallic–ionic
Examples:
• Covalent - ionic bonding: Ammonium Chloride (NH₄Cl)
• Covalent - metallic bonding: Copper(I) Chloride (CuCl)
• Covalent- ionic -metallic bonding: Copper Sulfate (CuSO₄)
Metallic bonding in elemental copper
Covalent bonding within the sulfate ion (SO₄²⁻)
Ionic bonding between Cu²⁺ and SO₄²⁻

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Bonding type-materials classification correlations

Ionic bonding Ceramics Ceramics Large bond energy

(Ionic & covalent bonding) large Tm
large E

Covalent bonding Polymers, ceramics

semiconductors Metals Variable bond energy
Metallic bonding moderate Tm
moderate E
Metallic bonding
Metals

Polymers Directional Properties

Covalent & secondary Secondary bonding dominates
Van der Waals Molecular solids small Tm
small E

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Review of atomic bonding
o Covalent Bonding:
• Electrons are shared between atoms
• Covalent bonds can result in materials with strong and weak bonding depends on how many electron
pairs are shared.
• Materials with covalent bonds tend to be brittle if they have strong bonding.
o Ionic Bonding:
• Atoms transfer electrons, resulting in oppositely charged ions that are held together by attractive
forces.
• Ionic materials, like ceramics, tend to be brittle because of their strong bonding.
• Ionic compounds typically have high melting points due to strong electrostatic attraction.
o Metallic Bonding:
• Electrons are not shared or transferred between individual atoms but form a "sea of electrons"
that move freely through the material.
• Metallic bonds allow for easier sliding of atoms past each other, leading to ductility
• The strength of metallic bonds can vary depending on the material. Stronger bonds lead to
stronger materials.
• Since electrons are free to move, metallic materials also exhibit excellent electrical and thermal
conductivity. 19
Properties from Bonding: Tm and α

• Bond length, r Melting Temperature, Tm Thermal expansion coefficient, α

r
Energy Energy
Energy
ro ro
Equilibrium spacing
r r
ro
r smaller Tm
Eo
larger α

Eo = “bond energy” larger Tm Eo smaller α

Tm is larger if Eo is larger. α is larger if Eo is larger.

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Impact of atomic bonding on mechanical properties
Type of atomic bonding directly influences the mechanical behavior of materials, determining
whether they are ductile, brittle, strong, or weak.
Understanding atomic bonding is crucial for materials selection for specific engineering applications
based on required mechanical properties.

o Strength: Strong bonds (covalent and ionic) typically result in stronger materials, while weaker
bonds (metallic and van der Waals) can lead to lower strength.
o Ductility/Brittleness: Materials with metallic bonds are generally ductile, while those with
covalent and ionic bonds tend to be brittle.
o Hardness: Covalent bonding generally produces hard materials, while metallic and ionic bonding
results in varying hardness depending on the material's structure.

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