BMFG 1213

ENGINEERING MATERIALS

Sem/Session : 1/2022-2023
Week 2
Chapter 2

Title : Atomic Structure & Bonding

1
 Course Learning Outcomes
Upon completion of this subject, students should be able to:

1. Explain the basic concepts of engineering materials in terms of

interatomic bonding and crystal structure
2. Analyze the properties of engineering materials based on its
structure.
3. Describe the processing methods for engineering materials.

2
 Learning Objectives

 To describe the underlying physical concepts

related to structure of matter.

 To examine the relationships between the structure

of atoms-bonds-properties of engineering materials.

3
 Chapter Outlines
2.1 Atomic Structure
- Atomic number
- Quantum number
- Electron configurations

2.2 Atomic bonding in solids

– Ionic
– Covalent
– Metallic
– Secondary
4
Atomic Structure Models

5
2.1.1 FUNDAMENTAL CONCEPTS

WHAT IS AN ATOM ?
1. The basic unit of an element that can undergo
chemical change.
2. Consists of three particles: protons, neurons and
electrons.

Components
Mass (g) Charge (C)
in atom

Proton 1.673 10-24 + 1.602 10-19

Neutron 1.675 10-24 0

Electron 9.109 10-28 - 1.602 10-19

Figure 2.1: model of an atom

Atoms = nucleus (protons & neutrons) + electrons 6

 Let’s Talk first…
Why do we need to learn
this???

7
Additional Info…

Silicon + metal

Polycrystalline
Silicon

8
 Periodic table of the elements

Atomic number, Z 29
Atomic weight, A
Cu
H 63.54 He
Li Be O F Ne
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra
9
 Atomic number, Z 29
Cu
Atomic weight, A 63.54

 The atomic number, (Z) is the number of protons in the nucleus of an

atom of an element. In neutral state, the atomic number is also equal
to the number of electrons in its charge clouds.
Atomic number (Z) = protons

 The atomic mass, (A) of an element is equal to the sum of the masses
of protons and neutrons within the nucleus.
Atomic mass = mass of protons + mass of neutrons

 The Avogadro number, (NA) of an element is the number of atoms or

molecules in a mole.
 The atomic mass unit, (amu) of an element is the mass of an atom
expressed as 1/12 the mass of a carbon atom. 10
2.1.2 ELECTRONS IN ATOMS
(a) Atomic Models
All of the physical laws of nature that account for
CLASSICAL the behavior of the normal world (including
MECHANICS Newton’s Law of Motion)
ATOMIC
MODELS
QUANTUM Quantum mechanics is a set of scientific principles
describing the known behavior of energy and
MECHANICS
matter that predominate at the atomic and
subatomic scales

 electron structure
BOHR’S WAVE MECHANICAL
MODEL MODEL  electron position
• by Neils Bohr using • Modification made to
Rutherford postulate Bohr’s atomic model by  electron energy
model. De Broglie, Heisenberg
and Schrodinger.
 electron configuration
11
 Quantum Mechanics

 branch of physics this is used to describe atomic and sub-atomic

entities. Electron may occupy only discrete energy levels or states.
 electron are permitted to have only specific values of energy.
 electron may change energy, but it must make a quantum jump either
to an allowed higher energy (absorption of energy) or to a lower energy
(emission of energy).

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(1) BOHR’S ATOMIC MODEL
Atomic model according to Bohr:
 Electrons are assumed to revolve around the atomic nucleus in discrete orbitals, and the
position of any particular electron is more or less well defined in terms of its orbital.
 Energies of electrons are quantized: electrons can have only specific energy values.
 Electron may change energy by making a quantum jump.
1. When atoms absorbed energy, the electrons become excited and jumped from low
energy levels (close to the nucleus) to high energy levels (farther out from nucleus)
2. Energy is emitted during the same transition from high energy levels to lower energy
levels.

Figure 2.2: Bohr’s atomic model 13

(Callister 8th ed.) Figure 2.3: Electron quantum jump (library.thinkquest.orgz)
(2) WAVE MECHANICAL ATOM MODEL

 subdivision of quantum mechanics that considers electron to have

both wave- like and particle- like characteristics
 overcome the limitation of Bohr Model (because of its ability to
explain several phenomenon involving electrons)
 using this model, every electron is characterized by four parameters
called Quantum Numbers
 with this model, an electron is no longer treated as a particle
moving in a discrete orbital; rather, position is considered to be the
probability of an electron’s being at various locations around the
nucleus

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(b) Quantum Numbers

 Using wave mechanics, every electron in an atom is characterized

by 4 parameters QUANTUM NUMBERS

 A set of four numbers, the values of which are used to label

possible electron states. Three of the quantum numbers are
integers, which also specify the size, shape and spatial orientation of
an electron’s probability density; the fourth number designates spin
orientation

 The quantum numbers arise from solution of Schrodinger’s equation

 Pauli Exclusion Principle: only one electron can have a given set
of the four quantum numbers

15
  Each orbit in the atomic model is associated with a definite
energy and therefore called as energy shell or energy level.
 Each orbital at discrete energy levels separate into electron
subshells & quantum numbers dictate the number of state within
each subshell.

Orbital/subshell
Energy level s orbital s orbital
orbital (l=0)
n=1 (l=0)

n=2
p orbital
(l=1)
n=3

n=1 n=2
Figure 2.6: Energy level and subshell 16
Energy level/shell
Four parameters of Quantum Numbers (QN):

 n -principal QN
 l -secondary QN @ orbital angular
momentum
 ml - third QN @ magnetic quantum number
 ms - fourth QN @ spin quantum number

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 1. Principle Quantum Number (n)
 Integer value used to specify the shell the electron belongs to
 It has positive integer values of 1,2,3… (n)
 Sometimes designated by letters K,L,M,N,O…
 K= 1,L= 2, M= 3, N= 4, O= 5…
 Related to distance of an electron from nucleus, or its position
 Related to the size of the shell, (i.e n=1 is the smallest)
 As ‘n’ increase, orbital become larger, means electrons has higher
energy and less tightly bound to the nucleus.

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Figure 2.7: Principal quantum number source : animatedscience.co.uk
 2. Orbital Quantum Number (ℓ)
 Specifies the subshell the electron occupies
 The value of ℓ is always (n-1) . Where n is the number of principle
shell.
ℓ = n -1

 Referred to as states s,p,d,f

l=0 , s state , so 2 electron

l=1 , p state , so 6 electron
l=2 , d state , so 10 electron
l=3 , f state , so 14 electron
(a) spherical (b) polar (c) cloverleaf (l = 2)
Figure 2.8: Shape of different orbital in the subshells

 These subshell is related to the shape of the electron subshell.

 The maximum number of electrons in subshell = 2(2ℓ+1)
 Principal QN No. electron in
the energy state
(n)

Hydrogen 1s1

Energy state
Orbital QN (ℓ)

20
  The allowable subshell and the number of electrons within each subshell is
given by table below.
Principal QN (n) @ QN 1

Orbital QN (ℓ) @ QN 2

21
 3. Magnetic Quantum Number (mℓ)
 Determine the number of energy states for each subshell
 For an s subshell, there is a single state. Why? Because there is
only one way in which a sphere (l = 0) can be oriented in space.

eV 4d
Energy
4p N-shell n = 4
3d
4s
Electron energy 3p
-1.5 M-shell n = 3
level 3s
-3.4 2p L-shell n = 2
2s
-13.6 1s K-shell n = 1

Orbital/ State Energy

subshell level/shell 22
22
Schematic representation of the relative energies of the
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electron for various shells and subshell
 4. Spin Quantum Number (ms)
 Specifies the value for the spin moment of the electron, which must be
oriented up or down.
 The two values possible are (+ ½ ) and (- ½ ) for each of the spin orientations.
 Pauli exclusion Principle : each electron state can hold no more than two
electrons, which must have opposite spins.

Q.N 4
Q.N 3
Q.N 2
Q.N 1

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 Additional
Summary Info…

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https://chem.libretexts.org/@api/deki/files/8998/Screen_shot_201
0-12-04_at_8.33.00_PM.png?revision=1

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Electronic Configurations

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 So…..how electron is
configure within an atom???

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 (c) Electron Configurations

1. Aufbau Principle:
 lower energy orbitals fill before higher
energy orbitals (fill-up lower energy first).
 Exp: the orbitals in the n=1 energy level will
fill up before the orbitals in the n=2 energy
level.
2. Hund's Rule:
 if 2 or more orbitals are available at the
same energy, one electron goes into each
until all of them are half full before pairing
up .
3. Pauli Exclusion Principle:
 no two electrons can be identified by the
same set of quantum numbers (i.e. must
have different spins). Writing Electron Configurations with the Aufbau
 the spin quantum number, ms ensure that Principle
two electrons within the same orbital have https://byjus.com/chemistry/electron-configuration/
unique sets of quantum numbers.
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S=
2e

p=
6e

d=
10 e

f=
14 e

The order of which electron fill up the orbitals is as follow:

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1s22s22p63s23p6 4s23d10 4p65s24d105p66s24f145d106p67s25f146d107p6
Pauli Exclusion Principle:
 To determine the manner in which these states are filled
with electrons
 Another quantum mechanical concept
 Stipulates that each electron state can hold no more
than two electrons (must opposite spin)

 s, p , d , f subshells = 2,6,10,14 electrons respectively

 E.g
H = 1s1
He = 1s2
Na = 1s2 2s2 2p6 3s1
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 Valence electron:
- are those that occupy the outermost filled shell
(important because they participate in the bonding
between atoms to form atomic and molecular
aggregates
- indicate the physical & chemical properties of solids

 Stable electron configurations:

- the states within the outermost or valence electron shell
are completely filled

e.g. neon 1s22s22p6

argon 1s22s22p63s23p6
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33
 Atomic number, Z 26
example: Fe (Z = 26) Fe
electron configuration is Atomic weight, A 55.847

1s2 2s2 2p6 3s2 3p6 3d 6 4s2

Highest energy
4d
n=4
4p
Principal Orbital 3d

state
letters or # of electrons
Quantum
subshell 4s

Energy
Numbers
3p n=3
Lowest energy state

3s

1 s 2
(ground state)

2p n=2
2s

1s n=1
34
34
Figure 2.5 Spin directions of unpaired electrons in d orbital

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 TRY NOW…
• Give the electron configurations of the
following elements.

Na= 11 Mn= 25
Mg= 12 Cu= 29
Al= 13 Br= 35
Si= 14 O= 8
Cr= 24

36
 Answer…
Na = 11 = 1s22s22p63s1
Mg = 12 = 1s22s22p63s2
Al = 13 = 1s22s22p63s23p1
Si = 14 = 1s22s22p63s23p2
Mn = 25 = 1s22s22p63s23p64s23d5
Cu = 29 = 1s22s22p63s23p64s23d9
Br = 35 = 1s22s22p63s23p64s23d104p5
O = 8 = 1s22s22p4
Cr = 24 = 1s22s22p63s23p63d54s1

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 Atomic Bonding
Formation & Types

38
 ELECTRON VALENCE
Most elements: electron configuration not stable.
Why?
 Valence (outer) shell usually not filled completely.
example: Carbon C
atomic number, Z = 6

1s2 2s2 2p2

valence electrons

 Electron that occupy the outermost (valence) shell.

 Valence electrons  those in unfilled shells (most elements) are not stable & filled
shells (inert gases) more stable.
 Participate in the bonding (unfilled shell) between atoms to form atomic & molecular
aggregates determine physical (optical, thermal & electrical) & chemical properties
39
 K (s)

L (s,p)

M (s,p,d)

N (s,p,d,f)
l=0 , s state , so 2 electron
l=1 , p state , so 6 electron
l=2 , d state , so 10 electron
l=3 , f state , so 14 electron

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 TYPES OF BONDING

A. PRIMARY BONDING

1. Ionic bonding : strong Coulomb interaction among negative atoms (have an extra

electron each) and positive atoms (lost an electron)

2. Covalent bonding: electrons shared between the molecules, to saturate the valency.

3. Metallic bonding: the atoms are ionized, losing some electrons from the valence

band. Those electrons form an electron sea, which binds the charged nuclei in place.

B. SECONDARY BONDING OR VAN DER WAALS BONDING

1. Fluctuating induced dipole

2. Polar induced dipole

3. Permanent dipole
41
Primary Bonding

42
 1.0 IONIC BONDING
 Definition: A coulombic interatomic bond that exist between two adjacent
and oppositely charged ions or by transferring of electron of metallic element to
the nonmetallic element
(coulombic force: a force between charged particles such as ions; the force is
attractive when the particles are of opposite charge)

 Form between metallic elements and nonmetallic elements

 Atoms of metallic element easily give up their valence electrons to the

nonmetallic atoms

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation)
+ - Cl (anion)
stable Coulombic stable 43
Attraction
 Normally atoms are neutral BUT to gain stability they have to either:

1.losing one or more valence electrons positively charged ions (cation)

2.gain one or more valence electrons negatively charged ions (anion)

 Due to its electronegativity (a measure of how willing atoms are to accept

electrons);

1.Metallic elements tend to lose electrons (highly electropositive)

2.Non-metallic elements tend to gain electrons (highly electronegative)

 The resulting charged will attract each other to form ionic bonding .

 Ionic bonding is termed as nondirectional: magnitude of the bond is equal in

all directions around an ion.

44
 Occurs between + and – ions

 Large difference in electronegativity required

 Strong, nondirectional bond

 Example: NaCl, LiF, Na20

45
 EXAMPLES: IONIC BONDING
• Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

46
47
 ELECTRONEGATIVITY
 Is defined as the degree to which an atom attracts electrons to itself
 Is measured on a scale from 0 to 4.1 and each is assigned a value on this scale
 Large values: tendency to acquire electrons.

Smaller electronegativity
-most electropositive
Larger electronegativity
-are alkali metals - are fluorine, oxygen and nitrogen,
-electronegativities ranging from 0.9 electronegativities of 4.1, 3.5 and 3.1
for cesium, rubidium,potassium to 1.0 for sodium respectively 48
and lithium
• Columns: Similar Valence Structure

inert gases
give up1e

accept 2e
accept 1e
give up 2e
give up 3e
Metal

Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg S Cl Ar
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

- Readily give up electrons - Readily acquire @ accept electrons
to become + ions @ cations to become – ions @ anions
- are metallic in nature - are nonmetallic in nature 49
 Electronegativity - a measure of how willing atoms are to
accept electrons

 Subshells with one electron – low electronegativity

 Subshells with one missing electron -high

electronegativity

 Electronegativity increases from left to right

 Metals are electropositive – they can give up their few

valence electrons to become positively charged ions

50
EXAMPLE:

51
52
53
GENERAL PROPERTIES OF IONIC
COMPOUND.

 Strong electrostatic attraction means

high melting and evaporation points.
 But usually hard and brittle solid at
room temperature.
 It does not conduct electricity except
for in molten state or when dissolve in
water.
 Ionic compounds are mostly water
soluble.

54
 2.0 COVALENT BONDING
 Definition: a primary interatomic bond that is formed by the sharing of electrons
between neighboring atoms

 Stable configuration are assumed by two or more elements sharing their electrons.

 It occurs because the atoms in the compound have similar tendency to gain electrons.

 Commonly occurs when two non metals bond together; for e.g. non-metallic molecules such as
Cl2,H2, F2, etc. or molecules containing dissimilar atoms like CH4, HNO3, H2O etc.

 Covalent molecules tend to exists as liquids or gases at room temperature.

 There are two subtypes of covalent bonds:

1. Polar bond; formed when electrons are unequally shared between two atoms
2. Non-polar bond; formed when they are equal attraction for electrons (equally share)

 Multiple Bonds:
1. Each pair of electrons shared between two atoms, a single covalent bond is formed.
2. Some atoms can share multiple pairs of electrons, forming multiple covalent bonds. (double bond,
triple bond)

 Covalent bond is directional: between specific atoms in the direction between 1 atom and another
55
that participates in the electron sharing.
56
57
58
 COVALENT BONDING- single bond ; polar (HCl) (ZH= 1, ZCL= 17)
Polar bond; formed when electrons are unequally shared between two atoms

This pair of atoms has a large difference in 2.1

electronegativities.

Electrons will spend almost all their time

around the Chlorine atom (but not strong
enough to pull electron to form ions) and 3.0
virtually no time around the Hydrogen
atom.

Chlorine has a slight negative charge

and Hydrogen carries a slight positive
charge

59
 COVALENT BONDING- single bond ; non-polar (Cl2) (ZCL= 17)
Non-polar bond; formed when they are equal attraction for electrons (equally share)

Chlorine molecules as Non-polar

bonding:

The values written beside the atoms 3.0 3.0

are from electronegativities table. The
difference is calculated which in this
case is zero.

This means that neither atom claims

more share of the pair of electrons,
so they spend equal time around
each.

60
 COVALENT BONDING- single bond ; non-polar (CH4) (ZC= 6, ZH= 1)
Non-polar bond; formed when they are equal attraction for electrons (equally share)

Electronegativity for
H and C is 2.1 and 2.5
respectively

61
 EXAMPLES: COVALENT BONDING
H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9 GaAs

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA) 62
 COVALENT BONDING- single bond ; non-polar

Why methane is also considered as non-polar?

 A molecule may be non-polar either because there

is (almost) no polarity in the bonds or because of
the symmetrical arrangement of polar bonds.
Representation of a methane
 In the methane molecule (CH4) the four C–H bonds molecule, with the blue sphere
are arranged tetrahedrally around the carbon atom. signifying carbon and the four red
spheres signifying hydrogen

 Each bond has polarity (though not very strong).

However, the bonds are arranged symmetrically so
there is no overall dipole in the molecule because
they cancel themselves out. Just like pulling the
rope in opposite directions.

electronegativity H = 2.1 63
electronegativity C = 2.5
COVALENT BONDING- Multiple bond ; nonpolar

 Multiple Bonds:
1.Each pair of electrons shared between two atoms, a single covalent bond is
formed.
2.Some atoms can share multiple pairs of electrons, forming multiple covalent
bonds. (double bond, triple bond)

Additional
Info…

64
GENERAL PROPERTIES OF COVALENT COMPOUND
 For covalent solids (formed by a system of continuous covalent bond):
1. Non-conductive in solid and molten state.
 no free electrons and no ions so they don’t conduct electricity
2. Very high melting point and non volatile (useful for high
temperature application, but high processing temperature)
3. Hard and incompressible diamond

4. Insoluble
5. Example: diamond, boron nitride, quartz (SiO2), Silicon carbide (SiC)

 For substances with covalent bonding:

1. Low melting and boiling point
2. Soft in the solid state
3. Solubility depends on the polarity of the molecules
4. Example: graphite, polymer graphite 65
 3.0 METALLIC BONDING
 Final primary bonding type, found in metals and their alloys.
 Valence electrons in metals are not bound to any particular atom in the solid  drift
through out the entire metal (electron sea).
 Remaining electrons and the atomic nuclei form the ‘ion core’  net positive charge.
 The free electron act as ‘glue’ to hold the ion cores together.
 Metals are good conductor as a consequence of their free electrons.
© 2003 Brooks/Cole Publishing / Thomson Learning™

© 2003 Brooks/Cole Publishing / Thomson Learning™

The metallic bond forms when atoms give up their
valence electrons, which then form an electron sea. When voltage is applied to a metal, the
The positively charged atom cores are bonded by electrons in the electron sea can easily move
mutual attraction to the negatively charged and carry a current 66
electrons
GENERAL PROPERTIES FOR METALS:
 Bonding may be weak or strong;
energies range from 68 kJ/mol (0.7
eV/atom) for mercury to 850 kJ/mol (8.8
eV/atom) for tungsten.
 High melting and boiling points. Their
respective melting temperatures are -39
and 3410C.
 Metals are good conductors of both
electricity and heat as a consequence of
their free electrons
© 2003 Brooks/Cole Publishing / Thomson Learning™
 Insoluble in all solvents
 Good ductility and workability-
 most metals and their alloys fail
in a ductile manner
 fracture occurs after the
materials have experienced
significant degrees of permanent
deformation.

When voltage is applied to a metal, the

electrons in the electron sea can easily move 67
and carry a current
Secondary Bonding

68
 4.0 SECONDARY BONDING
 Secondary or physical forces and energies are weaker than the
primary ones
 Exist in all atoms and molecules
 Arises from atomic or molecular dipoles
(electric dipole= exists whenever there is some separation of positive and
negative portions of an atom or molecule)

 The bonding results from the coulombic attraction between the positive end
of one dipole and the negative region of an adjacent one is as below:

Dipole interactions occur between

 induced dipoles
 between induced dipoles and polar molecules (which have permanent
dipoles), and
 between polar molecules. 69
PERMANENT DIPOLE BONDS:
1. Polar molecule – induced dipole bonds.
 Exist in some molecules due to its asymmetrical arrangement of positively and
negatively charged regions.
 Made of atoms with different electronegativity that are united by covalent bonding.
 It cause the molecules to attract to each other and can also induced dipoles in
adjacent non polar molecules
 Example: HCL

Hydrogen secondary
+ - bonding + -
Chlorine

70
PERMANENT DIPOLE BONDS:
2. Hydrogen Bonding
 Exist between adjacent polar molecules.
 Considered as the strongest among secondary bonds.
 It occurs between molecules in which hydrogen is covalently bonded to F, O or N
 Example: HF, H2O, NH3

© 2003 Brooks/Cole Publishing

/ Thomson Learning™

71
TEMPORARY FLUCTUATING DIPOLE
A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric (the overall spatial distribution of the electrons is
symmetric with respect to the positively charged nucleus)(e.g. H2, Cl2).
 Arises from interaction between dipoles.
Very weak electric dipole bonds due to asymmetric distribution of electron
densities.

general case: example: liquid H2

asymmetric electron
clouds
H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

72
Comparison of material & properties
by bonding types Additional
Info…

Callister 73
 intermolecular intramolecular
Summary

23
Inspirational Quotes for Today…

75
THANK YOU

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