MSE-101

Fundamentals of
Engineering Materials

Chapter 2
BONDING AND PROPERTIES
Dr. Ghufran ur Rehman

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BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?
• What types of bonds are there?
• What properties are inferred from bonding?

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Atomic Structure (Freshman Chem.)
• Atom –
• electrons – 9.11 x 10-31 kg
• protons
• Neutrons } 1.67 x 10-27 kg
• Atomic number
• = # of protons in nucleus of atom
• = # of electrons of neutral species

• Atomic mass
• expressed as the sum of the masses of protons and neutrons within the nucleus.
• number of neutrons (N) may be variable → isotopes
• Atomic mass unit = 1 amu = 1/12 mass of 12C ( scale established based on C )
• Atomic wt = wt of 6.023 x 1023 molecules or atoms

• 1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.
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Atomic Structure
• Valence electrons
determine all of the following properties

• Chemical
• Electrical
• Thermal
• Optical

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 Electronic Structure
• Electrons have wavelike and particulate properties.
• This means that electrons are in orbitals defined by a
probability.
• Each orbital at discrete energy level determined by
quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

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Electron Energy States
Electrons... • have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Adapted from Fig. 2.4,
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Callister 7e.
SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.

Valence (outer) shell

usually not filled
completely.

Why?

Adapted from Table 2.2,

Callister 7e.

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Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s Adapted from Fig. 2.4,
Callister 7e.

1s K-shell n = 1

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Electron Configurations
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons are most available for bonding and tend to
control the chemical properties

• example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

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 The Periodic Table

give up 1e

inert gases
give up 2e
• Columns:

accept 2e
accept 1e
Similar

give up 3e
Valence
Structure H He Adapted from
Li Be O F Ne Fig. 2.6,
Na Mg
Callister 7e.
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 electrons
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to become + ions. to become - ions.
Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

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

[Ne] [Ne]

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Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

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 net force FN between the two atoms

The origin of an attractive force FA depends on

the particular type of bonding that exists
between the two atoms, as discussed shortly.
Repulsive
forces arise from interactions between the
negatively charged electron clouds for the
two atoms and are important only at small
values of r as the outer electron shells of the
two atoms begin to overlap

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Ionic Bonding
• Energy – minimum energy most stable
• Energy balance of attractive and repulsive terms

Repulsive energy ER

-
A -
B
Interatomic separation r EN = EA + ER =
r rn
Net energy EN

Adapted from Fig. 2.8(b),

Callister 7e.
Attractive energy EA

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Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

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Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals dominate bonding
• Example: CH4
shared electrons
H from carbon atom
C: has 4 valence e-, CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 7e.

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Primary Bonding
• Metallic Bond -- delocalized as electron cloud
 (X A -X B )2 
 - 
• Ionic-Covalent Mixed Bonding - % ionic character = 1- e
4
 x 100
 
 
where XA & XB are Pauling electronegativities
(tendency for an atom of a given chemical element to attract shared electrons when forming a chemical bond. )

Ex: MgO XMg = 1.3
XO = 3.5

 (3.5 -1.3)2 
 - 
% ionic character = 1 - e 4  x (100%) = 70.2% ionic
 
 
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SECONDARY BONDING
Arises from interaction between dipoles

• Fluctuating dipoles

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer
Adapted from Fig. 2.14, Adapted from Fig. 2.13, Callister 7e.
Callister 7e.

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 Summary : Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury

Secondary smallest Directional

inter-chain (polymer)
inter-molecular 20
Properties From Bonding: Tm
• Bond length, r
• Melting Temperature, Tm
r Energy

• Bond energy, Eo
ro
Energy r
smaller Tm
unstretched length
ro
r larger Tm
Eo =
Tm is larger if Eo is larger.
“bond energy”
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Properties From Bonding : a
• Coefficient of thermal expansion, a

length, L o coeff. thermal expansion

unheated, T1
DL DL
= a (T2 -T1)
heated, T 2 Lo

• a ~ symmetry at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

E
smaller a
o
E larger a 22
o
Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large a
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