Brief Review of the Previous

Lecture

Atomic Structure and Inter-atomic Bonding

Bohr Atomic model
Electron Energies are Quantified
Comparison
between the
Bohr and
Wave-
mechanical
models

Electron
energies of
the
hydrogen
atom
 Electronic Structure
 Electrons have wavelike and particulate properties.

 Two of the wavelike characteristics are

– electrons are in orbitals defined by a probability

– each orbital at a discrete energy level is determined by
quantum numbers.

n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)

 = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n -1)
– Quantum # Designation
ml = magnetic 1, 3, 5, 7 (- to +)
ms = spin ½, -½

4
 Electronic Configurations

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

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

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

5
 Table 2.1

Summary of the relationships among the quantum

numbers n, l and m and numbers of orbitals
 ENGG 103
Materials in Design

Atomic Structure and Inter-atomic Bonding II

Callister Chapter 2
14 March 2016
Bonding Forces and Energies

When two atoms are brought

together, the stable inter-atomic
distance and the stable energy are
determined by a balance between
the attractive and repulsive forces

Remember, force is the first derivative

of the energy-interatomic separation
curve
Primary Interatomic Bonds

Ionic
Covalent
Metallic
 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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Ionic bonding in NaCl
Attractive and repulsive energies for two isolated
atoms as a function of the interatomic distance

Attractive energy

Repulsive energy

EN = EA + ER = A + Bn
r r
 Ionic Bonding

Energy – minimum energy most stable

– Energy balance of attractive and repulsive terms

EN = EA + ER = A + Bn
r r

Repulsive energy ER

Interatomic separation r
Net energy EN

Attractive energy EA

14
See Example Problem 2.2
Callister pp. 3 and 35
 Examples: Ionic Bonding
Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

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 Covalent Bonding
Similar electronegativity ∴ share electrons
Bonds determined by valence
– s & p orbitals dominate bonding

Example Hydrogen H2

Each H: has 1 valence e-,

needs 1 more
H H
Electronegativities
are the same.
shared 1s electron shared 1s electron
from 1st hydrogen from 2nd hydrogen
atom atom

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 The Metallic Bond

The free electrons shield the positively charges ion cores from the mutually
electrostatic repulsive forces

The metallic bond is therefore non-directional

As a consequence, metals are good conductors of heat and electricity

 Secondary Bonding
Arises from interaction between dipoles
Fluctuating dipoles
ex: liquid H 2
asymmetric electron clouds
H2 H2

+ - + - H H H H
secondary secondary
bonding bonding
Permanent dipoles-molecule induced
secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

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Secondary or van der Waals Bonds
Bonding in a Polymer
Fluctuating Induced Dipole Bonds
Polar Molecule Induced Dipole Bonds
 Permanent Dipole Bonds
Hydrogen Bonding

A single proton forms a bridge

between two negatively charged atoms
 Bonding and the Melting Point

• Bond length, r • Melting Temperature, Tm

Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

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Bonding and the Thermal Expansion Coefficient
Coefficient of thermal expansion, α
length, L o coeff. thermal expansion
unheated, T1
ΔL ΔL
= α (T2 -T1)
heated, T 2 Lo

α ~ symmetric at ro
Energy
unstretched length
ro
r α is larger if Eo is smaller.

E
larger α
o
E smaller α
o 26
Bonding Energies (kJ/mol) and Melting Temperatures (°C)
The Structure of Water

Ice
Each water molecule has 4
Each waterneighbours
nearest molecule has 4
nearest neighbours

Liquid water
Each water molecule has 4.5
nearest neighbours

Therefore more dense than

solid water
 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
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 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small α

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

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

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 Home Assignment

Tutorial videos
Bonding (p.33)
Bonding (p. 36)
Bonding (p.39)
Bonding videos (p. 40)
Bonding (p.41)

Concept check (p. 39)

Study the Summary carefully and thoroughly

Do the following problems:

2.22, 2.24, 2.27, 2.3FE, 2.4FE
Typical Multiple Choice Questions
1 + 8*(1/8) = 2

6*(1/2) + 8*(1/8) = 4
dF/dr at r = 𝒓𝟎 is proportional to E

The further apart atoms are,

the lower E will be
Lateral and longitudinal strains have opposite signs

Tensile strain
Lateral strain is zero

𝒍𝒍𝒍𝒍𝒍𝒍𝒍 𝒔𝒔𝒔𝒔𝒔𝒔 Lateral

𝝊=− strain
𝒕𝒕𝒕𝒕𝒕𝒕𝒕 𝒔𝒔𝒔𝒔𝒔𝒔
ε = 𝝈/E = (𝑙1 - 𝑙0 )/𝑙0

𝑙1 = (𝝈/E*𝑙0 )+ 𝑙0