Materials Science & Engineering

2023.1 semester

Mechanical Engineering Dep’t

Prof. Suh Wang Byuck

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 Chapter 2: Atomic Structure &
Interatomic Bonding

ISSUES TO ADDRESS...
• What characteristics of atoms promote
interatomic bonding?
• What types of interatomic bonds exist ?

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 Atomic Structure
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10 -27 kg

• atomic number = # of protons in nucleus of atom

• atomic mass unit = amu = 1/12 mass of 12C

A = Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1 g/mol
C 12.011
H 1.008
etc.

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 Atomic Structure (cont.)
• Some of the following properties are
determined by an atom's electronic structure:
1) Chemical
2) Electrical
3) Thermal
4) Optical

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 Electronic Structure
• Electrons have wave-like and particle-like
characteristics.
• Two wave-like characteristics are
– Electron position in terms of probability density
– shape, size, orientation of probability density
determined by quantum numbers

– Quantum # Designation/Values
n = principal (energy level shell) K, L, M, N, O (1, 2, 3, 4, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic (no. of orbitals) 1, 3, 5, 7 (-l to +l)
ms = spin ½ , -½

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

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
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 SURVEY OF ELEMENTS
• Most elements: Electron configurations not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• Why not stable? Valence (outer) shell usually not

completely filled.
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 Electron Configurations
• Valence electrons – those in outer unfilled
shells
• Filled shells are more stable – require more
energy to gain or lose electrons
• Valence electrons available for bonding and
tend to determine an atom’s chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

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 Electronic Configurations (cont.)
ex: Fe (atomic # = 26)
Electron configuration 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

1s K-shell n = 1
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 The Periodic Table
• Elements in each column: Similar valence electron structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H 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

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions. 10
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

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 Ionization Process
metal atom + nonmetal atom

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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 Ionic Bonding (cont.)
• Energy – minimum energy most stable
– Net energy = sum of attractive and repulsive energies
– Equilibrium separation when net energy is a minimum

EN = EA + ER = - A + Bn
r r
Repulsive energy ER

Interatomic separation r

Net energy EN
Fig. 2.10(b), Callister &
Rethwisch 10e.

Attractive energy EA

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 Ionic Bonding (cont.)
Predominant bonding in Ceramics
Examples:
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

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 Covalent Bonding
• Similar electronegativities  share electrons
• Bonds involve valence electrons – normally s and p
orbitals are involved
• Example: H2
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

Fig. 2.12, Calliser & Rethwisch 10e.

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Covalent Bonding: Bond Hybrization
• Carbon can form sp3 hybrid
orbitals

Fig. 2.14, Callister & Rethwisch 10e.

(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Fig. 2.13, Callister & Rethwisch 10e.

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 Covalent Bonding (cont.)
Hybrid sp3 bonding involving carbon
Example: CH4
C: each has 4 valence electrons,
needs 4 more
H: each has 1 valence electron,
needs 1 more

Electronegativities of C and H
are similar so electrons are
shared in sp3 hybrid covalent Fig. 2.15, Callister & Rethwisch 10e.
(Adapted from J.E. Brady and F. Senese, Chemistry:
bonds. Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

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 Mixed Bonding
• Most common mixed bonding type is Covalent-Ionic
mixed bonding

% ionic character = x (100%)

where XA & XB are electronegativities of the two

elements participating in the bond
Ex: MgO XMg = 1.2
XO = 3.5

æ -
(3.5-1.2)2 ö
ç
% ionic character = 1- e 4 ÷ x (100%) = 73.3%
ç ÷
è ø
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 Metallic Bonding
• Electrons delocalized to form an “electron cloud”

Fig. 2.19b, Callister & Rethwisch 10e.

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

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

• Permanent dipoles
secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer
linear polymer molecule
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 Properties Related to Bonding I:
Melting Temperature (Tm)
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = The larger Eo, the higher Tm
“bond energy”
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 Properties Related to Bonding II:
Coefficient of Thermal Expansion (α)
• Coefficient of thermal expansion, α
length, L o ΔL
= α (T2 -T1)
unheated, T1 Lo
ΔL
heated, T 2

The smaller Eo, the larger αl.

unstretched length • Increase in bond length is due to

Energy

ro asymmetry of the E vs. r curve. This

r results in an increase in al.
E
larger α • As E0 increases this asymmetry
decreases.
o
E smaller α
o 23
 Summary: Properties Related to
Bonding Type and Bonding Energy
Ceramics Large bond energy
(Ionic & covalent bonding): high Tm
large E
small αl

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate αl

Polymers Weak bond energy (between chains)

(Covalent & Secondary): Secondary bonding responsible for
most physical properties
low Tm
small E
large αl
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 SUMMARY
• A material’s chemical, electrical, thermal, and optical
properties are determined by electronic configuration.
• Valence electrons occupy the outermost unfilled
electron shell.
• Primary bonding types include covalent, ionic, and
metallic bonding.
• Secondary or van der Waals bonds are weaker than
the primary bonding types.
• The percent ionic character of a covalent-ionic mixed
bond between two elements depends on their
electronegativities.

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 ■End of Document

swbyuck@yu.ac.kr

출처 : 재료과학과 공학 제10판 – 박인규,이재갑, 김용석 옮김 – Wiley 시그마프레스 http://www.sigmapress.co.kr

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