Chapter 2: Atomic Structure &

Interatomic Bonding

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

Chapter 2 - 1
Atomic Structure (Freshman Chem.)
• atom – electrons – 9.11 x 10-31 kg
protons
}
neutrons 1.67 x 10 kg
-27

• atomic number = # of protons in nucleus of atom

= # of electrons in neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

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

Chapter 2 - 2
 Atomic Structure

• Some of the following properties

1) Chemical
2) Electrical
3) Thermal
4) Optical
are determined by electronic structure

Chapter 2 - 3
 Electrons in Atoms: Bohr Atom

• In the early years of the 20th century, atomic spectroscopy

indicated that electron energies are quantised.
– The Bohr planetary model of the atom is an early attempt to
visualise a system that would yield quantised energies.
– It is incomplete because it does not explain why the orbiting
electrons do not emit electromagnetic radiation.

nucleus

orbiting
electrons

Chapter 2 - 4
 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 discrete energy level is 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

Chapter 2 - 5
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J. Wulff,
Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 6
 Maximum number of states
n sub-shell # states max # electrons
sub-shell* shell
1 K s 1 2 2
s 1 2
2 L 8
p 3 6
s 1 2
3 M p 3 6 18
d 5 10
s 1 2
p 3 6
4 N 32
d 5 10
f 7 14
* # states x 2, because two electrons (with ± spin) can exist in each state

Chapter 2 - 7
 SURVEY OF ELEMENTS
• Most elements: Electron configuration 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 Adapted from Table 2.2,
Callister & Rethwisch 9e.
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? Valence (outer) shell usually not filled completely.

Chapter 2 - 8
 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

Chapter 2 - 9
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d valence
4p N-shell n = 4
electrons
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J.
Wulff, Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

Chapter 2 - 10
 The Periodic Table
• Columns: Similar Valence Structure

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

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

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.8,
Callister &
K Ca Sc Se Br Kr
Rethwisch 9e.
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.
Chapter 2 - 11
 Electronegativity
• Ranges from 0.9 to 4.1,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Chapter 2 - 12
 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]

Chapter 2 - 13
 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

Chapter 2 - 14
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - + n
r r
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig.
2.10(b), Callister &
Rethwisch 9e.

Attractive energy EA

Chapter 2 - 15
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 - 16
 Ionic bonding summary

• Properties of ionic bonding.

• Nondirectional: magnitude of bond is equal in all
directions around the ion.
• High bonding energies (~600 - 1500 kJ/mol).
• Reflected in high melting temperatures.
• Hard and brittle materials.
• Common bonding for ceramic materials.
• Electrically and thermally insulative materials.

Chapter 2 - 17
Ionic Bonding

Chapter 2 - 18
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• 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, Callister & Rethwisch 9e.

Chapter 2 - 19
 Bond Hybrization
• Carbon can form sp3 hybrid
orbitals

Fig. 2.14, Callister & Rethwisch 9e.

(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 9e.

Chapter 2 - 20
 Covalent Bonding: Carbon sp3
• Example: CH4

C: has 4 valence e-,

needs 4 more
H: has 1 valence e-,
needs 1 more

Electronegativities of C and H
are comparable so electrons
are shared in covalent bonds.
Fig. 2.15, Callister & Rethwisch 9e.
(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Chapter 2 - 21
Covalent Bonding

Chapter 2 - 22
 Metallic bonding

• Most common in bonding of metals and their alloys.

• Primary bond for metals and their alloys.
• Bonding may be weak or strong, depending upon
atoms involved.
• In metallic bonding the valence electrons are
delocalised.
A metallic bond is non-directional
(bonds form in any direction)
 atoms pack closely.

Chapter 2 - 23
 Metallic bonding

• Because the donated

electrons are freely
mobile, the electrical
conductivity of metals is
high.
• Heat can also be
transmitted by
electrons, so metals are
good thermal
conductors.

Chapter 2 - 24
 Metallic bonding

• Metallic bonds may be weak or strong.

• Bonding energies: range from 68 kJ/mol (0.7
eV/atom) for Hg to 850 kJ/mol (8.8 eV/atom) for W.
• Melting temperatures: -39 C for Hg and 3410 C for
W.
• Stronger bonds lead to higher melting temperature:
• atomic scale property  macroscale property.

Chapter 2 - 25
Metallic bonding

Chapter 2 - 26
 Bonding Energies and
Melting temperatures

Type Substance Energy Melt. Temp

(eV/atom) (°C)
NaCl 3.3 801
Ionic
MgO 5.2 2800
Si 4.7 1410
Covalent
C 7.4 >3550
Hg 0.7 -39
Al 3.4 660
Metallic
Fe 4.2 1538
W 8.8 3410

Chapter 2 - 27
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

% ionic character = x (100%)

where XA & XB are Pauling electronegativities

Ex: MgO XMg = 1.3
XO = 3.5

Chapter 2 - 28
 Secondary Bonding
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.20,
Callister & Rethwisch 9e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.22,
Callister & Rethwisch 9e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

Chapter 2 - 29
 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
Chapter 2 - 30
 Properties From Bonding: Tm
• 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”

Chapter 2 - 31
 Properties From Bonding: α
• 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 Chapter 2 - 32
 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

Chapter 2 - 33
 ANNOUNCEMENTS
Reading: Sections 2.2 through 2.7

Core Problems: 2.1, 2.3, 2.4, 2.6, 2.9, 2.11,

2.13, 2.22, 2.24, 2.25, 2.27

Self-help: View all the videos in the study

resources on Primary and Secondary bonding

Chapter 2 - 34