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.)

} 1.67 x 10-27 kg

Chapter 2 - 2

Atomic Structure (Freshman Chem.)

atomic mass unit, amu ( a way to compute atomic weight) = 1/12
mass of 12C (most common isotope of carbon)

In one mole of a substance, there are 6.022x1023 atoms or

molecules.
1 amu/atom(or molecule in a compound) = 1 g/mol

Example: atomic weight of iron is 55.85 amu/atom, or 55.85 g/mol.

We use g/mol (or kg/kmol) in this book.

Chapter 2 - 3

Discuss Example Problem 2.1 in class.

Four naturally occurring isotopes of Cerium:
0.185% of 136Ce with an atomic weight of 135.907 amu
0.251% of 138Ce with an atomic weight of 137.906 amu
88.45% of 140Ce with an atomic weight of 139.905 amu
11.114% of 142Ce with an atomic weight of 141.909 amu
Calculate the average atomic weight of Ce.

The average atomic weight of a hypothetical element M,

=

: fraction of occurrence of isotope (i.e., the percentage-ofOccurrence divided by 100)

: the atomic weight of the isotope

Chapter 2 - 4

Atomic Structure

Some of the following properties

1)
2)
3)
4)

Electrical
Thermal
Optical
Deteriorative

are determined by electronic structure (behavior

of electrons in atoms and crystalline solids)
Quantum mechanics: set of principles and laws that govern
systems of atomic and subatomic entities

Chapter 2 - 5

Bohr model vs wave-mechanical model

Bohr Model (Significant limitations):

Electrons are assumed to revolve
around the atomic nucleus in
discrete orbitals

Wave-mechanical model: electrons

position is considered to be the
probability of an electrons being at
various locations around the
nucleus.

Chapter 2 - 6

Electronic Structure-Electron Energy States

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.)
= second-azimuthal (orbitals)
s, p, d, f (0, 1, 2, 3,, n -1)

Electrons...
have discrete energy states
tend to occupy lowest available energy
Chapterstate.
2- 7

Electron Energy States

Quantum #
n = principal (energy level-shell)
= second-azimuthal (orbitals)

Designation
K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n -1)

Chapter 2 - 8

Electronic Structure-Electron Energy States

Notes:

The smaller the principal quantum number, the

lower the energy level;
For example:
energy of a 1s < energy of a 2s < energy of a 3s

Within each shell, the energy of a subshell level

increases with the value of the l quantum number.
For example:
energy of a 3d > energy of a 3p> energy of a 3s.

There may be overlap in energy of a state in one

shell with states in an adjacent shell, which is
especially true of d and f states.
For example:
The energy of a 3d state is generally greater than
that of a 4s.

Chapter 2 - 9

Electron Configurations
Valence electrons those that occupy the
outermost shell
Filled shells are 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 - 10

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Atomic #
Hydrogen
1
Helium
2
Lithium
3
Beryllium
4
Boron
5
Carbon
6
...
Neon
10
Sodium
11
Magnesium
12
Aluminum
13
...
Argon
...
Krypton

18
...
36

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s2
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...

Adapted from Table 2.2,

Callister & Rethwisch 9e.

1s 2 2s 2 2p 6
(stable)
1s 2 2s 2 2p 6 3s 1
1s 2 2s 2 2p 6 3s 2
1s 2 2s 2 2p 6 3s 2 3p 1
...
(stable)
1s 2 2s 2 2p 6 3s 2 3p 6
...
1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

Stable: Valence (outermost) electron shell (normally just s and

p) are completely filled.
Chapter 2 - 11

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

N-shell n = 4

3d

Adapted from Fig. 2.6, Callister &

Rethwisch 9e.

4s
Energy

valence
electrons

(From K. M. Ralls, T. H. Courtney, and J.

Wulff, Introduction to Materials Science and
Engineering, p. 22. Copyright 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 12

The Periodic Table

give up 1egive up 2egive up 3e-

accept 2eaccept 1einert gases

Columns: Similar Valence Structure

K Ca Sc

Se Br Kr

He

Li Be

F Ne

Na Mg

Cl Ar

Rb Sr

Cs Ba

Te

Adapted from
Fig. 2.8,
Callister &
Rethwisch 9e.

Xe

Po At Rn

Fr Ra

Electropositive elements:
Readily give up electrons
to become + ions.

Electronegative elements:
Readily acquire electrons
to become - ions.
Chapter 2 - 13

Electronegativity
Ranges from 0.9 to 4.1,
Large values: tendency to acquire electrons.

Larger
electronegativity

Smaller
electronegativity

Chapter 2 - 14

Bonding Forces and Energies

Forces between to adjacent atoms:
FN = FA + FR
(FN : net force, FA : attractive force, FR : repulsive force)

At the state of equilibrium: FA + FR = 0

Sometimes it is more convenient to work with the potential

energies (E) between two atoms instead of forces (F).

EN = EA + ER
At the state of equilibrium EN is minimum. (Bonding Energy)
Chapter 2 - 15

Bonding Forces and Energies

Bonding energy: represents the energy required to separate
two atoms to an infinite separation

A number of material properties depend on bonding energy:

melting temperature, phase at room temperature, coefficient of
thermal expansion, stiffness

Three types of primary (chemical) bonds: ionic, covalent, and

metallic

There are secondary (physical) forces in many solids.

- They are weaker than primary ones.
Chapter 2 - 16

Ionic bond

metal

donates
electrons

nonmetal
accepts
electrons

Dissimilar electronegativities
ex: MgO

Mg

1s2 2s2 2p6 3s2

[Ne] 3s2

Mg2+ 1s2 2s2 2p6

[Ne]

1s2 2s2 2p4

O2- 1s2 2s2 2p6

[Ne]

Chapter 2 - 17

Ionic Bonding

Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Na (metal)
unstable

Cl (nonmetal)
unstable
electron

Na (cation)
stable

+
Attraction

Cl (anion)
stable

Chapter 2 - 18

Ionic Bonding
Eq. 2.10

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 - 19

Ionic Bonding

Ionic bonding is typified by ceramic materials,

which are characteristically hard and brittle
and, furthermore, electrically and thermally
insulative.

Chapter 2 - 20

Examples: Ionic Bonding

Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Chapter 2 - 21

Covalent Bonding
similar electronegativity share electrons

Example: H2
Each H: has 1 valence e-,
needs 1 more

H2

Electronegativities
are the same.
shared 1s electron
from 1st hydrogen
atom

shared 1s electron
from 2nd hydrogen
atom

Fig. 2.12, Callister & Rethwisch 9e.

Chapter 2 - 23

Covalent Bonding
Most covalently bonded materials are
electrical insulators, or, in some cases,
semiconductors.
It is difficult to predict the mechanical
properties of covalently bonded materials on
the basis of their bonding characteristics.
(some strong, others weak; some brittle,
others ductile)
Chapter 2 - 24

Bond Hybridization
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 - 25

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 - 26

Metallic Bonding
Metallic bonding is found in metals and their alloys.
Valence electrons are not bound to any particular atom in the
solid and are more or less free to drift throughout the entire
metal (electron cloud).

Metals are good conductors of both electricity and heat as a

consequence of their free electrons.
Chapter 2 - 27

Secondary Bonding (van der Waals)

Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron
clouds

+
secondary
bonding

ex: liquid H 2
H2
H2

H H

H H
secondary
bonding

Adapted from Fig. 2.20,

Callister & Rethwisch 9e.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl
-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

Adapted from Fig. 2.22,

Callister & Rethwisch 9e.

secondary bonding
Chapter 2 - 28

Mixed Bonding
covalent-ionic, covalent-metallic, metallic-ionic
Ionic-Covalent Mixed Bonding
% ionic character %IC =

x (100%)

where XA & XB are the electronegativities of elements

Ex: MgO

XMg = 1.3
XO = 3.5

Chapter 2 - 29

Summary: Bonding
Type

Bond Energy

Ionic

Large!

Covalent

Variable
large-Diamond
small-Bismuth

Metallic

Variable
large-Tungsten
small-Mercury

Secondary

smallest

Comments
ceramics
semiconductors, ceramics
polymer chains

metals
inter-chain (polymer)
inter-molecular
Chapter 2 - 30

Summary: Primary Bonds

Tm: melting temperature
: thermal energy expansion

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

E: bonding energy

Large bond energy

large Tm
large E
small

Variable bond energy

moderate Tm
variable (moderate) E
moderate

Dominant Secondary bonding

small Tm
small E
large
Chapter 2 - 31

Suggested Problems for Chapter 2

2.1
2.2
2.4
2.9
2.10
2.17
2.18

2.25
2.1FE
2.2FE
2.3FE
2.4FE

Chapter 1 - 32