CHAPTER 2:

BONDING AND PROPERTIES

What promotes bonding?
What types of bonds are there?
How does bonding affect material
properties?
Much of a materials behavior can be
explained by the phenomena in this
chapter.
1

Order: Short vs Long Range

Atomic Structure
atom

electrons 9.11 x 10-31 kg

protons
1.67 x 10-27 kg
neutrons

atomic number = # of protons in nucleus of atom

= # of electrons of 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 = 1g/mol
C
H

12.011
1.008
3

Atomic Structure
Valence electrons determine the
following properties:
1)
2)
3)
4)

Chemical
Electrical
Thermal
Optical

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

Designation

n = principal (energy level-shell)

l = subsidiary (orbitals)
ml = magnetic

K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n -1)
1, 3, 5, 7 (-l to +l)

ms = spin

, -
5

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
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
7

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Hydrogen
Helium
Lithium
Beryllium
Boron
Carbon
...

Atomic #
1
2
3
4
5
6

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

Adapted from Table 2.2,

Callister & Rethwisch 3e.

Neon
Sodium
Magnesium
Aluminum
...

10
11
12
13

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
...

Argon
...
Krypton

18
...
36

1s 2 2s 2 2p 6 3s 2 3p 6
(stable)
...
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.

9

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

10

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

Xe

Po At Rn

Fr Ra

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

Electronegative elements:
Readily acquire electrons
to become - ions.

11

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
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
12

Electronegativity
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.

14

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

EN = EA + ER =

A
r

B
rn

Repulsive energy ER

Interatomic separation r
Net energy EN

Attractive energy EA
15

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm
Tm is larger if Eo is larger.

16

Properties From Bonding : a

Coefficient of thermal expansion, a
length, L o
coeff. thermal expansion
unheated, T1

DL
= a (T2 -T1)
Lo

DL

heated, T 2

a ~ symmetric at ro
Energy
unstretched length
ro

Eo
Eo

a is larger if Eo is smaller.

smaller a
larger a
17

Primary Bonding
Ionic
Covalent
Metallic
Bonding involves the valence electrons.
Bonding occurs due to the tendency of
the atoms to assume stable electron
structures (completely filled outer shells)
18

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

+
Coulombic
Attraction

Cl (anion)
stable

19

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]
21

Examples: Ionic Bonding

Predominant bonding in Ceramics

NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.
22

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: polymers, GaAs, InSb, SiC, CH4
H

C: has 4 valence e-,

needs 4 more

CH 4

H: has 1 valence e-,

needs 1 more

Electronegativities
are comparable.

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

23

Ionic-Covalent Mixed Bonding

% ionic character =

(X A -X B )2

4
1- e
x (100%)

where XA & XB are Pauling electronegativities

Ex: MgO

XMg = 1.3
XO = 3.5

(3.5 -1.3 )2

4
% ionic character 1 - e

x (100%) 70.2% ionic

24

Metallic Bonding
Metallic bonds have up to 3 valence
electrons that are not bound to a
specific atom.
They drift throughout the metal
forming a sea of electrons or
electron cloud.
The nonvalence electrons and
nuclei for the ion cores.
The free electrons act as a glue to
hold the ion cores together.
These are good conductors of heat
and charge (electricity).

Secondary Bonding (van der Waals)

Interaction between dipoles; dipoles are
a separation of charge (+/-).
Weaker forces (10kJ/mol) than primary
bonding, yet these bonds still influence
physical properties.
Secondary bonding exists in virtually all
atoms and molecules, but their
presence may be obscured by primary
bonding.
26

SECONDARY BONDING
Fluctuating dipoles

ex: liquid H 2
H2
H2

asymmetric electron
clouds

H H

H H

secondary
bonding

secondary
bonding

Permanent dipoles-molecule induced

-general case:

-ex: liquid HCl

H Cl

-ex: polymer

secondary
bonding

secondary
bonding

H Cl

secondary bonding
27

Bonding energies between 600 and 1500 kJ/mol (or 3 to 8 eV/atom)

are considered to be relatively large and will have correspondingly high
(large) melting points.

Summary: Bonding
Comments

Type

Bond Energy

Ionic

Large

Nondirectional (ceramics)

Covalent

Variable
large-Diamond
small-Bismuth

Directional
(semiconductors, ceramics
polymer chains)

Metallic

Variable
large-Tungsten
small-Mercury

Nondirectional (metals)

Coulombic force

Secondary
Van der Waals

smallest

Directional
inter-chain (polymer)
inter-molecular
30

Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

Large bond energy

large Tm
large E
small a

Variable bond energy

moderate Tm
moderate E
moderate a

Directional Properties
Secondary bonding dominates
small Tm
small E
large a

31