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Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH4
e -,

C: has 4 valence
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

Adapted from Fig. 2.10, Callister & Rethwisch 4e.

Chapter 2 - 1

Primary Bonding
Metallic Bond -- delocalized as electron cloud
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 = 1.2
XO = 3.5

( 3.5 1.2 )2

4
% ionic character 1 e

x (100%) 73.4% ionic

Chapter 2 - 2

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SECONDARY BONDING
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. 2.13,

Callister & Rethwisch 4e.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl

H Cl

secondary
bonding

secondary
bonding

H Cl

-ex: polymer

Adapted from Fig. 2.14,

Callister & Rethwisch 4e.

secondary bonding
Chapter 2 - 3

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)

Secondary

smallest

Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 4

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Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length

ro

larger Tm

r
Eo =
bond energy

Tm is larger if Eo is larger.

Chapter 2 - 5

Properties From Bonding :

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

L
= (T2 -T1)
Lo

heated, T2

~ symmetric at ro
Energy
unstretched length

ro
E
o

E
o

is larger if Eo is smaller.

larger
smaller
Chapter 2 - 6

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Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

Large bond energy

large Tm
large E
small

Variable bond energy

moderate Tm
moderate E
moderate

Directional Properties
Secondary bonding dominates
small Tm
small E
large

Chapter 2 - 7