CHAPTER 2:

BONDING AND PROPERTIES

ISSUES TO ADDRESS...
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?

Chapter 2 - 1

Atomic structure

Chapter 2 - 2

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

Chemical
Electrical
Thermal
Optical

Chapter 2 - 3

Atomic Structure (Freshman Chem.)

atom

electrons 9.11 x 10-31 kg

protons
-27 kg
1.67
x
10
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 6.023 x 1023 molecules or atoms

1 amu/atom = 1g/mol
C
H

12.011
1.008 etc.
Chapter 2 - 4

Electronic Structure
Electrons have wavelike and particulate
properties.
This means that electrons are in orbitals defined by a
probability.
Each orbital at discrete energy level 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

, -
Chapter 2 - 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
Adapted from Fig. 2.4,
Callister 7e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 6

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 7e.

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.

Chapter 2 - 7

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 - 8

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
Adapted from Fig. 2.4,
Callister 7e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 9

give up 1e
give up 2e
give up 3e

Columns: Similar Valence Structure

accept 2e
accept 1e
inert gases

The Periodic Table

He

Li Be

F Ne

Na Mg

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Se Br Kr
Te

Adapted from
Fig. 2.6,
Callister 7e.

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 - 10

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

Smaller electronegativity

Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (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.
Chapter 2 - 11

Bonding

Chapter 2 - 12

Bonding Forces and Energies

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
Adapted from Fig. 2.8(b),
Callister 7e.

Attractive energy EA
Chapter 2 - 13

Bonding Forces and Energies

Chapter 2 - 14

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

Notice the difference in sizes between the atom and the ion
Chapter 2 - 15

Ionic Bonding
Relatively high bonding
energies (600-1500
Kj/mol) which is reflected
in high melting
temperatures.

Example: NaCl
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

Examples: Ionic Bonding

Predominant bonding in Ceramics

NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (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.
Chapter 2 - 18

Covalent Bonding
similar electronegativity
share electrons
Bond is directional
Example: CH4
C: has 4 valence e-,
needs 4 more
H: has 1 valence e-,
needs 1 more

Electronegativities
are comparable.

CH 4
H

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

Adapted from Fig. 2.10, Callister 7e.

Chapter 2 - 19

Primary Bonding
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

Chapter 2 - 20

Metallic Bonding
Non directional bond
Good conductors for
both electricity and
heat as a
consequence of free
valence electrons

Metallic Bonding

Chapter 2 - 21

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 7e.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl

-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

Adapted from Fig. 2.14,

Callister 7e.

secondary bonding
Chapter 2 - 22

Comparison Between Bonding Enerigies

Chapter 2 - 23

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm
Tm is larger if Eo is larger.

Chapter 2 - 24

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 ~ symmetry at ro
Energy
unstretched length
ro

E
o

E
o

a is larger if Eo is smaller.

Larger a

Smaller a
Chapter 2 - 25

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 - 26

Summary: Bondings
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

Chapter 2 - 27

ANNOUNCEMENTS
Reading:

Reading: Chapter 3 (atomic structures)

Core Problems:

Self-help Problems:

Chapter 2 - 28