Chapter 2 - 1

ISSUES TO ADDRESS...
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?
Chapter 2: Atomic Structure &
Interatomic Bonding
Chapter 2 - 2
Atomic Structure (Freshman Chem.)
atom electrons 9.11 x 10
-31
kg
protons
neutrons
atomic number = # of protons in nucleus of atom
= # of electrons of neutral species

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

Atomic wt = wt of 6.022 x 10
23
molecules or atoms

1 amu/atom = 1g/mol

C 12.011
H 1.008 etc.
} 1.67 x 10
-27
kg
Chapter 2 - 3
Atomic Structure
Valence electrons determine all of the
following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
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 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)
m
l
= magnetic 1, 3, 5, 7 (-l to +l)
m
s
= spin , -
Chapter 2 - 5
Electron Energy States
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p
M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
have discrete energy states
tend to occupy lowest available energy state.
Electrons...
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
Chapter 2 - 6
Why? Valence (outer) shell usually not filled completely.
Most elements: Electron configuration not stable.
SURVEY OF ELEMENTS
Electron configuration
(stable)
...
...
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)
Atomic #


18
...
36
Element
1s
1
1 Hydrogen
1s
2
2 Helium
1s
2
2s
1
3 Lithium
1s
2
2s
2
4 Beryllium
1s
2
2s
2
2p
1
5 Boron
1s
2
2s
2
2p
2
6 Carbon
...
1s
2
2s
2
2p
6
(stable) 10 Neon
1s
2
2s
2
2p
6
3s
1
11 Sodium
1s
2
2s
2
2p
6
3s
2
12 Magnesium
1s
2
2s
2
2p
6
3s
2
3p
1
13 Aluminum
...
Argon
...
Krypton
Adapted from Table 2.2,
Callister & Rethwisch 8e.
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)

1s
2
2s
2
2p
2

valence electrons
Chapter 2 - 8
Electronic Configurations
ex: Fe - atomic # = 26
valence
electrons
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
1s
2s
2p
K-shell n = 1
L-shell n = 2
3s
3p
M-shell n = 3
3d
4s
4p
4d
Energy
N-shell n = 4
1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
Chapter 2 - 9
The Periodic Table
Columns: Similar Valence Structure
Adapted from
Fig. 2.6,
Callister &
Rethwisch 8e.
Electropositive elements:
Readily give up electrons
to become + ions.
Electronegative elements:
Readily acquire electrons
to become - ions.
g
i
v
e

u
p

1
e
-

g
i
v
e

u
p

2
e
-

g
i
v
e

u
p

3
e
-

i
n
e
r
t

g
a
s
e
s

a
c
c
e
p
t

1
e
-

a
c
c
e
p
t

2
e
-

O
Se
Te
Po At
I
Br
He
Ne
Ar
Kr
Xe
Rn
F
Cl S
Li Be
H
Na Mg
Ba Cs
Ra Fr
Ca K Sc
Sr Rb Y
Chapter 2 - 10
Ranges from 0.7 to 4.0,
Smaller electronegativity Larger electronegativity
Large values: tendency to acquire electrons.
Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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.
Electronegativity
Chapter 2 - 11
Ionic bond metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s
2
2s
2
2p
6
3s
2
O 1s
2
2s
2
2p
4

[Ne] 3s
2


Mg
2+
1s
2
2s
2
2p
6
O
2-
1s
2
2s
2
2p
6

[Ne] [Ne]
Chapter 2 - 12
Occurs between + and - ions.
Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl
Ionic Bonding
Na (metal)
unstable
Cl (nonmetal)
unstable
electron
+
-
Coulombic
Attraction
Na (cation)
stable
Cl (anion)
stable
Chapter 2 - 13
Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
Attractive energy E
A

Net energy E
N

Repulsive energy E
R

Interatomic separation r
r
A
n
r
B
E
N
= E
A
+ E
R
=
+
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.
Chapter 2 - 14
Predominant bonding in Ceramics
Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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.
Examples: Ionic Bonding
Give up electrons Acquire electrons
NaCl
MgO
CaF
2
CsCl
Chapter 2 - 15
C: has 4 valence e
-
,
needs 4 more
H: has 1 valence e
-
,
needs 1 more
Electronegativities
are comparable.
Adapted from Fig. 2.10, Callister & Rethwisch 8e.
Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH
4
shared electrons
from carbon atom
shared electrons
from hydrogen
atoms
H
H
H
H
C
CH
4
Chapter 2 - 16
Primary Bonding
Metallic Bond -- delocalized as electron cloud

Ionic-Covalent Mixed Bonding

% ionic character =

where X
A
& X
B
are Pauling electronegativities

%) 100 ( x


1 e

(X
A
X
B
)
2
4
|
\



|
.
|
|
|
ionic 73.4% (100%) x e 1 character ionic %
4
) 2 . 1 5 . 3 (

2
=
|
|
|
.
|

\
|
=

Ex: MgO X
Mg
= 1.2
X
O
= 3.5
Chapter 2 - 17
Arises from interaction between dipoles
Permanent dipoles-molecule induced
Fluctuating dipoles
-general case:
-ex: liquid HCl
-ex: polymer
Adapted from Fig. 2.13,
Callister & Rethwisch 8e.
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
SECONDARY BONDING
asymmetric electron
clouds
+ - + -
secondary
bonding
H H H H
H
2
H
2
secondary
bonding
ex: liquid H
2
H Cl H Cl
secondary
bonding
secondary
bonding
+ - + -
secondary bonding
Chapter 2 - 18
Type
Ionic
Covalent
Metallic
Secondary
Bond Energy
Large!
Variable
large-Diamond
small-Bismuth
Variable
large-Tungsten
small-Mercury
smallest
Comments
Nondirectional (ceramics)
Directional
(semiconductors, ceramics
polymer chains)
Nondirectional (metals)
Directional
inter-chain (polymer)
inter-molecular
Summary: Bonding
Chapter 2 - 19
Bond length, r
Bond energy, E
o
Melting Temperature, T
m

T
m
is larger if E
o
is larger.
Properties From Bonding: T
m

r
o
r
Energy
r
larger T
m

smaller T
m

E
o
=
bond energy
Energy
r
o

r
unstretched length
Chapter 2 - 20
Coefficient of thermal expansion, o
o ~ symmetric at r
o
o is larger if E
o
is smaller.
Properties From Bonding : o
=
o
( T
2
- T
1
)
A L
L
o
coeff. thermal expansion

A L
length, L
o
unheated, T
1
heated, T
2
r
o
r
smaller o
larger o
Energy
unstretched length
E
o

E
o

Chapter 2 - 21
Ceramics
(Ionic & covalent bonding):
Large bond energy
large T
m
large E
small o
Metals
(Metallic bonding):
Variable bond energy
moderate T
m
moderate E
moderate o
Summary: Primary Bonds
Polymers
(Covalent & Secondary):
Directional Properties
Secondary bonding dominates
small T
m

small E
large o