1

Atomic Structure
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
2
Atomic Structure
Valence electrons determine all of the
following properties
l) Chemical
2) Electrical
3) Thermal
4) Optical
3
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 (l, 2, 3, etc.)
= subsidiary (orbitals) s, p, d, l (0, l, 2, 3,., n -l)
m
/
= magnetic l, 3, 5, 7 (- to +)
m
s
= spin , -


4
Electron Energy States
1s
2s
2p
K-shell n 1
L-shell n 2
3s
3p M-shell n 3
3J
4s
4p
4J
Energy
N-shell n 4
have discrete energy states
tend to occupy lowest available energy state.
Electrons...
Adapted from Fig. 2.4,
Collisrer &Rernwiscn Se.
3
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
3J
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
3 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 fromTable 2.2,
Collisrer & Rernwiscn Se.
6
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)
ls
2
2s
2
2p
2
valence electrons


7
Electronic Configurations
ex: Fe - atomic # 26
valence
electrons
Adapted from Fig. 2.4,
Collisrer & Rernwiscn Se.
1s
2s
2p
K-shell n 1
L-shell n 2
3s
3p M-shell n 3
3J
4s
4p
4J
Energy
N-shell n 4
1s
2
2s
2
2p
6
3s
2
3p
6
3J
6
4s
2
8
The Periodic Table
Columns: Similar Valence Structure
Adapted from
Fig. 2.6,
Collisrer &
Rernwiscn Se.
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
9
Ranges from 0.7 to 4.0,
Smaller electronegativity Larger electronegativity
Large values: tendency to acquire electrons.
Adapted fromFig. 2.7, Collisrer &Rernwiscn Se. (Fig. 2.7 is adapted from Linus Pauling, Tne Norure o[ rne Cnemicol
BonJ, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
Electronegativity


EN Ion/CovaIent Character
> l.7 Mostly ionic
0.4 l.7 Polar covalent
< 0.4 Mostly covalent
0 Nonpolar covalent
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|
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


13
Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive terms
Attractive energy L
A
Net energy L
N
Repulsive energy L
R
Interatomic separation r
r
A
n
r
B
L
N
L
A
L
R


Adapted from Fig. 2.8(b),
Collisrer & Rernwiscn Se.
14
Predominant bonding in Ceramics
Adapted fromFig. 2.7, Collisrer &Rernwiscn Se. (Fig. 2.7 is adapted from Linus Pauling, Tne Norure o[ rne Cnemicol
BonJ, 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
13
C: has 4 valence e
-
,
needs 4 more
H: has 1 valence e
-
,
needs 1 more
Electronegativities
are comparable.
Adapted from Fig. 2.10, Collisrer & Rernwiscn Se.
Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s 8 p orbitals dominate
bonding
Example: CH
4
shared electrons
from carbon atom
shared electrons
from hydrogen
atoms
H
H
H
H
C
CH
4


l6
Primary Bonding
Metallic Bond -- delocalized as electron cloud
lonic-Covalent Mixed Bonding
% ionic character =

where X
A
& X
B
are Pauling electronegativities
%) l00 ( x
Ex: MgO X
Mg
= l.3
X
O
= 3.5

1e

X
A
X
B

2
4

% ionic character

1e

3. 31. 3
2
4

x 100% 70. 2% ionic
17
Arises from interaction between dipoles
Permanent dipoles-molecule induced
Fluctuating dipoles
-general case:
-ex: liquid HCl
-ex: polymer
Adapted from Fig. 2.13,
Collisrer & Rernwiscn Se.
Adapted from Fig. 2.14,
Collisrer & Rernwiscn Se.
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
secondary bondng
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


19
Bond length, r
Bond energy, L
o
Melting Temperature, T
m
T
m
is larger if L
o
is larger.
Properties From Bonding: T
m
r
o
r
Energy
r
larger T
m
smaller T
m
L
o

bond energy
Energy
r
o

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

L
length, L
o
unheated, T
1
heated, T
2
r
o
r
larger
smaller
Energy
unstretched length
L
o
L
o
21
Ceramics
(Ionic 8 covalent bonding):
Large bond energy
large T
m
large L
small
Metals
(Metallic bonding):
Variable bond energy
moderate T
m
moderate L
moderate
Summary: Primary Bonds
Polymers
(Covalent 8 Secondary):
Directional Properties
Secondary bonding dominates
small T
m
small L
large
secondary bondng