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MT 106

Chapter 2 - 1

Electronic Structure
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,, n1)
ml = magnetic
1, 3, 5, 7 (-l to +l)
ms = spin

, -

Chapter 2 - 2

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Electron Energy States

Chapter 2 -

Electron Energy States

4d
4p

N-shell n = 4

3d
4s
Energy

3p
3s

M-shell n = 3
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 4

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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 8e.

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

(stable)
1s 2 2s 2 2p 6 3s 2 3p 6
...
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 - 5

give up 1egive up 2egive up 3e-

accept 2eaccept 1einert gases

The Periodic Table

Columns: Similar Valence Structure

He

Li Be

Na Mg

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Ne

Se Br Kr
Te

Adapted from
Fig. 2.6,
Callister &
Rethwisch 8e.

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 - 6

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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 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.
Chapter 2 - 7

Atomic Interaction

Chapter 2 -

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Ionic bond metal

nonmetal

donates
electrons

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 - 9

Ionic Bonding
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 & Rethwisch 8e.

Attractive energy EA
Chapter 2 - 10

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Examples: Ionic Bonding

Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Acquire electrons

Give up 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.
Chapter 2 - 11

Ionic-Covalent Mixed Bonding

% ionic character =
where XA & XB are Pauling electronegativities

(X A X B )2

4
1 e
x (100%)

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 - 12

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Metallic Bonding

Chapter 2 - 13

SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron
clouds

secondary
bonding

Chapter 2 - 14

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SECONDARY BONDING
Permanent dipoles-molecule induced

-ex: liquid HCl

H Cl

secondary
bonding

H Cl

Chapter 2 - 15

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 - 16

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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 - 17

Properties From Bonding :

Coefficient of thermal expansion,
length, L o
coeff. thermal expansion
Th
e
im
ag
e
ca
nn
ot
be
dis
pl
ay
ed
.
Yo
ur
co
m
pu
ter
m
ay
no
t
ha
ve
en
ou
gh
m
e
m
or
y
to
op
en
th
e
im
ag
e,
or

unheated, T1

L
= (T2 -T1)
Lo

heated, T 2

~ symmetric at ro
Energy
unstretched length

ro
E
o

E
o

is larger if Eo is smaller.

larger
smaller
Chapter 2 - 18

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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 - 19

10