Chapter 2: Atomic Structure &

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

Chapter 2 - 1

Atomic Structure (Freshman Chem.)

atom

electrons 9.11 x 10-31 kg

protons
1.67 x 10-27 kg
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 6.022 x 1023 molecules or atoms
1 amu/atom = 1g/mol
C
H

12.011
1.008 etc.
Chapter 2 - 2

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

Chemical
Electrical
Thermal
Optical

Chapter 2 - 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)

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 - 4

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 & Rethwisch 8e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 5

Chapter 2 - 6

Chapter 2 - 7

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Atomic #
Element
Hydrogen
1
Helium
2
Lithium
3
Beryllium
4
Boron
5
Carbon
6
...
Neon
10
Sodium
11
Magnesium
12
Aluminum
13
...

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
...

Argon
...
Krypton

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)

18
...
36

Adapted from Table 2.2,

Callister & Rethwisch 8e.

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
...

Why? Valence (outer) shell usually not filled completely.

Chapter 2 - 8

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 - 9

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 & Rethwisch 8e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 10

give up 1egive up 2egive up 3e-

Columns: Similar Valence Structure

accept 2eaccept 1einert 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 &
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 - 11

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 - 12

Chapter 2 - 13

Chapter 2 - 14

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 - 15

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

Chapter 2 - 16

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 - 17

Chapter 2 - 18

Chapter 2 - 19

Examples: Ionic Bonding

Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons

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.
Chapter 2 - 20

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
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 & Rethwisch 8e.

Chapter 2 - 21

Chapter 2 - 22

Chapter 2 - 23

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 - 24

Chapter 2 - 25

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 8e.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl
-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

Adapted from Fig. 2.15,

Callister & Rethwisch 8e.

secondary bonding
Chapter 2 - 26

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 - 27

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm
Tm is larger if Eo is larger.

Chapter 2 - 28

Properties From Bonding :

Coefficient of thermal expansion,
length, L o
coeff. thermal expansion
This image cannot currently be
display ed.

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 - 29

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 - 30

Chapter 2 - 31

Chapter 2 - 32