CHAPTER 2:

Atomic Structure and Interatomic

Bonding
ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

Chapter 2- 1
 BOHR ATOM
orbital electrons:
n = principal
quantum number
n=3 2 1 Adapted from Fig. 2.1,
Callister 6e.

Nucleus: Z = # protons
= 1 for hydrogen to 94 for plutonium
N = # neutrons
Atomic mass A ≈ Z + N

Chapter 2- 2
 ELECTRON ENERGY STATES
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4p
Increasing energy

n=4 3d
4s
n=3 3p
3s
n=2 2p
2s
Adapted from Fig. 2.5,
n=1 1s Callister 6e.

Chapter 2- 3
STABLE ELECTRON CONFIGURATIONS
Stable electron configurations...
• have complete s and p subshells
• tend to be unreactive.

Z Element Configuration
2 He 1s 2 Adapted from Table 2.2,
10 Ne 1s 2 2s 2 2p 6 Callister 6e.

18 Ar 1s 2 2s 2 2p 6 3 s 2 3p 6
36 Kr 1s 2 2s 2 2p 6 3 s 2 3p 6 3d 10 4 s 2 4p 6

Chapter 2- 4
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
1s 2 2s 2 2p 2 Callister 6e.
Carbon 6
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4 6 (stable)

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

Chapter 2- 5
 THE PERIODIC TABLE
• Columns: Similar Valence Structure
give up 1e

inert gases
give up 2e

accept 2e
accept 1e
Metal
give up 3e
Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg S Cl Ar Adapted from
Fig. 2.6,
K Ca Sc Se Br Kr Callister 6e.

Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
Chapter 2- 6
 ELECTRONEGATIVITY
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.
H He
2.1 -
Li Be F Ne
1.0 1.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 6e. (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
 IONIC BONDING
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation)
+ - Cl (anion)
stable Coulombic stable
Attraction

Chapter 2- 8
 EXAMPLES: IONIC BONDING
• Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF 2 -
Li Be O F Ne
1.0 1.5 Cs Cl 3.5 4.0 -
Na Mg Cl Ar
0.9 1.2 3.0 -
K Ca Ti Cr Fe Ni Zn As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 2.0 2.8 -
Rb Sr I Xe
0.8 1.0 2.5 -
Cs Ba At Rn
0.7 0.9 2.2 -
Fr Ra
0.7 0.9

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 6e. (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- 9
 COVALENT BONDING
• Requires shared electrons
• Example: CH4 shared electrons
H
C: has 4 valence e, from carbon atom
CH 4
needs 4 more
H: has 1 valence e, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 6e.

Chapter 2- 10
 EXAMPLES: COVALENT BONDING
H2 O

column IVA
H2 F2
C(diamond)
H He
2.1
Si C - Cl 2
Li Be C O F Ne
1.0 1.5 2.5 2.0 4.0 -
Na Mg Si Cl Ar
0.9 1.2 1.8 3.0 -
K Ca Ti Cr Fe Ni Zn Ga Ge As Br Kr
0.8 1.0 1.5 1.6 1.8 1.8 1.8 1.6 1.8 2.0 2.8 -
Rb Sr Sn I Xe
0.8 1.0 1.8 2.5 -
Cs Ba Pb At Rn
0.7 0.9 1.8 2.2 -
Fr Ra
0.7 0.9
Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is GaAs
adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940,
3rd edition. Copyright 1960 by Cornell University.

• Molecules with nonmetals

• Molecules with metals and nonmetals
• Elemental solids (RHS of Periodic Table)
• Compound solids (about column IVA) Chapter 2- 11
 METALLIC BONDING
• Arises from a sea of donated valence electrons
(1, 2, or 3 from each atom).

+ + +

+ + +

+ + + Adapted from Fig. 2.11, Callister 6e.

• Primary bond for metals and their alloys

Chapter 2- 12
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - secondary + - H H H H
secondary
bonding Adapted from Fig. 2.13, Callister 6e. bonding

• Permanent dipoles-molecule induced

Adapted from Fig. 2.14,
secondary
-general case: + - bonding
+ - Callister 6e.

secondary Adapted from Fig. 2.14,

-ex: liquid HCl H Cl bonding H Cl Callister 6e.

second
-ex: polymer ary bondin
g

Chapter 2- 13
 SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular

Chapter 2- 14
 PROPERTIES FROM BONDING: TM
• Bond length, r • Melting Temperature, Tm
F
F Energy (r)
r

• Bond energy, Eo ro
r
Energy (r)
smaller T m
unstretched length
ro larger T m
r
Eo = Tm is larger if Eo is larger.
“bond energy”

Chapter 2- 15
 PROPERTIES FROM BONDING: E
• Elastic modulus, E cross
sectional
length, Lo
area A o
Elastic modulus
undeformed F L
L =E
Ao Lo
deformed F

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus Chapter 2- 16

 PROPERTIES FROM BONDING: 
• Coefficient of thermal expansion, 
length, Lo coeff. thermal expansion
unheated, T 1
L L
= (T2 -T1 )
heated, T 2 Lo

•  ~ symmetry at ro
Energy

ro
r  is larger if Eo is smaller.
larger 

small er 
Chapter 2- 17
 SUMMARY: PRIMARY BONDS
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
second
ary bondin small E
g
large 

Chapter 2- 18
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 2- 0