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 1
n=3 2 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.

Adapted from Fig. 2.5,

Callister 6e.

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

Adapted from Table 2.2,

Callister 6e.

Chapter 2- 4
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1 Adapted from Table 2.2,
1s22s22p2 Callister 6e.
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d10 4s246 (stable)

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

Chapter 2- 5
 THE PERIODIC TABLE
• Columns: Similar Valence Structure

Adapted
from Fig. 2.6,
Callister 6e.

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.

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

Chapter 2- 8
 EXAMPLES: IONIC BONDING
• Predominant bonding in Ceramics
NaCl
MgO
H He
2.1 CaF2 -
Li Be O F Ne
1.0 1.5 CsCl 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
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 6e.

Chapter 2- 10
 EXAMPLES: COVALENT BONDING
H2O

column IVA
H2 F2
C(diamond)
H He
2.1
SiC - Cl2
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

Adapted from Fig. 2.13, Callister 6e.

• Permanent dipoles-molecule induced

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

Adapted from Fig. 2.14,

-ex: liquid HCl Callister 6e.

-ex: polymer

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

• Bond energy, Eo

Tm is larger if Eo is larger.

Chapter 2- 15
 PROPERTIES FROM BONDING: E
• Elastic modulus, E
Elastic modulus

F L
=E
Ao Lo

• 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: a
• Coefficient of thermal expansion, a
coeff. thermal expansion
L
= a(T2-T1)
Lo

• a ~ symmetry at ro

a is larger if Eo is smaller.

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

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a

Chapter 2- 18