CHAPTER 2:

BONDING AND PROPERTIES

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.

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
1s 1
1s 2 (stable)
1s 2 2s 1
1s 2 2s 2
1s 2 2s 2 2p 1 Adapted from Table 2.2,
1s 2 2s 2 2p 2 Callister 6e.

...
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
...
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 4 6 (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 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
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
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

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 -T 1 )
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
 FORCES BETWEEN ATOMS

• At large distance, the forces between atoms

are negligible but as they approach each
other, each exerts force on the other.

Chapter 2- 19
 TYPES OF FORCES
1. Attractive force; FA
2. Repulsive force; FR
F N = F A + FR
At Equilibrium,
FN = 0
So that,
FA + F R = 0
Where:
FN = Net Force

Chapter 2- 20
ATTRACTIVE AND REPULSIVE ENERGY

Similarly,
EA + ER = 0
Where,
EA = -A/r

ER = B/rn

Where:
A, B and n are constant

Chapter 2- 21
To Solve the Equilibrium Net Energy, E0

1. Get the first derivative of EN with respect

to r (interionic spacing)
2. Equate the first derivative to zero
3. Solve for r0
4. Determine the value of E0

Chapter 2- 22
 Sample Problem 1

The net potential energy between two adjacent

ions, EN may be represented by:

EN = -A + B
r rn
Calculate the bonding energy E0 in terms of
the parameters.

Chapter 2- 23
 Sample Problem 2

For a K+-Cl- ion pair, attractive and repulsive

energies EA and ER, respectively, depend on the
distance between the ions accordingly to

EA = -1.436 ER = 5.86 x 10-6

r r9

For the expressions, energies are expressed in

electron volts and r in nanometers. Determine r0
and E0 values.
Chapter 2- 24
 Sample Problem 3

Determine the interionic spacing and bonding

energy at equilibrium for the expression

EN = -1.711 + 1.78 x 10-4

r r7

Chapter 2- 24
 % IONIC CHARACTER

% Ionic Character = {1 – e-0.25 (XA –XB)2} x 100

Where: XA and XB = electronegativity of the ions

Chapter 2- 25
 Sample Problem

• Determine the % ionic character of TiO2

Chapter 2- 26