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
Introduction to Materials Science

Chapter 2 Atomic Structure and

Interatomic Bonding

Chapter 2-
 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
 2003 Brooks/Cole Publishing / Thomson Learning

The figure shows

the metallic bond
forms when atoms
give up their
valence electrons,
which then form an
electron sea. The
positively charged
atom cores are
bonded by mutual
attraction to the
negatively charged
electrons. (Askeland).

Chapter 2-
 2003 Brooks/Cole Publishing / Thomson Learning
Figure 2.13 When voltage is applied to a metal, the electrons
in the electron sea can easily move and carry a current (Askeland).

Chapter 2-
 2003 Brooks/Cole Publishing / Thomson Learning

Figure 2.19 When voltage is applied to an ionic material, entire

ions must move to cause a current to flow. Ion movement is
slow and the electrical conductivity is poor (for Example 2-8)

Chapter 2-
 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
 Percent Ionicity: Ionic to metallic

Nature of the Bonds: Percent ionicity ( X A X B )2

(see text, where X is the electronegativity, page 29) %IC 1 e 4

%IC=1 %IC=0

Chapter 2-
 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
 Origin of Bonding Curve
arises from attractive plus repulsive interactions between atoms(ions)

Energy : Etotal EA ER Particular forms if EA and ER depends

upon atoms and quantum mechanics,
but often described by simple forms.

A B
EA and ER
r rn
(Z1e)(Z 2 e)
(e.g., Coulombic, A )
4 0
For NaCl, Z1=ZNa=+1 and Z2=ZCl= -1

Macroscopic consequences of generic Etotal shown in previous slides

Repulsive
force
dE dEA dER
Force : F Minus sign in force makes sure that,
dr r0 dr r0 dr r0 by definition, repulsive force is +
Attractive
force F = 0 at equilibrium r0: can find r0.

Chapter 2-
 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
Chapter 2-
 Figure 2.23 Atoms or
ions are separated by
and equilibrium
spacing that
corresponds to the
minimum inter-atomic
energy for a pair of
atoms or ions (or
when zero force is
acting to repel or
attract the atoms or
ions)

2003 Brooks/Cole Publishing / Thomson

Learning

Chapter 2-
 Coefficient of Thermal Expansion, a, or dL/dT

Linear Thermal Strain E

L(T)/L0 = L (T - T0)
r0
r
~ asymmetry at r0 r(T)
No asymmetry at r0
T2 Smaller E
No affect on r(T) or V(T) T1
Larger

Larger E
as E0 (less negative) Smaller

Parabolic E vs. r shape

Volume Thermal Strain
E~(r - r0)2
V/V0 = V (T - T0)

Symmetric well r(T)=r0: No expansion possible

Atoms just vibrate back and forth!
Chapter 2-
 (a) The 1s22s22p63s23p63d74s2 electron configuration is that of a transition metal because of an
incomplete d subshell.
(b) The 1s22s22p63s23p6 electron configuration is that of an inert gas because of filled 3s and 3p
subshells.

Chapter 2-
2-13

Chapter 2-
2-15

Chapter 2-
Chapter 2-