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

Chapter2AtomicStructureand
InteratomicBonding

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.
Increasing energy

4p
n=4 3d
4s
n=3 3p
3s
n=2 2p
2s
n=1 1s 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.

Z Element Configuration
2 He 1s2 Adapted from Table 2.2,
10 Ne 1s22s 22p6 Callister 6e.

18 Ar 1s22s22p63s23p6
36 Kr 1s22s22p63s23p63d104s24p6

Chapter 2-4
 SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s1
Helium 2 1s2 (stable)
Lithium 3 1s22s1
Beryllium 4 1s22s2
Boron 5 1s22s22p1 Adapted from Table 2.2,
1s22s22p2 Callister 6e.
Carbon 6
... ...
Neon 10 1s22s22p6 (stable)
Sodium 11 1s22s22p63s1
Magnesium 12 1s22s22p63s2
Aluminum 13 1s22s22p63s23p1
... ...
Argon 18 1s22s22p63s23p6 (stable)
... ... ...
Krypton 36 1s22s22p63s23p63d104s246 (stable)

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

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

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e
Metal

Nonmetal
H He
Li Be Intermediate Ne
O F
Na Mg Adapted
S Cl Ar
from Fig.
K Ca Sc Se Br Kr 2.6, 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 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 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
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
asymmetric electron ex: liquid H2
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.

seco n
-ex: polymer da r y
bo nd
in g

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 E A E R 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 Energy (r)
r

Bond energy, Eo ro
r
Energy (r)
smaller Tm
unstretched length
ro larger Tm
r
E o= Tm is larger if Eo is larger.
bond energy

Chapter 2-15
 PROPERTIES FROM BONDING: E
Elastic modulus, Ecross
sectional
length, L o
area Ao
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, L o coeff. thermal expansion
unheated, T1
L L
=(T2-T1)
heated, T2 Lo

~ symmetry at ro
Energy

ro
r is larger if Eo is smaller.

larger

smaller 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
seco n
da r y
bo nd
small E
in g
large

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

LargerE
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)The1s22s22p63s23p63d74s2electronconfigurationisthatofatransitionmetalbecauseofan
incompletedsubshell.
(b)The1s22s22p63s23p6electronconfigurationisthatofaninertgasbecauseoffilled3sand3p
subshells.

Chapter 2-
213

Chapter 2-
215

Chapter 2-
 Chapter 2-