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
Atomic Structure (Freshman Chem.)
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10 -27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons in neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

1 amu/atom = 1 g/mol
C 12.011
H 1.008 etc.

Chapter 2- 2
 Atomic Structure

• Some of the following properties

1) Chemical
2) Electrical
3) Thermal
4) Optical
are determined by electronic
structure

Chapter 2- 3
 Electronic Structure
• Electrons have wavelike and particulate properties.
• Two of the wavelike characteristics are
– electrons are in orbitals defined by a probability.
– each orbital at discrete energy level is determined by
quantum numbers.

– Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

Chapter 2- 4
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4
Adapted from Fig. 2.6, Callister &
3d Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J.
Wulff, Introduction to Materials Science and
4s Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2- 5
 SURVEY OF ELEMENTS
Most elements: Electron configuration not stable
because Valence (outer) shell usually not filled completely
Electron configuration
1s1
1s2 (stable)
1s22s1
1s22s2
1s22s22p1
1s22s22p2
...
1s22s22p6 (stable)
1s22s22p63s1
1s22s22p63s2
1s22s22p63s23p1
...
1s22s22p63s23p6 (stable)
...
1s22s22p63s23p63d10 4s246 (stable)

Chapter 2- 6
 Electron Configurations
• Valence electrons – those in unfilled
shells
• Filled shells more stable
• Valence electrons are most available for
bonding and tend to control the chemical
properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

Chapter 2- 7
 THE PERIODIC TABLE
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.8,
Callister &
K Ca Sc Se Br Kr
Rethwisch 9e.
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- 8
ATOMIC BONDING

r0: equilibirium
interatomic spacing
E0: bond energy

dE
E    Fdr, F  
dr

Chapter 2- 9
Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

Chapter 2- 10
 IONIC BONDING (Ceramics)
Example: NaCl
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in
electronegativity required.

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

Chapter 2- 11
 COVALENT BONDING
• Requires shared electrons • shared
H electrons from
Example: CH4 CH4 carbon atom
C: has 4 valence e, needs 4 more
H: has 1 valence e, needs 1 more H C H
Electronegativities are comparable.

H2O •shared

column IVA
H2 F2 H electrons from
C(diamond) hydrogen atoms
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 GaAs

Chapter 2- 12
 METALLIC BONDING
Primary bond for metals and
their alloys
Arises from a sea of donated
valence electrons

SECONDARY BONDING
Arises from interaction between Fluctuating or Permanent dipoles

example:
polymer

Molecular
chains Chapter 2- 13
 PROPERTIES FROM BONDING: TM
• Bond length, r • Melting Temperature, Tm
F
F

Energy
• Bond energy, Eo ro
r
Equilubrium
smallermT
Energy

interatomic
spacing
ro larger T
r m
bond energy
Tm is larger if Eo is larger.

Chapter 2- 14
 PROPERTIES FROM BONDING: E
Initial length
Cross • Elastic modulus, E
L0
sectional Energy
undeformed area A0
DL
unstretched length
deformed F ro Stretched r
r
Elastic modulus larger E
F DL Energies
=E
Ao Lo required
smaller E to
stretch
F
E E  curvature at ro
DL
 bond energy
Chapter 2- 15
 PROPERTIES FROM BONDING: a
• Coefficient of thermal expansion, a

coeff. of thermal expansion

DL
= a (T2-T1)
Lo

Energy a ~ symmetry at ro

ro a is larger
r if
Larger a bond energy, Eo is
smaller
Smaller a
Chapter 2- 16
 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- 17