ME 212 Materials

Science
Chapter 2: Atomic Structure and Interatomic Bonding
Previously
Metals
Ceramics
Polymers
Composites

Fiberglass composite Kevlar

Advanced Materials
(Semiconductors)

Nanometer scale
Materials Paradigm
Topics Covered in Ch. 2
• Models to define atomic structure
• What promotes bonding?
• Types of bonds
• Bonding’s influence on properties
Atomic Structure
• Atom  Electrons 9.11 x 10-31 kg
Protons 1.67 x 10-27 kg
Neutrons 1.67 x 10-27 kg
• Atomic number = # of protons in nucleus of atom
= # of electrons of neutral species
• A [=] atomic mass unit = amu = 1/12 mass of 12C
• Proton mass is 1.007277 amu
• Neutron mass is 1.008665 amu
• Atomic wt = wt of 6.022 x 1023 molecules or atoms
• 1 amu/atom = 1g/mol
Atomic Structure
• Avogadro’s Number = 6.022 x 1023 = NA
• Atomic or Molecular Weight = NA x Weight Per Atom
• Number of neutrons = N
• Number of protons = Z
• A=Z+N
• For a given element, the number of neutrons (N) may vary
• Isotopes
• Atomic weight of an element  Weighted average of the atomic masses of
atom’s isotopes
Example
• Cerium has four naturally occurring isotopes:
• 0.185% of 136Ce, with an atomic weight of 135.907 amu
• 0.251% of 138Ce, with an atomic weight of 137.906 amu
• 88.450% of 140Ce, with an atomic weight of 139.905 amu
• 11.114% of 142Ce, with an atomic weight of 141.909 amu.
• Calculate the average atomic weight of Ce.
Example
• One mole of solid MgO occupies a cube 22.37 mm on a side. Calculate
the density of MgO (in g/cm3).
• Atomic mass of Mg = 24.31 amu
• Atomic mass of O = 16.00 amu
Example
• Calculate the dimensions of a cube containing 1 mol of solid
magnesium.
• Density of Mg = 1.74 g/cm3
• Atomic mass of Mg = 24.31 amu

Length of a cube is:

Bohr Atomic Model
• Electrons revolve around nucleus in discrete orbitals (i.e. trajectory of
the electron is well defined)
• Energy is quantized (Quantum mechanical model)
• Only specific amount of energies, described by
quantum numbers
• Only specific trajectories are allowed
• Describe in terms of position and energy
• Found to have limitations
Wave-Mechanical Model
• Electron has both wave-like and particle-like
characteristics
• Electron does not move along a specific
trajectory
• A cloud of possible locations around nucleus
• Energy is quantized into shells and sub-shells
• Size
• Shape Defined by quantum numbers
• Spatial orientation

Comparison of Bohr (left) and

wave-mechanical (right) models
Quantum Numbers
Quantum Number Designation Refers to
Principal (n) K, L, M, N, O (1, 2, 3, 4, 5) Shell
Second (azimuthal) (l) s, p, d, f Sub-shell
Magnetic (ml ) 1, 3, 5, 7 (-l to +l) # orbitals in each
sub-shell
Spin (ms) ½, -½ Spin

• Pauli exclusion principle: No more than two electrons with opposing

spins may be present in each orbitals
Relationship Among Quantum
Numbers
 Orientation and Shapes of Orbitals
px, py, pz electron orbitals

s electron orbital
Orientation and Shapes of Orbitals

d electron orbitals

f electron orbitals

pressbooks.bccampus.ca/chem1114langaracollege
Electron Energy States
• Electrons have discrete energy states
• They tend to occupy lowest available energy state
4d
4p N-shell n = 4

3d
Increasing Energy

4s

3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Stable Electron Configurations
• Atoms:
• Having complete s and p subshells
• Unreactive
Element Atomic # Electron configuration
Helium 2 1s 2
Neon 10 1s 2 2s 2 2p6
Argon 18 1s 2 2s 2 2p6 3s 2 3p6
Krypton 36 1s2 2s 2 2p6 3s2 3p6 3d10 4s2 4p6

• Most elements do not have stable electron configuration

Survey of Elements
• Reason for unstable electron Element Atomic # Electron configuration
Hydrogen 1 1s 1
configurations? Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
• Valence (outer) shell not Beryllium 4 1s 2 2s 2
filled completely Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
• Remember valence ... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
electrons are the available Sodium 11 1s 2 2s 2 2p 6 3s 1
electrons for bonding and Magnesium 12 1s 2 2s 2 2p 6 3s 2
dictate many properties Aluminum
...
13 1s 2 2s 2 2p 6 3s 2 3p 1
...

Ex: C (1s2 2s2 2p2) Argon

...
18
...
1s 2 2s 2 2p 6 3s 2 3p 6
...
(stable)

Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

valence electrons
Atomic Structure
• Valence electrons determine all of the following properties
• Chemical
• Electrical
• Thermal
• Optical
Another Example
Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d valence
4p N-shell n = 4 electrons
3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
The Periodic Table

inert gases
give up 1e-

Columns: Similar Valence Structure

give up 2e-

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

Li Be O F Ne

Na Mg S Cl Ar

K Ca Sc Se Br Kr

Rb Sr Y Te I Xe

Cs Ba Po At Rn

Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons to become + ions. Readily acquire electrons to become - ions.
 Electronegativity
• Defines tendency to acquire electrons

Larger electronegativity
Smaller electronegativity

Smaller electronegativity Larger electronegativity

1. The atomic number of an element corresponds to the
number of:

a) protons
b) electrons
c) neutrons
d) number of protons and neutrons
2. Which of the following particles account for most of the
mass of an atom?

a) protons
b) electrons
c) neutrons
d) protons and neutrons
3. Which of the following particles account for most of the
volume of an atom?

a) protons
b) electrons
c) neutrons
d) protons and neutrons
4. The atomic weight corresponds to the mass of

a) protons
b) electrons
c) neutrons
d) protons and neutrons
e) none of the above
5. Elements in the last (8th) column of the periodic table are
called:

a) alkali
b) alkali earth
c) halogens
d) noble gases
6. Elements in the 7th column of the periodic table are
called:

a) alkali
b) alkali earth
c) halogens
d) noble gases
7. Which of the following elements are the most
electronegative?

a) alkali
b) alkali earth
c) halogens
d) noble gases
Ionic Bond
• Electron transfer from one atom to another
• Metal-nonmetal
• Dissimilar electronegativities
• Achieve stable electron configuration

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

[Ne] 3s2
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6
[Ne] [Ne]
Ionic Bonding
• Result of the coulombic attraction between oppositely charged species
• Non-directional
• Magnitude of bond is equal in all directions
Ionic Bonding Examples
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Ionic Bonding
• Strong bonds
• High melting temperatures
• Typical for ceramics
• Hard and brittle
• Electrically and thermally insulative
Attraction Force
• Coulombic attraction force between differently charged ions

• a is the separation distance btw centers of ions and

• Z is the valence of the ion

• q is the charge of a single electron ( )
• k0 is
Forces
• Attraction force 
• Can we bring two ions closer?
• Repulsive force
• Overlap of negative electric fields
• Two positively charged nuclei

• Experimentally determined
Net Bonding Force
• Net bonding force is the sum of
attraction and repulsive forces
Bonding Energy
• Force is the derivative of energy

• Equilibrium bond length at F=0

• To move ions from equilibrium
• Energy must be supplied
• Compressive or tensile
• and
Example
• Calculate the coulombic force of attraction and repulsive force
between Na+ and Cl- in NaCl.
• r for Na+ = 0.098 nm
• r for Cl- = 0.181 nm
a0 = 0.098 + 0.181 = 0.278 nm

V.C = J and J/m = N

Covalent Bonding
• Cooperative sharing of valence electrons between two adjacent atoms
• Found in materials whose atoms have similar electronegativity
• Stable electron configurations by the sharing of electrons between
adjacent atoms

Helium configuration

• Directional:
• Btw specific atoms and may exist only in the direction of participation
 shared electrons
H
Covalent Bonding CH 4
from carbon atom

H C H
• Many nonmetallic molecules
• Elemental molecules (Cl2, F2) shared electrons
H from hydrogen
• CH4, H2O atoms
• Elemental solids
• C, Si, Ge
• Can be very strong (diamond) or weak (bismuth)
• Mostly insulators (some are semiconductors) Cl2
Bond Hybridization
• Mixing (or combining) of two or more atomic
orbitals with the result that more orbital overlap
during bonding results
• Bonding hybrid orbitals are directional in nature
• Tetrahedral bonding  sp3
• Found in diamond
Bond Hybridization

• One 2s orbital mixes with two of the three 2p

orbitals—the third p orbital remains unhybridized
• Found in graphite
Metallic Bonding
• Found in metals and their alloys
• Valence electrons are not bound to a particular atom
• Electron cloud
• Nonvalence electrons and atomic nuclei forms ion cores
Metallic Bonding
• Involves electron sharing
• Nondirectional
• Think of free (delocalized) electrons
as glue holding ion cores together
• Bonding may be weak (Hg) or strong
(W)
• Free electrons responsible for heat
and current conduction
Primary and Secondary Bonds
• Major source of cohesion in materials are primary bonds
• Relies on electron transfer or electron sharing
• Ionic
• Covalent
• Metallic
• Also possible to get some bonding without e- transfer or sharing
• Called secondary, van der Waals, physical bonds
• Observed in inert gases
• Mechanism is similar to ionic bonding (attraction of opposite charges)
• No electron transfer occurs
Secondary Bonds
• Dipoles (atomic or molecular) are the source
• Dipole exists due to separation of positive and negative portions of an
atom (Charge symmetry ceases to exist)
• Induced dipoles or polar molecules
Induced Dipole Bonds
• Dipole can be induced in an electrically symmetric atom or molecule
• Bringing another atom nearby or vibrational motion distorts
symmetry
• Temporary and fluctuate with time
Polar Molecule - Induced Dipole
• Polar molecule: Asymmetrically arranged positively and negatively
charged regions
• This molecule induced an otherwise symmetrical molecule to form a
bond
• Stronger than induced dipole bonds
Permanent Dipole Bonds
• Coulombic forces between adjacent polar molecules
• Hydrogen bond is an example
• Strongest secondary bond
• Occurs between molecules in which hydrogen is covalently bonded to fluorine
(as in HF), oxygen (as in H2O), or nitrogen (as in NH3)
• H end of the bond is essentially a positively charged bare proton
• Positively charged end of the molecule can attract the negative end of an
adjacent molecule
Mixed Bonding
• When the bonding does not belong to a single type
• Covalent-ionic bond  Difference in electronegativity contributes to
ionic bonding
 (X A  X B )2 
  
• Ionic character (%) = 1 e

4
x (100) X are electronegativity
 
 

Ex: MgO XMg = 1.2


XO = 3.5
 
( 3.5  1.2 )2 
 
% ionic character  1  e 4
 x (100%) 73.4% ionic

 
Mixed Bonding
• Metallic-covalent mixed bonds:
• IIIA, IVA, and VA (e.g. B, Si, Ge, As, Sb)
• Metallic-ionic mixed bonds:
• Two metals with different electronegativity values (e.g. AuCu3)
• Covalent-secondary bonds:
• Polymers (C-H covalent bonds, between chains secondary bonds)
Mixed Bonding - Polyetyhlene
Example
Bonding Tetrahedron
Summary of Bonding Types
Type Bond Energy Comments
Ionic Large Nondirectional (ceramics)
Electron transfer
Variable Directional (polymer chains
Covalent Large for diamond and ceramics)
Small for bismuth Electron sharing

Variable
Metallic Nondirectional (metals)
Large for tungsten
Electron sharing
Small for mercury
Secondary Smallest Directional
Inter-chain (polymer)
Inter-molecular
Properties from Bonding
• Elastic modulus • Melting Temperature, Tm
Energy

ro
r

Slope is shallower for more Tm is larger if Eo is larger

flexible material
Properties from Bonding
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
DL DL
=a (T2 -T1)
heated, T2 Lo

Energy
unstretched length
ro
r a is larger if Eo is smaller.

Eo
larger a

Eo smaller a
Comparison of Primary Bonding on
Properties
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): small Tm
small E
secon
dary
bond large a
i ng