Textbooks

1. Materials Science and Engineering

William D. Callister, David G. Rethwisch
2. Principals of Materials Science and Engineering”
3rd Edition, William F. Smith
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 Atomic Structure & Bonding
ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

 Interatomic bonding
First step in understanding material properties

• Atomic Bonding in Solids

Energies vs. Forces

• Periodic Table

• Primary Interatomic Bonds

Ionic
Covalent
Metallic

• Secondary Bonding (Van der Waals)

• Molecules and Molecular Solids

 Review of Atomic Structure
Atoms = nucleus (protons and neutrons) + electrons

Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons

chemical identification of element

Isotope number  # neutrons

 Atomic mass units. Atomic weight.
Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).

The atomic mass of 12C atom is 12 amu.

Atomic weight: A
Weighted average of atomic masses of naturally
occurring isotopes.
Atomic weight of carbon is 12.011 amu.

Atomic weight is often in mass per mole.

A mole
Amount of matter with mass in grams equal to the atomic mass in amu
(A mole of carbon has a mass of 12 grams).

One Mole contains Avogadro’s number of atoms,

Nav = 6.023 × 1023.

Nav = 1 gram/1 amu.

Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
 Some simple calculations
Number density, n: (number of atoms per cm3)
Mass density, ρ (g/cm3)
Atomic mass, A (g/mol):

n = Nav × ρ / A

Graphite (carbon): ρ = 2.3 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol
= 1.15 × 1023 atoms/cm3

Diamond (carbon): ρ = 3.5 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol
= 1.75 × 1023 atoms/cm3

Water (H2O) ρ = 1 g/cm3, A = 18 g/mol

n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3

SIZE of a Atom or Molecule

If n = 6 × 1022 atoms/cm3
Mean separation between atoms L = (1/n)1/3 = 0.25 nm.
 scale of atomic structure in solids – a fraction of 1 nm
or a few Angstroms
One “molar” relative atomic mass of Carbon-12 u
=12 g.
Gram-mole / mole: mass (in gm) of the relative
molar atomic mass of that element.

What is the “one molar” relative atomic masses of

N, O, Al, Si, P,???
Numerical Problems (using the above mentioned
definitions)
Q. (a)What is the mass in grams of one atom of Cu?
(b) How many Cu atoms are in 1g of Cu?
(a) Atomic mass of Cu = 63.54 g/mol, No. of atoms in 63.54 g of Cu = 6.023
x 1023 atoms,
(63.54 g/mole)/(6.023x1023 atoms/mole) = ??? g of Cu atoms / 1 atom of Cu

Mass of 1 Cu atom in grams = 1.05 x 10-22 g.

(b) (6.023x1023 atoms/mole) /( 63.54 g/mole) = ??? atoms of Cu in 1 gm / 1 g

of Cu
No. of atoms in 1 g of Cu = 9.47 x 1021 atoms

Repeat the same procedure using other

elements e.g, Au, Si, Ge.
Q. How many atoms are there in 1 g of
Gold?
Q. What is the mass in grams of one atoms
of Molybdenum?
Q. The cladding of the coin consists of an alloy of 75 wt% Cu and 25 wt% Ni.
What the atomic percent Cu and atomic percent Ni contents of this
material?
Suppose in a 100g, there are 75g of Cu and 25g of Ni
So number of Gram-mole of Cu = 75 g / atomic mass of Cu = 75 g/63.54 g
mol = 1.1803 mol

Similarly, for Ni = 25g/58.69 g mol = 0.4260 mol

Total No. of moles = 1.6063 mol

Atomic % of Cu = mole of Cu / total moles

Question: A solder contains 52 wt% tin and

48 wt% lead. What are the atomic
percentages of Sn and Pb in the solder?
Question: What is the chemical formula of
an intermetallic compound that consists
of 49.18 wt% Cu and 50.82 wt% Au?

Question: A gold wire is 0.70 mm in

diameter and 8 cm in length. How many
atoms does it contain? The density of
gold is 19.3 g/cm3.
Question: A gold o-ring is used to form a
gastight seal in a high-vacuum chamber.
The ring is formed from a 80-mm length
of 1.5 mm diameter wire. Calculate the
no. of gold atoms in the o-ring.
Behenchod Salay Kanjar ke Bachay Kutti maa ke bachay
Electronic Structure of Atom

Photon:
∆E = hv
h is the planks constant = 6.63 x 10-34 J-s

∆E = hc/l
Question:Calculate the energy in joules (J)
and electron volts (eV) of the photon
whose wavelength is 121.6 nm. (1ev=
1.6 x 10-19J)
Ionization Energy
The minimum energy required to remove an electron from the atom.

Heisenberg’s Uncertainty Principle

The position and momentum of a small particle such as an electron can not be
determined simultaneously.
Probability of finding the electron in an Hydrogen atom is high at a radius of about
0.05 nm.
Quantum numbers

1. Principle quantum number, n: corresponds to the main energy levels

2. The subsidiary quantum number, l:Subenergy levels within the
main energy levels. Allowed values of l are 0, 1, 2, 3, 4……. n-1. s,p,d,f are
oribitals or subenergy levels or subshell.
3. The magnetic quantum number, ml: Spatial orientation of a single
atomic orbital and has little effect on the energy of an electron. Permissible
values are –l to +l.
4. Electron spin quantum number, ms: specifies two allowed spin
directions for an electron spinning on its own axis. Two electrons may occupy
the same orbital if they have opposite spin.

Pauli exclusion principle: no two electrons can have the same

set of four quantum numbers
Maximum number of electrons for Principle shell: 2n2

Atomic size

Electronic configurations of the elements

Electronic structure and chemical reactivity

Outermost electrons completely filled (Ne, Ar, Kr, Xe and Rn)

 Electrons in Atoms (I)
Electrons form a cloud around
the nucleus
Radius ~ 0.05 – 1nm.

Picture looks like a mini

planetary system. But Quantum
Mechanics says this analogy is
not correct
Electrons “orbits” are 'fuzzy‘
Can only discuss probability of finding it at some distance from the
nucleus.
Only certain “orbits” or shells are allowed.
Shells identified by principal quantum number n,
n related to size of radius (and energy)
n = 1, smallest; n = 2, 3 .. are larger.

Second quantum number l, defines subshells.

Two more quantum numbers characterize states within subshells.

 Electrons in Atoms (III)

Subshells by energy: 1s,2s,2p,3s,3p,4s,3d,4s,4p,5s,4d,5p,6s,4f,…

 Electrons fill levels in order of increasing energy (only n,  make a

significant difference).
Example: Iron, Z = 26: 1s22s22p63s23p63d64s2

 Outermost shell – the valence electrons

responsible for bonding. 23
 Periodic Table

Elements in same column share similar properties.

Group number  number of electrons available for bonding

0: Inert gases (He, Ne, Ar...) filled subshells: chem. inactive

IA: Alkali metals (Li, Na, K…) one electron in outer shell eager to give up electron
– chem. active

VIIA: Halogens (F, Br, Cl...) missing one electron in outer

shell - want to gain electron - chem. active
 Periodic Table - Electronegativity

Electronegativity - how willing atoms are to

accept electrons
Subshells with one electron - low electronegativity
Subshells with one missing electron -high electronegativity
Electronegativity increases from left to right

Metals are electropositive – can give up their few valence electrons

to become positively charged ions
 The electron volt (eV)
Energy unit convenient for atomic bonding

Electron volt –
energy lost / gained when an electron is taken through a potential
difference of one volt.
E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt

1 eV = 1.6 x 10-19 J
 Types of Bonding
Primary Bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)

Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

Covalent: electrons shared between the atoms.

Example - H2

Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material

Secondary Bonding: no e- transferred or shared

Interaction of atomic/molecular dipoles
Weak (< 100 KJ/mol or < 1 eV/atom)

 Fluctuating Induced Dipole (inert gases, H2, Cl2…)

 Permanent dipoles (polar molecules - H2O, HCl...)

 Ionic Bonding (I)
Mutual ionization by electron transfer
(remember electronegativity table) • Occurs between + and -
• Anion = negatively charged atom ions.
• Cation = positively charged atom • Large difference in
electronegativity required.
Ions are attracted by strong coulombic interaction
• Oppositely charged atoms attract
• An ionic bond is non-directional
Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer shell (Neon)

11 Protons Na 1S2 2S2 2P6 3S1 donates e-

11 Protons Na+ 1S2 2S2 2P6 10 e- left
Cl has 17 electron, 1 less than needed for a full outer shell (Argon)

17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e-

17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-
 Ionic Bonding (II)
e-
Na Cl Na+ Cl-
3s1 Half-filled 3p

• Electron transfer reduces energy of the system

• The ionic bonding forces are due to
• Na shrinks and Cl expands electrostatic or coulombic force of attraction of
oppositely charged ions.

• bonds forms due to decrease in pot. energy

Ionic bonds: very strong, nondirectional bonds

• Reduces the size of Na atom due to electron to proton
ratios.
• Increases the size of Cl atom due to electron to proton
ratios.

0.192nm 0.099nm 0.095nm 0.181nm

Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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.
Ions arrangement in ionic solids

Elemental ions have approximately spherical shape charge distributions

Elemental ions are smaller than their radius
Non-directional due to electrostatic attraction of symmetrical charges

Bonding energies of ionic solid

Ionic solids have high melting temp.

Lattice energy decrease as the ion increases in a group

Covalent Bonding

Small differences in Electronegativity

Sharing of electrons
After sharing energy decreases
Covalent Bonding Hydrogen molecule
 Covalent Bonding in Carbon

Carbon forms two covalent bonds

In some cases it forms four covalent bonds sp3 by hybridization

1s 2s 2p orbitals (half filled) 1s Four half filled orbitals

(sp3 orbitals)
Carbon in the form of diamond exhibit sp3 tetrahedral covalent bonding
Sp3 hybrid orbitals are directed symmetrically towards the corners of a tetrahedron

High hardness, high bond strength

and melting temp.
Covalent bonding in carbon-containing molecule

Benzene
 Covalent Bonding
Potential energy of system of covalent bonds

P.E.=

Depend on distances between atoms

38
AND angles between bonds
Metallic bonding
Occurs in the solids metals, that atoms are packed relatively close together in a
definite pattern, such that their outer electrons are attracted to the nucleus of
many neighbors (12 nearest neighbors for Cu)

Solid metals are visualized as positive

ion cores (atoms without their valence
elections)

Valence electrons are spread among

atoms in the form of low density
electron charge cloud or “electron
gas”. These electrons are weakly
bonded to positive ion cores and can
move in the crystal (free electrons).
In metallic bonding, no conditions of charge neutrality or electron pair is required
Non-directional due to bonding of valence electrons to many atoms
Minimum energy between a pair of atoms when the equilibrium distance ao is reached.

Multiatom metal crystals differ from those of single metal atom

Lower the energy but in different levels

Secondary bonding
Secondary bonds are weak in contrast to primary bonds
Driving force for the secondary bonds is the attraction of the electric diploes

Electric diploes are created when two equal and opposite charges are separated
 SECONDARY BONDING
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 8e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

44
 Properties From Bonding : a
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
DL DL
= a (T2 -T1)
heated, T 2 Lo

• a ~ symmetric at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

E
larger a
o
E smaller a
45 o
 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 Tm
small E
large a

46
Mixed bonding
1. Ionic-covalent bonding
2. Metallic-covalent bonding
3. Metallic-ionic bonding

1. Ionic-covalent bonding

Most covalent bonded molecules have some ionic binding and vice versa
Greater the difference in electronegativies, greater the ionic character of the bond
e.g, GaAs (3-5) and ZnSe (2-6)

2. Metallic-covalent bonding

In the transition metals involving dsp bonding orbitals

3. Metallic-ionic bonding

Significant difference in electronegativities that forms intermetallic compound

(NaZn13).