Materials Science

and
Engineering I

Chapter Outline
Review of Atomic Structure
Electrons, Protons, Neutrons, Quantum number
of atoms, Electron states, The Periodic Table
Atomic Bonding in Solids
Bonding Energies and Forces
Periodic Table
Primary Interatomic Bonds
Ionic, Covalent, Metallic
Secondary Bonding (Van der Waals)
Three types of Dipole Bonds
Molecules and Molecular Solids
Understanding of interatomic bonding is the first step
Towards understanding/explaining materials properties

1
 Structure of Atoms
ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged
Nucleus Electron Cloud

Diameter : 10 –14 m Mass : 9.109 x 10 –28 g

Accounts for almost all mass Charge : -1.602 x 10 –9 C
Positive Charge Accounts for all volume

Proton Neutron

Mass : 1.673 x 10 –24 g Mass : 1.675 x 10 –24 g

Charge : 1.602 x 10 –19 C Neutral Charge

Review of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons
Charges:
Electrons and protons have negative and positive charges of the same magnitude, 1.6 ×
10-19 Coulombs. Neutrons are electrically neutral.

Masses:
Protons and Neutrons have the same mass, 1.67 × 10-27 kg. Mass of an electron is much
smaller, 9.11 × 10-28 kg and can be neglected in calculation of atomic mass.

The atomic mass (A) = mass of protons + mass of neutrons

# protons gives chemical identification of the element
# protons = atomic number (Z)
# neutrons defines isotope number

2
 Atomic Number and Atomic Mass
Atomic Number = Number of Protons in the nucleus
Unique to an element
 Example :‐ Hydrogen = 1, Uranium = 92
Relative atomic mass = Mass in grams of 6.02 x 1023
( Avagadro Number) Atoms.
 Example :‐ Carbon has 6 Protons and 6 Neutrons. Atomic Mass =
12.
One Atomic Mass unit is 1/12th of mass of carbon atom.
One gram mole = Gram atomic mass of an element.
 Example :‐

One gram 6.023 x 1023

12 Grams
Mole of Carbon
Of Carbon
Carbon Atoms

2-3

Example Problem
A 100 gram alloy of nickel and copper consists of
75 wt% Cu and 25 wt% Ni. What are percentage of
Cu and Ni Atoms in this alloy?
Given:- 75g Cu Atomic Weight 63.54
25g Ni Atomic Weight 58.69

75 g
Number of gram moles of Cu =  1 .1803 mol
63 .54 g/mol
25 g
Number of gram moles of Ni =  0 .4260 mol
58 .69 g/mol
1.1803
Atomic Percentage of Cu = 100  73.5%
(1.1803 0.4260)
0 . 4260
Atomic Percentage of Ni =  100  25 . 5 %
(1 . 1803  0 . 4260 )
6

3
 7

Planck’s Quantum Theory

 Max Planck, discovered that atoms and molecules emit energy
only in certain discrete quantities, called quanta.
 James Clerk Maxwell proposed that the nature of visible light
is in the form of electromagnetic radiation.
 E = hυ = hc/λ
 Energy is always released in integer multiples of hυ

8 8

4
 Electron Structure of Atoms
Electron rotates at definite energy levels.
Energy is absorbed to move to higher energy level.
Energy is emitted during transition to lower level.
Energy change due to transition = ΔE = hc

Absorb Emit h=Planks Constant

Energy = 6.63 x 10-34 J.s

Energy
c= Speed of light
(Photon) (Photon)
λ = Wavelength of
light

Energy levels

Energy in Hydrogen Atom

Hydrogen atom has one proton and one electron
Energy of hydrogen atoms for different energy
levels is given by (n=1,2…..)
principal quantum numbers
13 . 6
E   2 ev
n
Example:- If an electron undergoes transition from
n=3 state to n=2 state, the energy of photon
emitted is
13 .6 13 .6
 E   2  2  1 .89 ev
3 2
Energy required to completely remove an electron
from hydrogen atom is known as ionization energy
2-7 10

5
Energy-Level diagram for the line
spectrum of hydrogen

11

12

6
 Quantum Numbers of Electrons of Atoms

Principal Quantum Subsidiary Quantum

Number (n) Number (l)
Represents main Represents sub energy
energy levels. levels (orbital).
Range 1 to 7. Range 0…n-1.
Larger the ‘n’ higher Represented by letters
the energy. s,p,d and f.
n=1 s orbital
n=2 (l=0)
n=2
n=1
n=3 p Orbital
(l=1)

13

Quantum Numbers of Electrons of Atoms (Cont..)

Magnetic Quantum Electron spin quantum

Number ml. number ms.
Represents spatial Specifies two directions
orientation of single of electron spin.
atomic orbital. Directions are clockwise
Permissible values are or anticlockwise.
–l to +l.
Values are +1/2 or –1/2.
Example:- if l=1,
ml = - Two electrons on same
1,0,+1. orbital have opposite
spins.
I.e. 2l+1 allowed values.
No effect on energy.
No effect on energy.

14

7
 S, p and d Orbitals

15

Electron Density
 Solution of the wave equation is in terms of a wave function,
ψ (orbitals).
 The square of the wave function represents electron
density.
 Boundary surface
representation.
 Total probability 0.1 nm

0.05 nm

16 16

8
Electron Structure of Multielectron Atom
Maximum number of electrons in each atomic shell is
given by 2n2.
Atomic size (radius) increases with addition of shells.
Electron Configuration lists the arrangement of
electrons in orbitals.
 Example :‐ Number of Electrons
Orbital letters

1s2 2s2 2p6 3s2

Principal Quantum Numbers

 For Iron, (Z=26), Electronic configuration is

1s2 2s2 2p6 3s2 3p6 3d6 4s2
17

Electronic Configurations
1s2 2s2 2p6 3s2 3p6 4s2 3d 6
ex: ZFe = 26

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

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1

18

9
 Orbital Box Diagram

 Elements are classified according to their ground state

electron configuration.

19

20

10
 Periodic Table

Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003.
21

Periodic Variations in Atomic Size

 Atomic size: half the distance between the nuclei of two
adjacent atoms (metallic radius) OR identical (covalent
radius).
 Affected by principal quantum number and size of the
nucleus.

22 22

11
 Atomic Structure

Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

23

Electron Structure and Chemical Activity

Except Helium, most noble gasses (Ne, Ar, Kr, Xe, Rn)
are chemically very stable
 All have s2 p6 configuration for outermost shell.
 Helium has 1s2 configuration

Electropositive elements give electrons during

chemical reactions to form cations.
 Cations are indicated by positive oxidation numbers
 Example:‐
Fe : 1s2 2s2 sp6 3s2 3p6 3d6 4s2
Fe2+ : 1s2 2s2 sp6 3s2 3p6 3d6
Fe3+ : 1s2 2s2 sp6 3s2 3p6 3d5

24

12
 Trends in Ionization Energy
 Energy required to remove an electron from its atom.
 First ionization energy plays the key role in the
chemical reactivity.
 As the atomic size
decreases it takes
more energy to
remove an electron.
 as the first outer core
electron is removed,
it takes more energy
to remove a second
outer core electron
25

Electron Structure and Chemical Activity (Cont..)

Electronegative elements accept electrons during

chemical reaction.
Some elements behave as both electronegative and
electropositive.
Electronegativity is the degree to which the atom
attracts electrons to itself
 Measured on a scale of 0 to 4.1
 Example :‐ Electronegativity of Fluorine is 4.1
Electronegativity of Sodium is 1.
Na Te N O Fl
Electro- Electro-

positive 0 K 1 W 2H Se 3 4 negative

26

13
 Electronegativity
• Ranges from  = 0.7 to 4.0, dimensionless!
• Large values: tendency to acquire electrons.

TM: Uniformly low EN

Larger electronegativity
27 27

The Periodic Table

H He

Li Be O F Ne

Na Mg S Cl Ar
Adapted from
K Ca Sc Se Fig. 2.6,
Br Callister
Kr
7e.
Rb Sr Y Te I Xe

Cs Ba Po At Rn

Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons

28
28

to become + ions. to become - ions.

14
 Trends in Electron Affinity
 Electron affinity: Tendency to accept one or more
electrons and release energy.
 Electron affinity increases (more energy is released
after accepting an electron) as we move to the right
across a period and decreases as we move down in a
group.
 Groups 6A and 7A have in general the highest electron
affinities.

29

Types of Bonding
Primary bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)
Three primary bonding combinations : 1) metal-nonmetal, 2) nonmetal-
nonmetal, and 3) metal-metal
Ionic: Strong Coulomb interaction among negative atoms (have an extra
electron each) and positive atoms (lost an electron). Example - Na+Cl-
Covalent: electrons are shared between the molecules, to saturate the
valency. Example -H2
Metallic: the atoms are ionized, loosing some electrons from the valence
band. Those electrons form a electron sea, which binds the charged
nuclei
Secondary
in place 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 dipole bonds (polar molecules - H2O, HCl...)

30

15
 Ionic Bonding (I)
Formation of ionic bond:
1.Mutual ionization occurs by electron
transfer (remember Electropositive Electronegative
Electron
electronegativity table) Element Atom
Transfer
Ion = charged atom
Anion = negatively charged atom Electrostatic
Cation = positively charged atom
Cation Anion
Attraction
2. Ions are attracted by strong coulombic +ve charge -ve charge
interaction
Oppositely charged atoms attract IONIC BOND
An ionic bond is non-directional (ions
may be attracted to one another in any
direction

31

Ionic Bonding - Example

Ionic bond – metal + nonmetal

donates accepts
electrons electrons

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

[Ne] 3s2
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6
[Ne] [Ne]

32
32

16
 Ionic Bonding - Example

3s1
3p6 Chlorine
Sodium
Atom
Atom
Cl
Na
I
O
N
I Chlorine Ion
Sodium Ion
C
Cl -
Na+
B
O
N
D

33

Ionic Force for Ion Pair

Nucleus of one ion attracts electron of another
ion.
The electron clouds of ion repulse each other
when they are sufficiently close.

Force versus separation

Distance for a pair of
oppositely charged ions
Figure 2.11
34

17
 Ion Force for Ion Pair (Cont..)

Z e Z e    Z Z e 2

F attractive   4  a  4  a 

1 2 1 2
2 2
0 0

Z1,Z2 = Number of electrons removed or

added during ion formation
e = Electron Charge
a = Interionic seperation distance
ε = Permeability of free space (8.85 x 10‐12c2/Nm2)
nb
F repulsive
 (n and b are constants)
n 1
a
2
Z Z e  nb
F net   4  a  a
1 2
2 n 1
0

Attraction Repulsion
Force35 Force

• Predominant bonding in Ceramics

NaCl

MgO

CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (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.

36
36

18
 Interionic Force - Example

Force of attraction between Na+ and Cl- ions

Z1 = +1 for Na+, Z2 = -1 for Cl-

e = 1.60 x 10-19 C , ε0 = 8.85 x 10-12 C2/Nm2
a0 = Sum of Radii of Na+ and Cl- ions
= 0.095 nm + 0.181 nm = 2.76 x 10-10 m

Na+ Cl-

a0
2 19
ZZe ( 1)( 1)(1.60  10 C )
2
 3.02  109 N
F attraction   4  a    4 (8.85 x 10 C /Nm2)(2.76 x 10
1 2
2 -12 2 -10
0
m)
37

Interionic Energies for Ion Pairs

Net potential energy for a pair of oppositely
charged ions =
2

E  Z Ze b
4  a  a
1 2
net n
0

Attraction Repulsion
Energy Energy

Energy Energy
Released Absorbed

Enet is minimum when ions are at equilibrium

seperation distance a0

38

19
39

40

20
 Ion Arrangements in Ionic Solids
Ionic bonds are Non Directional
Geometric arrangements are present in solids to
maintain electric neutrality.
 Example:‐ in NaCl, six Cl‐ ions pack around central Na+ Ions

Ionic packing
In NaCl
and CsCl

CsCl NaCl
Figure 2.13

2-20 41

Bonding Energies
Lattice energies and melting points of ionically
bonded solids are high.
Lattice energy decreases when size of ion
increases.
Multiple bonding electrons increase lattice
energy.

 Example :‐
NaCl Lattice energy = 766 KJ/mol
Melting point = 801oC
CsCl Lattice energy = 649 KJ/mol
Melting Point = 646oC
BaO Lattice energy = 3127 KJ/mol
Melting point = 1923oC

42

21
 Bonding Energy
 Consider production of LiF: result in the release of about 617 kJ/mole.
 Step 1. Converting solid Li to gaseous Li (1s22s1): 161 kJ/mole of energy.
 Step 2. Converting the F2 molecule to F atoms: 79.5 kJ/mole.
 Step 3. Removing the 2s1 electron of Li to form a cation, Li+: 520
kJ/mole.
 Step 4. Transferring or adding an electron to the F atom to form an anion,
F-: -328 kJ/mole.
 Step 5. Formation of an ionic solid from gaseous ions: lattice energy ,
unknown=-617 kJ – [161 kJ + 79.5 kJ + 520 kJ – 328 kJ] = -1050 kJ

Hess law △H0= △H1+△H2+△H3+△H4+△H5

△H5= △H0- △H1+△H2+△H3+△H4=-1050 kj

43 43

Covalent Bonding

In covalent bonding, outer s and p electrons are

shared between two atoms to obtain noble gas
configuration.
Takes place between elements
with small differences in
electronegativity and close by
in periodic table.
In Hydrogen, a bond is formed between
Overlapping Electron Clouds
2 atoms by sharing their 1s1 electrons
Electron
Pair
H + H H H
1s1 Hydrogen
44 Electrons Molecule

22
 Covalent Bonding - Examples
In case of F2, O2 and N2, covalent bonding is formed by sharing p
electrons
Fluorine gas (Outer orbital – 2s2 2p5) share one p electron to attain
noble gas configuration.

F + F F F F F
H Bond Energy=160KJ/mol

Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O O O O=O
Bond Energy=28KJ/mol
Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons

N + N N N N N
Bond Energy=54KJ/mol
45

Covalent Bonding

Formation of covalent bonds:

Cooperative sharing of valence electrons
Can be described by orbital overlap
Covalent bonds are HIGHLY directional
Bonds - in the direction of the greatest orbital overlap
Covalent bond model: an atom can covalently bondwith
at most 8-N’, N’ = number of valence electrons

46

23
 Covalent Bonding in Carbon

Carbon has electronic configuration 1s2 2s2 2p2

Ground State arrangement Indicates

carbon
Forms two
1s 2s 2p
Covalent
Two ½ filed 2p orbitals
bonds

Hybridization causes one of the 2s orbitals

promoted to 2p orbital. Result four sp3
orbitals.
Indicates
four covalent
1s 2p bonds are
Four ½ filled sp3 orbitals
formed

47

Structure of Diamond
Four sp3 orbitals are directed symmetrically toward
corners of regular tetrahedron.
This structure gives high hardness, high bonding
strength (711KJ/mol) and high melting
temperature (3550oC).

Carbon Atom Tetrahedral arrangement in diamond

48

24
 Carbon Containing Molecules

 In Methane, Carbon forms four covalent bonds with

Hydrogen. (hydrocarbons)
Methane
 Molecules are very weekly
molecule
bonded together resulting
in low melting temperature
(‐183oC). Intramolecular bonding: 1650 kl/mole;
intermolecular bonding: 8kj/mole
 Carbon also forms bonds with itself.
 Molecules with multiple carbon bonds are more
reactive. –unsaturated bond
 Examples:‐
H H
C C H C C H
H H Acetylene
Ethylene

Covalent Bonding in Benzene

Chemical composition of Benzene is C6H6.
The Carbon atoms are arranged in hexagonal ring.
Single and double bonds alternate between the
atoms. H

H C H

C C

C C H
H
C
H
Structure of Benzene Simplified Notations
Figure 2.23
50

25
 Metallic Bonding
Atoms in metals are closely packed in crystal
structure.
Loosely bounded valence electrons are attracted
towards nucleus of other atoms.
Electrons spread out among atoms forming
electron clouds. Positive Ion
These free electrons are
reason for electric
conductivity and ductility
Since outer electrons are
shared by many atoms,
metallic bonds are
Non‐directional
Valence electron charge cloud
Figure 2.24
51

Metallic Bonds (Cont..)

Overall energy of individual atoms are lowered by metallic
bonds
Minimum energy between atoms exist at equilibrium
distance a0
Fewer the number of valence electrons involved, more
metallic the bond is.
 Example:- Na Bonding energy 108KJ/mol,
Melting temperature 97.7oC
Higher the number of valence electrons involved, higher is
the bonding energy.
 Example:- Ca Bonding energy 177KJ/mol,
Melting temperature 851oC

52

26
 Mixed Bonding

Ionic‐Covalent Mixed Bonding

(  A   B )2

% ionic character = (1 e 4
) 100%
where A &  B are Pauling electronegativities

Ex: MgO XMg = 1.3

XO = 3.5

 (3.5 1.3 )2 
  
% ionic character  1  e 4  x (100%)  70.2% ionic
 
 

53

54

27
 Secondary Bonding
Secondary bonds are due to attractions of electric
dipoles in atoms or molecules.
Dipoles are created when positive and negative
charge centers exist.

Dipole moment=μ =q.d

+q -q
q= Electric charge
d = separation distance

Figure 2.26 d

There two types of bonds permanent and

fluctuating.

55

Fluctuating Dipoles
Weak secondary bonds in noble gasses.
Dipoles are created due to asymmetrical distribution
of electron charges.
Electron cloud charge changes with time.

Symmetrical Figure 2.27 Asymmetrical

distribution Distribution
of electron charge (Changes with time)

28
 Permanent Dipoles
Dipoles that do not fluctuate with time are
called Permanent dipoles.

 Examples:-
Symmetrical No Dipole
CH4 Arrangement moment
Of 4 C-H bonds

Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement

Hydrogen Bonds
Hydrogen bonds are Dipole‐Dipole interaction
between polar bonds containing hydrogen
atom.
 Example :‐
 In water, dipole is created due to asymmetrical
arrangement of hydrogen atoms.
 Attraction between positive oxygen pole and
negative hydrogen pole.
H

105 0
O
Hydrogen
H Bond
Figure 2.28

29