EME1166 MATERIALS

SCIENCE
Chapter 1
Atomic Structure &
Interatomic Bonding

Chapter 2 -
1
 1.1 INTRODUCTION
Some solid material properties depend on:
The geometrical atomic arrangements
Interactions between the constituent atoms and
molecules.

This chapter discusses:

1.Atomic structures
2.Electron configuration in atoms
3.Periodic table
4.Primary and Secondary Interatomic bonds

Chapter 2 -
2
 1.2 ATOMIC STRUCTURE
Each atom consists of
A very small nucleus which is composed of proton and
neutrons
Moving electrons encircling the centre nucleus.
The charge magnitude for both electrons and protons are the
same
1.602 x 10-19 C
But negative in sign for electrons and positive in sign for
protons
Neutrons are electrically neutral
Masses for these subatomic particles are very small:
Protons - 1.67 x 10-27 kg
Neutrons 1.67 x 10-27 kg
Electrons 9.11 x 10-31 kg

Chapter 2 -
3
 ATOMIC NUMBER (Z)
Each chemical element is characterized by the number of
protons in the nucleus
Z also equals the number of electrons in an electrically neutral
atom
For naturally occurring elements, the atomic number starts
from 1 (for hydrogen) to 92 (for uranium) in integer units.
ATOMIC MASS (A)
Expressed for a specific atom as the sum of the masses of
protons and neutrons within the nucleus.
The number of protons is the same for all atoms for a given
element BUT the number of neutrons (N) may be variable
Isotopes are the atoms of some elements which have two or
more different atomic masses
Atomic weight of an element is the weighted average of the
atomic masses of the atoms naturally occurring isotopes

Chapter 2 -
4
 ATOMIC MASS UNIT (amu)
Used to compute the atomic weight
The most common isotope of Carbon ( Carbon 12 ) is used in
this scale.

1 amu = mass of 12C

Within this scheme, the masses of protons and neutrons are

slightly greater than unity; and :
A Z + N (approximately equal to)
Therefore, the atomic weight of an element or the molecular
weight of a compound can be specified on the basis of :
amu pre atom (molecule)
Or mass per mole of molecule
Since in one mole of a substance, there are 6.022 x 1023
(Avogadros number) atoms or molecules:
Atomic wt = wt of 6.022 x 1023 molecules or atoms
1 amu/atom (or molecule) = 1g/mol
Chapter 2 -
5
 1.3 ELECTRONS IN ATOMS
QUANTUM MECHANICS
A set of principles and laws that govern systems of atomic and
subatomic entities.
BOHR ATOMIC MODEL
Electrons are assumed to revolve around the atomic nucleus
in discrete orbitals
The position of any particular electron is more or less well
defined in terms of its orbital

Chapter 2 -
6
 Another quantum-mechanical principle stipulates that the energies
of the electrons are quantized.
Electrons are only permitted to have specific values of energy.
An electron may only change energy with a quantum jump to
another energy state (level) either by absorption of energy (to
a higher energy state) or emission of energy (to a lower
energy state)
Adjacent states or levels are separated by finite energies.

Chapter 2 -
7
 WAVE MECHANICAL MODEL
The electron is considered to exhibit both wavelike and
particle-like characteristics.
Position of the electron is considered to be the probability of
an electrons being at various locations around the nucleus.
Position can be described by a probability distribution or
electron cloud.

Chapter 2 -
8
 QUANTUM NUMBER
Based on wave mechanics, each electron in an atom is
characterized by four parameters called quantum numbers.
The Size, Shape and Spatial orientation of an electrons
probability density are specified by three of these quantum
numbers.
Principal quantum number (n) related to the distance of
an electron from the nucleus, or its position.
Second quantum number (l) signifies the subshells s, p, d
or f; which relates to the shape of the electron subshell.
Number of subshells is limited by the magnitude of n.
Third quantum number (ml) determines the number of
energy states for each subshell.
Fourth quantum number (ms) associated with the spin
moment of each electron;
1 1which must be oriented either up or
down. Values of + 2 and - 2 are given for each of the spin
orientation.
Bohr energy levels separate into electron subshells, and
quantum numbers dictate the number of states within each
subshell.
Therefore the Bohr Model was further refined by wave
Chapter 2 -
mechanics; where the three quantum numbers represent 9
 Quantum # Designation
n = principal (energy level-shell)K, L, M, N, O (1, 2, 3, etc.)
Chapter 2 -
10
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,, n -1)
 Note:
The smaller the principal quantum number, the lower the
energy level.
Within each shell, the energy of a subshell level increases with
the value of the l quantum number.
An overlap in energy of a state in one shell with states in an
adjacent shell is possible; especially for d and f states.
Chapter 2 -
11
1.4 ELECTRON CONFIGURATION
Pauli Exclusion principle
A quantum-mechanical concept used to determine the manner
in which electrons fill the electron states.
Each electron state can hold no more than two electrons, and
both electrons must have opposite spins. Refer to TABLE 2.1
in SLIDE 10.
For most atoms, electrons fill up the lowest possible energy
states in the electron shells and subshells.
An atom is said to be in ground state when all the electrons
occupy the lowest possible energies in accordance with the
foregoing restrictions.
Electron configuration
Represents the manner in which the electron states are
occupied.
The number of electrons in each subshell s indicated by a
subscript after the subshell designation.
Example: H (atomic number = 1)
1s1
Chapter 2 -
C (atomic number = 6) 1s2 2s2 2p2 12
 Valence Electrons
These are electrons that occupy the outermost shell
Participate in the bonding between atoms to form atomic and
molecular aggregates
Many of the physical and chemical properties of solids depend
on these valence electrons
Stable electron configurations
Atoms having states within the outermost or valence
electrons are completely filled
Example: Inert gases (Neon, Argon, Krypton and Helium)
are virtually unreactive.
For Ne, Ar and Kr, the occupation of just the s and p states
for the outermost shell in filled by a total of 8 electrons.
Sometimes, the s and p orbitals combine to form hybrid spn
orbitals, where n indicates the number of p orbitals involved,
which may have value of 1, 2 or 3.
One of the reasons for the formation of hybrid orbitals is a
lower energy state for the valence electrons.
Chapter 2 -
13
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

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
Adapted from Fig. 2.4,
Callister & Rethwisch Chapter
8e. 142 -
 Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
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)
Why? Valence (outer) shell usually not filled completely.
Chapter 2 -
15
 1.5 THE PERIODIC TABLE
Elements have been classified according to their electron
configuration in the periodic table.
Elements have been arranged in increasing atomic number, in
7 horizontal rows called periods.
All elements arrayed in a given column or group have similar
valence electron structures, as well as chemical and physical
properties.
These properties change gradually, moving horizontally across
each period and vertically down each columns
Summary
GROUP 0 inert gases with filled electron shells and stable
electron configurations.
GROUPS VIIA (halogens) and VIA elements having one or
two electrons deficient from having stable structures.
GROUPS IA and IIA alkali and alkaline earth metals have
one or two electrons in excess of stable structures.
GROUPS IIIB though IIB transition metals having partially
filled d electron states.
GROUPS IIIA, IVA and VA elements with characteristics
Chapter 2 -
intermediate between metals and nonmetals by virtue of16 their
 Most of the elements in the periodic table really come under the
metal classification
Sometimes termed electropositive elements capable of
giving up their few valence electrons to become positively
charged ions
In addition, elements situated on the right-hand side of the table
are electronegative. These elements
readily accept electrons to form negatively charged ions
or sometimes, they share electrons with other atoms.
It is a general rule that electronegativity increases in moving from
left to right and from bottom to top
Atoms are more likely to accept electrons if their outer shells are
almost full, and if they are less shielded (closer to) from the
nucleus

Chapter 2 -
17
 inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-
H 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 Readily acquire electrons
to become + ions. to become - ions.
Chapter 2 -
18
Electronegativity values for elements
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Electronegativity increases from left to right, and from bottom to

top Chapter 2 -
19
 1.6 ATOMIC BONDING IN SOLIDS
BONDING FORCES AND ENERGIES
Consider the reaction between two atoms as they are brought
close together
At large distances, the interactions between the two atoms are
negligible.
At small separation distances, each atom exerts forces on the
other.
These forces are called attractive (FA) and repulsive (FR)
The attractive force depends on the particular type of
bonding that exist between the two atoms
The repulsive force arise from the interactions between the
negative charged electron clouds and are important only at
small values of iteratomic distance (r)

Chapter 2 -
20
 The net force FN
between the two atoms
is the sum of both the
attractive and repulsive
components:

FN = FA + FR

Note from diagram (a)

that when FA and FR
balance, there is no net
force:

FA + FR = 0

and a state of equilibrium exists.

Centers of both atoms

will remain separated by
r0

Chapter 2 -
21
 Alternatively, it is also possible to substitute the forces between
the two atoms with potential energies (as shown in Figure(b) of
SLIDE#21). Mathematically, energy (E) and force (F) are related
as:

Therefore, for atomic system:

EN = EA + ER

Net curve is the sum of the attractive and repulsive curves.

The minimum in the net energy curve corresponds to the
equilibrium spacing r0.
The bonding energy for the two atoms E0, corresponds to the
energy at his minimum point. This represents the energy that
would be required to separate the two atoms to an infinite
distance.
Chapter 2 -
22
 Three types of primary or chemical bond are found in solids:
Ionic
Covalent
Metallic
Bonding involves the valence electrons
Nature or type of bond will depend on the electron structure of the
atoms
Primary bonds occur due to the tendency of the atoms to
assume stable electron structure by completely filling the
outermost electron shell
Secondary or physical forces also exist in solids but they are
weaker than primary bonds. These bonds still do influence the
physical properties of some materials.

Chapter 2 -
23
1.7 PRIMARY INTERATOMIC BONDS
i. IONIC BONDING
Found in compounds that compose of both metallic and
nonmetallic elements
Metallic atoms easily give up their valence electrons to the
nonmetallic atoms
As a result, both atoms will acquire stable electron
configurations and also additional electrical charge (become
ions)

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

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

Chapter 2 -
24
 The attractive bonding forces are coulombic; where different
electrical charge ions attract each other

The attractive energy EA and repulsive energy ER for two

isolated ions is a function of the interatomic distance:
A B
EA ER
r rn

A, B and n are constants depending on the particular ionic system; value of n is

Chapter 2 -
approx. 8. 25
 A B
EN = EA + ER =
r rn

Repulsive energy ER

Interatomic separation r

Net energy EN

Attractive energy EA

Chapter 2 -
26
 Ionic bonding is termed nondirectional since the magnitude of the
bond is equal in all directions around an ion
In order for ionic materials to be stable, all the positive ions must
have as nearest neighbors negatively charges ions in a three-
dimensional scheme, and vice versa
For ceramic materials, the predominant bonding is ionic.
Bonding energies are relatively large which is reflected by the high
melting temperatures shown in TABLE 2.3 (SLIDE#28).
General characteristic properties of ionic materials:
Hard
Brittle
Electrically insulative
Thermally insulative
these properties are a direct consequence of the
electron configurations and/or the nature of the ionic
bonds

Chapter 2 -
27
Chapter 2 -
28
 Ionic Bonding > Predominant bonding in Ceramics

NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 -
29
 ii. COVALENT BONDING
Stable electron configurations are achieved by the sharing
of electrons between adjacent atoms
Two atoms which are covalently bonded will each contribute
at least one electron to the common covalent bond. This
shared electron can be considered to belong to both atoms

C: has 4 valence e-, shared electrons

needs 4 more H
CH 4 from carbon atom
H: has 1 valence e-,
needs 1 more H C H

shared electrons
Carbon now has 4 additional shared from hydrogen
H
electrons. Therefore total of eight atoms
valence electrons and the electron
structure of neon.
Chapter 2 -
30
 Covalent bond is bidirectional. It is between specific atoms and
may only exist in the direction between one atom and another
that participates in the electron sharing
Examples of covalent bonding:
Nonmetallic elemental molecules (H2, Cl2, F2, etc)
Molecules containing dissimilar atoms ( CH4, H2O, HNO3,
HF, etc)
Elemental solids such as diamond (carbon), silicon and
germanium
Solid compounds located on the right-hand side of the
periodic table such as gallium arsenide (GaAs) and silicon
carbide (SiC)
Number of covalent bonds is determined by the number of
valence electrons
For N valence electrons, an atom can covalently bond with
at most 8-N other atoms

Chapter 2 -
31
 Covalent bonds may be:
Very strong as in diamond, which is very hard and has a
very high melting temperature (>3550C)
Very weak as in bismuth, which melts at about 270C
Refer to TABLE 2.3 (SLIDE#28) for the melting temperatures
for a few covalently bonded materials.

It is possible to have interatomic bonds that are partially ionic

and partially covalent .
In fact, very few compounds exhibit pure ionic or covalent
bonding.
For a compound, the degree of either bond type depends on
the relative positions of the constituent atoms in the periodic
table (the difference in their electronegativities)
The wider the separation in the periodic table, the more
ionic the bond
The closer the atoms in the periodic table, the greater the
degree of covalency

Chapter 2 -
32
 Ionic-Covalent Mixed Bonding
(X A X B )2

x ( 100 %)
1 e 4
% ionic character =


where XA & XB are Pauling electronegativities of
the respective elements

Ex: MgO XMg = 1.2

XO = 3.5

( 3.5 1.2 )2

% ionic character 1 e 4
x (100%) 73.4% ionic


Chapter 2 -
33
 iii. METALLIC BONDING
This type of bonding is found in metals and their alloys
Metallic materials have one, two or at most, three valence
electrons
These electrons are not bound to any particular atoms in
the solid. It can be viewed as an electron cloud which can
drift throughout the entire metal
Remaining nonvalence electrons and atomic nuclei form the
ion cores, which possess a net positive charge equal in
magnitude to the total valence electron charge per atom

The free electrons shield the

positively charged ion cores from
mutually repulsive electrostatic
forces.

Chapter 2 -
34
 Therefore metallic bonding is nondirectional in character
The free electrons also act as glue to hold the ions cores
together
Refer to TABLE 2.3 (SLIDE#28) for bonding energies and
melting temperatures for several metal examples
Metallic bonding is found for elements in GROUP IA and IIA;
and for all elemental metals
General characteristic properties of metallic materials:
Good conductor of heat
Good conductor of electricity
At room temperature, most metals fail in a ductile manner
(fracture occurs after the material have experienced
significant degrees of permanent deformation)
these properties can be explained due to the presence
of free electrons.

Chapter 2 -
35
REVIEW OF THE PRIMARY BONDS
1. Ionic
Electrostatic attraction between oppositely charged
ions
2. Covalent
Electron sharing between two adjacent atoms such
that each atom assumes stable electron configuration
3. Metallic
Positively charged ion cores are shielded from one
another, and also glued together by the sea of valence
electrons

Chapter 2 -
36
 1.8 SECONDARY BONDING
Secondary or van der Waals or physical bonding are weak
compared to primary or chemical bonds.
It exists between virtually all atoms or molecules, but its
presence may be obscured of any of the three primary bonding
types is present
Secondary bonding is evidenced for inert gases which have
stable electron structures, and in addition between molecule
structures that are covalently bonded
This type of bonding forces arise from atomic and molecular
dipoles.
An electric dipole exists whenever there is some
separation of positive and negative portions of an atom or
molecule.
The bonding results from the coulombic attraction between
the positive end of one dipole and the negative region of an
adjacent dipole.

Chapter 2 -
37
 Dipole interactions occur:
Between induced dipoles
Between induced dipoles and polar molecules (which have
permanent dipoles)
Between polar molecules
1. FLUCTUATING INDUCED DIPOLE BONDS
A dipole may be created or induced in an atom or molecule
that is normally electrically symmetric (the overall spatial
distribution of the electrons is symmetric with respect to the
positively charged nucleus)
Constant vibrational motion can create small electric
dipoles
One of these dipoles can produce a displacement of the
electron distribution of an adjacent molecule or atom, which
induces the second one also to become a dipole that is then
weakly attracted and bonded to the first.

Chapter 2 -
38
2. POLAR MOLECULE-INDUCED DIPOLE BONDS
Polar molecules are molecules where permanent dipole
moments exist virtue of an asymmetrical arrangement of
positively and negatively charged regions
Example: hydrogen chloride molecule

Polar molecules can also induce dipoles in adjacent

nonpolar molecules, and a bond will form as a result of
Chapter
392 -
3. PERMANENT DIPOLE BONDS
Van der Waals forces will also exist between adjacent polar
molecules
The hydrogen bond is a special case of this type of polar
molecular bond.
It is found between some molecules that have hydrogen
as on of their constituents.
It is also the strongest secondary bonding type.
It occurs between molecules in which hydrogen is
covalently bonded to fluorine, oxygen and nitrogen
In H-F, H-O or H-N bond, the single hydrogen electron is
shared with the other atom
The hydrogen end of the bond is essentially a positively
charged bare proton that is unscreened by any electrons
It will then attract the negative end of an adjacent
molecule
The single proton forms a bridge between the two
negatively charged atoms
The magnitude of the hydrogen bond is generally higher
Chapter
402 -
than other types of secondary bonds
 1.9 MOLECULES
Many of the common molecules found are composed of the
groups of atoms that are bonded together by strong covalent
bonds.
Examples:
Elemental diatomic molecules (F2, O2, H2, etc.)
Compounds (H2O, CO2, HNO3, C6H6, CH4, etc.)
In condensed liquid and solid states, the bonding between
molecules are weak secondary bonding
Low melting and boiling temperatures
Gases at ordinary or ambient temperatures and pressures
On the other hand, many modern polymers (being molecular
materials composed of extremely large molecules) exist as
solids.
Some of their properties are strongly dependant on the
presence van der Waals and hydrogen secondary bonds

Chapter 2 -
41
 1.10 SUMMARY
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

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

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury

Secondary smallest Directional

inter-chain (polymer)
inter-molecular

Chapter 2 -
42
 Properties From Bonding: Tm
Bond length, r Melting Temperature, Tm

Energy
r

Bond energy, Eo r
o r
Energy
smaller Tm

unstretched length larger Tm

r
o r
Eo = Tm is larger if Eo is larger.
bond energy

Chapter 2 -
43
 Properties From Bonding :
Coefficient of thermal expansion,

length, Lo coeff. thermal expansion

unheated, T1
L L
Lo
= (T2 -T1)
heated, T2

~ symmetric at ro

Energy

unstretched length
r
o is larger if Eo is smaller.
r
larger
E
o smaller
E
o Chapter 2 -
44
 Primary Bonds
Ceramics Large bond energy
large Tm
(Ionic & covalent bonding): large E
small

Metals Variable bond energy

moderate Tm
(Metallic bonding):
moderate E
moderate

Polymers Directional Properties

Secondary bonding dominates
(Covalent & Secondary):
small Tm
secon
da
small E
ry bo
nding large

Chapter 2 -
45