EG 244 - MATERIALS SCIENCE

Atomic Structure and Interatomic Bonding

 Have You Ever Wondered?

• What is nanotechnology?
• Why is carbon, in the form of diamond, one of the
hardest materials known, but as graphite is very soft
and can be used as a solid lubricant?

• How is silica, which forms the main chemical in beach

sand, used in an ultrapure form to make optical fibers?
To characterize the structure of materials at various length
scales we use;

• atomic structure;
• short- and long-range atomic arrangements;
• nanostructure;
• microstructure; and
• macrostructure.

When we traverse across length scales we get different

perspectives of properties. Order, properties, etc. may seem
very different at different length scales.
Atomic structure

• nucleus consisting of protons and neutrons and the

electrons surrounding the nucleus
• structure of atoms affects the types of bonds that hold
materials together
• The diameter of atoms typically is measured using the
angstrom unit (Å or 10-10 m or 0.1 nm).
 Short- and long-range atomic arrangements

Crystalline Amorphous
• Long range order • Short range order
• Atoms are well arranged • Atoms arranged at random
• Atoms or ions arranged in a • Atoms or ions show a particular
three-dimensional pattern that order only over relatively short
repeats over much larger distances (1 to 10 Å).
distances (from ~10 nm to cm.) • Examples include glass
• Examples include metals etc.
Nanostructure

• Materials science and engineering is at the forefront of

nanoscience and nanotechnology
• Nanoscience is the study of materials at the nanometer
length scale
• Nanotechnology is the manipulation and development
of devices at the nanometer length scale.
• The nanostructure is the structure of a material at a
length scale of 1 to 100 nm.
Microstructure

• The microstructure is the structure of materials at a

length scale of 100 to 100,000 nm or 0.1 to 100
micrometers

• The microstructure typically refers to features such as

the grain size of a crystalline material and others
related to defects in materials.
Macrostructure

• Macrostructure is the structure of a material at a

macroscopic level where the length scale is > 100µ𝑚.
• Features that constitute macrostructure include
- porosity
- surface coatings, and
- internal and external microcracks.
Atomic Structure and
Interatomic Bonding

10
 Material Science
Objectives

• To learn about the structure of atoms

• To learn about the bonding between atoms and
• how these form a foundation for the properties of
materials
• This will help us categorize materials as
- metals, semiconductors, ceramics, or polymers.
• Help us draw some general conclusions concerning the
mechanical properties and physical behaviors of these
four classes of materials.
11
 Atomic structure: Elementary Particles

• Matter is made of small particles called atoms

Nucleus: Protons and Neutrons

Atom
Circled by moving electrons
• Electrons -ve
• Protons +ve
• Neutrons: Neutral
• ALL ATOMS at their normal state are electrically neutral
12
 Atomic structure: elementary particles

• Atomic particles are infinitesimally small as well as

their masses
• Each chemical element from naturally occurring
elements ( hydrogen-1 to uranium-92) is
characterized by the number of protons in the
nucleus or simply the atomic number (Z).
• An electrically neutral atom has Z electrons.
• Atomic Mass (A): Sum of the masses of protons and
neutrons within nucleus
• Number of neutrons (N) may vary for different atoms
of an element. So, some elements may have two or
more atomic masses.
13
 Atomic number and atomic mass number
 Protons and neutrons contribute to the whole mass of an
atom
 The atomic mass number (or atomic weight), M, indicates
the total number of protons and neutrons in the nucleus.
 Quoted values of atomic mass number are based on the
atomic mass unit (a.m.u) which is 1/12 th the mass of an
atom of the isotope of carbon which has a nucleus with 6
protons and 6 neutrons.
 The a.m.u has a measured mass of 1.6598 x 10−27 kg.
 Quoted values for atomic mass number are not all
integers because of:
(1) Mass defect
(2) Existence of isotopes 14
 Atomic structure

Table 2.1: Sub-atomic particles

Particle Mass (kg) Charge (C) Relative Relative

mass charge
Proton 1.672 𝑥 10−27 1.602 𝑥 10−19 1 +1

Neutron 1.675 𝑥 10−27 0 1 0

Electron 0.910 𝑥 10−30 1.602 𝑥 10−19 0 -1

15
 Atomic number and atomic mass number
• Mass defect describes the mass lost during the formation of
nuclei.
• Difference between the mass of an atom and the mass of
its individual particles.
• According to Einstein’s theory of relativity, mass and energy
are related, thus 𝑬=𝒎𝒄𝟐 where m is the mass (kg), c is the
velocity of light (3 𝑥 108 𝑚/𝑠), E is the energy (J).
• Energy equivalent of mass defect is per nucleon is the
binding energy per nucleon
• The value of mass defect per nucleon, and hence nuclear
binding energy, varies with the atomic mass number (Fig
2.1)
• Elements with the greatest mass defect values are those
with atomic numbers in the range 40 to 100.
16
Fig.2.1 Relationship between mass defect and atomic mass number
(Source: John, 1992)
 Atomic number and atomic mass number

• From Fig. 2.1, it is seen that when elements of high atomic mass
number disintegrate into nuclei of lower mass number (i.e. with
higher mass defect values, mass will be converted into a large
energy emission
• This is the principle involved in nuclear fission reactions and
harnessed in nuclear reactors for power generation.
• A nuclear fusion of hydrogen nuclei to form helium would result in
a very large emission of energy (principle used in ‘hydrogen’ bomb)
• In chemical reactions, as opposed to nuclear reactions, the
changes which occur are confined to the outer electron shells
• Energy changes in chemical reactions are of an extremely small
order in comparison with the energy changes accompanying
nuclear reactions
18
 Isotopes and isotones

• Isotopes are atoms of the same element which possess different

atomic mass numbers, ie there is a variation in the number of
neutrons in the nuclei.
• Two isotopes of hydrogen occur i.e. normal hydrogen (Z=1, M=1)
and deuterium (Z=1, M=2). Third hydrogen isotope, tritium (z=1,
M=3) is formed by the bombardment of lithium and boron by
neutrons. Tritium is radioactive
• Carbon has three isotopes with mass numbers 12, 13 and 14 (C-14
is radioactive). C-14 permits the use of carbon dating techniques for
determining the age of ancient remains
• Other non-naturally occurring isotopes are created by means of
nuclear reactions. These are radioactive and disintegrate
spontaneously with the emission of radiation.
• Isotones are nuclei of different elements with same atomic 20
mass number eg Ar-40 (18p,22n) and Ca-40 (20p, 20n)
 Atomic structure

• Atomic weight: Weighted average of the atomic

masses of the atom’s naturally occurring isotopes.
• Atomic mass unit (amu): 1⁄12 of the atomic mass of
the carbon i.e., A=12.000
A≈Z+N

• In One mole of a substance : 6.023 x 1023 Atoms or

Molecules

21
 Atomic structure

At.No (Z)

At.Weight (A)

22
 Atomic models

• With time, in the latter part of nineteenth century,

electrons could not be explained in terms of classical
mechanics

• A set of new principles and laws that govern systems of

atomic and subatomic entities were established and
came to be known as quantum mechanics (beyond
scope of our study)

23
 Bohr atomic model

• Electrons are assumed to revolve around atomic

nucleus in discrete orbitals
• Position of any particular electron is more or less well
defined in terms of orbitals
• Electrons are permitted to have only specific values of
energy (electron energy is quantized)
Orbital

Schematic representation Bohr

atom
24
 Atomic models

Bohr atomic model

• Electrons are permitted to have only specific values of
energy ( energy levels or states).
• They may change these levels by absorbing energy, there
by going to a higher level or emitting energy by going to
lower levels
• Energy is absorbed or emitted in discrete packets called
quanta, where 1 quantum of energy = hf, where h is
Planck’s universal constant (6.62 𝑥 10−34 Js) and f is
frequency of radiation.
• Bohr model was found to have significant limitations
because of its inability to explain several phenomena
involving electrons 25
 Atomic models

Wave-mechanical model
To overcome deficiencies in Bohr’s Model.
• Electron is both wave-like and particle-like
• Electron is no longer a particle in a discrete orbital
• Electron can be at various locations in a discrete orbital
(uncertainty of location)
• The two models, Bohr and Wave-mechanical are used in
our study
• Model usage will depend on which one gives a simpler
explanation

26
Electron configuration

27
 Electron configuration

 Quantum theory requires that four quantum numbers be defined

to give a complete description of the energy state of an electron
 First or principal number, n, (n=1,2,3,4,etc) is description of general
energy level of electron in in terms of distance from nucleus i.e.
shell containing electron and is denoted K=1; L=2; M=3; N=4; O=5;
P=6 and Q=7.
 Second quantum number, l, (l= 0 to n-1) is a measure of angular
momentum of electron and is denoted by s, p, d and f; s=0; p=1;
d=2; f=3
 Third quantum number, 𝒎𝒍 , describes magnetic moment of an
electron
 Fourth quantum number, 𝒎𝒔 , (𝑚𝑠 =+/- ½ ) considers motion within
an electron .
 The four quantum numbers must be defined to fix the energy level
of an electron. 28
 Electron configuration

• Values of energy that are permitted for electrons called

electron states can be filled using the Pauli exclusion
principle
• This principle states that each electron state can hold no
more than two electrons which have opposite spins
• Therefore, 𝑠, 𝑝 𝑑 and 𝑓 subshells can each accommodate
2, 6, 10 and 14 electrons respectively
• Not all possible states in an atom are filled with
electrons. Electron configuration or structure of an atom
will therefore represent how the states are occupied

29
 Electron configuration

Examples of notations:
Hydrogen, H

Table 1
He Na
1s2 1s2 2s2 2p6 3s1
2 (Z*) 11 (Z*)

30
 Electron configuration

• For the purpose of our discussion we will concentrate on

the outermost shell.
• The electrons in the outermost shell are commonly
known as valence electrons
• These electrons are important as they participate in
bonding between atoms to form atomic and molecular
aggregates
• They (valence electrons) also determine the physical and
chemical properties of solids by virtue of their bonding
• When all the outermost shell are filled with electrons,
they are said to have a stable configuration
32
 Electron configuration

Stable electronic configuration: Outermost shell is

completely filled with electrons

Table 2: Inert gases

Ne Ar Kr
1s2 2s2 2p6 1s2 2s2 2p6 3s2 1s2 2s2 2p6 3s2 3p6 3d10 4s2
3p6 4p6
10 (Z*) 18 (Z*) 36(Z*)

Reason for inertness: No incompletely filled outermost

shell
33
 Electron configuration
Comments on the periodic table

• All elements in the periodic table can be classified

according to electron configuration
• Most of the elements come under metal classification.
These elements are sometimes called electropositive
elements and indicate that they are capable of giving up
their few valence electrons to become positively charged
ions
• Elements situated on the right-hand side of the table are
electronegative. They readily accept electrons to form
negatively charged ions or sometimes share electrons
with other atoms 34
Types of Bonding in solids

35
 Bonding forces and energies

• To understand many physical properties of materials, a

knowledge of interatomic forces that bind atoms
together is crucial
• We here consider two atoms brought together in close
proximity from infinite separation and look at the forces
that come into play

36
Bonding forces and energies

Figure 1
37
 Bonding forces and energies

• In bringing two atoms together, two forces arise,

• the force of attraction and
• the force of repulsion.
• The two forces are a function of the separation or
interatomic distance
• Force of attraction 𝐹𝐴 depends on a particular type of
bonding that exists between the two atoms
• When two atoms are close by and their outer
electrons overlap, a strong repulsive force 𝐹𝑅 comes
into play
• Net force is the sum of the two forces
𝐹𝑁 = 𝐹𝑅 + 𝐹𝐴 38
 Bonding forces and energies

• When 𝐹𝑅 and 𝐹𝐴 are balanced or equal

𝐹𝑅 + 𝐹𝐴 = 0
and there is no net force.
• The absence of a net force implies that the
arrangement is in equilibrium
• At equilibrium point, the centers of the two atoms
remain separated by the equilibrium spacing 𝑟0 and for
many atoms 𝑟0 is approximately 0.3𝑛𝑚
• A mathematical relationship between energy (𝐸) and
force (𝐹) is given by

𝐸= 𝐹 𝑑𝑟
39
 Bonding forces and energies

𝐸𝑁 = 𝐹𝑁 𝑑𝑟
∞
𝑟 𝑟

𝐸𝑁 = 𝐹𝐴 𝑑𝑟 + 𝐹𝑅 𝑑𝑟
∞ ∞

𝐸𝑁 = 𝐸𝐴 + 𝐸𝑅

• 𝐸𝑁 , 𝐸𝐴 and 𝐸𝑅 are the net, attractive and repulsive

energies for two isolated and adjacent atoms
40
 Bonding forces and energies

• From figure 1, the bonding energy for the two atoms 𝐸𝑜

represents the energy that would be required to
separate two atoms to an infinite separation
• Materials having large bonding energy typically have
high melting temperatures, those with lower bonding
energy are in gaseous state and intermediate bonding
energies in liquids
• Therefore, a number of material properties depend on
the bonding energy and bonding type

41
 The nucleus and Radioactivity

 Presence of neutrons plays major role in ensuring stability of

atomic nucleus, but nature of nuclear binding is not fully
understood
 Elements with atomic numbers greater than 83 do not possess
stable nuclei
 The large nuclei disintegrate spontaneously, emitting energy and
particles (radioactivity)
 Three types of particle emissions exist, namely α-(equal to helium
nucleus), β-particles (equal to an electron) and γ-radiation (high
frequency radiation)
 Rate of radioactive decay is proportional to activity at that instant

42
 The nucleus and Radioactivity

 If I is activity at some time t, then

𝑑𝐼
= −λ𝐼 λ – radioactive constant
𝑑𝑡

 When above equation is integrated, it gives

𝐼 = 𝐼𝑜 exp(− λ𝑡) 𝐼𝑜 is initial activity at zero time

 Important characteristic of any radioactive substance is its half

life (T), or the time required for half of radioactive nuclei to
disintegrate, i.e
𝐼𝑜
𝐼𝑇 = = 𝐼𝑜 exp(− λ𝑇) or λ𝑇 = ln 2 0.693
2 λ=
𝑇 43
Example 1

Q. Radioactive cobalt-60 has a half-life of 5.3 years. What is the

radioactive constant for cobalt-60 and how long would it take for
the activity of a sample of cobalt-60 to reduce to 85 % of its
original value ?

A. 5.3 years = 1.67 𝑥 108 s

0.693 0.693
λ= = = 4.14 𝑥 10−9 𝑠 −1
𝑇 1.67 𝑥 108

𝐼𝑡 = 0.85 𝐼𝑜 = 𝐼𝑜 exp(− λ𝑡)

ln 0.85 = −λ𝑡 −ln 0.85

𝑡= = 3.92 𝑥 107 𝑠 = 1.24 𝑦𝑒𝑎𝑟𝑠
λ
 Bonding forces and energies

• There are a three types of primary or chemical bonding

namely:
• Ionic
• Covalent and
• Metallic
• For each type of bonding, valence electrons are involved.
Generally, each of these three bonding arises because
atoms want to assume a stable electron configuration

45
 Bonding forces and energies

Ionic bonding
• Takes place In compounds which have metallic and non-
metallic elements
• Happens due to transfer of electrons

46
 Bonding forces and energies

Ionic bonding

47
 Bonding forces and energies

Ionic bonding

• Both the metallic and nonmetallic have a net electrical

charge since electrons and protons in each atom no
longer match
• Metallic elements become positively charged ions while
nonmetallic become negatively charged
• The bonding arising from this arrangement of two
different elements is called ionic bonding
• The more valence electrons the metal transfers, the
stronger the bond and can be evidenced in the melting
point 48
 Bonding forces and energies

Ionic bonding
• Melting point of sodium chloride where one electron is
involved is 801℃ , Magnesium oxide , where two
electrons are involved is 2640℃, and zirconium carbide
where four electrons are involved is 3500℃

• Ionic compounds are characteristically hard and brittle

49
 Bonding forces and energies

Ionic bonding
 The sodium and chloride ions, being of opposite charge,
will be strongly attracted to one another by an attractive
force, 𝐹𝐴
𝑞2
𝐹𝐴 =
4𝜋𝜖𝑜 𝑟 2

where q is charge on each ion

𝜖𝑜 is permissivity of a vacuum
r is separation distance between ions

50
 Bonding forces and energies

Ionic bonding
• Ionic bonds are said to be nondirectional, implying that
the magnitude of the bonds is equal in all directions
around an ion
• Bonding energies in ionic compounds are relatively high
and are a cause of their high melting temperatures

51
 Covalent Bonding

• Sharing of electrons between adjacent atoms. e.g, 𝐶𝐻4

H
∙∙
H: C : H
∙∙
H

Source: William D. Callister 7th

edition , chapter 2 page
28,figure2.10
C: 4 valence electrons
H: 1 valence electron
52
 Covalent Bonding

• Directional: between special atoms; only in the

direction of participation. e.g, 𝐻2𝑂, 𝐻𝑁𝑂3, 𝐻𝐹

• N: no. of valence electrons

• An atom can bond with (8-N) other atoms

𝐶𝑙 𝑁 = 7 8−𝑁 =1 𝐶𝑙 + 𝐶𝑙 = 𝐶𝑙2

𝐶 𝑁=4 8−𝑁 =4 carbon can bond with four

hydrogen atoms

53
• Covalent bonds are strong
e.g, Diamond melting point > 3550°𝐶 (6400°𝐹)
or, covalent bonds can be weak
e.g, Bismuth melting point: 270°𝐶 (518°𝐹)
• Polymers: Covalent bonds
• Partially ionic + partially covalent: possible
• Wider separation in the periodic table: Ionic
• Closer together in the periodic table: Covalent

54
 Bonding forces and energies

Covalent bonding
• Covalent bonds can be described as directional i.e. the
bond is between specific atoms and may exist only in
the direction between one atom and another that
participates in the electron sharing

Chlorine (Cl) Tellurium (Te) Antimony (Sb)

𝑁=7 𝑁 = 6: spiral 𝑁 = 5: corrugated
chain sheets
55
 Bonding forces and energies

Covalent bonding
• The percentage ionic character of a bond between
elements A and B ( A being the most electronegative)
may be approximated by the expression

2
% Ionic character = {1 − exp[ −0.25 𝑋𝐴 − 𝑋𝐵 ]} ×
100

Where
𝑋𝐴 and 𝑋𝐵 are the electronegativity values for the
respective elements and can be found from the following
figure. 56
 Bonding forces and energies

Figure: electronegativity values of elements

57
 Bonding forces and energies

Covalent bonding

• The vast field of industrial polymers is also

predominantly concerned with covalent bonds

58
 Bonding forces and energies

Metallic bonding
• Metals have 1, 2 or 3 valence electrons
• Valence electrons are not bound to an atom, but are free
to drift through the entire metal. i.e, forming an “electron
cloud” (-ve)
• Remaining non-valence electrons and the atomic nuclei
form the ionic core (+ve)
• Free valence electrons shield the +ve ion core
• Non-directional
• Free valence electrons hold the ion core together
• Good conductors
59
 Bonding forces and energies

Metallic bonding
Iron cores

Sea of valence electrons

60
 Bonding forces and energies

Metallic bonding

• The bonds are also nondirectional because of the

electrostatic attraction between ions and electrons
• The bonds also explain the high thermal and electrical
conductivity of metals
• Since the valence electrons are not bound to any
particular atom they can move through the lattice
under the application of an electric potential, causing
a current flow, and can also by a series of collisions
with neighbouring electrons, transmit thermal energy
rapidly through the lattice 61
 Bonding forces and energies

Metallic bonding

• Metallic objects are opaque due to their bonding

• If a ray of light falls on a metal, the electrons ( being
free) can absorb the energy of the light beam, thus
preventing it from passing through the crystal and
rendering the metal opaque
• The electrons which absorb the energy are excited to
high energy levels and subsequently fall back to their
original values with the emission of light energy.
• In principle, the light is reflected back from the surface
of the metal, thus the high reflectivity of metals
62
 Secondary bonding

Van der Waal bonds

Secondary = van der Waals = physical (as opposite to
chemical bonding that involves e- transfer) bonding results from
interaction of atomic or molecular dipoles and is weak, ~0.1
eV/atom or ~10 kJ/mol.

Permanent dipole moments exist in some molecules (called polar

molecules) due to the asymmetrical arrangement of positively and
negatively regions (HCl, H2O). Bonds between adjacent polar
molecules – permanent dipole bonds – are the strongest among
secondary bonds.
63
 Secondary bonding

Polar molecules can induce dipoles in adjacent non-polar

molecules and bond is formed due to the attraction
between the permanent and induced dipoles.

Even in electrically symmetric molecules/atoms an electric

dipole can be created by fluctuations of electron density
distribution. Fluctuating electric field in one atom A is felt
by the electrons of an adjacent atom, and induce a dipole
momentum in this atom. This bond due to fluctuating
induced dipoles is the weakest (inert gases, H2, Cl2).

64
 Secondary bonding

“Hydrogen bond” – secondary bond formed between two

permanent dipoles in adjacent water molecules.
• The strongest and most important example of dipole
interaction occurs in compounds between hydrogen
and nitrogen, oxygen or fluorine

Molecules:
Primary bonds inside,
secondary bonds
among each other

65
 Practice
Answer the following questions fully, giving
explanations where necessary:
(1) Write down the values of M(atomic mass
number or atomic weight) and Z(atomic
number) for:
(a) the element X formed from thorium-232
after six α and four β emissions
(b) the element Y formed from uranium-238
after six α and two β emissions

(Z=90 for thorium; Z=92 for uranium)

(2) The remains of wooden artifacts were
excavated from an archeological site and were
found to be emitting β particles at a rate of
210 per second per kg of wood. A living tree
absorbs the radioactive isotope carbon-14
and is mildly radioactive, emitting 255 β
particles per second per kg of wood. Estimate
the age of the remains, assuming that the
half-life period of carbon-14 is 5000 years.
(3) The elements X, Y and Z have atoms with
outer electron shell configurations containing
4,7 and 8 electrons respectively. State and
describe the type of bonding which is likely to
occur in the following cases:
(i) between atoms of X
(ii) between atoms of Y
(iii) between atoms of Z
(iv) between one atom of X and four atoms of
Y