Atomic Structure and Interatomic Bonding

BSP 170 - Materials Science

 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.
Atomic structure

• nucleus consisting of protons and neutrons and

the electrons surrounding the nucleus
• understand how atomic structure affects
the properties, behavior
• 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).
 Short- and long-range atomic

Crystalline Amorphous
• Long range order • Examples include metals etc.
• Atoms are well arranged
• Atoms or ions arranged in a
three-dimensional pattern that

distances (from ~10 nm to

repeats over much larger

cm.)
 Short- and long-range atomic
• Short range order
• Atoms arranged at random
• Atoms or ions show a
particular order only over
relatively short distances (1
to 10 Å).
• Examples include glass
Nanostructur

• 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.
Nanostructur
Microstructur

• 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

macroscopic level where the length scale is >

• Macrostructure is the structure of a material at a

100µ𝑚.
• Features that constitute macrostructure include
- porosity
- surface coatings, and
- internal and external microcracks.
Atomic Structure and
Interatomic Bonding

9
 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.
1
 Atomic structure: Elementary

• 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

1
 Atomic structure: elementary

• 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.
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 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 mas 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

 The a.m.u has a measured mass of 1.6598 𝑥 10−27 kg.

protons and 6 neutrons.

 Quoted values for atomic mass number are not all

integers because of:
(1) Mass defect
1
(2) Existence of isotopes
 Atomic structure

Table 2.1: Sub-atomic particles

Particle Mass (kg) Charge (C) Relative Relative

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

1.675 𝑥
10−27
Neutron 0 1 0

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

14
 Atomic

• 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 10<23 Atoms

or Molecules

1
 Atomic

At.No (Z)

At.Weight (A)

1
 Atomic number and atomic mass number

Mass Defect
 This occurs when measured mass of atom does not equate with
sum of mases of protons, neutrons and electrons

related, thus 𝑬 = 𝒎𝒄𝟐

 According to Einstein’s theory of relativity, mass and energy are

where m is the mass (kg), c is the velocity of light (3 𝑥 108𝑚/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.
1
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 (ie
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
 Isotopes and

• 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 ie 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
2
 Atomic

• 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)

2
2
 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
2
 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

Planck’s universal constant (6.62 𝑥 10−34 Js) and f is

quanta, where 1 quantum of energy = hf, where h is

frequency of radiation.
• Bohr model was found to have significant limitations
because of its inability to explain several phenomena
involving electrons 2
 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

2
Electron configuration

2
 Electron

 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 ie 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;

 Third quantum number, 𝒎𝒍, describes magnetic moment of

s=0; p=1; d=2; f=3

 Fourth quantum number, 𝒎𝒔, (𝑚𝑠 =+/- ½ ) considers motion

an electron

within an electron .
 The four quantum numbers must be defined to fix the energy
 Electron
level of an electron.
 Electron

• 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

• Therefore, 𝑠, 𝑝 𝑑 and 𝑓 subshells can each

no more than two electrons which have opposite spins

2, 6, 10 and 14 electrons respectively

accommodate

• 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
 Electron

Examples of notations:
Hydrogen, H

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

2
 Electron

• 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
3
0
 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
 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 3
Types of Bonding in solids

3
 Bonding forces and

• 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

3
Bonding forces and

Figure 1
3
 Bonding forces and

• 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

• Force of attraction 𝐹𝐴 depends on a particular type of

interatomic distance

bonding that exists between the two atoms

electrons overlap, a strong repulsive force 𝐹𝑅

• When two atoms are close by and their outer

comes into play

𝐹𝑁 = 𝐹𝑅 + 𝐹𝐴
• Net force is the sum of the two forces
3
 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

remain separated by the equilibrium spacing 𝑟0 and for

• At equilibrium point, the centers of the two atoms

many atoms 𝑟0 is approximately 0.3𝑛𝑚

• A mathematical relationship between energy (𝐸) and
force (𝐹) is given by

𝐸 = න 𝐹 𝑑𝑟
3
 Bonding forces and
𝑟

𝐸𝑁 = න 𝐹𝑁 𝑑𝑟
∞
𝑟 𝑟

𝐸𝑁 = න 𝐹𝐴 𝑑𝑟 + න 𝐹𝑅 𝑑𝑟
∞ ∞

𝐸𝑁 = 𝐸𝐴 + 𝐸𝑅

3
 Bonding forces and
• 𝐸𝑁 , 𝐸𝐴 and 𝐸𝑅 are the net, attractive and
repulsive energies for two isolated and adjacent atoms

3
 Bonding forces and

𝐸𝑜 represents the energy that would be required to

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

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

4
 The nucleus and

 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

4
 The nucleus and

 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(− 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 0.693
𝐼𝑇 = 2 = 𝐼𝑜 exp(− λ𝑇)or λ𝑇 =
λ= 4
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 108s

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

𝐼𝑡 = 0.85 𝐼𝑜 = 𝐼𝑜 exp(− λ𝑡)

ln 0.85 = −λ𝑡 −ln 𝑡 =

0.85 λ
= 3.92 𝑥 107𝑠 = 1.24 𝑦𝑒𝑎𝑟𝑠
 Bonding forces and

• 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

4
 Bonding forces and

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

4
 Bonding forces and

Ionic bonding

4
 Bonding forces and

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
4
 Bonding forces and

Ionic bonding

involved is 801℃ , Magnesium oxide , where two

• Melting point of sodium chloride where one electron is

electrons are involved is 2640℃, and zirconium carbide

where four electrons are involved is 3500℃

• Ionic compounds are characteristically hard and brittle

4
 Bonding forces and

Ionic bonding
 The sodium and chloride ions, being of opposite charge,

force, 𝐹𝐴
will be strongly attracted to one another by an attractive

𝐹𝐴 = 𝑞2
4𝜋𝜖 𝑟2
𝑜

𝜖�𝑜 is permissivity of a vacuum

where q is charge on each ion

4
 Bonding forces and
r is separation distance between ions

4
 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

5
 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
C: 4 valence electrons 28,figure2.10

H: 1 valence electron
 Covalent Bonding

the direction of participation. e.g, 𝐻2𝑂,

• Directional: between special atoms; only in

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
• 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

52
 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

𝑁=7 𝑁 = 6: spiral 𝑁 = 5: corrugated

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

chain sheets
5
 Bonding forces and

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

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

𝑋𝐴 and 𝑋𝐵 are the electronegativity values for the

Where

respective elements and can be found from the following

figur 5
 Bonding forces and

Figure: electronegativity values of elements

5
 Bonding forces and

Covalent bonding

• The vast field of industrial polymers is also

predominantly concerned with covalent bonds

5
 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
5
 Bonding forces and energies

Metallic bonding
Iron cores

Sea of valence electrons

5
 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
5
 Bonding forces and

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
6
 Bonding forces and
metals

6
 Bonding forces and

Van der Waal bonds

• The three strong primary types of atomic bond( ionic,

covalent and metallic) all occur because of the need for
atoms to achieve a stable electron configuration
• However, even when a stable electron configuration
exists, some form of bonding force between the
molecules must be present since these elements will all
liquefy and ultimately solidify at low temperatures
• Van der Waal forces are universal to all atoms and
molecules but are normally so weak that their effect is
overwhelmed when primary bonds are present
6
 Bonding forces and

Hydrogen bonds

• For hydrogen bond, highly polar molecules form when

hydrogen covalently bonds to a nonmetallic element

6
 Bonding forces and

Hydrogen bonds

• The strongest and most important example of dipole

interaction occurs in compounds between hydrogen
and nitrogen, oxygen or fluorine

6
 Assignment No.1A
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
th
Due date: 18 January, 2019