Lecture 2:

Atomic Structure and Interatomic Bonding

By:
Assoc. Prof. Ir. Dr. Wong Yew Hoong
Department of Mechanical Engineering | Faculty of Engineering
Universiti Malaya| Kuala Lumpur | Malaysia

1
 Introduction
• In some instances, atomic structure and the type of interatomic
bonding in solids allow the understanding of a material’s properties.

• Some important properties of materials depend on the geometrical

atomic arrangements and the interactions among constituent atoms
or molecules.

• Example: Metals are relatively dense in comparison to polymers or

ceramics due to highly ordered arrangement of their atoms.

2
 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 –19 C
Positive Charge Accounts for all volume

Proton
Mass : 1.673 x 10 –24 g
Charge : 1.602 x 10 –19 C

Neutron
Mass : 1.675 x 10 –24 g
Neutral Charge 3
 Structure of Atoms
• The mass of an atom is contributed by proton and neutron.

• Atomic mass = masses of protons + masses of neutron within the nucleus

Example: Carbon has 6 Protons and 6 Neutrons. Hence, atomic mass = 12.

• Isotope – Atoms of the same element that have different atomic masses.

4
 Structure of Atoms
• Each element is characterized by the number of protons in the nucleus called the atomic
number (Z).

• The atomic mass (A) of an atom is expressed as the sum of the masses of protons and
neutrons within the nucleus.

• For a given element, the number of protons is the same for all atoms, but the number of
neutrons (N) may be variable.

• Thus atoms of an element can have different atomic masses and called isotopes.

• Example: Carbon-12 (12C), Carbon-13 (13C), Carbon-14 (14C)

5
 Structure of Atoms
• Atomic weight of an element corresponds to the average of atomic masses of the atom’s
naturally occurring isotopes.

• For computations of atomic weight, the atomic mass unit (amu) may be used.

• 1 amu is defined as 1/12 of the atomic mass of Carbon-12.

1 amu/atom (or molecule) = 1 g/mol

1 mole of a substance contains 6.022 x 1023 (Avogadro’s number) atoms or molecules

• Example: 1 mol of carbon = 12 g of carbon = 6.022 x 1023 carbon atoms

6
Periodic Table

7
 Activity 1
If the atomic weight of copper is 63.54 g/mol,

1. What is the weight (in gram) of one atom of copper?

2. How many copper atoms are in 1 g of copper?

1 𝑚𝑜𝑙 𝐶𝑢 63.54 𝑔 −𝟐𝟐 𝒈 𝑪𝒖

1 𝑎𝑡𝑜𝑚 𝐶𝑢 × × = 𝟏. 𝟎𝟓𝟓 × 𝟏𝟎
6.022 × 1023 𝑎𝑡𝑜𝑚𝑠 𝐶𝑢 1 𝑚𝑜𝑙 𝐶𝑢

6.022 × 1023 𝑎𝑡𝑜𝑚𝑠 𝐶𝑢

= 𝟗. 𝟒𝟖 × 𝟏𝟎𝟐𝟏 𝑪𝒖 𝒂𝒕𝒐𝒎𝒔
63.54 𝑔

8
 Activity 2
A 100 g alloy of nickel (Ni) and copper (Cu) consists of 75 wt% Cu and 25 wt% Ni. What are percentage
of Cu and Ni atoms in this alloy?
Note: Atomic weight of Cu is 63.54 g/mol
Atomic weight of Ni is 58.69 g/mol

In 100g of the 75 wt% Cu – 25 wt% Ni alloy, there are 75 g of Cu and 25 g of Ni.

75 𝑔 25 𝑔
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙 𝑜𝑓 𝐶𝑢 = = 𝟏. 𝟏𝟖𝟎𝟑 𝒎𝒐𝒍 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙 𝑜𝑓 𝑁𝑖 = = 𝟎. 𝟒𝟐𝟔𝟎 𝒎𝒐𝒍
63.54 𝑔/𝑚𝑜𝑙 58.69 𝑔/𝑚𝑜𝑙

1.1803 𝑚𝑜𝑙
𝐴𝑡𝑜𝑚𝑖𝑐 𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝐶𝑢 = = 𝟕𝟑. 𝟓% 𝒐𝒓 𝟕𝟑. 𝟓 𝒂𝒕%
1.1803 + 0.4260 𝑚𝑜𝑙
0.4260 𝑚𝑜𝑙
Cu73.5Ni26.5
𝐴𝑡𝑜𝑚𝑖𝑐 𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑁𝑖 = = 𝟐𝟔. 𝟓% 𝒐𝒓 𝟐𝟔. 𝟓 𝒂𝒕%
1.1803 + 0.4260 𝑚𝑜𝑙
9
 Periodic Table
Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 1e
accept 2e
give up 3e
H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister 7e.
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. 10
 Valence Electrons
Valence electrons determine the
following properties:

1) Chemical

2) Electrical

3) Thermal

4) Optical

11
 Classical Mechanics – Quantum Mechanics

• Classical Mechanics cannot explain

phenomena involving electrons in
atom, e.g. why electrons do not “fall”
into the nucleus.

• This has motivated the

establishment of a set of principles
and laws that govern the atomic
system, called Quantum Mechanics.

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 Quantum Mechanics Principles
Early development: Bohr atomic model

• Electrons are assumed to revolve around

the atomic nucleus in discrete orbital
called Sommerfeld orbits.

• The position of any particular electron is

more or less well-defined in terms of its
orbital.

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 Quantum Mechanics Principles
Early development: Bohr atomic model
• The energy of electrons are quantized, i.e.
electrons are permitted to have only
specific values of energy.
• Electrons may change energy, but in
doing so it must make a quantum jump.
• Energy is absorbed when an electron
moves to a higher energy level and
emitted during transition to a lower
energy level.

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Energy in Hydrogen Atom
Bohr atomic model for hydrogen
• Hydrogen atom has one proton and one electron.
• Energy of hydrogen atoms for different energy levels is given by:
13.6 (n = 1, 2, …)
𝐸 = 2 𝑒𝑉 principal quantum numbers
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 𝑒𝑉 = 1.89 𝑒𝑉
3 2
• Energy required to completely remove an electron from hydrogen atom is known as
ionization energy.
15
Energy States for Bohr Hydrogen Atom

16
Is Bohr model useful enough
to describe and to understand
the atomic structure?

17
 Wave-Mechanical Model
• Bohr atomic model is an oversimplified
model, thus it works only for a very
simple atom, e.g. hydrogen atom.

• The wave-mechanical model is used to

improve Bohr model.

• In wave-mechanical model, an electron

is considered to have wave-like and
particle-like characteristics.

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 Wave-Mechanical Model
General features / characteristics

• The exact position of an electron at any instant time cannot be determined

(Heisenberg’s uncertainty principle).

• The position is described by a probability distribution or electron cloud.

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 Bohr and Wave-Mechanical Atom Models

Bohr model Wave-mechanical model

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 Quantum Numbers
• Using wave mechanics, an electron is characterized by 4 parameters called quantum numbers.

• The size, shape and spatial orientation of electron’s probability density are specified by 3 of
these quantum numbers:

1. Principle quantum number (n)

2. Subsidiary quantum number (l)

3. Third quantum number (ml)

4. Electron spin quantum number (ms)

• No two electrons can have the same set of four quantum numbers.

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Quantum Numbers

22
Quantum Numbers

23
 Quantum Numbers

Bohr Wave-mechanical
model model

24
 Electron Configuration
• The previous discussion focuses on electron
states, i.e. permitted values of energy for
electrons.

• The manner in which these states are filled with

electrons are described by the Pauli exclusion
principle, another quantum-mechanical
concept.

• The principle stipulates that each electron state

can hold no more than two electrons, which
must have opposite spin.

25
How to write or denote the
electronic configuration for a
chemical element?

26
 Electron Configuration
• For most atoms, the electrons fill up the lowest possible energy states in the
electron shells and subshells with two electrons (having opposite spins) in
each state.
• Atomic size (radius) increases with the addition of shells.

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 Electron Configuration
Maximum number of electrons in each atomic shell is given by 2n2
(n = principal quantum number).

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 Electron Configuration
• Electron configuration lists the arrangement of electrons in orbital.
• Example: Magnesium (Mg)

Orbital letters Number of Electrons

1s2 2s2 2p6 3s2

Principal Quantum Numbers

29
 Electron Configuration
• The orderly building up of the electronic structure is not always followed, particularly when
the atomic number is large and the d and f levels begin to fill.

• Example: Iron (Fe) has atomic number 26

1s2 2s2 2p6 3s2 3p6 3d 8

but the actual structure however is:

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

The unfilled 3d level causes the magnetic behavior of iron.

• Valence electrons: The number of electron in an atom that participate in bonding or chemical
reactions. Usually, the valence is the number of electrons in the outer s and p energy levels.
30
 Electron Configurations
Example: Iron (Fe) has atomic number 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 31
Electron Configurations

32
Electron Configurations

33
Relative Sizes of Atoms

34
 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 (He) has 1s2 configuration.

• Electropositive elements are metallic in nature. They 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

35
Electron Structure and Chemical Activity
• 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 negative
K 1 W 2H Se 3 4

36
 Electron Structure and Chemical Activity
• Electrons occupying the outermost filled shell are called valence electrons.

Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

• Valence electrons are very important since they participate in the bonding
between atoms.

• Many of physical and chemical properties of solids are based on these valence
electrons.

37
 Electronegativity
• Ranges from 0.7 to 4.0
• Large values: tendency to acquire electrons

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical 38
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
Electronegativity

39
Summary of electronic structure – chemical property
relationships for metals and nonmetals

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 Atomic Bonding
• Atoms tend to reach stable (noble) configuration.

• This is achieved by creating chemical bonding between atoms since in the

bonded state there is a net decrease in the potential energy of atoms.

• In the bonded state, atoms are in a more stable energy condition than when
they are unbonded.

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 Atomic Bonding
Atomic Bond

Primary Bond Secondary Bond

Ionic Bonds Permanent Dipole

Bonds
Covalent Bonds

Fluctuating Dipole
Metallic Bonds
Bonds
42
 Primary Bond
Atomic Bond

Primary Bond Secondary Bond

Ionic Bonds Permanent Dipole

Bonds
Covalent Bonds

Fluctuating Dipole
Metallic Bonds
Bonds
43
 Ionic Bonding
• Ionic bonding – the bond formed between two different atom species when one atom
(cation) donates its valence electrons to the second atom (anion). Ionic bonding is
due to electrostatic force of attraction between cations and anions.

• Strong atomic bonds due to transfer of electron.

• It can form between metallic (highly electropositive) and nonmetallic elements

(highly electronegative).

• Electrons are transferred from electropositive to electronegative atoms.

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 Ionic Bonding
Electropositive Electronegative
Element Electron Atom
Transfer

Electrostatic
Attraction
Cation Anion
+ve charge -ve charge

IONIC BOND

45
 Ionic Bonding

Sodium Atom, Na (0.192nm) Sodium Ion (Na+)(0.095nm)

Chlorine Atom (Cl) (0.099nm) Chlorine Ion (Cl –)(0.181nm)

46
 Ionic Bonding
• 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 47
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
 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.
Fnet = Fattractive + Frepulsive

Force versus separation

Distance for a pair of
oppositely charged ions

48
 Ionic Bonding

Z1 and Z2 = number of electrons removed or added during ion formation

e = electron charge
a = interionic separation distance
ε = Permeability of free space (8.85 x 10-12c2/Nm2)

n and b are constants

49
Activity 3: Attractive Force in Ionic Bonding

Calculate the 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 Na+ Cl-
a0 = Sum of radii of Na+ and Cl- ions
= 0.095 nm + 0.181 nm = 2.76 x 10-10 m a0

= −3.02 × 10−9 𝑁

50
 Ion Arrangements in Ionic Solids
• When ions pack together in solid, they do so with no preferred orientation since
electrostatic attraction of symmetrical charges is independent of the orientation of
the charges.

• In this view, the ionic bond is non-directional in character.

51
 Bonding Energy of Ionic Solids
• 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

52
Bonding Energy of Ionic Solids

53
 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.
Overlapping Electron Clouds

54
 Covalent Bonding
Hydrogen (H2)
• In hydrogen, a bond is formed between 2 atoms by sharing their 1s1 electrons.

• The highest electron charge cloud density is in the region of overlap between the
hydrogen atom nuclei.

Electron
Pair

H + H H H
1s1 Hydrogen
Electrons Molecule

55
Covalent Bonding
Silicon (Si)

56
 Covalent Bonding
Molecule of Methane (CH4)

• Each of two covalently-bonded atoms contribute at least one electron to the bond.
• In methane, carbon forms four covalent bonds with hydrogen.
• Molecules are very weekly bonded together resulting in low melting temperature
(-183oC).

57
 Covalent Bonding
Ethylene (C2H4), Acetylene (C2H2)

• Carbon also forms bonds with itself.

• Molecules with multiple carbon bonds are more reactive.

• Examples:
H H
C C H C C H
H H Acetylene
Ethylene

58
 Covalent Bonding
• In order for the covalent bonds to be formed, the atoms must be arranged so the bonds have a
fixed directional relationship with one another and form specific angles.

• In this view, the ionic bond is directional in character.

Molecule of Methane
(CH4)

59
 Covalent Bonding
• 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 60
 Covalent Bonding
• Covalent bonds can be very strong as well. As a result, covalently bonded
materials are very hard and strong.

• High melting point, which means they could be useful for high temperature
application.

• Since the valence electron are locked in bonds between atoms and are not
readily available for conduction.

61
 Covalent Bonding
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 62

Bonding Energy of Covalent Bond

63
 Metallic Bonding
• Found in metals and their alloys.

• In metals in the solid state, atoms are

packed relatively close together in a
systematic arrangement or crystal
structure.

• Since atoms are so close, their outer

valence electrons are attracted to the
nuclei of their numerous neighbors and
thus are not bound to any particular Crystalline copper
nucleus.

64
 Metallic Bonding
• Metallic bond defined as elements have electropositive atoms that donate
their valence electrons to form a “sea” of electrons surrounding the atoms.

• Atoms in metals are closely packed in crystal structure.

• Loosely bounded valence electrons are attracted towards nucleus of other

atoms.

• The valence electrons are weakly bonded crystal; called as free electrons.

• These free electrons are reason for electrical conductivity and ductility.
65
 Metallic Bonding
• Since outer electrons are shared by many
atoms, metallic bonds are non-directional.

• Because their valence electrons are not

fixed in any one position, most pure metals
are good electrical conductors. Under
influence of an applied voltage, the valence
electrons move, causing a current to flow if
the circuit is complete.

• Relatively high Young’s modulus and good

ductility.

66
Bonding Energy of Metallic Bond

67
 Atomic Bonding
Atomic Bond

Primary Bond Secondary Bond

Ionic Bonds Permanent Dipole

Bonds
Covalent Bonds

Fluctuating Dipole
Metallic Bonds
Bonds
68
 Secondary Bonding
• Also called van der Waals bonding.

• It is relatively weak in comparison to primary bonding.

• A secondary bond developed between atoms and molecules as a result of

interactions between dipoles that are induced or permanent.

• Arise from the attraction of electric dipoles in atoms or molecules. An electric

dipole exists whenever there is some separation of positive and negative
charges.

69
 Secondary Bonding
• Dipoles in atoms or molecules create dipole moments, μ defined as the charge
value multiplied by the separation distance.

• There two types of bonds: permanent and fluctuating.

70
 Fluctuating Dipole Bond
• Due to constant vibrational motion, electron cloud charge of an atom changes
with time resulting to distortion of electrical symmetry.

• Fluctuating dipoles are created due to fluctuating asymmetrical distribution

of electron charges.

71
 Fluctuating Dipole Bond
• Due to constant vibrational motion, electron cloud charge of an atom changes
with time resulting to distortion of electrical symmetry.

• Fluctuating dipoles are created due to fluctuating asymmetrical distribution

of electron charges.

72
 Permanent Dipole Bond
• Weak bonding among covalently bonded molecules can be created if the
molecules contain permanent dipoles, i.e. dipoles which do not fluctuate with
time.

73
 Permanent Dipole Bond
• Weak bonding among covalently bonded molecules can be created if the
molecules contain permanent dipoles, i.e. dipoles which do not fluctuate with
time.

74
 Permanent Dipole Bond
Hydrogen bonding in water due to permanent dipole
• 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.

105 0
O
Hydrogen
H Bond
75
 Permanent Dipole Bond
Hydrogen bonding in water due to permanent dipole

a) Permanent dipole nature of the water molecule.

b) Hydrogen bonding among water molecules due to permanent dipole attraction. 76
Permanent Dipole Bond
Polyvinyl chloride (PVC)

77
 Permanent Dipole Bond

Note: If the net dipole moment is zero or negligibly small, the bond and molecule are
considered to be non-polar. Atoms that have similar electronegativity values tend to
form chemical bonds with a very small dipole moment.

78
Comparison of Bonding Energy

79
 Summary: Bonding
Type Bond Energy Feature
Ionic Large Non-directional (ceramics)
Covalent Varies: Directional
Large – Diamond (semiconductors, ceramics, polymer chains)
Small – Bismuth
Metallic Varies: Non-directional (metals)
Large – Tungsten
Small – Mercury
Secondary Smallest Directional
inter-chain (polymer)
inter-molecular

80