CHAPTER 2

NMK 12003
ENGINEERING MATERIALS

ATOM STRUCTURE AND BONDING

Fakulti Kejuruteraan & Teknologi Elektronik (FKTEN),
Universiti Malaysia Perlis (UniMAP)
 MATERIALS SCIENCE & ENGINEERING

LEARNING OBJECTIVES:

1. Describe the nature and structure (i.e., atomic number, mass

numbers and atomic masses) of an atom as well as its
electronic structure (Quantum number, Energy Levels and
atomic orbitals).
2. Describe the difference between metal, metalloids and non-
metals.
3. Describe various types of primary bonds i.e.(ionic, covalent
and metallic bonding),mixed bonding and secondary bonds
along with the differentiation between them.
 ATOMS
Atoms are the basic structural unit of all engineering materials.
It is the basic unit of an element that can undergo chemical
change.

Atoms consist mainly of three basic subatomic particles:

• Protons
• Neutrons
• Electrons

Electrons vary in the amount of energy they possess, and they

occur at certain energy levels/electron shells.

Electron shells determine how an atom behaves when it

encounters other atoms.
ATOMS STRUCTURE

❑ Neutrons : Electrically neutral

❑ Protons : Positively charged (+)
❑ Electrons : Negatively charged (-)
 ATOMIC NUMBERS & ISOTOPES
A

Z
C
❑ Atomic number, Z : Number of protons.
❑ Mass number, A : Sum number of protons and neutrons.
e.g., Number of neutrons in iodine-131 (131I) –From the periodic table
that I →53rd element (53 protons).
Number of neutrons to be 78 (131 − 53).
❑ Not all atoms of the same element necessarily have the same
number of neutrons, although they all have the same number of
protons.
❑ Isotopes : Same atomic number (i.e., number of protons) BUT
different mass numbers.
e.g., Hydrogen (H) atom has three isotopes: 11𝐻 (hydrogen), 21𝐻
(deuterium), and 31𝐻 (tritium).
PERIODIC TABLE
 ATOMIC MASS & AVOGADRO’S NUMBERS

The mass of an atom, atomic mass is expressed in

atomic mass units (amu). – Equivalent to atomic mass
in units of grams(g).

❑One mole/gram-mole(mol) of a substance is equal to

6.022× 10²³ atoms of that substance (such as atoms,
molecules, or ions). The number 6.022×10²³ is known
as Avogadro's number/Avogadro's constant.
 EXAMPLE 1

1. What is the mass in grams of 1 atom of Fe?

• Given atomic mass of Fe is 55.849g/mol.

Fe = 55.849 grams and contains 6.022×10²³ atoms

** Meaning 6.022×10²³ atoms of Fe mass in grams is 55.849
55.849𝑔
1 𝑎𝑡𝑜𝑚 =
6.022 𝑋1023 𝑎𝑡𝑜𝑚𝑠

= 9.277 x 𝟏𝟎−𝟐𝟑 𝒈𝒓𝒂𝒎𝒔/𝒂𝒕𝒐𝒎

 EXAMPLE 1

2. How many atoms are there in 1 grams of Fe?

• Given atomic mass of Fe is 55.849g/mol.

Fe = 55.849 grams and contains 6.022×10²³ atoms

** Meaning 55.849 grams of Fe contains 6.022×10²³ atoms

6.022 𝑋1023 𝑎𝑡𝑜𝑚𝑠
1 𝑔𝑟𝑎𝑚 𝑜𝑓 𝐹𝑒 ℎ𝑎𝑠 = 55.849𝑔

= 1.078 x 𝟏𝟎𝟐𝟐 𝒂𝒕𝒐𝒎𝒔 𝒐𝒇 𝑭𝒆

 EXAMPLE 2
An intermetallic compound has the chemical formula NixAly, where x and y are
simple integers, and consists of 42.04 wt% nickel and 57.96 wt% aluminum.
What is the simplest formula of this nickel aluminide?
* Given atomic mass of Ni is 58.71g/mol and Al is 26.98g/mol

First, determine the mole fraction of nickel & aluminum in this compound.
Using a basis of 100 g of the compound, we have 42.04 g of Ni and 57.96 g of
Al.
42.04
No. of moles of Ni = = 𝟎. 𝟕𝟏𝟔𝟎 𝒎𝒐𝒍
58.71
57.96
No. of moles of Al = = 𝟐. 𝟏𝟒𝟖 𝒎𝒐𝒍
26.98
Total = 0.7160+2.148 2.864 mol

 Mole fraction of Ni = 0.7160 / 2.864 = 0.25

Mole fraction of Al = 2.148 / 2.864 = 0.75
The simplest formula in terms of gram-mole fraction becomes 𝑵𝒊𝟎.𝟐𝟓 𝑨𝒍𝟎.𝟕𝟓.
To express this in integer form we multiply both fractions by 4, resulting in
𝑵𝒊𝑨𝒍𝟑.
 THE ELECTRONIC STRUCTURE OF ATOMS
❑ Electrons have wavelike and particulate properties. This means
that electrons exist in orbitals defined by a probability.
– Bohr’s Theory coupled with Schrodinger's models.
❑ Each orbital is located at a discrete energy level determined by
quantum numbers.
 THE ELECTRONIC STRUCTURE OF ATOMS
Electron energy states
• Have discrete energy states.
• Tend to occupy lowest available energy state first.
THE ELECTRONIC STRUCTURE OF ATOMS
The electrons fill the first available principal
energy levels first. They fill the lowest
energy subshells first, that is, s, followed
by p, d, and finally f. The s, p, d, and f sub-
energy levels will allow a maximum of 2, 6,
10, and 14 electrons, respectively.

Two forms of expressing the orbital

occupancy:
(1) electron configuration
(2) orbital box diagram.

Electron configuration notation consists of

the value of the principal shell, n, followed
with the letter designation of the subshell,
ℓ, and finally the number of electrons in
that sublevel presented as a superscript.
THE ELECTRONIC STRUCTURE OF ATOMS
**SPECIAL CASE: 𝐀𝐟𝐭𝐞𝐫 𝟑𝒑𝟔 , 𝒘𝒊𝒍𝒍 𝒇𝒊𝒍𝒍 𝒖𝒑 𝟒𝒔 𝒇𝒊𝒓𝒔𝒕 𝒃𝒆𝒇𝒐𝒓𝒆
𝒇𝒊𝒍𝒍𝒊𝒏𝒈 𝒖𝒑 𝟑𝒅
e.g. : Scandium (Sc) with 21 electrons.
1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6
− Will account for 18 electrons.
− 3 electrons remain to complete the Sc electronic
structure.
Chronologically, one would assume that the next three
electrons
would fill the 3d orbital, thus completing the
configuration with
3𝑑 3 . But the next orbital to be filled is 4s and not 3d.
-Because the 4s energy level is lower than 3d (due to
shielding and penetration effects- lowest energy levels
are always occupied first)
1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠 2 3𝑑1
 THE ELECTRONIC STRUCTURE OF ATOMS
Elements are considered stable when it complete the maximum
electrons in each subshell.
 THE ELECTRONIC STRUCTURE OF ATOMS

Valence electrons – those in unfilled shells

❑ Filled shells are more stable.
❑ Valence electrons are most available for bonding and tend to
control the chemical properties
example:C (atomic number = 6)
 PERIODIC TABLE

❑ Classified all the elements based on the electron configuration

in the periodic table.
❑ The element situated with increasing atomic number in 7
horizontal rows : Periods.
❑ All the elements arrayed in 1 column/group (8 groups)
– Represent number of valence electrons and have similar :
❑ Valence electrons
❑ Chemical properties
❑ Physical properties
PERIODIC TABLE
 METAL, METALLOIDS, NON-METAL

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 Po
Cs Ba At Rn

Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
 METAL, METALLOIDS,NON-METAL

Electropositive elements:
❑ Reactive metals (Metallic) in nature & give up electrons in
chemical reactions to produce positive ions (cations).
❑ Most electropositive ~ groups 1A & 2A
Electronegative elements :
❑ Reactive non-metals (Nonmetallic) in nature & accept
electrons in chemical reactions to produce negative ions
(anions).
❑ Most electronegative ~ groups 6A & 7A

Metalloids (Can be metallic/non-metallic) :Groups 3A up to 5A can

behave electropositive/ electronegative manner.
 METAL, METALLOIDS,NON-METAL
Electronegativity : Measure of the tendency of an atom to attract a bonding
pair of electrons using Pauling scale.
-Indicating the degree by which they attract electrons to themselves. The
electronegativity of each atom is presented in a range of 0.8 to 4.0.
- As expected, nonmetals are more electronegative than metals, while
metalloids have intermediate electronegativities.
 METAL, METALLOIDS,NON-METAL
Summary of some of the electronic structure-chemical
property relationships for metals & nonmetals
 INTERATOMIC BONDING

In general, why does bonding between atoms occur?

The driving force behind the formation of bonds between atoms is
that each atom seeks to be in the most stable state. Through
bonding with other atoms, the potential energy of each bonding
atom is lowered, resulting in a more stable state.
Types of atomic & molecular bonds

Primary (strong bond) Secondary (weak bond)

• Ionic bonds • Permanent dipole bonds
Depends on
their • Covalent bonds • Fluctuating dipole bonds
valence • Metallic bonds
electrons.
 IONIC BONDS

❑ Ionic bonding arises from the electrostatic attraction between

oppositely charged ions-(metal and non-metal, i.e. Between
atoms with large differences in their electronegativity which
means strong bonding).
❑ In the process of ion formation, an electron or a number of
electrons may be transferred from a highly electropositive
element (eg; Na) to a highly electronegative one(eg; Cl). –
- Metal elements donate e- & nonmetal element gain electron.
❑ The ionic bond in solids is nondirectional.
❑ Ionic materials: Hard, Brittle, Electrically and thermally
insulative (no free electrons).
IONIC BONDS
IONIC BONDS
IONIC BONDS
 EXAMPLE

Describe the ionic bonding process between a pair of Na

and Cl atoms. Which electrons are involved in the bonding
process?
• The ionic bonding process between a pair of Na and Cl
atoms involves a transfer of the outer 3s1 electron of the Na
atom to the 3p vacancy in the Cl atom.

• Thus, the Na ion formed has the Ne (Neon) electron

configuration while the Cl ion has the Argon (Ar) electron
configuration.

• 𝑁𝑎 (1𝑠 2 2𝑠 2 2𝑝6 𝟑𝒔𝟏 )→ 𝑁𝑎 + (1𝑠 2 2𝑠 2 2𝑝6 )

• 𝐶𝑙(1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 𝟑𝒑𝟓 )→ 𝐶𝑙 − (1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 )
 EXAMPLE

After ionization, why is the sodium ion smaller than the

sodium atom?

• After ionization to the Na+, the Na atom becomes smaller

because the electron-to-proton ratio of the Na atom is
decreased when the Na+ ion forms. Also, the outer third
shell no longer exists once the 3s1 electron is lost by the Na
atom.
 BONDING FORCES

❑ As two atoms approach each other, two forces exist :

❑ Attractive force
❑ Repulsive force
• The +ve nucleus of one ion will attract the -ve charge cloud of
the other ion and vice versa. As a result, interionic distance, a,
decreases, and they become closer. As the ions come closer,
the negative electron charge clouds will interact, and a repulsion
force is developed.
• These two opposing forces will eventually balance each other to
a net force of zero, and that is when the equilibrium interionic
distance, a0 , is reached and a bond is formed.
INTERIONIC FORCES FOR AN ION PAIR

AT EQUILIBRIUM
𝑭𝒂𝒕𝒕𝒓𝒂𝒄𝒕𝒊𝒗𝒆 + 𝑭𝒓𝒆𝒑𝒖𝒍𝒔𝒊𝒗𝒆 = 𝟎
-Atomic center become separated by
𝒂𝟎 (𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝒔𝒑𝒂𝒄𝒊𝒏𝒈 𝒐𝒓
𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒊𝒓𝒊𝒖𝒎 𝒊𝒏𝒕𝒆𝒓𝒊𝒐𝒏𝒊𝒄
𝒅𝒊𝒔𝒕𝒂𝒏𝒄𝒆)
INTERIONIC FORCES FOR AN ION PAIR

ELECTRON CHARGE =𝟏. 𝟔𝟎 𝑿 𝟏𝟎−𝟏𝟗 𝑪

INTERIONIC FORCES FOR AN ION PAIR
 EXAMPLE
Calculate the attractive force between a pair of K+ and Br- ions that just
touch each other. Assume the ionic radius of the K+ ion to be 0.133 nm
and that of the Br- ion to be 0.196 nm.

Permittivity of free space, Є= 8.85x10-12 C2/Nm2

 INTERIONIC FORCES FOR AN ION PAIR

Bonding energy (Enet): Energy at equilibrium separation, i.e.,

energy required to separate the two atoms to an infinite
separation (i.e., break them apart).

Magnitude of bonding energy & shape of energy vs.

interatomic separation curve depends on material & type of
atomic bonding.
 INTERIONIC FORCES FOR AN ION PAIR
Enet may be determined using tis equation. While the net force at equilibrium, when
the bond is formed, is zero, the potential energy of the bond is at its lowest Emin.
The minimum energy, Emin, may be determined by substituting a0 into it..
Emin is negative as shown, which indicates that if one wanted to break the bond, an
amount of energy equal to , Emin must be expended.
EXAMPLE
 ION ARRANGEMENTS IN SOLID
Ionic bond is nondirectional in character (no separate single
molecules exist).

The number of cations that can pack around an anion (packing

efficiency) is determined by two factors: (1) their relative sizes
and (2) Electrical/charge neutrality.

Ionic packing
arrangements in (a)
CsCl and (b) NaCl.
8 Cl- ions can pack
around Cs:, but only 6
Cl- can pack around a
Na+ ion.
 COVALENT BONDING
❑ Primary type of bonding which arises from the reduction in
energy associated with the overlapping of half-filled orbitals of
two atoms.
❑ Occur mostly between atoms with small differences in
electronegativity & close to each other in the periodic table
(mostly between non metals)
❑ Atoms share their outer s & p electrons with others.
❑ Single covalent bond : Each of two atoms contributes 1
electron to form an electron pair bond ~ Energy small ~ More
stable.
❑ Multiple electron-pair bonds can be formed by one atom with
itself or other atoms.
❑ The covalent bonding between atoms is can represented by
the Lewis electron dot representation.
 COVALENT BONDING

❑ Covalent bonds are directional & the bonding electrons do

not stay in fixed positions between atoms.
❑ Materials with covalent bonding are electrically & thermally
insulative- Poor electrical and thermal conductivity.
❑ Materials that consist of covalent bonds : Mostly formed from
gas molecules, liquid molecules & low-melting solid molecules.
❑ Covalent bonds between atoms are quite strong (difficult to
break), but attractions between molecules/compounds, or
intermolecular forces, can be relatively weak.
❑ Have low boiling & melting points (i.e., boil or melt very easily).
❑ Soft or brittle solid forms - Weak intermolecular forces makes
the solid form of covalent molecular compounds easy to distort
or break.
 COVALENT BONDING

Covalent Bonding in Diatomic Molecules

 COVALENT BONDING
Covalent Bonding in the Hydrogen molecule
 COVALENT BONDING

Covalent Bonding in Carbon Containing Molecules

 COVALENT BONDING
Covalent Bonding in Hydrocarbon Molecules
 MIXED BONDING-IONIC COVALENT MIXED
❑ Close elements bond covalently. Far elements bond ionically.
But few compounds exhibit pure ionic or pure covalent bonding.
❑ Most covalent-bonded molecules have some ionic bonding, and
vice versa..
❑ For a compound, the degree depends on relative positions of
atoms in periodic table (i.e., electronegativity).
❑ The greater the difference in the electronegativities of the
elements involved in a mixed ionic-covalent bond, the greater
the degree of ionic character of the bond.
❑ Pauling proposed the following equation to determine the
percentage ionic character of bonding in a compound AB:
(𝑥 𝐴 −𝑥 𝐵 )2
% 𝑖𝑜𝑛𝑖𝑐 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 = 1 − 𝑒− 4 ∗ 100%
IONIC-COVALENT MIXED BONDING
 METALIC BONDING

❑ Primary type of bonding involving the interaction of valence

electron/electrons of one atom with many surrounding atoms.
❑ This interaction leads to a reduction in energy of the system
considered.
❑ The valence bonding electrons of these bonds are sometimes
regarded as an “electron gas” bonding the positive ion cores of
atoms.
❑ The metallic bond - Three-dimensional & nondirectional,
similar to the ionic bond.
❑ However, since there are no anions involved, there are no
electrical neutrality restrictions. The metallic cations are also
not as rigid as they are in ionic solids.
❑ In contrast to the directional covalent bonds, there are no
shared localized electron pairs between atoms; metallic bonds
are therefore weaker than covalent bonds.
 METALIC BONDING

The circles with the inner positive signs -

Positive-ion cores & Charge clouds around
the ion cores - Dispersed valence electrons.
All the atoms contribute their valence
electrons to a “sea of electrons”/ “electron
charge cloud” These valence electrons are
delocalized, move freely in the sea of
electrons, and do not belong to any specific
atoms (free electrons)
The nuclei & the remaining core electrons of
tightly packed atoms form a cationic (a
positive core - Because Lost their valence
electrons).
What keeps the atoms together in solid metals is the attraction
force between the +ve ionic core (metal cations) and the
–ve electron cloud. This is referred to as metallic bonding.
 SECONDARY BONDING OR VAN DER WAALS BONDING

❑ The driving force for primary atomic bonding : Lowering of the

energy of the bonding electrons.
❑ The driving force for secondary bonding : Attraction of the
electric dipoles contained in atoms/molecules.
❑ Electric dipoles interact with each other by electrostatic
(Coulombic) forces, and thus atoms or molecules containing
dipoles are attracted to each other by these forces.
❑ Even though the bonding energies of secondary bonds are
weak, they become important when they are the only bonds
available to bond atoms or molecules together.
❑ Can be divided by:
• Fluctuating Dipoles
• Permanent Dipoles
 SECONDARY BONDING OR VAN DER WAALS BONDING

Arises from interaction between dipoles

• Fluctuating dipoles
ex: liquid H 2
asymmetric electron clouds
H2 H2

+ - secondary + - H H H H
secondary
bonding bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding
H Cl

-ex: polymer
 FLUCTUATING DIPOLES
These electric dipoles, formed due to the asymmetrical
electron charge distribution within the atoms, change in
both direction and magnitude with time.

This type of bond is electrostatic in nature, very weak and

nondirectional.
Electron charge distribution in a noble
gas atom.
(a) An idealized symmetric charge
distribution in which the negative and
positive charge centers are
superimposed at the center.
(b) The actual asymmetric distribution of
electrons causing a temporary dipole.
 PERMANENT DIPOLES
❑ Secondary type of bonding between molecules possessing
permanent electric dipoles.
❑ The bonds, formed by the electrostatic attraction of the
dipoles, are directional in nature.

Permanent dipole nature of Hydrogen bonding among

the water molecule water molecules due to
permanent dipole attraction
THANK YOU