Atomic Structure and

Interatomic Bonding
(Chapter 2 of Callister)

Coordinator: An Mai, PhD, PEng

 What is an Atom?

2
 Atoms, Molecules, and Compounds

• Atoms:
o possess mass
o contain positive nuclei
o contain electrons
o occupy volume
o attract one another
o combine to form molecules

3
 Atoms – Fundamental Concepts

• Each atom consists of a very small

nucleus, composed of protons and
neutrons, and is encircled by moving
electrons.
• Atomic number = no. of protons in the
nucleus.
• Atomic mass = sum of masses of protons
and neutrons within the nucleus.
• What is an atomic weight?
https://www.geeksforgeeks.org/atomic-nucleus/

4
 Atoms, Molecules, and Compounds Cont.

• A molecule is a combination of two or more

atoms held together in a specific shape by
attractive forces.
• The simplest is a molecule containing two
of the same atoms.
• Compound – a substance that contains more
than one element.
• For example, water is composed of hydrogen and
oxygen

5
 Electrons

• Behaves like a particle or wave?

Source: https://www.sciencefacts.net/wave-particle-duality.html
6
 Electrons: Structure of Atoms

• Electrons have BOTH wavelike Particle-like:

and particulate properties. electrons exist in a
point orbiting a Wave-like: electrons
nucleus have a probability of
existing in a place
• Two of the wavelike
characteristics are
– electrons are in orbitals defined by a
probability.
– each orbital at discrete energy level
is determined by quantum numbers.

7
 Electron Energy States
Adapted from Fig. 2.6, Callister &
Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J. Wulff,
Introduction to Materials Science and
Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)
4d
Electrons... 4p N-shell n = 4
• have discrete energy states
3d
• tend to occupy lowest
available energy state. 4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
8
 Recall that …
• Key Concepts: Each atomic electron energy level is
associated with a specific three-dimensional atomic
orbital.
• The principal quantum number (n) designates the
principal electron shell of the atom.
• The azimuthal quantum number (l) describes the shape
of a given orbital (s, p, d, or f).
• The magnetic quantum number (ml) ranges from –l to +l.
• The spin quantum number (ms) can be + ½ or − ½.

9
 Recall that…

• s-orbital is a sphere
• p-orbitals: 3 possibilities (px, py, pz)
• d-orbitals: 5 possibilities
• dxy, dyz, dxz, dx2-y2, dz2

• What about f-orbitals?

10
11

Survey of Elements
• Most elements: Electron configurations not stable. WHY??

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
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)
 Electron Configurations

• Valence electrons – those in unfilled shells

• Filled shells are more stable – require more energy to gain or
loose electrons
• Valence electrons are most available for bonding and tend to
control the chemical properties

• example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

12
 Electron Configurations Example

ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d valence
4p N-shell n = 4
electrons = 8
3d
4s

Energy 3p M-shell n = 3 Adapted from Fig. 2.6, Callister &

Rethwisch 9e.
3s (From K. M. Ralls, T. H. Courtney, and J.
Wulff, Introduction to Materials Science and
Engineering, p. 22. Copyright © 1976 by John
Wiley & Sons, New York. Reprinted by
2p L-shell n = 2
permission of John Wiley & Sons, Inc.)

2s

1s K-shell n = 1
13
 Recall Aufbau Principle

• Aufbau Principle:
• Electrons will
occupy the
orbitals having
lower energies
before occupying
higher energy
orbitals.

14
 Quick Example

• What is the electron configuration of Fe2+?

• What about Fe3+?

15
 Example

• 2.9 Give the electron configurations for the following ions: Al3+, Cu+,
Ba2+, Br-, and O2-.
• You can look up the atomic number for each of these elements!

16
 The Periodic Table
• Elements in each column have similar valence electron structure!

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
Adapted from
K Ca Sc Se Br Kr Fig. 2.8,
Callister &
Rb Sr Y Te I Xe Rethwisch 9e.

Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
17
to become + ions. to become - ions.
 Electronegativity

• Ranges from 0.7 to 4.0,

• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

18
 Types of Chemical Bonds
• 3 types of primary or chemical bond in
solids.
• Involves sharing or transfer of electrons.
• Secondary bonds are also found in
solids.
• Attractive forces between + and – charges.
• Weaker than primary!
• Type of bond depends on valence
electrons and electron structures.
• Bonding arises from the tendency to
assume a stable electron structure!

19
 Ionic Bonding
Ionic bond = metal + nonmetal

DONATES ACCEPTS
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4 Electronegativities: 1.2 and 3.5
[Ne] 3s2 for Mg and O, respectively!
O will accept electrons
Mg will donate electrons

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

20
[Ne] [Ne]
 Ionic Bonding Cont.
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity.
• Example: NaCl

Na (metal) Cl (nonmetal) This bond is formed due to the

unstable unstable electrostatic force of attraction
electron between oppositely charged ions →
Ionic bond forces can be calculated
from electrostatic/Coulombic
Na (cation) + - Cl (anion) equations
stable Coulombic stable
Attraction
21
 Notation – Lewis Structure

1) Write the element

symbol.
2) Chlorine is in the 7th
group, so it has 7
Na Cl
valence electrons.
3) Starting at the right,
draw 4 electrons, or
dots, counter-
clockwise around the
element symbol. Then
add the remaining 3 by
pairing them.
Na Cl
22
23

Ionic Bonding - Predominant bonding in Ceramics!

NaCl

MgO
CaF2

CsCl

Acquire electrons

Give up electrons Acquire electrons

 Covalent Bonding

• Similar electronegativity  share electrons

• Bonds determined by valence electrons– s & p orbitals
dominate bonding
• Example: H2 H 2

Each H: has 1 valence e-,

needs 1 more H H

Electronegativities
are the same. Shared 1s Shared 1s
electron from 1st electron from 2nd
hydrogen atom hydrogen atom
Fig. 2.12, Callister & Rethwisch 9e.
24
 Examples

• What type of bond exists in diamond?

• What about silicon, germanium, gallium
arsenide (GaAs), indium antimonide
(InSb), and silicon carbide (SiC)?
• What about these compounds?
• CH4, H2O, HNO3, and HF
https://wou.edu/chemistry/courses/online-chemistry-
textbooks/ch105-consumer-chemistry/ch105-chapter-4-shape-
• It is difficult to predict mechanical characteristics-compounds/

properties of covalent bonded

materials based on bonding
characteristics alone.
25
 Covalent Bonding of Carbon - Bond Hybridization

• Carbon can form sp3 hybrid orbitals

Fig. 2.14, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)
26
 Bond Hybridization – sp2

27
 More Bond Hybridizations for Carbon

sp3 => sigma bonds, all

single bonds
Eg: diamond

sp2 => 1 sigma bond, 1 pi

bond, allows double bond
formation
Eg: graphite

sp => 1 sigma bond, 2 pi

bonds, allows triple bond
formation
Eg: C2H2
28
 VSEPR Theory
• Valence shell electron pair
repulsion
• Valence electron pairs surrounding
an atom tend to repel each other
• Greater repulsion → higher in energy
→ less stable!
• VSEPR predicted molecular geometry
that minimized repulsion
• Use to predict 3D molecular
geometry

29
 Nomenclature Used in VSEPR

• A = Central atom
• X = bonding atom
• E = non-bonded electrons
• m = integer number of bonding atoms
• n = integer number of non-bonded
electrons

30
 Molecular Shapes

Formula Type Molecular Shape Geometry Bond Angle

AX2 Planar 180°

AX3 Trigonal 120°

Planar

AX4
Tetrahedral 109.5°
31
 VSEPR Examples

• H2O
• CH4
• NH3

• What about CO2?

• What about C2H6?

From socratic.org
32
 VSEPR and Multiple Bonds

• VSEPR theory predicts that double and triple bonds have stronger
repulsive forces than single bonds!
• Similar to lone pairs of electrons, multiple bonds occupy more space
around the central atom → bond angles are slightly distorted.
• Examples:

CH2O CH2C(CH3)2
33
 Summary for VSEPR

• Molecule shapes can be predicted

• Unpaired valence electrons often take slightly more space than
bonded electrons, which may change bond angles slightly
• Bond angles in most molecules or extended solids can be predicted
using VSEPR theory
• Double and triple bonds have stronger repulsive forces than single
bonds, similar to the effects of lone electron pairs

34
 Metallic Bonding

• Primary bonding type found in metals and their alloys.

• Electrons delocalized to form an “electron cloud”

35
Fig. 2.19b, Callister & Rethwisch 10e.
 Metallic Bonding Cont.

• Examples: Fe, Al, Au, Ag, Mg, etc

• Non-directional bonding
• Electrons are delocalized through the solid
• Only occurs in pure metals or alloys (no electron sharing)

36
 Secondary Bonding (van der Waals Bonding)
• Secondary bonding exists in all atoms and molecules.
• Bonding energies are relatively weak; ranging from 4 – 30 kJ/mol.
• No sharing or electrons transfer.
• Secondary bonds are possible between atoms or groups of atoms (held
together by primary bonds).
• Intermolecular – between atoms or groups of atoms
• Intramolecular – primary bonds
• Secondary bonding forces arise from attractive forces between
atomic or molecular dipoles

*From Khan
Academy
37
 Secondary Bonding (van der Waals Bonding) Cont.

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

+ - + - H H H H
secondary secondary
bonding bonding
• Permanent dipoles

+ - secondary + -
-general case:
bonding

H Cl secondary H Cl
-ex: liquid HCl
bonding

-ex: polymer
linear polymer molecule
38
 Hydrogen Bonding

• Special type of secondary bonding, where

hydrogen is one of the constituents.
• Examples: HF, H20, NH3
• Magnitude of hydrogen bond is generally
higher than other types of secondary bonds.
• Melting and boiling temperatures for HF,
H20, NH3 are high.

39
 Directional versus Non-Directional Bonding

• Directional bonding (covalent and some secondary bonding)

• Electrons or shared electrons are localized in a specific area between
atoms
• Can only exist because of location of electrons or dipole moment
• Non-directional bonding (ionic and metallic bonding)
• Electrons cannot be localized in a specific location between atoms
• Bonding forces are the same in all directions around the atom

40
 Example

• 2.27 What type(s) of bonding would be expected for each of the

following materials:
• brass (a copper-zinc alloy)
• Epoxy
• barium sulfide (BaS)
• solid xenon
• Bronze
• Nylon
• aluminum phosphide (AIP)?

41
 Mix Bonding

42
 Mixed Bonding Cont.
• Most common mixed bonding type is Covalent-Ionic mixed bonding

% ionic character = x ( 100 %)

where XA & XB are electronegativities of the two

elements participating in the bond

Ex: MgO XMg = 1.2

XO = 3.5

æ -
(3.5-1.2)2 ö
ç
% ionic character = 1- e 4 ÷ x (100%) = 73.3%
ç ÷
è ø
43
 Try by Yourself

• Compute the percents ionic character of the interatomic bond that

forms between C and H
• Additional information:
• Electronegativity of C and H is 2.5 and 2.1, respectively.

44
 Bonding Energies

45
 Bond Energies Cont.

46
 Bond Energies Cont.

• There are two kind of attractive forces in a molecule – intramolecular

and intermolecular.
• Intramolecular forces hold atoms together within a molecule.
• Intermolecular forces bond molecules together.

47
 Intramolecular Forces of Attraction

• Types of intramolecular
forces of attraction:
• Ionic bond
• Covalent bond
• Metallic bond

*From Khan Academy

48
 Intermolecular Forces of Attraction

• Types of intermolecular forces:

• Dipole-dipole interactions
• Hydrogen bond
• van der Waal forces (London
dispersion forces)

49
 Intermolecular Forces of Attraction Cont.

50
 Intermolecular Forces vs. Boiling and Melting Points

• Boiling and melting points of compounds depend on the type and

strength of the intermolecular forces present.
• Rule of thumb:
• The stronger the intermolecular forces the more energy required to break
those forces!
• This means that ionic and polar covalent compounds having higher boiling
and melting points.

51
 Intermolecular Forces vs. Boiling and Melting Points Cont.

52
 Interatomic - Bonding Forces and Energies

• Net force, FN, between two atoms is the

sum of attractive and repulse force.
FN = FA + FR
• At equilibrium, there is no net force.
FN = 0 → FA = FR
At this equilibrium, the distance between the atoms is
denoted by r0
• Energy and force are related: 𝐸 = ‫𝑟𝑑𝐹 ׬‬

53
 Interatomic - Bonding Forces and Energies Cont.
• Energy – minimum energy most stable
• Net energy = sum of attractive and repulsive energies
• Equilibrium separation when net energy is a minimum

EN = EA + ER = - A + B
r rn
Repulsive energy ER 1
𝐴= 𝑍 𝑒 𝑍2 𝑒
4𝜋𝜖0 1

B and n are constants

Interatomic separation r

Net energy EN Fig. 2.10(b), Callister &

Rethwisch 10e.

Attractive energy EA
54
55

Relationship Between Bonding Energy and 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 = The larger Eo, the higher Tm
“bond energy”
56

Relationship Between Bonding Energy and αl

• Coefficient of thermal expansion, αl
length, L o ΔL
Lo
= αl (T2 -T1)
unheated, T1
ΔL

heated, T 2
The smaller Eo, the larger αl

unstretched length
r • Increase in bond length is due to asymmetry of
Energy

o
r the E vs. r curve. This results in an increase in al.
larger αl • As E0 increases this asymmetry decreases.
Eo
Eo smaller αl
 Summary
• The evolution of the atom and our understanding of its
structure has brought us to the age of the Quantum state
of the atom
• Valence electrons are responsible for most of the
chemical reactivity of atoms and play a vital role in the
bonds that form between atoms
• Covalent and Ionic bonds are two primary bonding types
that involve sharing electrons or transferring electrons
between atoms, respectively.
• The percent ionic character of a covalent-ionic mixed
bond between two elements depends on their
electronegativities.
• Secondary bonds are weaker and does not involve any
electrons transfer or sharing.
• A material’s chemical, electrical, thermal, and optical
properties are determined by electronic configuration.
58

Summary: Properties Related to Bonding Type

and Bonding Energy
Ceramics Large bond energy
high Tm
(Ionic & covalent bonding): large E
small αl

Metals Variable bond energy

moderate Tm
(Metallic bonding):
moderate E
moderate αl

Polymers Weak bond energy (between chains)

(Covalent & Secondary): Secondary bonding responsible for
most physical properties
low Tm
small E
large αl
 Example

2.18 The net potential energy between two adjacent ions, EN, may be
represented by the sum of Equations 2.9 and 2.11; that is,

Calculate the bonding energy E0 in terms of the

parameters A, B, and n

59
 Try by Yourself

60
 Suggested Problems from Chapter 2 of Callister

• 2.9, 2.13, 2.16

• 2.21, 2.22(a), 2.24
• 2.27
• 2.1FE, 2.2FE, 2.3FE

61