10/11/2024

IE 223 / IE0242: Materials

Science & Engineering

Dr. Rula Allaf

Associate Professor of Industrial Engineering

Chapter 2: Atomic Structure

& Interatomic Bonding

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

1
 10/11/2024

Introduction
• It should be clear that all matter is made of atoms. From the
periodic table, it can be seen that there are only ~ 110 different
kinds of atoms in the entire Universe. These same 110 atoms
form thousands of different substances.

• Metals behave differently than ceramics,

and ceramics behave differently than polymers.

• To understand the structure of a material, the type of atoms

present and how the atoms are arranged and bonded must be
known.

• The properties of matter depend on which atoms are used and

how they are bonded together.

Fundamental Concepts
• Each atom consists of very small nucleus composed of
protons (+ 1.602x10-19 C) and neutrons (neutral), and
electrons (- 1.602x10-19 C) that orbit around the nucleus.
• Mass – electrons – 9.11 x 10-31 kg
protons ~same 1.67 x 10-27 kg
neutrons

• Each chemical element is characterized by its atomic

number (Z) and atomic mass (A).
• Atomic number (Z) = # of protons in nucleus of atom
= # of electrons of neutral atoms

*This chapter/book sometimes refers to the structure of an atom ≡ electron configuration (e.g. Na:
1s2 2s2 2p6 3s1) as atomic structure, which we refer to as subatomic structure when we refer to the
whole material structure levels described in Chapter 1.

2
 10/11/2024

Fundamental Concepts
• The atomic mass (A) of a specific atom may be
expressed as the sum of the masses of protons and
neutrons.
• The number of neutrons (N) for atoms of an element
may be variable resulting in isotopes.
• The atomic weight of an element corresponds to the
weighted average of the atomic masses of the atom’s
naturally occurring isotopes.
• The atomic weight of an element or the molecular
weight of a compound may be specified on the basis
of amu (atomic mass unit) per atom (molecule) or
mass per mole of material.

Fundamental Concepts
• Atomic mass unit, amu = 1/12 atomic mass of
12C (A=12.00000 amu)

• One mole of a substance contains 6.022 x 1023

(Avogadro’s number) atoms or molecules.

• 1 amu/atom = 1g/mol

C 12.011 amu/atom or 12.011 g/mol

H 1.008 amu/atom or 1.008 g/mol

3
 10/11/2024

Electrons in Atoms / Atomic models

• The set of principles and laws that govern the behavior of
atomic and subatomic entities is known as quantum mechanics

• One early result of quantum mechanics was the simplified

Bohr atomic model, in which electrons are assumed to
revolve around the atomic nucleus in discrete orbitals, and
the position of any electron is well defined in terms of its
orbital.
• Energies of electrons are quantized—that is, electrons are
permitted to have only specific values of energy.

➢ The Bohr model represents an early attempt to

describe electrons in atoms, in terms of both
position (electron orbitals) and energy
(quantized energy levels).

Atomic models/ wave-mechanical model

• The electron is considered to exhibit both wavelike and particle-like
characteristics. Its position is described by a probability distribution or
electron cloud.
• In wave mechanics, every electron in an atom is characterized by four
parameters called quantum numbers. The size, shape, and spatial
orientation of an electron’s probability density (or orbital) are specified by
three of these quantum numbers.

4
 10/11/2024

Atomic models/ wave-mechanical model

• Electrons are present with different specific energies surrounding the
nucleus of the atom; electrons fill up the lowest possible energy states in
the electron shells and subshells, two electrons (having opposite spins)
per state when atom is in ground state. (Pauli exclusion principle)

• The electron configuration or structure of an

atom represents the way these states are
occupied
• Conventional notation:
Na(Z=11)1s2 2s2 2p6 3s1

Electrons in Atoms
• Na(Z=11)1s2 2s2 2p6 3s1
• C(Z=6) 1s2 2s2 2p2
• Valence electrons: electrons that occupy the outermost shell.
• When states within the outermost or valence electron shell are
completely filled, atoms have “stable electron configurations”.
• Normally, this corresponds to the occupation of just the s and p states for
the outermost shell by a total of eight electrons, as in neon, argon, and
krypton; one exception is helium, which contains only two 1s electrons.
• Elements (Ne, Ar, Kr, and He) are the inert, or noble gases, which are
virtually unreactive chemically.

• Some atoms of the elements that have unfilled valence shells

assume stable electron configurations by gaining or losing
electrons to form charged ions, or by sharing electrons with
other atoms. “This is the basis for atomic bonding in solids”

10

5
 10/11/2024

The Periodic Table

Elements have been classified according to electron configuration in the
periodic table.
Seven horizontal rows called periods with increasing atomic number

inert gases
Columns: Similar Valence Structure
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
Alkali metals

K Ca Sc Se Br Kr Electronegativity:
Rb Sr Y Te I Xe term used to
describe an
Cs Ba Po At Rn
atom’s attraction
Fr Ra for the electrons
in a bond.
Transition metals
Ranges from 0.7
Electropositive elements: Electronegative elements: to 4.0
Readily give up electrons to become + ions. Readily acquire electrons to become – ions or share.

11

Atomic Bonding in Solids

• Many of the physical properties of materials relate to the interatomic
forces that bind the atoms together.
• Consider the interaction between two isolated atoms as they are brought
into proximity from an infinite separation
• At large distances, the interactions are negligible, but as the atoms
approach, each one exerts forces on the other. Forces are of two types,
attractive and repulsive, and the magnitude of each is a function of the
separation or interatomic distance, r.
– The origin of an attractive force FA
depends on the type of bonding that
exists between the two atoms.
– Repulsive forces FR arise from
interactions between the negatively
charged electron clouds, most
pronounced at small r values when
the outer electron shells of the two
atoms begin to overlap.
12

6
 10/11/2024

Atomic Bonding in Solids

• A state of equilibrium exists when the attractive and repulsive
forces are equal, i.e., they are in balance. At the state of
equilibrium, the two atoms will be separated by the equilibrium
spacing r0. (r0≅0.3nm)
• Once in this position, the two atoms will counteract any attempt to
separate them by an attractive force, or to push them together by a
repulsive action.

r0
• Net potential energy is minimum at equilibrium spacing, r0.
• The bonding energy for these two atoms, E0, corresponds to the
energy at this minimum point; it represents the energy that would
be required to separate these two atoms to an infinite separation.
• Some material properties depend on E0

melting Temperature Tm is larger if Eo is larger.

coefficient of thermal expansion  is larger if Eo is smaller.

13

Atomic Bonding in Solids

• Three different types of primary or chemical bond are
found in solids- ionic, covalent, and metallic *.
– The bonding involves the valence electrons;
– the nature of the bond depends on the electron structures of the
constituent atoms.
– In general, each of these three types of bonding arise from the
tendency of the atoms to assume stable electron structures, like
those of the inert gases, by completely filling the outermost
electron shell.
• Secondary or physical forces and energies are also found
in many solid materials; they are weaker than the primary
ones, but nonetheless influence the physical properties of
some materials.

* Some interatomic bonds can be mixed; e.g. partially ionic and partially covalent.

15

7
 10/11/2024

Ionic Bonding
Ionic bond – metal + nonmetal

donates accepts
electrons electrons
Dissimilar electronegativities
Requires electron transfer

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4 (Nonmetal)
(metal)
unstable [Ne] 3s2 unstable

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

(cation) [Ne] Coulombic [Ne] (anion)
stable stable
Attraction
• The attractive bonding forces are coulombic (electrostatic):
they occur between + and - ions.
16

Ionic Bonding
• Ionic bonding is nondirectional
• E0 ranges between 600 and 1500 kJ/mol, a
relatively high energy, as reflected in high Tm.
• Consequently, from the electron configuration
and/or the nature of ionic bonding; ionic
materials are characteristically hard, brittle,
and electrically and thermally insulative.
• Predominant bonding in Ceramics
• Examples: NaCl, MgO, CaF2

17

8
 10/11/2024

Covalent Bonding
• Similar electronegativity  share electrons
• Each atom will contribute at least one electron to the bond and
the shared electrons may be considered to belong to both atoms.
• Example: methane - CH4 H shared electrons
C: has 4 valence e-, needs 4 more from carbon atom
H: has 1 valence e-, needs 1 more
H C H

Electronegativities are comparable. shared electrons

from hydrogen
H atoms
• Examples: non-metallic elemental molecules (H2, CL2, F2),
molecules of dissimilar atoms (CH4, H2O, HF), elemental solids
such as diamond (carbon), silicon, germanium, other solid
compounds, e.g. SiC, and polymers (intramolecular bonds), etc.

C or Si

18

Covalent Bonding
• Covalent bonding is directional, that is, it is between specific
atoms and may only exist in the direction between one atom and
another that participates in the electron sharing

• Covalent bonds may be very strong, as in diamond, which is very

hard and has a very high melting temperature, or they may be
very weak, as with bismuth, which melts at a low Tm.

• Since the electrons participating in covalent bonds are tightly

bound to the bonding atoms, most covalently bonded materials
are electrical insulators, or, in some cases, semiconductors.

• Mechanical behaviors of these materials vary widely: some are

relatively strong, others are weak; some fail in a brittle manner,
whereas others experience significant amounts of deformation
before failure.

19

9
 10/11/2024

Metallic Bonding
• Found in metals and their alloys.
• Electrons sea model for bonding scheme:
valence electrons (3 at most per atom) are not
bound to any particular atom in the solid and
they are more or less free to drift throughout
the entire metal- form a “sea of electrons” or
“electron cloud”.
• The atomic nuclei and remaining nonvalence
electrons form what are called ion cores, which
possess a net positive charge equal in
magnitude to the total valence electron charge
per atom.
• These free electrons act as a glue to hold the positive ion cores
together (electrostatic attraction). They shield the positively
charged ion cores from mutually repulsive electrostatic forces.
21

Metallic Bonding
• The metallic bond is nondirectional in character.
• Bonding may be weak (Hg - Mercury) or strong (W-Tungsten).
• Because of free electrons; metals are good conductors of both
electricity and heat.
On the contrary, because of the absence of large number of free
electrons; ionically and covalently bonded materials are typically
electrical and thermal insulators.

• At room temperature, most metals and their alloys are ductile—that is,
they experience significant degrees of permanent deformation before
fracture.

22

10
 10/11/2024

Secondary (physical) Bonding

• Secondary, van der Waals, or physical bonds are weak in
comparison to the primary or chemical ones
• Their presence is evidenced for inert gases and between
molecules in molecular structures that are covalently
bonded (intermolecular forces)
• Forces arises from interaction between dipoles
• An electric dipole exists whenever there is some separation
of positive and negative portions of an atom or molecule.

• The bonding results from the coulombic attraction between

the positive end of one dipole and the negative region of an
adjacent one (bond is directional)
• 3 types:
23

1) Fluctuating induced dipole bonds

asymmetric electron
clouds

+ - + -
secondary
bonding

2) Permanent dipoles (polar)-induced dipole bonds

secondary
H Cl bonding + -

The strongest secondary

bonding type, the hydrogen
3) Permanent dipole bonds bond, is a special case of polar
molecule bonding. It occurs
liquid HCl secondary between molecules in which
H Cl bonding H Cl hydrogen is covalently bonded
to fluorine, oxygen, or nitrogen

24

11
 10/11/2024

Molecules
• Many of the common molecules are composed of groups of
atoms that are bound together by strong covalent bonds
(elemental diatomic molecules, e.g. F2, O2, H2, and some
compounds, e.g. CO2, CH4, H2O)
• In the condensed liquid and solid states, bonds between
molecules are weak secondary ones. Thus molecular materials
have relatively low melting and boiling temperatures
• Most of those that have small molecules composed of a few
atoms are gases at ordinary, or ambient, temperatures and
pressures.
• Many polymers, being molecular materials composed of
extremely large molecules, exist as solids; some of their
properties are strongly dependent on the presence of van der
Waals and hydrogen secondary bonds.
Intramolecular bonding:
covalent bonding
-ex: polymer
Intermolecular bonding:
secondary bonding
25

Mixed Bonding
• For many real materials, the
atomic bonds are mixtures of
two or more of the extremes
(i.e., mixed bonds).

26

12
 10/11/2024

Summary: Bonding
Type Bond Energy Comments
Ionic Large Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular

27

Summary: Primary Bonds

Ceramics Large bond energy
(Ionic & some covalent large Tm
character bonding): large E
small 

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate 

Polymers
(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large 
Tm : melting temperature
E : modulus of Elasticity (stiffness)
 : coefficient of thermal expansion
28

13
 10/11/2024

Chapter Problems

Cerium has four naturally occurring isotopes: 0.185% of 136Ce, with an atomic
weight of 135.907 amu; 0.251% of 138Ce, with an atomic weight of 137.906
amu; 88.450% of 140Ce, with an atomic weight of 139.905 amu; and 11.114%
of 142Ce, with an atomic weight of 141.909 amu. Calculate the average
atomic weight of Ce.

Compute the percent ionic character (%IC) of the interatomic bonds for the
following compounds: TiO2, ZnTe, CsCl, InSb, and MgCl2.

29

14