INTRODUCTION TO

ENGINEERING MATERIALS

ATOMIC STRUCTURE AND

INTERATOMIC BONDING

YESHITLA TSEGAW

Materials Science and Engineering: An Introduction, William D. Callister and David. G. Rethwisch,
John Wiley & Sons 2014 (9th edition)
 Outline

 Atomic Structures
 Atomic Models
 Electron Configurations and Periodic Table
 Interatomic Bonding
Learning Objectives

After studying this chapter, you should be able to do the following:

1.Name the two atomic models cited, and note the differences between them.
2.Describe the important quantum-mechanical principle that relates to
electron energies.
3.(a) Schematically plot attractive, repulsive, and net energies versus
interatomic separation for two atoms or ions. (b) Note on this plot the
equilibrium separation and the bonding energy.
4. (a) Briefly describe ionic, covalent, metallic, hydrogen, and van der
Waals bonds. (b) Note which materials exhibit each of these bonding types.
ATOMIC STRUCTURE
 The properties of solid materials depend on geometrical atomic
arrangements, and the interactions among atoms or molecules.

 Atoms consists of a small nucleus composed of

protons and neutrons, which is encircled by
moving electrons in their orbitals, specific energy
levels.

atom – electrons 9.11 x 10-31 kg

protons
neutrons
} 1.67 x 10-27 kg

atom – electrons -1.602x 10-19 C

protons +1.602x 10-19 C
neutrons 0
 Every chemical element (X) is characterized by the atomic number which is
equal to number of protons in the nucleus.
Atomic number

X
Atomic number (Z) = # of protons in nucleus of atom
= # of electrons of neutral
species
Z
Atomic mass (A) = sum of the masses of protons and
of neutron within nucleus Atomic
mass
A
 Atomic mass is measured in atomic mass unit (amu)
 1 amu = 1/12 mass of 12C (most common isotope of carbon) measured in
grams
 Isotopes: atoms that have the same atomic number but different atomic
mass number.
 Atomic weight of an element corresponds to the weighted average of the
atomic masses of the atom’s naturally occurring isotopes.
Example_1: Calculate the average atomic weight of copper

The element copper has two naturally occurring isotopes with mass numbers of 63 and
65. The relative abundance and atomic masses are 69.2% for a mass of 62.93amu and
30.8% for a mass of 64.93amu

Answer: = 63.5 amu

The atomic weight of an element may be specified by amu/atom or g/mol
1 mol = 6.023x1023 atoms (Avogadro’s number)
1 amu/atom = 1g/mol
ATOMIC MODELS
Quantum Mechanics
Classical Mechanics Quantum Mechanics Concepts
As   intensity increases Intensity has a maximum Black body radiation
As E  the  e- removal The removal of e- requires Photoelectric effect
increases a threshold

As a particle or wave Both De Broglie hypothesis

 = h/mu
Know a position & u Know position or u Heisenberg uncertainty
principle

 The understanding of the behavior of electrons in atoms and crystalline solids

necessarily involves the concept of quantum mechanics.
 At microscopic level, an electron behaves as a particle and as a wave (dual nature
of matter).
Bohr Model

 The electrons moves in a circular orbit at fixed

distances from the nucleus.
 electron is found only in specific circular paths
(orbitals),

 Energy of the electrons are quantized. Each orbit

has a fixed energy. These fixed energies an
electron are called energy levels
 Electrons move from one energy level to
another energy level if the electrons gained or
lose the right amount of energy.

m e Z2e 4
E n  2 2 2
8 o n h
Drawbacks of Bohr’s Model
 The Bohr’s model could not explain the
spectra of atoms containing more than one
electrons.
 In Bohr's equation, the momentum and
position of electron were well defined.
 But, according to Heisenberg's
uncertainty principle, it is impossible to
measure the position and momentum of E0 13.6
electrons precisely. En  2
 2 eV
n n

 The Bohr’s model could not explain the

electric field and magnetic field effect on
spectra (Stark effect and Zeeman effect).
Wave Mechanical Model

 Schrodinger develops mathematical equations to describe the motion of electrons

in atoms.
 The quantum mechanical model, comes from the mathematical solutions to the
Schrodinger equation.

 In this model, the position is considered to be the

probability of an electron’s being at various locations
around the nucleus (probability distribution or electron
cloud ).
 The electron exhibits a dual nature: both wave and
particle like characteristics.
Quantum numbers

 In wave mechanics, every electron in an atom is characterized by four parameters

called quantum numbers.
 The size, shape and special orientation of orbitals are specified by three of these
quantum numbers.

Principal quantum numbers (n) 1s

 Related to energy level (shell)

2s
 Represents the main energy level of electron, size of
the orbitals and distance from nucleus
 Shells designated by K, L, M, N, … (n = 1, 2, 3 …7)

3s
 Azimuthal quantum numbers (l)
 l signifies the subshell and represents
orbital angular quantum
 The values of l are restricted by the
magnitude of n, its values varies l = 0 to l
=n–1
f=3
 Energy of the subshells
 l describe to the shape of orbitals d=2

S=0
P=1

S for sphere P for petal D for double petal F for flower

 Magnetic quantum numbers (ml)
 ml the number of energy states per l ml #
subshell orbitals
 All orbitals within each subshell are s 0 1
identical in energy. p -1, 0, 1 3
 ml = a number - l to +l d -2, -1, 0, 1, 2 5
f -3, -2, -1, 0, 1, 7
 ml describes the orientation of orbital 2, 3
in space
D-ORBITALS
 Spin quantum numbers (ms)

 Describes the spin of the electron in orbital

 There are two type of directions for the spin

 Spin up, ms = +½
 Spin down, ms = -½
 An orbital can hold 2 electrons that spin in
opposite directions.
Example: What is the maximum number of electrons
a) in the 5th main energy level?
b) n = 3, l = 2

a) 2(n2) = 2(52) = 50
b) 2(2l +1) =2(2*2 +1) = 10
Electron Configurations

 Electron configuration is the distribution of electrons of an atom or molecule

in atomic or molecular orbitals
 Electrons are arranged according to a few rules.
 Pauli’s Exclusion Principle
 Aufbau Principle
 Hund’s Rule
Pauli’s Exclusion Principle

 No two electrons in an atom can have the same 4 quantum numbers.

 Each electron has a unique “address”

1. Principal #  energy level

2. Ang. Mom. #  sublevel (s,p,d,f)
3. Magnetic #  orbital
4. Spin #  electron
 Aufbau Principle

 electrons fill the lowest available energy

orbitals before filling the high energy
orbitals

Hund’s Rule
 Orbitals of equal energy are each occupied by single electron before any orbital
is occupied by a second electron (single occupied electrons have same spin).

N (1s2 2s2 2p3)

1s 2s 2p
Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 4s23d 6

4d
4p N-shell n = 4valence
electrons
3d 26 e-
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1 K-shell n = 1
s
Example_1
What is the electron configuration of Fe +2, Fe3+ and S2-?

Solution: Use some principles and rules.

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

Fe2+ (24 e-) 1s22s2 2p6 3s2 3p6 3d 6

S - atomic # = 16 1s2 2s2 2p6 3s2 3p4

S2- (+2e-) 1s22s2 2p6 3s2 3p6

THE PERIODIC TABLE
 All the elements have been classified according to electron configuration in the
periodic table.
 Grouped into 7 horizontal rows and 18 vertical column.
 elements in the same group showed similar chemical and physical properties.
 Electronegativity: the ability of an atom in a bond to pull an electron
 Electronegativity ranges from 0.7 to 4.1
 Large values: tendency to acquire electrons

electropositvity electronegativity

In general , electronegativity increases in moving from left to right and from bottom to top
ATOMIC BONDING IN SOLIDS
Bonding Force and Energy

 Many of the physical properties of materials is predicted on a knowledge of

the interatomic forces that bind the atoms together.
 At large distances, the interactions are negligible, but as the atoms approach,
each exerts forces on the other.
 Attractive force, FA
Both depends on the interatomic distance (r).
 Repulsive force, FR

 The an attractive force depends on the particular type of bonding between the
two atoms.
 Repulsive forces arise from interactions between the negatively charged
electron clouds of the two atoms begin to overlap and are important only at
small values of separation distance, r.
 The net force FN between the two atoms is sum of both attractive and
repulsive components.

 At equilibrium state the net force becomes zero, that is the attraction and
repulsive forces is balanced.

 Sometimes it is more convenient to work with the potential energies

between two atoms instead of forces.
 For atomic system
 As two atoms approach one another,
they at first experience an attraction,
then repel at small values of r

 The net force becomes zero at

equilibrium interatomic radius and
the potential energy will be minimum
at equilibrium spacing

 The bonding energy, Eo, corresponds

to the energy at this minimum point
 represents the energy required to
separate the two atoms to an infinite
separation.
Bonding energy, Curve shape and Bonding types

 Many of the materials properties depend on Eo, curve shape and bonding type.
 Bonding energies related to melting temperatures
 the larger the bonding energy the higher the Tm, vice versa.
 Mechanical stiffness of a material depends on the shape of force versus
interatomic separation.
 the slope relatively stiff material at the r = r 0 position will be quite steep; the
slopes are shallower for more flexible materials.

 Thermal expansion coefficient (l) is related to the shape of its E vs r curve

 The deep and narrow trough correlates with a low coefficient of thermal
expansion
PRIMARY INTERATOMIC BONDS

 Primary bonds – are relatively stronger, and exist in almost all solid materials.
 Ionic, Covalent and Metallic bonds.

 Secondary bonds – are relatively weaker than the primary bonds, however, they
influence the physical properties of some materials.
 The nature of primary bond depends on electron arrangement in respective atoms.

 Atoms tend to acquire stable electron arrangement in their valence orbitals by

transferring (ionic), sharing (covalent and metallic) valence electrons.
 This leads to formation of bonds, bonds invariably involves valence electrons.
Ionic Bonding

 This primary bond exists between two atoms when the transfer of electrons
results in one of the atoms to become negative and another positive ions.
 Metals easily give up their valance electrons to nonmetallic atoms
 Nonmetals gain electrons to achieve the octet rule
 Sodium chloride (NaCl) is the classic ionic material.
 A sodium atom can assume the electron structure of neon by a transfer of one
valence electron in 3s orbital to a chlorine atom.
 The ionic bond is the direct consequence of
columbic force (electrostatic force) between
charged atoms.
 It is a balance between attraction force due
to the ionic charge and repulsion force due
to the nuclear cores of the ions
 For isolated ions the attraction energy

 Similarly, the repulsive energy

Where o is the permittivity of a vacuum o = 8.85x10 -12

F/m), |Z1| and |Z2| the absolute values for valance of the In which A and B are constants
two ions and e is the electronic charge 1.60x10 -19 C depending upon the system. The
value of n is usually taken as 8.
 Properties of Ionic Compounds
 Bonds are nondirectional: magnitude of bond is equal in all directions around the
ion.

 High bonding energies: relatively large (600 - 1500 kJ/mol), reflected in high
melting temperature

 Generally hard and brittle materials most common bonding for ceramics materials

 Electrically and thermally insulative materials

Example_2
The atomic radii of K and Br ions are 0.138 and 0.196 nm, respectively.
a) Calculate the force of attraction between these two ions at their equilibrium interionic
separation
b) What is the force of repulsion at this same separation distance?

Solution  A 
d  1
dE A  r  A A z1e z2e 
a) FA = = = 4 o
dr dr r2
1 e = 1.602 *10-19C
 FA  2
| z1 | e | z 2e | e  ε0 = 8.85 * 10-12 F/m
4r  o

FA 
1
4 o r 2
| z 1 | e | z 2 | e  
1
-12 2
4(8.85x10 F / m)(r )
| Z
1 | 
1.602x10-19
C | Z 2 | 
1.602x10
-19
C 
(2.31x10 -28 N.m 2 )| z1 || z 2 |  ro = rK+ + rBr- = 0.334*10-9 m

r2  |z1| = |+1| = 1 and |z2| |-1| = 1
(2.31x10-28 N.m 2 )(1x1)
FA  9 2
2.07 x10  9 N b) FR - FA - 2.07 x10  9 N
(0.334x10 )
 Covalent Bonding
 Covalent bond is formed when two atoms shared some electrons, each atoms
contributes at least one electron.
 Similar electronegativity
 Shared electrons belong to both atoms
 Most common covalent bonded compounds.
 Nonmetallic elemental molecules: H2, Cl2, F2,etc.
 Molecules containing dissimilar atoms: such as CH4, H2O, HNO3 and HF.
 Elemental solids: diamond, Si and Ge; and other solid compounds GaAs, InSb,
SiC.
H shared electron
shared electrons
from hydrogen from carbon

H C H

H
methane (CH4)
 Properties of Covalent Compounds
 Bonds are directional: that is, it is between specific atoms and may exist only in a
direction between one atom and another that participates in the other sharing.

 The bonds can be either strong or weak, depending upon the atoms involved in
the bond.
 Diamond: extremely strong bond Tm > 3350 C

 Bismuth: weak bond Tm  270 C

 Metallic Bonding
 Metallic bonds are found in metals and their alloy, when atoms shared large
number of electrons.
A relatively simple model:
 metals usually have, at most 3 valence electrons

 the electrons are not bound to any particular

atom in the solid
 these electrons belong to the metal as a whole,
forming a “sea of electrons” or an “electron
cloud”.
 The remaining nonvalance electrons and atomic
nuclei form net positive ion cores, equal in Ion core Sea of valance
magnitude to the total valance charge per atom. electrons

 The delocalized electrons act as a “glue” to hold the ion cores together.
 Properties of Metallic Solids
 Metals are good conductors of both electricity and heat: as consequence of their
free electrons.
 The bonds can be either strong or weak, depending upon the atoms
 Tungsten – strong bond (650 kJ/mol), Tm  3414 C
 Mercury – weak bond (68 kJ/mol), Tm  -39 C

 Nondirectional bonding, the bonds form in any direction  atoms pack closely
 SECONDARY BONDING OR VAN DER WAALS BONDING

 Secondary bonds, van der Waals bonds, are weak in comparison to the primary or
chemical bonds,
 Bonding energies range between 4 – 30 kJ/mol.
 Secondary bonds are possible between atoms or groups of atoms, which
themselves are joined together by primary ( ionic or covalent) bonds.

 It arise from atomic or molecular dipoles.

 An electric dipole exists whenever there is asymmetric electron distribution.

 Dipole interactions occur between induced dipoles, between induced dipoles and
polar molecules and between polar molecules.

 Secondary or van der waals bonds are sometimes called physical (as opposite to
chemical bonding that involves electrons).
Fluctuating induced dipole bonds
 A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric.
 All atoms have constant vibrational motion and it causes electrical symmetry and
create small dipoles.

 This dipole can in turn produce a displacement of the electron cloud of an

adjacent molecule or atom (induced dipole).

 The fluctuating induced dipoles is the weakest forces (inert gases, H 2, Cl2 molecules).
Polar Molecule – induced dipole bonds
 Permanent dipole moments exist in some molecules by virtue of an asymmetrical
electron distributions.
 Polar molecules can also induce dipoles in adjacent nonpolar molecules, and a
bond forms as a result of attractive between the two molecules.
Nonpolar atoms

Permanent dipole bonds

 Permanent dipole moments exist in some

molecules due to the positively charge and
negative regions.
 Hydrogen Bonds

 The strongest secondary bonding types (~50 kJ/mol), a special case of polar
molecule bonding.

 It is found to exist between some polar molecules

that have hydrogen as one of the constituents (such
as in HF, H2O or NH3)

 The hydrogen nucleus is extremely small and positively charged and fluorine,
oxygen and nitrogen being very electronegative.

 Hydrogen bond formed between a positive localized charge of H atoms and

highly negative localized charge on the F, O an N atoms
 Mixed Bonding
 The four bonding types ionic, covalent,
metallic, and van der Waals, formed a
bonding tetrahedron.
 The atomic bonds are a mixture of two
or more of these extremes.

covalent - metallic mixed bonds

 Semi-metals, properties intermediate b/n metals and nonmetals.
 Some elements B, Si, Ge, As, Sb, Te, Po & At

metallic - ionic mixed bonds

 Compounds composed of two metals with large electronegativities difference.
 Common for alloys: Cu3Zn2, TiAl3, AuCu3 , CsAu
covalent - ionic mixed bonds
 For mixed covalent – ionic bonds, there is some ionic character to most covalent
bonds and some covalent character to ionic ones.
 Fractional ionic character (f) increases with difference in electronegativity.
-0.25(XA  XB)2
f =1 e
CaF2 (89%)
SiC (12 %)
SUMMARY ON INTERATOMIC BONDING
Type Bond Energy Comments
Ionic Large Nondirection (ceramics)

Covalent Variables Directional

Large – diamond Semiconductors, ceramics
Small – bismuth polymer chains
metallic Variables Nondirection (metallic)
Large – Tungsten
Small – mercury
Secondary Smallest Inter – chains (polymer)
Inter – molecular
 Question ?

THANK YOU!!
 Concept Check Questions

1. Why are the atomic weights of the elements generally not integers? Cite two
reasons
Answer: The atomic weights of the elements ordinarily are not integers because: (1)
the atomic masses of the atoms normally are not integers (except for 12C), and
(2) the atomic weight is taken as the weighted average of the atomic masses of an
atom's naturally occurring isotopes
1. Give electron configurations for the Fe3+and S2- ions
Answer: The Fe3+ ion is an iron atom that has lost three electrons. Since the
electron configuration of the Fe atom is 1s22s22p63s23p63d64s2 the
configuration for Fe3+ is 1s22s22p63s23p63d5. The S2- ion a sulfur atom that has
gained two electrons. Since the electron configuration of the S atom is
1s22s22p63s23p4, the configuration for S2- is 1s22s22p63s23p6
1. Explain why covalently bonded materials are generally less dense than ionically or
metallically bonded ones.
Answer: Covalently bonded materials are less dense than metallic or ionically
bonded ones because covalent bonds are directional in nature whereas
metallic and ionic are not; when bonds are directional, the atoms cannot pack
together in as dense a manner, yielding a lower mass density.