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Engineering Materials
Atomic structure and interatomic bounding
Dr. Aneela Wakeel (Lec-2)
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Importance of atomic structure

Valence electrons determine all of the following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
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Fundamentals of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons
Charges:
Electrons (-): protons(+) 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.

Masses:
Protons and Neutrons ~1.67 × 10-27 kg.
Electron 9.11 × 10-31 kg
Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons

chemical identification of element

Isotope number  # neutrons

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Atomic mass units. Atomic weight.
Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).
The atomic mass of 12C atom is 12 amu.

Atomic weight: A
Weighted average of atomic masses of naturally occurring isotopes.
Atomic weight of carbon is 12.011 amu.

Atomic weight is often in mass per mole.

A mole
Amount of matter with mass in grams equal to the atomic mass in amu
(A mole of carbon has a mass of 12 grams).

One Mole contains Avogadro’s number of atoms,

Nav = 6.023 × 1023.

Nav = 1 gram/1 amu.

Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
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Some simple calculations
Number density, n: (number of atoms per cm3)
Mass density, ρ (g/cm3)
Atomic mass, A (g/mol):
n = Nav × ρ / A

Graphite (carbon): ρ = 2.3 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 2.3 g/cm3 / 12 g/mol
= 1.15 × 1023 atoms/cm3

Diamond (carbon): ρ = 3.5 g/cm3, A = 12 g/mol

n = 6×1023 atoms/mol × 3.5 g/cm3 / 12 g/mol
= 1.75 × 1023 atoms/cm3

Water (H2O) ρ = 1 g/cm3, A = 18 g/mol

n = 6×1023 molecules/mol × 1 g/cm3 / 18 g/mol
= 3.3 × 1022 molecules/cm3

SIZE of a Atom or Molecule

If n = 6 × 1022 atoms/cm3
Mean separation between atoms L = (1/n)1/3 = 0.25 nm.
 scale of atomic structure in solids – a fraction of 1 nm
or a few Angstroms
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How many number of atoms per cm3 in

2.5gram/cm3 of iron.
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Electrons in Atoms (I)- Bohr atomic model

• electrons are assumed to revolve

around the atomic nucleus in discrete
orbitals
• the position of any particular electron
is more or less well defined in terms of
its orbital

• The energies of electrons are quantized;

that is, electrons are permitted to have
only specific values of energy.
• An electron may change energy, but in
doing so it must make a quantum jump
either to an allowed higher energy (with
absorption of energy) or to a lower
energy (with emission of energy)
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Wave mechanical model

Figure 2.3 Comparison of
the (a) Bohr and (b) wave mechanical
atom models
A wave-mechanical model, in in terms of electron
distribution. (Adapted from
which the electron is considered to Z. D. Jastrzebski,The
Nature and Properties of
exhibit both wave-like and Engineering Materials,3rd
particle-like characteristics. With edition, p. 4.

this
model, an electron is no longer
treated as a particle moving in a
discrete orbital; rather, position is
considered to be the probability of
an electron’s being at various
locations around the nucleus. In
other words, position is described
by a probability distribution or
electron cloud.
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Quantum numbers
Using 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 are
specified by three of these quantum numbers.
(n) Shells are specified by a principal
quantum number n, which may take on (l) The second quantum number, signifies the
integral values beginning with unity; subshell, which is denoted by a
sometimes these shells are designated by lowercase letter—an s, p, d,or f; it is related to
the letters K, L, M, N, O, and so on. This the shape of the electron subshell.
quantum number is related to the distance
of an electron from the nucleus, or its
position.

(ml) The number of energy states for each a spin moment, which must be oriented either
subshell is determined by the third quantum up or down. Related to this spin moment is the
number, For an s subshell, there is a single fourth quantum number ms, for
energy state, whereas for p, d, and f subshells, which two values are possible ( +1/2 and -1/2 ),
three, five, and seven states exist, respectively one for each of the spin orientations.
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Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
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Electronic configuration
• Most elements: Electron configuration not stable.
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 Adapted from Table 2.2,
Callister & Rethwisch 8e.
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)

• Why? Valence (outer) shell usually not filled completely.

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Electron Configurations
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons are most available for
bonding and tend to control the chemical
properties

• example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons
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Electronic Configurations
ex: Fe - atomic # = 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
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
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Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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The Periodic Table

inert gases
give up 1e-
• Columns: Similar Valence Structure
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
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.
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Atomic bonding in solids

 =+ (net force which is function of

interatomic separation)

 +=0 (state of equilibrium)

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Force-potential
r
energy relationship for two atoms
0

Repulsive energy ER
 
𝐸=∫ 𝐹𝑑 𝑟
Interatomic separation r

Net energy EN

A B
EN = EA + ER = - +
r rn
Attractive energy EA

Stable at minimum energy E0 for radius r0.

Force = dE/dr = 0 at r0
r0
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Bonding Forces and Energies

Example: Calculate the force of attraction between a K+
and an O2- ion the centers of which are separated by a
distance of r0 =1.5 nm.
Solution
The attractive force between two ions FA is just the derivative with respect to
the interatomic separation of the attractive energy expression, Equation 2.8,
which is just

 A   The constant A=(). Since the valences of the

d 
dEA  r  A K+ and
FA = = = O2- ions
dr dr r2
(Z1 and Z2) are +1 and -2, respectively,
Z1 = 1 and Z2 = 2, then


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(Z1e) (Z 2 e)
FA =
40r 2

(1)(2)(1.602  1019 C) 2
=
(4)() (8.85  1012 F/m) (1.5  109 m) 2

=2.05  10^(-10 ) N
 Calculatethe force of attraction between a and on ion
the centers of which are separated by a distance of
1.25nm.
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The electron volt (eV)

Energy unit convenient for atomic bonding

Electron volt –
energy lost / gained when an electron is taken through a potential
difference of one volt.
E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt

1 eV = 1.6 x 10-19 J
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Types of Bonding
Primary Bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)

Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

Covalent: electrons shared between the atoms.

Example - H2

Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material

Secondary Bonding: no e- transferred or shared

Interaction of atomic/molecular dipoles
Weak (< 100 KJ/mol or < 1 eV/atom)

 Fluctuating Induced Dipole (inert gases, H2, Cl2…)

 Permanent dipoles (polar molecules - H2O, HCl...)

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Ionic Bonding (I)
Mutual ionization by electron transfer
(remember electronegativity table)
• Anion = negatively charged atom
• Cation = positively charged atom
Ions are attracted by strong coulombic interaction
• Oppositely charged atoms attract
• An ionic bond is non-directional
Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer shell (Neon)

11 Protons Na 1S2 2S2 2P6 3S1 donates e-

11 Protons Na 1S 2S 2P
+ 2 2 6 10 e -
left
Cl has 17 electron, 1 less than needed for a full outer shell (Argon)

17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e-

17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-
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Typical ionic bond: metal + nonmetal

accepts donates
electrons electrons
• The greater the difference in electronegativity, the greater the tendency to
form an ionic bond.
• Consider magnesium and oxygen with electronegativities of 1.31 and 3.44.
• Here’s what happens when Mg and O come near one another:

 Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

(Ne + 3s2)  (Ne – 2p2)

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

(Ne) (Ne)
cation anion electron(s)

+ -
Coulombic
Attraction
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Examples: Ionic Bonding

• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 4e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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Ionic bonding in a crystal

• In a crystal, a cation (+ charge) is attracted not only by the nearest

anions, but to a lesser extent by those farther away.
• Similarly, it is repelled by all other cations.
• The sum of the energy due to all attractions and repulsions is known
as the Madelung energy. This is approximately 60% greater than the
energy of attraction for isolated ions the same distance apart as in the
lattice.
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Covalent Chemical Bonds

• Atoms with almost the same electronegativity share electrons
leading to hybrid electronic structures.
• The bonds are very directional, unlike ionic bonds.
• Example:
shared electrons
H from carbon atom
CH 4

H C H

shared electrons
H from hydrogen
atoms

 Methane orbitals
• Hybrid orbitals
 Covalent orbitals
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Mixed Ionic-Covalent Bonding

• Ionic-Covalent Mixed Bonding  
( X A  X B )2 
• Approximate fraction ionic character  1  e 4 
   
where XA & XB

are the two Pauling electronegativities.


Example: MgO. Using the 1960 values in the text,

XMg = 1.2 and XO = 3.5,
the equation above predicts that the bond between Mg and O has
about 73% ionic character and 27% covalent.
Using the revised values given on Wikipedia,
XMg = 1.31 and XO = 3.44,
the equation above predicts that the bond between Mg and O has
about 68% ionic character and 32% covalent.
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Metallic bonding
• Occurs with atoms that easily give up electrons.
• In a solid, these “conduction” electrons form a cloud or sea.
• No two electrons can have exactly the same quantum number, and so
they have a range of energies. Each “exists” throughout the solid.
• The attraction between the positively charged metal ions and the
electron cloud is what causes metallic bonding.
• Non directional.
• These “conduction” electrons
carry electric current and heat.
• Mixtures of metals sometimes
form intermetallic compounds.
• Animation (in full-screen
projection mode):

Another animation: http://mypchem.com/myp9/myp9c/myp9c_swf/metal_vib.htm

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Secondary Bonding (I)

Secondary = physical bond
(as opposite to chemical bond that involves e- transfer) Interaction of dipoles
Is weak, ~0.1 eV/atom or ~10 kJ/mol.

+ _ + _
-two dipoles attract
Permanent dipoles exist in some molecules
polar molecules: e.g. HCl, H2O
Due to asymmetry of positive and negative regions Strongest among secondary bonds.

Polar molecule induces a dipole in adjacent non-polar molecule.

Attraction between the permanent and induced dipoles.

Fluctuations of electron density distribution in one atom A is felt by the electrons of an

adjacent atom:
Mutual dipoles induced (van der Waals)
This bond is the weakest (He-Ne, H2 - H2).
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Secondary Bonding (II)

Example: hydrogen bond in water. The H end of the molecule is

positively charged and can bond to the negative side of another
H2O molecule (the O side of the H2O dipole)

H H

-
+ +
Dipole

“Hydrogen bond” – secondary bond formed between two

permanent dipoles in adjacent water molecules.
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Secondary Bonding (III)

Hydrogen bonding in liquid water

from a molecular-level simulation

Molecules: Primary bonds inside, secondary bonds among each other

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Secondary (van der Waals) bonds

Arises from interaction between electric dipoles

• Dipoles fluctuating rapidly and interacting

asymmetric electron e.g. liquid H2
clouds H2 H2

+ - + - H H H H

• Permanent dipoles
-general case: + - + -

-ex: liquid HCl H Cl H Cl

-ex: polymer second

a ry b on Within an organic molecule the bonding is
ding
mostly covalent, while between molecules
the bonding is mostly van der Waals.
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Hydrogen bonds
• Between hydrogen atoms and the nearby negative end of a molecular dipole, to
strongly electronegative atoms such as O or N.
• Partly covalent and partly electrostatic.
• Much stronger than van der Waals bonds.
• Determines the unusual properties of water liquid and solid.
• Also occurs with other molecules, and even between parts of complex molecules
such as proteins.
• http://en.wikipedia.org/wiki/Hydrogen_bond
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Table 2.3.
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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
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Properties From Bonding: Melting point

Interaction energy E Melting Temperature, Tm

versus atomic separation r Energy
Energy

unstretched bond length ro

ro r
r
Eo smaller Tm
“bond energy”
larger Tm
Atomic separation r
Tm is larger when Eo is larger

r
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Properties From Bonding: Thermal expansion

Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
DL DL
= a (T2 -T1)
heated, T2 Lo

Energy

ro
r a is larger when Eo is smaller

Eo larger a
Eo smaller a
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Boundary-property summary
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
second
a r y b on
di n g
small E
large a
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Home work
 
Atomic Structure and Bonding
 
Q 1: For a K+−Cl− ion pair, attractive and repulsive energies EA and ER,
respectively, depend on the distance between the ions r, according to
 
EA =
 
ER =
 
For these expressions, energies are expressed in electron volts per K+−Cl− pair,
and r is the distance in nanometers. The net energy EN is just the sum of the two
expressions above.
(a) Superimpose on a single plot EN, ER, and EA versus r up to 1.2 nm.
(b) On the basis of this plot, determine
(i) the equilibrium spacing r0 between the K+ and Cl−ions, (0.28nm)
(ii) the magnitude of the bonding energy E0 between the two ions. (-4.6eV)
(c) Mathematically determine the r0 and E0 values using the solutions to Problem
2.14 and compare these with the graphical results from part (b).
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Home work

Atomic structure and bonding

Q 2: Make a plot of bonding energy versus melting temperature for the

metals listed in Table 2.3. Using this plot, approximate the bonding energy
for copper, which has a melting temperature of 1084°C. (3.6eV)
Q 3: The atomic radii of K+ and Br- ions are 0.138 and 0.196nm,
respectively; calculate the force of attraction between these two ions at their
equilibrium interionic separation. What is the force of repulsion at the same
separation distance? (2.07e-9N, -2.07e-9N)
Q 4: Compute the percent ionic character of the interatomic bonds for the
following compounds:
TiO2, ZnTe, CsCl, InSb, and MgCl2. (63.2%, 6.1%, 73.4%, 1%, 55.5%)
Q 5: Calculate the force of attraction between a K= and O2- ion whose
centers are separated by a distance of 1.6nm. (1.8e-10N)