Lecture 10

Solids and their Properties

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 10 | Semester 2: 2020-2021
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Crystalline vs. Amorphous Solids - Review
Crystalline
Regular 3-D pattern
Particles arranged in an orderly geometric
pattern – we call these crystalline solids
(e.g., salt and diamonds)
Amorphous:
No regular pattern

Particles randomly distributed

without any long-range pattern –
we call these amorphous
solids (e.g., plastic, glass and
charcoal)
Diamond
C (s, diamond)

Charcoal
C (s, amorphous)

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Crystalline Solids

Different geometric arrangements

depend on the crystal type which is
characterized by:

 lattice parameters/constants
(measures of length or angle, that define the size and shape of
the unit cell of a crystal lattice)

Crystal lattice - the (lattice) points

 coordination number form a regular pattern throughout the
crystal
(number of nearest neighbors)
Unit cell - the smallest portion of the
crystal that, if repeated in all three
 type of bonding directions, gives the crystal
We can focus on the unit cell to
study a crystal

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Types of unit cells
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Types of cubic unit cells
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Simple Cubic Body-Centered Cubic Face-Centered Cubic

(BCC) (FCC)

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 Types of cubic unit cells

How many atoms per unit cell?

Simple Cubic
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Types of cubic unit cells
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Simple Cubic Body-Centered Cubic Face-Centered Cubic

1 atom per unit cell (BCC): 2 atoms/unit cell (FCC): 4 atoms/unit cell

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Unit Cells – Coordination Number

The coordination number is the number of nearest

neighbor particles to a single particle in the crystal

Type of cubic unit cell?

• Simple cubic

Coordination number?
• 6

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Unit Cells – Coordination Number
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coordination number = ?
FCC
BCC

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Packing Efficiency

Arrangements for stacking spheres, each one

characterized by a packing efficiency (percentage of total
volume occupied by spheres)

Packing efficiency describes the total volume occupied by

atoms in the unit cell

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Packing Efficiency

For a given atom radius:

the higher the coordination,
the higher the packing efficiency

Cell Type Coordination # Packing Efficiency

Simple cubic 6 52%
Body-centered cubic 8 68%
Face-centered cubic 12 74%
(cubic closest packing)
Hexagonal 12 74%
Calculation: Using atomic radius and the unit cell information.

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Packing Efficiency
Most metallic elements pack in hexagonal closest packing lattice.

Closest packing of first and

second layers

Hexagonal closest
packing (abab ... )
(74%)

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Packing Efficiency

Many ionic compounds are FCC.

Ex: NaCl – two interspersed FCC lattices

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Structures of Simple
The structures Ionicionic
of simple Compounds
compounds

In simple ionic structures

 space is filled as compactly as possible
 ions of one charge are surrounded by as many ions as
possible of the opposite charge
 positive and negative ions touch
 Ionic structures are determined by two principal factors
 the relative sizes of the ions
 the ratio of the numbers of positive and negative
ions in the compound (e.g., Li2O, NaCl, …)

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The structures
Structures of simple
of Simple ionicCompounds
Ionic compounds

In simple ionic structures we usually find the anions, which are

normally larger than the cations, arranged in a simple cubic or a
closest packed array.
 Relatively small cations occupy tetrahedral holes
 Larger cations occupy octahedral holes
 Even larger cations occupy larger cubic holes in a simple
cubic array of anions

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 10 | Semester 2: 2020-2021
15 huynhkimlam.iu@gmail.com / lamhuynh.info
Types of Crystalline solids (bond/lattice point types)

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Crystalline solids

Atomic Crystals

 Lattice points occupied by atoms

 Held together by intermolecular
forces (dispersion)
 Soft, very low melting point
 Poor thermal and electrical
Cubic closest packing of
frozen argon (face- centered
cubic unit cell).
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conductors

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Crystalline solids

Molecular Crystals

 Lattice points occupied by

molecules
 Held together by intermolecular
forces
 Dispersion, dipole-dipole, H
bonds Cubic closest packing of
frozen methane. Only one
 Fairly soft, low to moderate CH4 molecule is shown.
melting point Copyright @ 2007 by The McGraw-Hill Companies, Inc.

 Poor thermal and electrical

conductors

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Crystalline solids

Ionic Crystals

 Lattice points occupied

by cations and anions
 Held together by
electrostatic attraction
 Hard, brittle and high
melting point The sodium chloride structure.
 Good thermal and Copyright @ 2007 by The McGraw-Hill Companies, Inc.

electrical conductors
when molten

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Crystalline solids

Metallic Crystals

 Lattice points occupied

by metal atoms
 Held together by metallic
bonds
 Soft to hard, low to very
high melting point
 Excellent thermal and
electrical conductors,
malleable and ductile
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Crystalline solids
Graphite

Covalent Crystals

 Lattice points occupied

by atoms
 Held together by
covalent bonds Diamond
 Very hard, very high
melting point
 Usually poor thermal and
electrical conductors

Copyright @ 2007 by The McGraw-Hill Companies, Inc.

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 Conductor,
Semiconductor
& Insulator

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 10 | Semester 2: 2020-2021
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Molecular Orbital Band Theory
The band of molecular orbitals in lithium metal

The orbital energies are so

close together that they
form a continuous band.

The valence electrons

enter the lower energy
portion (valence band),
while the higher energy
portion (conduction band)
remains empty.

In lithium (and other

metals), the valence and
conduction bands have no
gap between them.

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Energy Gaps

In Molecular Orbital Band Theory:

The lower energy MOs are occupied by the valence
electrons and make up the valence band.
The empty MOs that are higher in energy make up the
conduction band

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Insulators, Semiconductors, and Metals

Conductors (metals). The valence and conduction bands of a

conductor have no gap between them, so electrons flow when even
a tiny electrical potential difference is applied. When the
temperature is raised, greater random motion of the atoms hinders
electron movement, which decreases the conductivity of a metal.

Semiconductors (metalloids). In a semiconductor, a relatively

small energy gap exists between the valence and conduction
bands. Thermally excited electrons can cross the gap, allowing a
small current to flow. Thus, in contrast to a conductor, the
conductivity of a semiconductor increases when it is heated.

Insulators (nonmetals). In an insulator, the gap between the

bands is too large f or electrons to jump even when the substance
is heated, so no current is observed

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Superconductivity

When metals conduct at ordinary temperatures, electron

flow is restricted by collisions with atoms vibrating in
their lattice sites. Such restricted flow appears as
resistive heating and represents a loss of energy.

To conduct with no energy loss-to superconduct requires

extreme cooling to minimize atom movement. This
remarkable phenomenon had been observed in metals
only by cooling them to near absolute zero, which can be
done only with liquid helium (bp = 4 K; price = $11/L).

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Conductivity
Improving Improvement
Semiconductors
Conduction by Doping
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To make semiconductors better

conductors, add impurities (dopants) to
contribute extra electrons (negative
charge) or extra holes (positive charge).

For Si (group 4A):

– elements with 5 valence electrons contribute an extra electron
to the lattice (donor dopant)
– elements with 3 valence electrons accept an electron from the
silicon (acceptor dopant)

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Conductivity Improvement
Semiconductors

Si
[Ne]3s23p2

n-type semiconductor p-type semiconductor

donor impurities acceptor impurities
P B
[Ne]3s23p3 [Ne]3s23p1
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End of lecture 10

Thank you!

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London Dispersion
FactorsForces
Affecting London Forces

Huynh Kim Lam Chemistry for Engineers (CH011IU) - Lecture 15 - Spring 2011
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London Dispersion Forces (need revision)

Which hydrocarbon among these straight-chain alkanes has the

highest boiling point?

CH3CH2CH2CH3 CH4 CH3CH2CH2CH2CH2CH3

Lowest Highest

If hydrocarbons have the same molecular weight, the molecule with the least branching
will possess the highest boiling point.

Consider isomers of C6H14

Boiling Point 60oC 69oC 58oC

Huynh Kim Lam Chemistry for Engineers (CH011IU) - Lecture 15 - Spring 2011
31 huynhkimlam.iu@gmail.com