Solid-State Chemistry

Copyright © 2011 Northeastern University Department of Chemistry & Chemical Biology

Crystal Chemistry
Crystalline materials are so
called because they…
Possess a well-defined shape
Contain far-reaching atomic order at
the particle level
The NaCl lattice is shown to the
right

Amorphous (Greek: amorphos:

“without form”) materials
Have poorly defined shapes
Lack long-range particulate ordering
throughout the sample
Amorphous silica, SiO2 is shown at
right
Classifying Crystalline Solids
• Atomic Solids:
– Noble Gases are the only examples
– Atoms held together by weak London-
Dispersion Forces
– Physical Properties
• Low melting point
• Low boiling poiont
• Low heat of vaporization
Classifying Crystalline Solids

• Metallic Solids
– Metallic bonding present where each metal
cation lies in a “sea” of mobile electrons
– Physical Properties
• High electrical conductivity
• High thermal conductivity
• Luster
• Malleability
• Varying melting points
• Varying hardness
Classifying Crystalline Solids

• Molecular Solids
– Individual molecules occupy lattice points
– Various intermolecular forces present
• Dispersion
• Dipole-Dipole
• H-bonding
– Low melting points
– Wide range in physical properties due to
different possible intermolecular forces
Classifying Crystalline Solids

• Ionic Solids
– Oppositely charged particles electrostatically attracted
– The whole (not partial) charges impart very strong
interparticulate forces
– The unit cell has the same anion-cation ratio as the
empirical formula
– Many ionic crystals display CCP
– These properties impart very high melting and boiling
points
– Electrical conductivity is low in solid state but high in
the liquid state (mobile ions needed)
Classifying Crystalline Solids

• Network-Covalent Solids
– Strong covalent bonds hold atoms together
– Extremely high melting and boiling points
– Conductivity and hardness depends on
bonding arrangement
– Good Examples:
• Diamond
• Graphite
Amorphous Solids

• Contain small ordered regions connected

by large disordered regions
• Examples:
– Charcoal
– Rubber
– Glass
Crystal Lattices & Unit Cells

• A lattice is a regular,
repeating pattern of
points (particles) with
identical surroundings

• A unit cell is the

smallest portion of the
crystal which, if repeated
in all three directions,
yields the crystal
Crystal Lattices & Unit Cells
• If we look at any single point in a lattice, we
note there are several equidistant neighboring
points

CN = 8 for this
body-centered
cubic unit cell

• The number of nearest neighbors surrounding

a point on the crystal is called a coordination
number (CN)
Crystal Lattices & Unit Cells
• While there are a total of 7 crystal systems
and 14 unit cells, we shall devote our
attention to the cubic system
• There are three types of cubic systems we
will study:
– Simple-cubic system
– Body-centered cubic system
– Face-centered cubic system
The Simple-Cubic (SC) System
• Centers of eight identical particles 1/8 atom
define corners of the cube located
at each
• Particles touch along the cube’s corner
edges
• No diagonal contact occurs
• Each particle has CN = 6
– Four in its own layer
– One in above layer
– One in below layer
• One SC unit cell contains 1 atom

 8 _ corners  1 / 8 _ atom 
   1 _ atom / SC _ unit _ cell
 1 _ SC _ unit _ cell  1 _ corner 
The Body-Centered Cubic System
• Identical particles exist… 1 atom 1/8 atom
– At each cube corner located located
– In cube center at center at each
• Atoms at corners do not touch corner

• Corner atoms _do_ touch the atom in

the center
• Each particle has 8 neighbors. . .
– Four above
– Four below
• Each particle has CN=8
• One BCC unit cell contains 2 atoms…
 8 _ corners   1 / 8 _ atom 
1 _ atom      2 _ atom / BCC _ unit _ cell
 1 _ BCC _ unit _ cell  1 _ corner 
The Face-Centered Cubic System
1/8 atom
• Identical particles lie at located
– Each corner ½ atom
Per face at each
– Each cube face corner
• No particles are present in the center of
the cube
• Corner atoms touch atoms in the centers
• Corner atoms do not touch one another
• Each particle has CN=12
• One FCC atom has 4 atoms

 6 _ faces   1 / 2 _ atom   8 _ corners   1 / 8 _ atom 

         4 _ atom / FCC _ unit _ cell
 1 _ FCC _ unit _ cell   1 _ face   1 _ FCC _ unit _ cell   1 _ corner 
How Layering Affects Cell Type

• In A, we see a layer of spheres lying next to one

another
• If spheres are directly above, we have an SC
arrangement (B)
• If spheres lie over the holes, we have a BCC
arrangement (C )
Dimensions of an SC Unit Cell
• X-Ray Diffraction (XRD) studies facilitate our
understanding of unit-cell measurements
• In an SC unit cell, each edge has a
measurement of two atomic (ionic) radii
• Hence, the measurement of one edge is 2r
Dimensions of a BCC Unit Cell
• In a BCC unit cell, spaces lie
between the edges of atoms on
each corner
• Because the unit cell is still a
cube, sides A and B must be
equal
• Using the Pythagorean
Theorem, the length of the
diagonal, C can be found by
adding the squares of A and B:
C2 = A2 + B2
• And because A and B are equal
in length: C2 = A2 + A2 or C=2A2
Dimensions of a BCC Unit Cell
• You will note the hypotenuse D inscribed in the last
diagram cuts clear across the center of the cube
(and consists of 4 total radii)

D
A

• This gives D2 = C2 + A2 (Note: C2 = 2A2)

• So D2 = 3A2
• This means D = √3A
4r
• Because D = 4r, A 
3
Dimensions of an FCC Unit Cell
• In an FCC unit cell, you will note that A
and B are, again equal
• Notice, in this case, that C is comprised of
the diameter of one atom and the radii of
two others…
Dimensions of an FCC Unit Cell
• While the length of C can be calculated, we
are still without a way to calculate the length of
edge, A!
• Let’s remember that corner atoms in an FCC
cell _do_ touch the atom on the face

C
B

A
• Notice this diagonal, D, has a length of 4r
Dimensions of an FCC Unit Cell
• Because C is 4r, and A and B are the same length..
C2 = 2A2
• IF C = 4r, then (4r)2 = 2A2
• This gives 16r2 = 2A2 or A  8r
Helpful Formulae for Unit-Cell Calculations
Atomic Packing Efficiency
• Packing Efficiency is the percent of the total unit cell volume
occupied by particles, themselves
• Here are the packing efficiencies of the unit cell types
discussed
– Simple Cubic
• 52% Matter
• 48% Empty
– Body-Centered Cubic
• 68% Matter
• 32% Empty
– Hexagonal & Face-Centered Cubic: Even More Efficient
– More on this Next!
Hexagonal Closest Packing
• Alternating layers of atoms ababa
• After each a layer, the b layer lies over the
diamond-shaped holes
• The following a layer places the spheres directly
over the spheres in the first a layer
• Packing efficiency is 74%
Cubic Closest Packing
• Three pairs of atoms in an abcabc arrangement
• Each third layer has atoms covering all open white
spaces
• Consistent with the FCC unit cell
• Packing efficiency is also 74%
Hexagonal & Cubic Closest Packing
Cover tetrahedral holes Cover octahedral holes
“Holes” in the Structure
• The packing arrangements
shown earlier impart
various types of holes in
the crystal structure
– Trigonal holes
• Formed by three atoms
intersecting
– Tetrahedral holes
• Formed by one atom topping a
trigonal hole
– Octahedral holes
• Formed by two oppositely
oriented trigonal holes atop
one another
“Holes” in the Structure
• The diagrams display how these holes originate
“Holes in the Structure”
• Notice how which holes are covered gives rise to the
packing arrangements described earlier!
Density Calculation Based on Unit Cell
•Density is a measurement of the amount of
matter per unit volume
•We can, thus, calculate the density of a
substance based on its unit cell

Example: Tungsten is a body-centered

cubic lattice with a metallic radius of 139 pm.
What is its density?
Density Calculation Based on Unit Cell

Answer:

Recall this volume formula for a BCC lattice:

64 3
ratom 3

9
Thus, we can calculate the volume:
 1m   100cm  8

r 139 pm 12

   1.39 x10 cm
 1x10 pm   1m 
64 3
V 
9

1.39 x10  8 cm 3.31x10  23 cm 3
3
Density Calculation Based on Unit Cell

Answer (Cont’d):
• It is further known that a BCC unit cell
contains 2 atoms total.
• We can convert atoms of tungsten to grams

 2 _ atoms _ W   1 _ mol _ W   183.84 g _ W 

   23
   6.11x10  22 g _ W
 1 _ unit _ cell   6.022 x10 atoms _ W   1 _ mol _ W 
m 6.11x10  22 g _ W 3
d   18. 5 g / cm
V 3.31x10  23 cm 3

• Actual value = 19.25 g/cm3.

Empirical-Formula Calculation
• Recall a unit cell has the same number of
each atom as that found in the empirical
formula:

• Example: A cubic unit call has Ca at each

corner, O at the center of each face, and
Ti at its body center. What is the empirical
formula for the mineral?
Empirical-Formula Calculation
Answer:
Ceramics

• Ceramics are nonmetallic, nonpolymeric solids hardened by

heating to high temperatures
• Clay ceramics consist of silicate microcrystals fired at
1500oC
Si2Al2O5(OH)4(s)  Si2Al2O7(s) + 2 H2O(g)

• Bricks, porcelain, glazes, and other clay ceramics are useful

due to hardness and resistance to heat and chemicals
• Today’s high-tech ceramics incorporate excellent electronic
and magnetic properties
• Current research seeks to overcome the inherent brittleness
of ceramics
Liquid Crystals
• Liquids are materials which flow like
liquids but pack with a crystalline-like order
at the molecular level
• These materials are found in …
– Digital watches
– Calculators
– Computers
– Cell membranes
Liquid Crystals
• Note how molecules
which form liquid
crystals…
– Have rod-like shapes
– Presence of certain
groups
– Many have a
molecular dipole
Types of Liquid Crystals

• Nematic: molecules lie in same direction but ends

are not aligned
• Cholesteric: more ordered where molecules in
each layer are rotated by a fixed angle with respect
to the next layer
• Smectic: molecules are mostly ordered, parallel to
one another, and stacked over each other
Amorphous Solids

• Amorphous solids are characterized by

somewhat ordered regions connected by
large, disordered regions
• Examples include:
– Charcoal
– Rubber
– Glass
• Quartz, noted for its ccp structure can be
melted and then cooled rapidly to prevent
recrystallization
Amorphous Solids

• The result is a glass

• Glass is, in fact, often called a supercooled
liquid

The molecular structure of quartz

Summary
• Crystalline substances possess a highly ordered array of
atoms
• Different types of crystalline substances exist (atomic,
molecular, metallic, ionic, network-covalent)
• Amorphous substances have small areas of order with
larger areas of reduced order
• Three main unit cells were discussed
• The packing efficiency of each unit cell is determined by
the placement of atoms with respect to each hole type
• Both density and empirical formula can be determined by
a unit cell
• Ceramic and liquid crystals are unique crystalline
substances with specific applications