CRYSTAL

STRUCTURES
 CRYSTAL STRUCTURES
•LEARNING OUTCOMES
At the end of the discussion, the students
should be able to:

 understand the nature of crystals and ways of packing

spheres to form different unit cells;
 explain the structures, types, and properties of crystals;
and
 understand how to determine the dimensions of a crystal
structure using X-ray diffraction.

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 CRYSTAL STRUCTURES
• Crystallization
the process in which dissolved solute comes out of solution
and forms crystals
• Two categories of solids
1. crystalline
2. amorphous

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 CRYSTAL STRUCTURES cont.
• Crystalline solids
– have well defined shapes because their
particles—atoms, molecules, or ions—occur
in an orderly arrangement
– consist of particles tightly packed into
a regular array called a lattice

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 CRYSTAL STRUCTURES cont.
• Lattice
the three-dimensional arrangement of points created by
choosing each point to be at the same location within each
particle of a crystal; thus, the lattice consists of all points
with identical surroundings

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 CRYSTAL STRUCTURES cont.
• A Portion of 3-D lattice

• 2-D analogy for unit cell and lattice

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 CRYSTAL STRUCTURES cont.
• Beauty of Crystalline Solids
Wulfenite Beryl (emerald) Quartz (amethyst)

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 CRYSTAL STRUCTURES cont.
• Amorphous solids (without form)
– have poorly defined shapes because their
particles lack an orderly arrangement
throughout the sample
• Examples
– rubber, glass, obsidian (volcanic glass) – lack a regular
three-dimensional arrangement of atoms

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 CRYSTAL STRUCTURES cont.
• Unit cell
the basic repeating structural unit of a crystalline solid

• Extension in three dimensions

• Note: Black sphere (also called a lattice point)
represents an atom, ion or molecule.

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 CRYSTAL STRUCTURES cont.
• Many substances crystallize in one of three cubic unit
cells. These differ in the arrangement of the particles
and, therefore, in the number of particles per unit cell
and how efficiently they are packed.

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 CRYSTAL STRUCTURES cont.
• Seven types of unit cells
Angle is defined by edges b and c, angle by edges a
and c, and angle by edges a and b.

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 CRYSTAL STRUCTURES cont.
• Seven types of unit cells cont.

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 CRYSTAL STRUCTURES cont.
• Three types of cubic unit cells
1. Simple cubic cell (scc)
 a unit cell in which a particle occupies each corner
of a cube
 the basic, repeating unit in the array of spheres
 The particles touch along the cube edges but they do not
touch diagonally along the cube faces or through its center.

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 CRYSTAL STRUCTURES cont.
• An expanded portion of the crystal shows that the coordination
number of each particle is 6: four in its own layer, one in the layer
above, and one in the layer below.

• A simple cubic unit cell

contains 8 x 1/8 particle
= 1 particle

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 CRYSTAL STRUCTURES cont.
• Coordination number
the number of atoms (or ions) surrounding an atom (or ion) in a
crystal lattice
• Its value gives a measure of how tightly the spheres are packed
together—the larger the coordination number, the closer the spheres
are to each other.

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 CRYSTAL STRUCTURES cont.
2. Body-centered cubic (bcc) cell
• Identical particles lie at each corner and in the
center of the cube.
• Those at the corners do not touch each other, but they
all touch the one in the center.
• Each particle is surrounded by eight nearest neighbors,
four above and four below
Coordination number: 8

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 CRYSTAL STRUCTURES cont.
• A body-centered cubic unit cell contains 8 x 1/8 particle
= 1 particle plus 1 particle in the center
Total = 2 particles

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 CRYSTAL STRUCTURES cont.
3. Face-centered cubic (fcc) cell
• Identical particles lie at each corner and in the center of each face but
not in the center of the cube.
• Particles at the corners touch those in the faces but not each other.

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 CRYSTAL STRUCTURES cont.
• A face-centered cubic unit cell contains 8 x 1/8 particle
= 1 particle plus one-half particle in each of the six faces
= 6 x ½ particle
= 3 particles
Total = 1 + 3 = 4 particles

Coordination Number: 12

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 CRYSTAL STRUCTURES cont.
• Packing Efficiency and the Creation of Unit Cells
Unit cells result from the ways atoms pack together, which are
similar to the ways that macroscopic spheres—marbles, golf
balls, fruit—are packed.

The efficient packing of fruit

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 CRYSTAL STRUCTURES cont.
• Packing efficiency
the percentage of the volume of the unit cell occupied by the
spheres

Higher coordination number Greater packing efficiency

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 CRYSTAL STRUCTURES cont.
• Simple cubic unit cell
• In the first layer, each sphere lies next to another
horizontally and vertically; note the large diamond-
shaped spaces.
• Cutaway portion

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 CRYSTAL STRUCTURES cont.
• Simple cubic unit cell cont.
• If the spheres in the next layer lie directly over those in the first, the
packing is based on the simple cubic unit cell (pale orange cube, lower
right corner).
• The spheres occupy only 52% of the unit-cell volume.
• 48% is empty space between them.
• This is a very inefficient way to pack spheres,
so neither fruit nor atoms are typically packed
this way.

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 CRYSTAL STRUCTURES cont.
• Body-centered cubic unit cell
• The second layer (colored green for clarity) is placed on the diamond-shaped
spaces in the first layer.
• The third layer is packed onto the diamond-shaped
spaces in the second, which makes the first and third
layers line up vertically.
Packing efficiency is 68%
• Several metallic elements, including chromium and iron, have a crystal
structure based on this unit cell.

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 CRYSTAL STRUCTURES cont.
• Hexagonal and face-centered cubic unit cells
• Spheres are packed most efficiently in these cells. First, in
the bottom layer (labeled a, orange), every other row is
shifted laterally so that the large diamond-shaped spaces
become smaller triangular spaces. Then the second layer
(labeled b, green) is placed over these spaces.

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 CRYSTAL STRUCTURES cont.
• In layer b, some spaces are orange because they lie above
spheres in layer a, whereas other spaces are white because
they lie above spaces in layer a. The third layer can be
placed in either of two ways, which gives rise to two
different unit cells:
Hexagonal unit cell (packing efficiency – 74%
Face-centered unit cell (packing efficiency – 74%

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 CRYSTAL STRUCTURES cont.
• Four ways of packing identical spheres in cubic system
Note: Face-centered cubic (fcc) is equivalent to cubic closest packed (ccp)

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 CRYSTAL STRUCTURES cont.
• Five Types of Crystalline Solids
Atomic Solids
• Individual atoms held together only by dispersion forces
• Noble gases [Group 8A (18)] are the only substances that form such
solids. The very weak forces among the atoms mean melting and boiling
points and heats of vaporization and fusion are all very low.

Cubic closest packing of frozen argon (face-centered cubic unit

cell)

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 CRYSTAL STRUCTURES cont.
Molecular Solids
• Individual molecules occupy the lattice points.
• Various combinations of dipole-dipole, dispersion, and H-bonding forces account for a
wide range of physical properties.
• Most molecular solids have much higher melting points than atomic solids (noble gases)
but much lower melting points than other types of solids.
• Methane crystallizes with a face-centered cubic unit cell, and the center
of each carbon is the lattice point.
Cubic closest packing (face-centered unit cell) of frozen CH4

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 CRYSTAL STRUCTURES cont.
Ionic Solids
• The unit cell contains particles with whole, rather than partial, charges
• The interparticle forces (ionic bonds) are much stronger than the van der
Waals forces in atomic or molecular solids.
• Ionic compounds adopt several different crystal structures, but many use
cubic closest packing.

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 CRYSTAL STRUCTURES cont.
• Metallic Solids
• Most metallic elements crystallize in one of the two closest packed structures.
• Powerful metallic bonding forces hold atoms together.
• The properties of metals—high electrical and thermal conductivity, luster, and
malleability—result from their delocalized electrons.
• Crystal structures of metals
A: Copper adopts cubic closest packing.
B: Magnesium adopts hexagonal closest packing

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 CRYSTAL STRUCTURES cont.
• Network Covalent Solids
• Strong covalent bonds link the atoms; separate particles are not present.
• These substances adopt a variety of crystal structures depending on the details of
their bonding.
• All network covalent solids have extremely high melting and boiling points, but their
conductivity and hardness vary.
• Two examples with the same composition but strikingly different
properties are the two common crystalline forms of elemental carbon,
graphite and diamond.

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 CRYSTAL STRUCTURES cont.
• Properties of Diamond and Graphite

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 CRYSTAL STRUCTURES cont.
• Properties of Crystalline Solids
Nonpolar molecular solids are arranged in order of increasing molar mass.

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 CRYSTAL STRUCTURES cont.
• X-Ray Diffraction by Crystals
• X-ray diffraction
refers to the scattering of X rays by the units of a crystalline solid
• The scattering, or diffraction, patterns produced are used to
deduce the arrangement of particles in the solid lattice.

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 CRYSTAL STRUCTURES cont.
• Typical X-ray diffraction setup

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 CRYSTAL STRUCTURES cont.
• Consider the scattering of X rays by atoms in two parallel planes
 Initially, the two incident rays are in phase with each other (their maxima
and minima occur at the same positions). The upper wave is scattered, or
reflected, by an atom in the first layer, while the lower wave is scattered by
an atom in the second layer. In order for these two scattered waves to be in
phase again, the extra distance traveled by the lower wave must be an
integral multiple of the wavelength (λ) of the X ray.

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 CRYSTAL STRUCTURES cont.
• BC + CD = 2d sin = n n = 1, 2, 3, . . .
or
2d sin = n Bragg equation
where = angle between the X rays and the plane of the crystal
d = distance between adjacent planes
• The reinforced waves produce a dark spot on a photographic film
for each value of that satisfies the Bragg equation.

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 CRYSTAL STRUCTURES cont.
• Reflection of X rays from two layers of atoms

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 CRYSTAL STRUCTURES cont.
• Problem
Copper adopts cubic closest packing, and the edge
length of the unit cell is 361.5 pm. What is the atomic
radius of copper?

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 CRYSTAL STRUCTURES cont.
• Solution
Using Pythagorean theorem
C=
• Since the unit is a cube, A = B
C=
• To solve for r, C = 4r r=

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 CRYSTAL STRUCTURES cont.
• Edge length and atomic (ionic) radius in the three cubic
unit cells

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 CRYSTAL STRUCTURES cont.
• Problem
X rays of wavelength 0.154 nm strike an aluminum crystal;
the rays are reflected at an angle of 19.3. Assuming that n = 1,
calculate the spacing between the planes of aluminum atoms
(in pm) that is responsible for this angle of reflection.
Conversion factor: 1 nm = 1000 pm.

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 CRYSTAL STRUCTURES cont.
• Solution
d= ; n=1
=
d = 233 pm

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 CRYSTAL STRUCTURES cont.
• Practice Exercise
1. X rays of wavelength 0.154 nm are diffracted from a crystal at an angle of
14.17°. Assuming that n = 1, calculate the distance (in pm) between layers in
the crystal.
2. How many atoms are in a body-centered cube, assuming that all atoms
occupy lattice points?
3. Copper crystallizes in a face-centered cubic lattice (the Cu atoms are at the
lattice points only). If the density of the metal is 8.96 g/cm3, what is the unit cell
edge length in pm?

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 REFERENCES
• Chang, R. & Goldsby, K.A. (2016). Chemistry (12th ed.).
New York: McGraw-Hill Education.

• Petrucci, R.H., Herring, F.G., Madura, J.D., & Bissonette, C.

(2011). General chemistry: Principles and modern
applications (10th ed.). Toronto: Pearson Canada, Inc.

• Silderberg, M.S. (2013). Principles of general chemistry (3rd

ed.). New York: The McGraw-Hill Companies, Inc.

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 WEBSITES/VIDEOS
• https://www.youtube.com/watch?v=FkRQa6cvkB8
• https://www.youtube.com/watch?v=4uyijq75tX8
• https://courses.lumenlearning.com/chemistryformajors/chapter/lattic
e-structures-in-crystalline-solids-2/
• https://ocw.mit.edu/resources/res-3-004-visualizing-materials-
science-fall-2017/student-projects-by-year/EPFL2017/a-basic-and-
fun-introduction-to-crystalline-structures/a-basic-and-fun-
introduction-to-crystalline-structures-english/

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