CRYSTALS

Crystalline Solids
When cooled slowly, atomic and molecular building blocks can
assemble into well-ordered minimum-energy structures:
Crystals
Examples
CuSO
4
5H
2
O
Quartz SiO
2

Cholesterol
Ag
Cu
MnB(OH)
3

Comparison: Amorphous solids
Lack an ordered internal
structure
common examples include
glass, candle wax, butter,
and plastics.
Unit Cells
Crystals consist of repeating asymmetric units
which may be atoms, ions or molecules.
The space lattice is the pattern formed by the
points that represent these repeating
structural units.
If repeated (translated) in 3 dimensions, the
entire crystal is recreated.

Crystal Lattice and Unit Cell
The unit cell is the minimum repeating unit
necessary to describe the crystal.

Parameters Describing a Unit Cell
Each unit is described by how the edge lengths
and the angles are related to each other

Crystal systems
Arrangements for stacking spheres, each one
characterized by a packing efficiency
(percentage of total volume occupied by
spheres)
There are 7 types
Including additional lattice pts to some of the 7 basic
shapes generates14 Bravais cells
Bravais cells describe all possible packing
arrangements with greatest simplicity and symmetry.

Structure Lattice Points
Primitive, or Simple Only at the corners
Face-Centered
at the corners and also at the
centers of the faces
Body-centered lattice points at the corners
and at the center
Base-centered
at the corners and at centers
of two opposite faces
SC FCC BCC
Primitive Body-Centered
Cubic
Tetragonal
Hexagonal (elementary cell
continued to show hex.
symmetry)
Rhombohedral
Primitive Body-centered Face-centered Base face-
centered
Orthorhombic
Primitive Base face-centered
Triclinic
Monoclinic
Coordination Number, CN
No. of touching neighbors if spheres are identical

Simple cubic unit cell
CN = 6. (4 in layer, 1 above, 1 below)

Body-centered cubic unit cell
CN # = 8. (4 above and 4 below.)

Face-centered cubic unit cell
CN = 12. (4 in layer, 1 above, 1 below, 6
faces)


# of Atoms/Unit Cell
Atoms in corners are
within the cell
Atoms on faces are
within the cell
A center atom in a BCC is completely enclosed in
unit cell

An edge atom belongs to 4 unit cells.
of an edge atom belongs to the unit cell
# of Atoms/Unit Cell
A face-centered
cubic unit cell
contains a total of 4
atoms: 1 from the
corners, and 3 from
the faces.
No. of atoms per unit cell in elemental solids
1
8
atom
body atom corners
BCC: 8 1
corner unit cell unit c
2
ell
| |
+ =
|
\ .
1
8
atom
corners
Simple Cubic: 8
corner unit cell
1
| |
=
|
\ .
1
8
1
2
atom
corners face atom faces
FCC: 8 6
corner unit ce
4
ll face unit cell
| | | |
+ =
| |
\ . \ .
1
8
1
2
Base centered or End centered:
atom
corners face atom baces
8 2
corner unit cell face unit cell
2
| | | |
+ =
| |
\ . \ .
Relationship between edge length a, of cube
and atomic radius r, in elemental solids
Simple Cubic (SC)
a
a = 2R
Where:
R = atomic radius
a = lattice parameter
Packing fraction = 54%
CN = 6
Body Centered Cubic (BCC)
a =
4R
3
Where:
R = atomic radius
a = lattice parameter
a
Packing fraction
= 68%
CN = 8
Face Centered Cubic (FCC)
a = 2R 2
Where:
R = atomic radius
a = edge length
Packing Factor
=74%
CN= 12
Structures and Properties of Solids
The unit cell is the smallest volume that shows the
characteristics of the crystal.

The unit cell therefore can be used to calculate
theoretical properties of the crystal like its density.

( ) ( )
( ) ( )
no. of atoms per unit cell atomic mass
volume of unit cell Avogadro's no.
=
Exercises
1. Nickel has an FCC unit cell. The density of Ni is 6.84
g/cm
3
. Calculate the atomic radius of Ni.

2. Iridium has an FCC unit cell with an edge length of
383.3 pm. Calculate the density of solid Ir.

3. Barium has a BCC structure. If the atomic radius of
Ba is 222 pm, calculate the density of the solid Ba.

4. A metallic solid with atoms in an FCC unit cell with
an edge length of 392 pm, has a density of 21.45
g/cm
3
. Calculate the atomic mass and radius of the
metal. Identify the metal.

5. The radius of gold is 144 pm, and the density is
19.32 g/cm
3
. Does elemental gold have an FCC or a
BCC structure?

6. Potassium crystallizes in a cubic unit cell with an
edge length of 0.5247 nm. The density of
potassium is 0.856 g/cm
3
. Determine whether this
element crystallizes in a simple cubic, a body
centered, or face-centered cubic unit cell.

7. Iron crystallizes in a body-centered cubic unit cell
with an edge length of 287 pm. What is the radius
of an iron atom (in pm)?

8. Iron metal has a density of 7.86 g/cm3 and a molar
mass of 55.85 g. Use this information and the data
in the preceding problem to calculate Avogadros
number.

PROBLEM SET:

1. Calcium metal has a density of 1.55 g/cm
3
and
crystallizes in a cubic unit cell with an edge length
of 558.2 pm.
a. How many Ca atoms are in one unit cell?
b. In which of the three cubic unit cells does
calcium crystallizes?

2 . A group 3A metal has a density of 2.7 g/cm
3
and a
cubic unit cell with an edge length of 404 pm.
Reaction of 1.07 cm
3
chunk of the metal with an
excess HCl gives a colorless gas that occupies 4 L at
23
0
C and a pressure of 740 mm Hg.
a. Identify the metal
b. Is the cubic unit cell primitive, body-centered, or
face-centered?
c. What is the atomic radius of the metal atom (in
pm)?

3. At 1425
0
C, iron crystallizes in a body-centered cubic
lattice whose edge length is 2.43 . Assuming the
atoms to be packed spheres, calculate
a. the radius of the spheres
b. the distance between centers of
neighboring spheres
c. the no. of Fe atoms per unit cell
d. the total volume occupied by the atoms

Packing of Spheres
For Simple Cubic:
The first layer is spaced with a = 2R
Then the second layer is placed with every atom
directly atop the one below
CN = 6
Packing not efficient


For a body-centered cubic lattice (BCC):
a =
4
3
R
Then, the 2 nd layer is placed over the spaces between
atoms.
Finally, a 3 rd layer lines up directly over the atoms in the
first.
Still not a close-packed structure.
Packing fraction = 68%
Coordination number = 8
(bi-prism)
Close Packing: Efficient Packing of Identical
Spheres
The higher the coordination no. of the crystal is,
the greater the no. of particles in a given volume,
and the more efficient the packing is.
CN = 4 CN = 6
For efficient packing,
start with a hexagonal array of atoms in a plane
(layer A)

Interstitial sites or holes
B: the upright triangles
C: the upside down triangles



Stacking of close-packed planes
first layer = A
second layer = B
third layer:
C: Cubic close packing, (ccp)
A: Hexagonal close packing, (hcp)

Shift every other row in the
first layer to compress
packing
The Close-Packed Crystal Systems
Cubic closest packing,
Place second layer over
triangular spaces
Third layer over gaps that
remain
abcabc
Hexagonal closest packing, HCP
Shift every other row in the
first layer
to compress packing
Place second layer over
triangular spaces
Third layer directly over the
atoms of the first
abab
Coordination # = 12
(3 above, 6 in the plane,
3 below)
closest packing of first
and second layers
layer a
layer b
layer a
hexagonal
closest
packing
abab
layer c
cubic closest
packing
abcabc
Packing is said to be of ABAB type
HCP
Packing Efficiency
This may be expressed in terms of:
a. Coordination No.= no. of nearest (touching)
neighbors





In an HCP,





( ) ( )
b. Packing Factor or Packing Fraction, PF
no. of atoms per unit cell atomic volume
PF=
volume of unit cell
( )
3
atoms
unit cell
3
4
0.74 or 74
4
3
PF =
4
2
%
t
| |
|
\ .
=
| |
|
\ .
r
r
Packing of spheres.
simple cubic
(52% packing efficiency)
body-centered cubic
(68% packing efficiency)
Cell Type Coordination
No
Packing
Efficiency
Simple cubic 6 52%
Body-centered cubic 8 68%
Face-centered cubic
aka, (cubic closest
packing)
12 74%
Hexagonal 12 74%