You are on page 1of 8

Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

CRYSTAL STRUCTURES WITH CUBIC UNIT CELLS

Crystalline solids are a three dimensional collection of individual atoms, ions, or whole
molecules organized in repeating patterns. These atoms, ions, or molecules are called
lattice points and are typically visualized as round spheres. The two dimensional layers
of a solid are created by packing the lattice point “spheres” into square or closed packed
arrays. (Figure 1). Which packing arrangement makes the most efficient use of space?

square array close-packed array


Figure 1: Two possible arrangements for identical atoms in a 2-D structure

Stacking the two dimensional layers on top of each other creates a three dimensional
lattice point arrangement represented by a unit cell. A unit cell is the smallest collection
of lattice points that can be repeated to create the crystalline solid. The solid can be
envisioned as the result of the stacking a great number of unit cells together. The unit
cell of a solid is determined by the type of layer (square or close packed), the way each
successive layer is placed on the layer below, and the coordination number for each
lattice point (the number of “spheres” touching the “sphere” of interest.)

Primitive (Simple) Cubic Structure


Placing a second square array layer directly over a first square array layer forms a
"simple cubic" structure. The simple “cube” appearance of the resulting unit cell (Figure
3a) is the basis for the name of this three dimensional structure. This packing
arrangement is often symbolized as "AA...", the letters refer to the repeating order of the
layers, starting with the bottom layer. The coordination number of each lattice point is
six. This becomes apparent when inspecting part of an adjacent unit cell (Figure 3b).
The unit cell in Figure 3a appears to contain eight corner spheres, however, the total

1
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

number of spheres within the unit cell is 1 (only 1/8th of each sphere is actually inside the
unit cell). The remaining 7/8ths of each corner sphere resides in 7 adjacent unit cells.

Figure 3a: Figure 3b: Figure 3c:


Square Array Layering Simple Cubic Space Filling Simple Cubic

The considerable space shown between the spheres in Figures 3a is misleading: lattice
points in solids touch as shown in Figure 3b. For example, the distance between the
centers of two adjacent metal atoms is equal to the sum of their radii. Refer again to
Figure 3a and imagine the adjacent atoms are touching. The edge of the unit cell is then
equal to 2r (where r = radius of the atom or ion) and the value of the face diagonal as a
function of r can be found by applying Pythagorean’s theorem (a2 + b2 = c2) to the right
triangle created by two edges and a face diagonal (Figure 4a). Reapplication of the
theorem to another right triangle created by an edge, a face diagonal, and the body
diagonal allows for the determination of the body diagonal as a function of r (Figure 4b).

e
d
e g
d e
g
e

edge

Figure 4a Figure 4b

2
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

Few metals adopt the simple cubic structure because of inefficient use of space. The
density of a crystalline solid is related to its "percent packing efficiency" (1). The
packing efficiency of a simple cubic structure is only about 52%. (48% is empty space!)
How would you find the volume of a unit cell and the volume of atoms in a unit cell?

(1) % packing efficiency = volume of atoms in a unit cell x 100


volume of unit cell

Body Centered Cubic Structure


A more efficiently packed cubic structure is the "body-centered cubic" (bcc). The first
layer of a square array is expanded slightly in all directions. Then, the second layer is
shifted so its spheres nestle in the spaces of the first layer (Figures 5a, b). This repeating
order of the layers is often symbolized as "ABA...". Like Figure 3, the considerable
space shown between the spheres in Figures 5 is misleading: spheres are closely packed
in bcc solids and touch along the body diagonal. The packing efficiency of the bcc
structure is about 68%. The coordination number for an atom in the bcc structure is
eight. How many total atoms are there in the unit cell for a bcc structure? Draw a
diagonal line connecting the three atoms marked with an "x" in Figure 5b. Assuming the
atoms marked "x" are the same size, tightly packed and touching, what is the value of this
body diagonal as a function of r, the radius? Find the edge and volume of the cell as a
function of r.

Figure 5a: Figure 5b: Figure 5c:


Square Array Layering Body Ctr’d Cubic (bcc) Space Filling bcc

3
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

Cubic Closest Packed (ccp)


A cubic closest packed (ccp) structure is created by layering close packed arrays. The
spheres of the second layer nestle in half of the spaces of the first layer. The spheres of
the third layer directly overlay the other half of the first layer spaces while nestling in half
the spaces of the second layer. The repeating order of the layers is "ABC..." (Figures 6
& 7). The coordination number of an atom in the ccp structure is twelve (six nearest
neighbors plus three atoms in layers above and below) and the packing efficiency is 74%.

x x x

x x x x x x x x

Figure 6: Close packed Array Layering. The 1st and 3rd layers are represented by light
spheres; the 2nd layer, dark spheres. The 2nd layer spheres nestle in the spaces of the 1st
layer marked with an “x”. The 3rd layer spheres nestle in the spaces of the 2nd layer that
directly overlay the spaces marked with a “·” in the 1st layer.

Figure 7a & 7b: Two views of the Cubic Close Packed Structure

4
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

If the cubic close packed structure is rotated by 45° the face centered cube (fcc) unit cell
can be viewed (Figure 8). The fcc unit cell contains 8 corner atoms and an atom in each
face. The face atoms are shared with an adjacent unit cell so each unit cell contains ½ a
face atom. Atoms of the face centered cubic (fcc) unit cell touch across the face diagonal
(Figure 9). What is the edge, face diagonal, body diagonal, and volume of a face
centered cubic unit cell as a function of the radius?

C
45o
rotation
B

Figure 8: The face centered cubic unit cell is drawn by cutting a diagonal plane through
an ABCA packing arrangement of the ccp structure. The unit cell has 4 atoms (1/8 of
each corner atom and ½ of each face atom).

4r

Figure 9a: Figure 9b:


Space filling model of fcc. The face of fcc. Face diagonal = 4r.

5
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

Ionic Solids
In ionic compounds, the larger ions become the lattice point “spheres” that are the
framework of the unit cell. The smaller ions nestle into the depressions (the “holes”)
between the larger ions. There are three types of holes: "cubic", "octahedral", and
"tetrahedral". Cubic and octahedral holes occur in square array structures; tetrahedral and
octahedral holes appear in close-packed array structures (Figure 10). Which is usually the
larger ion – the cation or the anion? How can the periodic table be used to predict ion
size? What is the coordination number of an ion in a tetrahedral hole? an octahedral
hole? a cubic hole?

Tetrahedral Octahedral Octahedral Cubic


Figure 10. Holes in ionic crystals are more like "dimples" or "depressions" between the
closely packed ions. Small ions can fit into these holes and are surrounded by larger ions
of opposite charge.

The type of hole formed in an ionic solid largely depends on the ratio of the smaller ion’s
radius the larger ion’s radius (rsmaller/rlarger). (Table 1).
Table 1: Radius Ratio & Hole Type
Hole Type Radius Ratio
Tetrahedral 0.225 – 0.414
Octahedral 0.414 – 0.732
Cubic 0.732 – 1.000

Empirical Formula of an Ionic Solid


Two ways to determine the empirical formula of an ionic solid are: 1) from the number
of each ion contained within 1 unit cell 2) from the ratio of the coordination numbers of
the cations and anions in the solid.

6
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

Table 2: Position of atom and fraction contained in a single unit cell:


Position of Atom # of Adjacent Cells Fraction Contained Within a
in the Unit Cell Sharing Atom Single Unit Cell
1
Cube Corner 8 /8
Edge 4 ¼
Face 2 ½
Internal 1 1

Example: Find the empirical formula for the ionic compound shown in Figures 11 & 12.
First Method: When using the first method, remember most atoms in a unit cell are
shared with other cells. Table 2 lists types of atoms and the fraction contained in the unit
cell. The number of each ion in the unit cell is determined: 1/8 of each of the 8 corner X
ions and 1/4 of each of the 12 edge Y ions are found within a single unit cell. Therefore,
the cell contains 1 X ion (8/8 = 1) for every 3 Y ions (12/4 = 3) giving an empirical
formula of XY3. Which is the cation? anion? When writing the formula of ionic solids,
which comes first?

Figure 11a: Figure 11b:


Unit cell of ionic solid XY3. Space filling unit cell of ionic solid XY3.

Second Method: The second method is less reliable and requires the examination of the
crystal structure to determine the number of cations surrounding an anion and vice versa.
The structure must be expanded to include more unit cells. Figure 12 shows the same
solid in Figure 11 expanded to four adjacent unit cells. Examination of the structure
shows that there are 2 X ions coordinated to every Y ion and 6 Y ions surrounding every
X ion. (An additional unit cell must be projected in front of the page to see the sixth Y
ion ). A 2 to 6 ratio gives the same empirical formula, XY3.

7
Reading: Crystal Structures with Cubic Unit Cells Revised 5/3/04

Figure 12: Four unit cells of an ionic solid with formula XY3.

You might also like