material science

Structures of Crystalline Solids

Submitted by
Abdulrahman Mustafa AL-Driewi

To
Dr. Hasan AL-dabbas
Structures of Crystalline Solids

Crystalline solids have regular ordered arrays of components held

together by uniform intermolecular forces, whereas the components of
amorphous solids are not arranged in regular arrays. With few
exceptions, the particles that compose a solid material, whether ionic,
molecular, covalent, or metallic, are held in place by strong attractive
forces between them. When we discuss solids, therefore, we consider
the positions of the atoms, molecules, or ions, which are essentially
fixed in space, rather than their motions (which are more important in
liquids and gases). The constituents of a solid can be arranged in two
general ways: they can form a regular repeating three-dimensional
structure called a crystal lattice, thus producing a crystalline solid, or
they can aggregate with no particular order, in which case they form an
amorphous solid (from the Greek ámorphos, meaning “shapeless”).

Figure 1: (left) Crystalline faces. The faces of crystals can intersect at right angles, as in galena
(PbS) and pyrite (FeS2), or at other angles, as in quartz. (Right) Cleavage surfaces of an
amorphous solid. Obsidian, a volcanic glass with the same chemical composition as granite
(typically KAlSi3O8), tends to have curved, irregular surfaces when cleaved.
Crystalline solids, or crystals, have distinctive internal structures
that in turn lead to distinctive flat surfaces, or faces. The faces
intersect at angles that are characteristic of the substance. When
exposed to x-rays, each structure also produces a distinctive
pattern that can be used to identify the material. The
characteristic angles do not depend on the size of the crystal;
they reflect the regular repeating arrangement of the component
atoms, molecules, or ions in space. When an ionic crystal is
cleaved (Figure 1, for example, repulsive interactions cause it to
break along fixed planes to produce new faces that intersect at
the same angles as those in the original crystal. In a covalent
solid such as a cut diamond, the angles at which the faces meet
are also not arbitrary but are determined by the arrangement of
the carbon atoms in the crystal.

Figure 2: Cleaving a Crystal of an Ionic Compound along a Plane of Ions. Deformation of the ionic crystal
causes one plane of atoms to slide along another. The resulting repulsive interactions between ions with
like charges cause the layers to separate.

Crystals tend to have relatively sharp, well-defined melting points

because all the component atoms, molecules, or ions are the
same distance from the same number and type of neighbors; that
is, the regularity of the crystalline lattice creates local
environments that are the same. Thus the intermolecular forces
holding the solid together are uniform, and the same amount of
thermal energy is needed to break every interaction
simultaneously.
Amorphous solids have two characteristic properties. When
cleaved or broken, they produce fragments with irregular, often
curved surfaces; and they have poorly defined patterns when
exposed to x-rays because their components are not arranged in
a regular array. An amorphous, translucent solid is called a glass.
Almost any substance can solidify in amorphous form if the liquid
phase is cooled rapidly enough. Some solids, however, are
intrinsically amorphous, because either their components cannot
fit together well enough to form a stable crystalline lattice or they
contain impurities that disrupt the lattice. For example, although
the chemical composition and the basic structural units of a
quartz crystal and quartz glass are the same—both are SiO2 and
both consist of linked SiO4 tetrahedra—the arrangements of the
atoms in space are not. Crystalline quartz contains a highly
ordered arrangement of silicon and oxygen atoms, but in quartz
glass the atoms are arranged almost randomly. When molten
SiO2 is cooled rapidly (4 K/min), it forms quartz glass, whereas
the large, perfect quartz crystals sold in mineral shops have had
cooling times of thousands of years. In contrast, aluminum
crystallizes much more rapidly. Amorphous aluminum forms only
when the liquid is cooled at the extraordinary rate of 4 × 1013 K/s,
which prevents the atoms from arranging themselves into a
regular array.

Figure 3: The lattice of crystalline quartz (SiO2). The atoms form a regular arrangement in a
structure that consists of linked tetrahedra.
In an amorphous solid, the local environment, including both the
distances to neighboring units and the numbers of neighbors,
varies throughout the material. Different amounts of thermal
energy are needed to overcome these different interactions.
Consequently, amorphous solids tend to soften slowly over a wide
temperature range rather than having a well-defined melting
point like a crystalline solid. If an amorphous solid is maintained
at a temperature just below its melting point for long periods of
time, the component molecules, atoms, or ions can gradually
rearrange into a more highly ordered crystalline form.
Crystals have sharp, well-defined melting points; amorphous solids do not.

Crystals

Because a crystalline solid consists of repeating patterns of its

components in three dimensions (a crystal lattice), we can
represent the entire crystal by drawing the structure of the
smallest identical units that, when stacked together, form the
crystal. This basic repeating unit is called a unit cell. For example,
the unit cell of a sheet of identical postage stamps is a single
stamp, and the unit cell of a stack of bricks is a single brick. In
this section, we describe the arrangements of atoms in various
unit cells.

Figure 4: Unit Cells in Two Dimensions. (a–c) Three

two-dimensional lattices illustrate the possible choices
of the unit cell. The unit cells differ in their relative
locations or orientations within the lattice, but they are
all valid choices because repeating them in any
direction fills the overall pattern of dots. (d) The
triangle is not a valid unit cell because repeating it in
space fills only half of the space in the pattern.
Unit cells are easiest to visualize in two dimensions. In many
cases, more than one unit cell can be used to represent a given
structure, as shown for the Escher drawing in the chapter opener
and for a two-dimensional crystal lattice in Figure 4. Usually, the
smallest unit cell that completely describes the order is chosen.
The only requirement for a valid unit cell is that repeating it in
space must produce the regular lattice. Thus, the unit cell in
Figure 4. is not a valid choice because repeating it in space does
not produce the desired lattice (there are triangular holes). The
concept of unit cells is extended to a three-dimensional lattice in
the schematic drawing in Figure 5.

Figure 5: Unit Cells in Three Dimensions. These images show (a) a three-dimensional unit cell
and (b) the resulting regular three-dimensional lattice.

The Unit Cell

There are seven fundamentally different kinds of unit cells, which
differ in the relative lengths of the edges and the angles between
them (Figure 6). Each unit cell has six sides, and each side is a
parallelogram. We focus primarily on the cubic unit cells, in which
all sides have the same length, and all angles are 90°, but the
concepts that we introduce also apply to substances whose unit
cells are not cubic.

Figure 6: The General Features of the Seven Basic Unit Cells. The lengths of the edges of the unit cells are
indicated by a, b, and c, and the angles are defined as follows: α, the angle between b and c; β, the angle
between a and c; and γ, the angle between a and b.Cubic: a = b=c, alpha= beta=gamma = 90 degrees.
Tetragonal: a=b, alpha = beta = gamma = 90 degrees. Orthorhombic: alpha = beta = gamma = 90 degrees.
Monoclinic: alpha = gamma = 90 degrees. Hexagonal: a = b, alpha = beta = 90 degrees, gamma = 120
degrees. Rhombohedral: a = b = c, alpha = beta= gamma. Triclinic: all different.

If the cubic unit cell consists of eight component atoms,

molecules, or ions located at the corners of the cube, then it is
called simple cubic (Figure 7). If the unit cell also contains an
identical component in the center of the cube, then it is body-
centered cubic (bcc) (Figure 7). If there are components in the
center of each face in addition to those at the corners of the
cube, then the unit cell is face-centered cubic (fcc) (Figure 7).
Figure 7: The Three Kinds of Cubic Unit Cell. For the three kinds of cubic unit cells, simple cubic (a),
body-centered cubic (b), and face-centered cubic (c), there are three representations for each: a ball-
and-stick model, a space-filling cutaway model that shows the portion of each atom that lies within the
unit cell, and an aggregate of several unit cells. Simple cubic is made of eight quarters of spheres. Body
center cubic is made of eight quarters of sphere with a sphere in the middle. Face centered cubic is
made of eight quarters of spheres and six half spheres.

As indicated in Figure 7, a solid consists of a large number of unit

cells arrayed in three dimensions. Any intensive property of the
bulk material, such as its density, must therefore also be related
to its unit cell. Because density is the mass of substance per unit
volume, we can calculate the density of the bulk material from
the density of a single unit cell. To do this, we need to know the
size of the unit cell (to obtain its volume), the molar mass of its
components, and the number of components per unit cell. When
we count atoms or ions in a unit cell, however, those lying on a
face, an edge, or a corner contribute to more than one unit cell,
as shown in Figure 7. For example, an atom that lies on a face of
a unit cell is shared by two adjacent unit cells and is therefore
counted as 1/2 atom per unit cell. Similarly, an atom that lies on
the edge of a unit cell is shared by four adjacent unit cells, so it
contributes 1/4 atom to each. An atom at a corner of a unit cell is
shared by all eight adjacent unit cells and therefore
contributes 1/8 atom to each. The statement that atoms lying on
an edge or a corner of a unit cell count as 1/4 or 1/8 atom per
unit cell, respectively, is true for all unit cells except the
hexagonal one, in which three unit cells share each vertical edge
and six share each corner (Figure 7), leading to values
of 1/3 and 1/6 atom per unit cell, respectively, for atoms in these
positions. In contrast, atoms that lie entirely within a unit cell,
such as the atom in the center of a body-centered cubic unit cell,
belong to only that one unit cell.
Reference
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