3.

Solids: The Crystal Structure

Solids can be divided into two categories: crystalline and amorphous. Examples

• Crystalline solid, such as quartz which possesses rigid and

long-range order; atoms, molecules, or ions occupy
specific positions. The arrangement of atoms, molecules,
or ions in a crystalline solid is such that the net attractive
intermolecular forces are at their maximum.

• The forces responsible for the stability of any crystal can

be ionic forces, covalent bonds, van der Waals forces,
hydrogen bonds, or a combination of these forces. Solids
are most stable in crystalline form.

• Amorphous solids. Solids are formed rapidly its atoms or

molecules do not have time to align themselves and may
become locked in positions other than those of a regular
crystal. The resulting is a lack of well defined structure.

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 Virtually all we know about crystal structure has been learned from X-ray diffraction studies. (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 crystalline solid.

• Definition:
The 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.

• Every crystalline solid can be described in terms of one of the seven types of unit cells shown below.

The geometry of the cubic unit cell is

particularly simple because all sides and all
angles are equal. We are going to adopt it to
understand the cristal structure

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The black spheres
represent either atoms
or molecules: The lattice
point

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• The way the spheres are arranged in layers determines what type of unit cell we have.

3.1. Simple cubic cell (scc)

• Here the basic, repeating unit in this array of spheres is called a simple cubic cell (scc). One sphere is in contact with
four spheres in its own layer, one sphere in the layer above, and one sphere in the layer below.

• Each sphere in this arrangement is said to have a coordination number of 6 because it has six immediate neighbors. The
coordination number is defined as the number of atoms (or ions) surrounding an atom (or ion) in a crystal lattice.

• Because each corner sphere is shared by eight unit cells and there are eight corners in a cube, there will be the
equivalent of only one complete

(a) Top view of one layer of spheres.

(b) Definition of a simple cubic cell.
(c) Because each sphere is shared by eight unit cells and there
are eight corners in a cube, there is the equivalent of one
complete sphere inside a simple cubic unit cell

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3.2. The body-centered cubic cell (bcc)
• A body-centered cubic arrangement differs from a simple cube in that the second layer of spheres fits into the
depressions of the first layer and the third layer into the depressions of the second layer.

• The coordination number of each sphere in this structure is 8 (each sphere is in contact with four spheres in the layer
above and four spheres in the layer below).

• Because every unit cell in a crystalline solid is adjacent to other unit cells, most of a cell’s atoms are shared by
neighboring cells.

• A body-centered cubic cell contains the equivalent of two complete spheres, one in the center and eight shared
corner spheres

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3.3. The face-centered cubic cell (fcc)
• In the face-centered cubic cell there are spheres at the center of each of the six faces of the cube in addition to the
eight corner spheres and the coordination number of each sphere is 12.

• A face-centered cubic cell contains four complete spheres—three from the six face-centered atoms and one from the
eight shared corner spheres

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The Figure shows a unit cell and its
extension in three dimensions. Each
sphere represents an atom, an ion,
or a molecule and is called a lattice
point.

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The relationship between the edge length (a) and radius (r) of atoms in the simple cubic cell (scc), body-centered cubic
cell (bcc), and face-centered cubic cell (fcc).

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 4. Bonding in Solids
The structure and properties of crystalline solids, such as melting point, density, and hardness, are determined
by the attractive forces that hold the particles together. We can classify crystals according to the types of
forces between particles: ionic, molecular, covalent, and metallic

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 4.1.Ionic Crystals
• Ionic crystals consist of ions held together by ionic bonds.
• The structure of an ionic crystal depends on the charges on the cation and anion and on their radii.
• Ionic solids have high melting points, an indication of the strong cohesive force holding the ions
together.
• These solids do not conduct electricity because the ions are fixed in position. However, in the molten
state or dissolved in water, the ions are free to move, and the resulting liquid is electrically conducting.

Crystal structures of (a) CsCl, (b) ZnS, and (c) CaF 2. In each case, the cation is the smaller sphere.

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 4.2.Molecular Crystals
• Molecular crystals consist of atoms or molecules held together by van der Waals forces and/or hydrogen
bonding.
An example of a molecular crystal is solid sulfur dioxide (SO2), in which the predominant attractive force is
dipole-dipole interaction. Other examples CO2, I2, P4, and S8
• Molecules in molecular crystals are packed together as closely as their size and shape allow. Because van
der Waals forces and hydrogen bonding are generally quite weak compared with covalent and ionic bonds,
molecular crystals are more easily broken apart than ionic and covalent crystals. Indeed, most molecular
crystals melt below 200°C.

Models of the packing of molecules in two molecular solids, I2 and carbon dioxide or Dry ice
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 4.3. Covalent Crystals
• In covalent crystals, atoms are held together entirely by covalent bonds in an extensive three-dimensional
network. No discrete molecules are present, as in the case of molecular solids.
• Well-known examples are the two allotropes of carbon:

In Diamond. Each carbon In graphite. Carbon atoms are

is tetrahedrally bonded to arranged in six-membered rings. The
four other carbon atoms. distance between successive layers is
The strong covalent bonds 335 pm. The layers are held together
in three dimensions by the weak van der Waals forces.
contribute to diamond’s The covalent bonds in graphite
unusual hardness and account for its hardness; however,
high melting point because the layers can slide over
(3550°C). one another it reduces hardness.

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 4.4.Metallic Crystals
• Every lattice point in a crystal is occupied by an atom of the same metal. The bonding in metals is quite
different from that in other types of crystals.
• In a metal, the bonding electrons are spread (or delocalized) over the entire crystal.
The great cohesive force resulting from delocalization is responsible for a metal’s strength, which increases
as the number of electrons available for bonding increases.
For example, the melting point of sodium, with one valence electron, is 97.6°C, whereas that of aluminum,
with three valence electrons, is 660°C.

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Example.3

Gold (Au) crystallizes in a cubic close-packed structure (the face-centered cubic unit cell) and has a density of 19.3 g/cm 3.
Calculate the atomic radius of gold in picometers.

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Example. 4

Calculate the density of metallic iron, which has a body-centered cubic unit cell with an edge length of 286.6 pm.

Strategy:

Determine the number of iron atoms per unit cell.

Calculate the mass of iron atoms in the unit cell from the molar mass and Avogadro’s number. Then divide the mass by the
volume of the cell.

Solution:
Each unit cell of metallic iron contains two Fe atoms. The molar mass of iron is 55.85 g/mol. Because density is mass per
unit volume, we need to calculate the mass of the iron atoms in the unit cell from the molar mass and Avogadro’s number
and then divide the mass by the volume of the cell (making sure to use suitable units to get density in g/cm3):

 This result compares well with the tabulated experimental value of 7.874 g/cm

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