12.

1: Crystalline and Amorphous Solids

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Feb 2, 2015
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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. The learning objective of this module is to know the characteristic properties of
crystalline and amorphous solids.

Introduction
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 morphos, meaning shapeless).

(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 12.1), 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 12.1: 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 sameboth
are SiO2 and both consist of linked SiO4 tetrahedrathe 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.

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.

Note

Crystals have sharp, well-defined melting points; amorphous solids do not.

Summary
Solids are characterized by an extended three-dimensional arrangement of atoms, ions, or
molecules in which the components are generally locked into their positions. The components
can be arranged in a regular repeating three-dimensional array (a crystal lattice), which results in
a crystalline solid, or more or less randomly to produce an amorphous solid. Crystalline solids
have well-defined edges and faces, diffract x-rays, and tend to have sharp melting points. In
contrast, amorphous solids have irregular or curved surfaces, do not give well-resolved x-ray
diffraction patterns, and melt over a wide range of temperatures.

Conceptual Problems
1. Compare the solid and liquid states in terms of

a. rigidity of structure.

b. long-range order.

c. short-range order.

2. How do amorphous solids differ from crystalline solids in each characteristic? Which of the
two types of solid is most similar to a liquid?

a. rigidity of structure

b. long-range order

c. short-range order

3. Why is the arrangement of the constituent atoms or molecules more important in determining
the properties of a solid than a liquid or a gas?

4. Why are the structures of solids usually described in terms of the positions of the constituent
atoms rather than their motion?

5. What physical characteristics distinguish a crystalline solid from an amorphous solid?

Describe at least two ways to determine experimentally whether a material is crystalline or
amorphous.

6. Explain why each characteristic would or would not favor the formation of an amorphous
solid.

a. slow cooling of pure molten material

b. impurities in the liquid from which the solid is formed

 c. weak intermolecular attractive forces

7. A student obtained a solid product in a laboratory synthesis. To verify the identity of the solid,
she measured its melting point and found that the material melted over a 12C range. After it had
cooled, she measured the melting point of the same sample again and found that this time the
solid had a sharp melting point at the temperature that is characteristic of the desired product.
Why were the two melting points different? What was responsible for the change in the melting
point?

Conceptual Answers
3. The arrangement of the atoms or molecules is more important in determining the properties of
a solid because of the greater persistent long-range order of solids. Gases and liquids cannot
readily be described by the spatial arrangement of their components because rapid molecular
motion and rearrangement defines many of the properties of liquids and gases.

7. The initial solid contained the desired compound in an amorphous state, as indicated by the
wide temperature range over which melting occurred. Slow cooling of the liquid caused it to
crystallize, as evidenced by the sharp second melting point observed at the expected temperature.

Classes of Crystalline Solids

Crystalline substances can be described by the types of particles in them and the types
of chemical bonding that takes place between the particles. There are four types of
crystals: (1) ionic, (2) metallic, (3) covalent network, and (4) molecular. Properties
and several examples of each type are listed in the following table and are described in
the table below.

Table 12.7.112.7.1: Crystalline Solids - Melting

Type of Crystalline Solid Examples (formulas) Mel

NaClNaCl
Ionic
CaF2CaF2

HgHg
Metallic
NaNa
 Table 12.7.112.7.1: Crystalline Solids - Melting

Type of Crystalline Solid Examples (formulas) Mel

AuAu

WW

BB

Covalent Network CC (diamond)

SiO2SiO2

H2H2

I2I2
Molecular
NH3NH3

H2OH2O

Ionic crystals -- The ionic crystal structure consists of alternating positively-charged

cations and negatively-charged anions (see figure below). The ions may either be
monatomic or polyatomic. Generally, ionic crystals form from a combination of Group 1
or 2 metals and Group 16 or 17 nonmetals or nonmetallic polyatomic ions. Ionic crystals
are hard and brittle and have high melting points. Ionic compounds do not conduct
electricity as solids, but do conduct when molten or in aqueous solution.
 Figure 12.7.112.7.1: NaClNaCl crystal.

Metallic crystal -- Metallic crystals consist of metal cations surrounded by a "sea" of

mobile valence electrons (see figure below). These electrons, also referred to as
delocalized electrons, do not belong to any one atom, but are capable of moving
through the entire crystal. As a result, metals are good conductors of electricity. As seen
in the table above, the melting points of metallic crystals span a wide range.

Figure 12.7.212.7.2: Metallic crystal lattice with free electrons able to move among
positive metal atoms.

Covalent network crystals -- A covalent network crystal consists of atoms at the lattice
points of the crystal, with each atom being covalently bonded to its nearest neighbor
atoms (see figure below). The covalently bonded network is three-dimensional and
contains a very large number of atoms. Network solids include diamond, quartz, many
metalloids, and oxides of transition metals and metalloids. Network solids are hard and
brittle, with extremely high melting and boiling points. Being composed of atoms rather
than ions, they do not conduct electricity in any state.
 Figure 12.7.312.7.3: Diamond is a network solid and consists of carbon atoms
covalently bonded to one another in a repeating three-dimensional pattern. Each carbon
atom makes for single covalent bonds in a tetrahedral geometry.

Molecular crystals -- Molecular crystals typically consist of molecules at the lattice

points of the crystal, held together by relatively weak intermolecular forces (see figure
below). The intermolecular forces may be dispersion forces in the case of nonpolar
crystals, or dipole-dipole forces in the case of polar crystals. Some molecular crystals,
such as ice, have molecules held together by hydrogen bonds. When one of the noble
gases is cooled and solidified, the lattice points are individual atoms rather than
molecules. In all cases, the intermolecular forces holding the particles together are far
weaker than either ionic or covalent bonds. As a result, the melting and boiling points of
molecular crystals are much lower. Lacking ions or free electrons, molecular crystals
are poor electrical conductors.

Figure 12.7.412.7.4: Ice crystal structure.

Some general properties of the four major classes of solids are summarized in
Table 12.7.212.7.2.

Table 12.7.212.7.2: Properties of the Major Classes of Solids

 Ionic Solids Molecular Covalent Metallic Solids
Solids Solids

*Many exceptions exist. For example, graphite has a relatively high

electrical conductivity within the carbon planes, and diamond has the
highest thermal conductivity of any known substance.

poor conductors poor conductors poor conductors good conductors of

of heat and of heat and of heat and heat and electricity
electricity electricity electricity*

relatively high low melting point high melting melting points depend
melting point point strongly on electron
configuration

hard but brittle; soft very hard and easily deformed

shatter under brittle under stress; ductile
stress and malleable

relatively dense low density low density usually high density

dull surface dull surface dull surface lustrous

EXAMPLE 12.7.112.7.1
Classify Ge, RbI, C6(CH3)6, and Zn as ionic, molecular, covalent, or metallic solids and
arrange them in order of increasing melting points.

Given: compounds

Asked for: classification and order of melting points

Strategy:

A. Locate the component element(s) in the periodic table. Based on their positions,
predict whether each solid is ionic, molecular, covalent, or metallic.
B. Arrange the solids in order of increasing melting points based on your
classification, beginning with molecular solids.

Solution:
A Germanium lies in the p block just under Si, along the diagonal line of semimetallic
elements, which suggests that elemental Ge is likely to have the same structure as Si
(the diamond structure). Thus Ge is probably a covalent solid.

RbI contains a metal from group 1 and a nonmetal from group 17, so it is an ionic
solid containing Rb+ and I ions.

The compound C6(CH3)6 is a hydrocarbon (hexamethylbenzene), which consists of

isolated molecules that stack to form a molecular solid with no covalent bonds
between them.

Zn is a d-block element, so it is a metallic solid.

B Arranging these substances in order of increasing melting points is straightforward,

with one exception. We expect C6(CH3)6 to have the lowest melting point and Ge to have
the highest melting point, with RbI somewhere in between. The melting points of metals,
however, are difficult to predict based on the models presented thus far. Because Zn
has a filled valence shell, it should not have a particularly high melting point, so a
reasonable guess is

C6(CH3)6 < Zn ~ RbI < Ge.

The actual melting points are C6(CH3)6, 166C; Zn, 419C; RbI, 642C; and Ge, 938C.
This agrees with our prediction.

EXERCISE 12.7.112.7.1
Classify CO2, BaBr2, GaAs, and AgZn as ionic, covalent, molecular, or metallic solids
and then arrange them in order of increasing melting points.

Answer: CO2 (molecular) < AgZn (metallic) ~ BaBr2 (ionic) < GaAs (covalent). The
actual melting points are CO2, about -15.6C; AgZn, about 700C; BaBr2, 856C; and
GaAs, 1238C.

Summary
Ionic crystals are composed of alternating positive and negative ions. Metallic crystals
consist of metal cations surrounded by a "sea" of mobile valence electrons. Covalent
crystals are composed of atoms which are covalently bonded to one another. Molecular
crystals are held together by weak intermolecular forces.

Contributors
 Properties of Solids
As you should remember from the kinetic molecular theory, the molecules in solids are
not moving in the same manner as those in liquids or gases. Solid molecules simply
vibrate and rotate in place rather than move about. Solids are generally held together
by ionic or strong covalent bonding, and the attractive forces between the atoms, ions,
or molecules in solids are very strong. In fact, these forces are so strong that particles
in a solid are held in fixed positions and have very little freedom of movement. Solids
have definite shapes and definite volumes and are not compressible to any extent.

There are two main categories of solidscrystalline solids and amorphous

solids. Crystalline solids are those in which the atoms, ions, or molecules that make
up the solid exist in a regular, well-defined arrangement. The smallest repeating
pattern of crystalline solids is known as the unit cell, and unit cells are like bricks in a
wallthey are all identical and repeating. The other main type of solids are called the
amorphous solids. Amorphous solids do not have much order in their structures.
Though their molecules are close together and have little freedom to move, they are
not arranged in a regular order as are those in crystalline solids. Common examples of
this type of solid are glass and plastics.

There are four types of crystalline solids:

Ionic solidsMade up of positive and negative ions and held together by electrostatic
attractions. Theyre characterized by very high melting points and brittleness and are
poor conductors in the solid state. An example of an ionic solid is table salt, NaCl.

Molecular solidsMade up of atoms or molecules held together by London dispersion

forces, dipole-dipole forces, or hydrogen bonds. Characterized by low melting points
and flexibility and are poor conductors. An example of a molecular solid is sucrose.

Covalent-network (also called atomic) solidsMade up of atoms connected by

covalent bonds; the intermolecular forces are covalent bonds as well. Characterized as
being very hard with very high melting points and being poor conductors. Examples of
this type of solid are diamond and graphite, and the fullerenes. As you can see below,
graphite has only 2-D hexagonal structure and therefore is not hard like diamond. The
sheets of graphite are held together by only weak London forces!
Metallic solidsMade up of metal atoms that are held together by metallic bonds.
Characterized by high melting points, can range from soft and malleable to very hard,
and are good conductors of electricity.

CRYSTAL STRUCTURES WITH CUBIC UNIT CELLS (From

https://eee.uci.edu/programs/gchem/RDGcrystalstruct.pdf)

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. (See Below).

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
collectionof 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
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.

The considerable space shown between the spheres in Figures 3b is misleading: lattice
points in solids touch as shown in Figure 3c. For example, the distance between the
centers of two adjacent metal atoms is equal to the sum of their radii. Refer again to
Figure 3b 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 Pythagoreans 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).
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". The packing
efficiency of a simple cubic structure is only about 52%. (48% is empty space!)

Body Centered Cubic (bcc) 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 3b, the
considerable space shown between the spheres in Figure 5b 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.
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%.

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

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 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?
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 of each face atom).

Figure 9a:Space filling model of fcc. Figure 9b: The face of fcc. Face diagonal = 4r.

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?

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
ions radius the larger ions radius (rsmaller/rlarger). (Table 1).

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.
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?

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.
Summary:

Simple Cubic: 1 Body Centered

total atom per Cubic: 2 atoms
Face Centered Cubic: 4
cell (1/8 each per cell (1 in
corner) atoms per cell
center and 1/8
(1/2 per face and 1/8
for each corner)
for each corner)