9.

2: The Solid State of Matter

Skills to Develop
Define and describe the bonding and properties of ionic, molecular, metallic, and covalent network crystalline
solids
Describe the main types of crystalline solids: ionic solids, metallic solids, covalent network solids, and molecular
solids
Explain the ways in which crystal defects can occur in a solid

When most liquids are cooled, they eventually freeze and form crystalline solids, solids in which the atoms, ions, or
molecules are arranged in a definite repeating pattern. It is also possible for a liquid to freeze before its molecules become
arranged in an orderly pattern. The resulting materials are called amorphous solids or noncrystalline solids (or, sometimes,
glasses). The particles of such solids lack an ordered internal structure and are randomly arranged (Figure 9.2.1).

Figure 9.2.1 : The entities of a solid phase may be arranged in a regular, repeating pattern (crystalline solids) or
randomly (amorphous).
Metals and ionic compounds typically form ordered, crystalline solids. Substances that consist of large molecules, or a
mixture of molecules whose movements are more restricted, often form amorphous solids. For examples, candle waxes
are amorphous solids composed of large hydrocarbon molecules. Some substances, such as boron oxide (Figure 9.2.2),
can form either crystalline or amorphous solids, depending on the conditions under which it is produced. Also, amorphous
solids may undergo a transition to the crystalline state under appropriate conditions.

Figure 9.2.2 : (a) Diboron trioxide, B2O3, is normally found as a white, amorphous solid (a glass), which has a high
degree of disorder in its structure. (b) By careful, extended heating, it can be converted into a crystalline form of B2O3,
which has a very ordered arrangement.
Crystalline solids are generally classified according the nature of the forces that hold its particles together. These forces
are primarily responsible for the physical properties exhibited by the bulk solids. The following sections provide
descriptions of the major types of crystalline solids: ionic, metallic, covalent network, and molecular.

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Ionic Solids
Ionic solids, such as sodium chloride and nickel oxide, are composed of positive and negative ions that are held together
by electrostatic attractions, which can be quite strong (Figure 9.2.3). Many ionic crystals also have high melting points.
This is due to the very strong attractions between the ions—in ionic compounds, the attractions between full charges are
(much) larger than those between the partial charges in polar molecular compounds. This will be looked at in more detail
in a later discussion of lattice energies. Although they are hard, they also tend to be brittle, and they shatter rather than
bend. Ionic solids do not conduct electricity; however, they do conduct when molten or dissolved because their ions are
free to move. Many simple compounds formed by the reaction of a metallic element with a nonmetallic element are ionic.

Figure 9.2.3 : Sodium chloride is an ionic solid.

Metallic Solids
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms Figure 9.2.4. The structure of
metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The
atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many
useful and varied bulk properties. All exhibit high thermal and electrical conductivity, metallic luster, and malleability.
Many are very hard and quite strong. Because of their malleability (the ability to deform under pressure or hammering),
they do not shatter and, therefore, make useful construction materials. The melting points of the metals vary widely.
Mercury is a liquid at room temperature, and the alkali metals melt below 200 °C. Several post-transition metals also have
low melting points, whereas the transition metals melt at temperatures above 1000 °C. These differences reflect
differences in strengths of metallic bonding among the metals.

Figure 9.2.4 : Copper is a metallic solid.

Covalent Network Solids

Covalent network solids include crystals of diamond, silicon, some other nonmetals, and some covalent compounds such
as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of
covalent bonds. The atoms in these solids are held together by a network of covalent bonds, as shown in Figure 9.2.5. To
break or to melt a covalent network solid, covalent bonds must be broken. Because covalent bonds are relatively strong,
covalent network solids are typically characterized by hardness, strength, and high melting points. For example, diamond
is one of the hardest substances known and melts above 3500 °C.

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Figure 9.2.5 . A covalent crystal contains a three-dimensional network of covalent bonds, as illustrated by the structures
of diamond, silicon dioxide, silicon carbide, and graphite. Graphite is an exceptional example, composed of planar sheets
of covalent crystals that are held together in layers by noncovalent forces. Unlike typical covalent solids, graphite is very
soft and electrically conductive.

Molecular Solids
Molecular solids, such as ice, sucrose (table sugar), and iodine, as shown in Figure 9.2.6, are composed of neutral
molecules. The strengths of the attractive forces between the units present in different crystals vary widely, as indicated by
the melting points of the crystals. Small symmetrical molecules (nonpolar molecules), such as H2, N2, O2, and F2, have
weak attractive forces and form molecular solids with very low melting points (below −200 °C). Substances consisting of
larger, nonpolar molecules have larger attractive forces and melt at higher temperatures. Molecular solids composed of
molecules with permanent dipole moments (polar molecules) melt at still higher temperatures. Examples include ice
(melting point, 0 °C) and table sugar (melting point, 185 °C).

Figure 9.2.6 : Carbon dioxide (CO2) consists of small, nonpolar molecules and forms a molecular solid with a melting
point of −78 °C. Iodine (I2) consists of larger, nonpolar molecules and forms a molecular solid that melts at 114 °C.

Properties of Solids
A crystalline solid, like those listed in Table 9.2.1 has a precise melting temperature because each atom or molecule of the
same type is held in place with the same forces or energy. Thus, the attractions between the units that make up the crystal
all have the same strength and all require the same amount of energy to be broken. The gradual softening of an amorphous
material differs dramatically from the distinct melting of a crystalline solid. This results from the structural
nonequivalence of the molecules in the amorphous solid. Some forces are weaker than others, and when an amorphous
material is heated, the weakest intermolecular attractions break first. As the temperature is increased further, the stronger
attractions are broken. Thus amorphous materials soften over a range of temperatures.
Table 9.2.1: Types of Crystalline Solids and Their Properties
Type of Solid Type of Particles Type of Attractions Properties Examples

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 Type of Solid Type of Particles Type of Attractions Properties Examples

hard, brittle, conducts

electricity as a liquid but
ionic ions ionic bonds NaCl, Al2O3
not as a solid, high to very
high melting points
shiny, malleable, ductile,
conducts heat and
atoms of electropositive
metallic metallic bonds electricity well, variable Cu, Fe, Ti, Pb, U
elements
hardness and melting
temperature
atoms of electronegative very hard, not conductive,
covalent network covalent bonds C (diamond), SiO2, SiC
elements very high melting points
variable hardness, variable
brittleness, not
molecular molecules (or atoms) IMFs H2O, CO2, I2, C12H22O11
conductive, low melting
points

Graphene: Material of the Future

Carbon is an essential element in our world. The unique properties of carbon atoms allow the existence of carbon-
based life forms such as ourselves. Carbon forms a huge variety of substances that we use on a daily basis, including
those shown in Figure 9.2.7. You may be familiar with diamond and graphite, the two most common allotropes of
carbon. (Allotropes are different structural forms of the same element.) Diamond is one of the hardest-known
substances, whereas graphite is soft enough to be used as pencil lead. These very different properties stem from the
different arrangements of the carbon atoms in the different allotropes.

Figure 9.2.7 : Diamond is extremely hard because of the strong bonding between carbon atoms in all directions.
Graphite (in pencil lead) rubs off onto paper due to the weak attractions between the carbon layers. An image of a
graphite surface shows the distance between the centers of adjacent carbon atoms. (credit left photo: modification of
work by Steve Jurvetson; credit middle photo: modification of work by United States Geological Survey)
You may be less familiar with a recently discovered form of carbon: graphene. Graphene was first isolated in 2004 by
using tape to peel off thinner and thinner layers from graphite. It is essentially a single sheet (one atom thick) of
graphite. Graphene, illustrated in Figure 9.2.8, is not only strong and lightweight, but it is also an excellent conductor
of electricity and heat. These properties may prove very useful in a wide range of applications, such as vastly improved
computer chips and circuits, better batteries and solar cells, and stronger and lighter structural materials. The 2010
Nobel Prize in Physics was awarded to Andre Geim and Konstantin Novoselov for their pioneering work with
graphene.

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 Figure 9.2.8 : Graphene sheets can be formed into buckyballs, nanotubes, and stacked layers.

Crystal Defects
In a crystalline solid, the atoms, ions, or molecules are arranged in a definite repeating pattern, but occasional defects may
occur in the pattern. Several types of defects are known, as illustrated in Figure 9.2.9. Vacancies are defects that occur
when positions that should contain atoms or ions are vacant. Less commonly, some atoms or ions in a crystal may occupy
positions, called interstitial sites, located between the regular positions for atoms. Other distortions are found in impure
crystals, as, for example, when the cations, anions, or molecules of the impurity are too large to fit into the regular
positions without distorting the structure. Trace amounts of impurities are sometimes added to a crystal (a process known
as doping) in order to create defects in the structure that yield desirable changes in its properties. For example, silicon
crystals are doped with varying amounts of different elements to yield suitable electrical properties for their use in the
manufacture of semiconductors and computer chips.

Figure 9.2.9 : Types of crystal defects include vacancies, interstitial atoms, and substitutions impurities.

Summary

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 Video 9.2.1 : An overview of solids.
Some substances form crystalline solids consisting of particles in a very organized structure; others form amorphous
(noncrystalline) solids with an internal structure that is not ordered. The main types of crystalline solids are ionic solids,
metallic solids, covalent network solids, and molecular solids. The properties of the different kinds of crystalline solids are
due to the types of particles of which they consist, the arrangements of the particles, and the strengths of the attractions
between them. Because their particles experience identical attractions, crystalline solids have distinct melting
temperatures; the particles in amorphous solids experience a range of interactions, so they soften gradually and melt over
a range of temperatures. Some crystalline solids have defects in the definite repeating pattern of their particles. These
defects (which include vacancies, atoms or ions not in the regular positions, and impurities) change physical properties
such as electrical conductivity, which is exploited in the silicon crystals used to manufacture computer chips.

Glossary
amorphous solid
(also, noncrystalline solid) solid in which the particles lack an ordered internal structure

covalent network solid

solid whose particles are held together by covalent bonds

crystalline solid
solid in which the particles are arranged in a definite repeating pattern

interstitial sites
spaces between the regular particle positions in any array of atoms or ions

ionic solid
solid composed of positive and negative ions held together by strong electrostatic attractions

metallic solid
solid composed of metal atoms

molecular solid
solid composed of neutral molecules held together by intermolecular forces of attraction

vacancy
defect that occurs when a position that should contain an atom or ion is vacant

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard
Langley (Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax
College is licensed under a Creative Commons Attribution License 4.0 license. Download for free at
http://cnx.org/contents/[email protected]).
Adelaide Clark, Oregon Institute of Technology

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 Crash Course Chemistry: Crash Course is a division of Complexly and videos are free to stream for educational
purposes.

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