The Britannica Guide To Matter PDF

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First Edition
Britannica Educational Publishing
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Introduction by Erik Gregersen
Library of Congress Cataloging-in-Publication Data
The Britannica guide to matter / edited by Erik Gregersen.
p. cm.(Physics explained)
In association with Britannica Educational Publishing, Rosen Educational Services.
Includes bibliographical references and index.
ISBN 978-1-61530-381-6 (eBook)
1. MatterPopular works. I. Gregersen, Erik. II. Title: Guide to matter. III. Title: Matter.
QC171.2.B67 2011
530.4dc22
2010024080
Cover www.istockphoto.com / dra_schwartz
On page x: Aurora borealis as seen from Yellowknife, Northwest Territories, Canada.
Auroras are a beautiful phenomenon caused by plasma in Earths space environment. David
Brosha Photography/Flickr/Getty Images
On page xviii: Bathers enjoy the hot springs in Slovakias Low Tatras National Park. Water
is visible in three forms of matter: liquid (pooled water), gaseous (steam), and solid (ice and
snow). isifa/Getty Images
On pages 1, 9, 39, 56, 73, 115, 164, 197, 228, 256, 258, 267: Water in all its forms, represented by the famous Blue Lagoon in Iceland. Shutterstock.com
Contents
Introduction
Chapter 1: Matter and Its Phases

General Considerations
System Variables
The Phase Rule
Phase Diagrams
1
2
3
3
5
Chapter 2: Properties of Gases

Kinetic-Molecular Picture
Numerical Magnitudes
Intermolecular Separation and
Average Speed
Mean Free Path and Collision
Rate
Molecular Sizes
Summary of Numerical
Magnitudes
Free-Molecule Gas
Continuity of Gaseous and Liquid
States
Behaviour and Properties
Equilibrium Properties
Transport Properties
9
9
10
Chapter 3: Kinetic Theory of Gases

Ideal Gas
Pressure
Effusion
Thermal Transpiration
Viscosity
Thermal Conductivity
Diffusion and Thermal Diffusion
Boltzmann Equation
39
39
39
43
44
45
47
50
51
11
12
14
16
18
19
22
23
29
26
31
Deviations from the Ideal Model

Equation of State
53
53
54
Chapter 4: Properties of Liquids

Transitions Between States of Matter
Behaviour of Pure Liquids
Phase Diagram of a Pure
Substance
Representative Values of PhaseDiagram Parameters
Behaviour of Substances Near
Critical and Triple Points
Surface Tension
Molecular Structure of Liquids
Speed of Sound and Electric
Properties
56
58
60
Chapter 5: Liquid Solutions and

Solubility
Classes of Solutions
Electrolytes and Nonelectrolytes
Weak Electrolytes
Endothermic and Exothermic
Solutions
Properties of Solutions
Composition Ratios
Colligative Properties
Transport Properties in Solutions
Thermodynamics and Intermolecular
Forces in Solutions
Energy Considerations
Effects of Molecular Structure
Molecular Structure and Charge
Distribution
61
60
62
64
67
67
70
73
75
75
76
77
78
79
82
86
90
89
93
93
95
96
122
Effects of Chemical Interactions

Theories of Solutions
Activity Coefficients and Excess
Functions
Regular Solutions
Athermal Solutions
Associated and Solvated Solutions
Solutions of Electrolytes
Solubilities of Solids and Gases
Chapter 6: Crystalline Solids and
Liquid Crystals
Basic Units of Solids
Long- and Short-Range Order
Categories of Crystals
Structure
The Unit Cell
Structures of Metals
Structures of Nonmetallic
Elements
Structures of Binary Crystals
Alloys
Crystal Defects
Determination of Crystal
Structures
Types of Bonds
Ionic Bonds
Covalent Bonds
Metallic Bonds
Molecular Binding
Hydrogen Bonding
Crystal Growth
Vapour Growth
Growth from Solution
Growth from the Melt
Dendritic Growth
98
100
100
102
105
106
108
112
124
115
116
118
119
120
120
121
123
125
127
129
132
135
136
137
140
142
144
144
145
147
147
151
131
148
Liquid Crystals
Structure and Symmetry
Optical Properties
Chapter 7: Amorphous Solids and
Quasicrystals
Amorphous Solids
Distinction Between Crystalline
and Amorphous Solids
Preparation of Amorphous Solids
Atomic-Scale Structure
Properties of Oxide Glasses
Properties and Applications of
Amorphous Solids
Quasicrystals
Properties
152
152
159
164
164
165
168
171
175
162
176
183
183
194
Chapter 8: Plasma
The Development of Plasma Physics
Plasma Oscillations and Parameters
Basic Plasma Physics
Plasma Formation
Methods of Describing Plasma
Phenomena
Determination of Plasma
Variables
Waves in Plasmas
Applications of Plasmas
Natural Plasmas
Extraterrestrial Forms
Solar-Terrestrial Forms
197
198
201
204
204
Chapter 9: Clusters
Comparison with Bulk Matter
Comparison with Molecules
Methods of Study
228
231
235
236
207
200
208
210
216
219
219
220
206
Preparation of Clusters
Ionization and Sorting of
Clusters
Computer Simulation of Cluster
Behaviour
Structure
Clusters with Icosahedral
Structures
Clusters of Simple Metal Atoms
Network Structures
Physical Properties
Liquid and Solid Phases
Electric, Magnetic, and Optical
Properties
Chemical Properties
Conclusion
Glossary
Bibliography
Index
237
238
239
240
241
242
243
245
246
236
248
250
254
256
258
267
241
INTRODUCTION
7 Introduction
atter is one of the most basic subjects of physics.

One could say that everything else depends on it.
Matter is everything from raindrops that fall from the
sky to the wind that rustles grassy fields, to the stars that
shine in the most distant galaxies. This book goes beyond
these and other manifestations of manner to examine its
primary components, its behaviours, and the scientific
discoveries that have made the study of matter possible.
The ordinary experience of matter encompasses three
different types or phases: solid, liquid, and gas. These
phases follow how a substance holds itself together. Solids
remain, for lack of a better word, solid. Liquids do not
hold themselves together. They need to be contained, as
anyone who has dropped a glass of water on the ground
has discovered. Once contained, liquids pool and settle
to the lowest part of the container. Gases also need to be
contained. However, they neither pool nor settle. They fill
a container.
Gases are made of atoms or molecules. Aside from
collisions, there is no relation between one atom or molecule and another atom or molecule. Since collisions are
the most important process in a gas, knowing physical
parameters such as the distance between molecules, the
average speed at which a molecule travels, how far a molecule travels before it collides with another molecule, and
how often molecules collide can reveal much about how
gases work. The molecules travel at a speed determined
by the temperature. Temperature can be considered as a
measurement of the kinetic energy in a gas.
The chief way to describe a gas is the ideal gas equation of state, which says that the pressure of a gas times
its volume is equal to a constant times the temperature.
Equations of state are formulas that relate pressure,
volume, and temperature, and are extremely useful for
describing a materials behavior. For example if the volume
xi
The Britannica Guide to Matter
of a gas is increased and the temperature is held constant,

this would mean that the gass pressure would have to
decrease. (This last is Boyles law, which has been known
since 1662.)
The limiting conditions of matter also can be discerned using the concept of the phase diagram. The
three phases are not immutable categories. By changing
the temperature of a substance, it is possible to go from
one phase to another. The transmutability of water is the
most recognizable example of this. When the temperature drops below 0 C (32 F), liquid water freezes into ice.
When the temperature rises above 100 C (212 F), liquid
water evaporates into steam.
It is also possible to go from one phase to another by
changing the pressure. For example, by increasing the pressure, water vapour can be condensed into liquid. Because
both pressure and temperature are important in determining the phase of a substance, the phase diagram, which
graphs temperature on the horizontal axis and pressure
on the vertical axis, is quite important. The temperatures
and pressures where, for example, water vapour condenses
form a curved line in the phase diagram. These curved
lines can intersect at interesting points on the phase diagram called the triple point and the critical point. At the
triple point the curves demarcating sublimation (solid to
gas), fusion (solid to liquid), and vaporization (gas to liquid) intersect. At this point, gas, liquid, and solid are in
equilibrium with each other. At the critical point, the line
of vaporization ends and the line between gas and liquid is
blurred so the substance is a single fluid.
Solids are classified on the basis of the order of their
internal structure, with the most ordered of all being
the crystalline solids. Crystals have what is called longrange order, wherein the place of any atom in the crystal
xii
7 Introduction
can be pinpointed once one knows the basis of its structure. The basis of any crystalline structure is the unit cell,
which is repeated over and over throughout the crystal.
The main unit cells (hexagonal close packed, face-centred
cubic, and body-centred cubic) occur in many materials with extremely different compositions. These crystal
structures were deduced as far back as 1912 by German
physicist Max von Laue, who aimed a beam of X rays at a
crystal to produce a diffraction pattern, which is a regular
series of spots. By examining the spacing of the spots, one
can deduce how far apart are the atoms in a crystal. Von
Laue won the Nobel Prize in Physics for this discovery.
As mentioned, the solidity of solids arises from the
fact that the atoms are bound together. There are four main
types of bonds. In ionic bonds, such as in table salt (a.k.a.
sodium chloride), atoms exchange electrons so as to fill
their outermost electron shells. In covalent bonds, atoms
share electrons. In metallic bonds, electrons can travel
throughout the crystal unbound from their atoms. (These
conduction electrons allow metals to be excellent conductors of electricity.) In molecular bonding, also referred
to as the van der Waals force, interactions between the
dipole momentsthe measure of how charge is distributed within a moleculeof neighbouring molecules that
arise on a quantum mechanical level bind the two molecules together. The van der Waals force is unlike other
forces such as the gravitational force between two masses
or the Coulomb force between two charges, in which the
strength of the force decreases as the square of the distance. If the distance between two masses is doubled, the
gravitational force falls to one-quarter of its original value.
The van der Waals force decreases as the seventh power
of the distance. If the distance between two molecular
dipole moments is increased, the force falls to 1/128th of
xiii
its original value. Therefore the van der Waals force has
quite a short range.
Aside from the three forms of gas, liquid, and solid are
intermediate forms that partake of the properties of two
different phases. One of these forms is the liquid crystal,
which has some of the properties of a liquid and some
of a crystalline solid. For example, in the nematic liquid
crystal form, the molecules do not have translational symmetry but they do have rotational symmetry. This form of
matter is pervasive in todays computerized society in the
LCD, or liquid crystal display.
The amorphous solid is held together by the same
chemical bonds that bind the crystalline solids. However,
it lacks the pattern that rigidly describes the crystal.
Amorphous solids do not have unit cells, some of which
can have very unusual structures. Plastics have molecular
structures that consist of long chains of up to 100,000
atoms, with these long chains randomly tangled together
like shoelaces in a bag.
Glass is an amorphous solid and not a crystal, as one
would suppose. It is a long-standing urban legend that
glass is actually a liquid that flows very, very slowly. Thus,
the pieces of stained-glass windows in Gothic cathedrals
are supposedly thicker at the bottom than at the top, having had centuries to flow. (Presumably in millennia, these
medieval masterpieces would be puddles on the ancient
stones beneath them.) However, glass is indeed solid. As
for the stained-glass mystery, it appears that the pieces
of glass were originally made thicker at the bottom.
Another intermediate form is that of the quasicrystals,
so called because they have some of the regular pattern
behaviour of crystals but also the irregularity of the amorphous solids. Quasicrystals are one of the most recent
types of matter to be discovered, in 1984. Quasicrystals
xiv
7 Introduction
display the interesting mathematical property of quasiperiodicity, meaning that the pattern of the crystal can be
mathematically described but the pattern never repeats
itself. More than 100 quasicrystals are known. Such an
unusual substance has one very down-to-earth application
as a nonstick coating for pots and pans.
Beyond solid, liquid, and gas there is plasma, which
has been called the fourth state of matter. Plasmas are gas
in which the atoms are ionized such that there are as many
atoms that are negatively charged as positively charged.
This state of matter is of great interest to astronomers,
since nearly the entire universe is occupied by plasma.
The interiors of stars are in a plasma state. The vast spaces
between the stars, the interstellar medium, is not empty
space, but is filled with a tenuous plasma of hydrogen. In
the solar system, the spaces between the planetsthe
interplanetary mediumis filled with the plasma of the
solar wind, charged particles blown outwards by the Sun.
Earths magnetic field stretches out into space in the magnetosphere, and the solar wind plasma within it gives rise
to the beautiful aurorae.
On Earths surface, plasma is also a subject of great
interest. There are plasma TVs, in which a small plasma
is created in cells behind the screen. This plasma gives
rise to ultraviolet light that excites the phosphors on the
screen that emit in visible light. Since plasma TVs do not
need the electron beam apparatus required in regular televisions, they are much thinner. Aside from bringing to
many the latest reality television shows, plasmas are also
of great interest in the energy field. Some scientists hope
to make controlled nuclear fusion a reality and thus power
everything by the same process that makes the Sun shine.
To do this requires confining an extremely hot plasma in
a small space.
xv
Clusters are another form of matter, made up of groups

of atoms and molecules that form in solids and liquids.
These groups have unusual properties in that they occupy
the space between individual atoms and bulk matter,
that is, objects closer to the sizes of everyday experience.
For example, in something like a block of wood, nearly all
of the atoms are on the inside. In a cluster of tens of atoms,
most of the atoms are on the surface. This means that the
atoms in the bulk are surrounded by other atoms, while
those in the cluster have the freedom to leave. Also since
the cluster is smaller than the block of wood, the effects of
quantum mechanics are much more prominent. A block
of wood can be in any one of billions of quantum states.
The cluster of 10 atoms can only be in a few states.
The most famous cluster is buckminsterfullerene, a
spherical molecule of 60 carbon atoms (C60), named after
Buckminster Fuller, the maverick architect whose geodesic domes prefigure this clusters structure. The discovery
of C60 led to an entire family of fullerenes, including a
cylindrical tube of carbon, or nanotube, which may someday become the material for extremely strong cables.
The subject of matter contains nearly everything
in everyday experience and much that is beyond it.
Despite the seemingly reductive classification of every
substance into three phases (four, if plasma is included),
the material presented in this volume shows that initial
classification to be merely the beginning steps in the
understanding of matter.
xvi
Chapter 1
Matter and
Its Phases
atter is the material substance that constitutes

the observable universe and, together with energy,
forms the basis of all objective phenomena. At its most
fundamental level, matter is composed of elementary
particles, known as quarks and leptons (the class of
elementary particles that includes electrons). Quarks
combine into protons and neutrons and, along with electrons, form atoms of the elements of the periodic table,
such as hydrogen, oxygen, and iron. Atoms may combine
further into molecules such as the water molecule, H2O.
Large groups of atoms or molecules in turn form the bulk
matter of everyday life.
However, all matter of any type shares the fundamental property of inertia, whichas formulated within Isaac
Newtons three laws of motionprevents a material body
from responding instantaneously to attempts to change
its state of rest or motion. The mass of a body is a measure
of this resistance to change. For example, it is enormously
harder to set in motion a massive ocean liner than it is to
push a bicycle. Another universal property is gravitational
mass, whereby every physical entity in the universe acts
so as to attract every other one, as first stated by Newton
and later refined into a new conceptual form by Albert
Einstein.
Depending on temperature and other conditions,
matter may appear in any of several states. At ordinary
temperatures, for instance, gold is a solid, water is a
liquid, and nitrogen is a gas, as defined by certain characteristics: solids hold their shape, liquids take on the
1
shape of the container that holds them, and gases fill an

entire container. These states can be further categorized
into subgroups. Solids, for example, may be divided into
those with crystalline or amorphous structures or into
metallic, ionic, covalent, or molecular solids, on the basis
of the kinds of bonds that hold together the constituent
atoms. Less clearly defined states of matter include plasmas, which are ionized gases at very high temperatures;
foams, which combine aspects of liquids and solids; and
clusters, which are assemblies of small numbers of atoms
or molecules that display both atomic-level and bulklike
properties.
These states of matter are called phases. The three
fundamental phases of matter are solid, liquid, and gas
(vapour), but others are considered to exist, including
crystalline, colloid, glassy, amorphous, and plasma phases.
When a phase in one form is altered to another form, a
phase change is said to have occurred.
General Considerations
A system is a portion of the universe that has been chosen for studying the changes that take place within it in
response to varying conditions. A system may be complex,
such as a planet, or relatively simple, as the liquid within
a glass. Those portions of a system that are physically distinct and mechanically separable from other portions of
the system are called phases.
Phases within a system exist in a gaseous, liquid, or
solid state. Solids are characterized by strong atomic
bonding and high viscosity, resulting in a rigid shape.
Most solids are crystalline, inasmuch as they have a
three-dimensional periodic atomic arrangement. Some
solids (such as glass) lack this periodic arrangement and
are noncrystalline, or amorphous. Gases, which consist
2
7 Matter and Its Phases
of weakly bonded atoms with no long-range periodicity,

expand to fill any available space. Liquids have properties intermediate between those of solids and gases. The
molecules of a liquid are condensed like those of a solid.
Liquids have a definite volume, but their low viscosity enables them to change shape as a function of time.
The matter within a system may consist of more than
one solid or liquid phase, but a system can contain only a
single gas phase, which must be of homogeneous composition because the molecules of gases mix completely in
all proportions.
System Variables
Systems respond to changes in pressure, temperature, and
chemical composition, and, as this happens, phases may
be created, eliminated, or altered in composition. For
example, an increase in pressure may cause a low-density
liquid to convert to a denser solid, while an increase in
temperature may cause a solid to melt. A change of composition might result in the compositional modification
of a preexisting phase or in the gain or loss of a phase.
The Phase Rule

The classification and limitations of phase changes are
described by the phase rule, as proposed by the American
chemist J. Willard Gibbs in 1876 and based on a rigorous
thermodynamic relationship. The phase rule is commonly
given in the form P + F = C + 2. The term P refers to the
number of phases that are present within the system,
and C is the minimum number of independent chemical
components that are necessary to describe the composition of all phases within the system. The term F, called the
variance, or degrees of freedom, describes the minimum
3
theoretical chemist J. Willard Gibbs, whose work changed the face of

physical chemistry. Hulton Archive/Getty Images
4
number of variables that must be fixed in order to define a

particular condition of the system.
Phase Diagrams
Phase relations are commonly described graphically in
terms of phase diagrams. Each point within the diagram
indicates a particular combination of pressure and temperature, as well as the phase or phases that exist stably at
this pressure and temperature.
Unary Systems
For example, in the diagram for silicon dioxide, SiO2, all
phases have the same composition. The diagram in that
case is a representation of a one-component (unary)
system, in contrast to a two-component (binary), threecomponent (ternary), or four-component (quaternary)
system. The phases coesite, low quartz, high quartz,
tridymite, and cristobalite are solid phases composed of
silicon dioxide; each has its own atomic arrangement and
distinctive set of physical and chemical properties. The
most common form of quartz (found in beach sands and
granites) is low quartz. The region labeled anhydrous melt
consists of silicon dioxide liquid.
Different portions of the silicon dioxide system may
be examined in terms of the phase rule. Consider a point A
where a single solid phase existslow quartz. Substituting
the appropriate values into the phase rule P + F = C + 2 yields
1 + F = 1 + 2, so F = 2. For point A (or any point in which only
a single phase is stable) the system is divarianti.e., two
degrees of freedom exist. Thus, the two variables (pressure
and temperature) can be changed independently, and the
same phase assemblage continues to exist.
For a point B located on the boundary curve between
the stability fields of low quartz and high quartz, these two
5
phases coexist at all points along this curve. Substituting

values in the phase rule (2 + F = 1 + 2) will cause a variance of
1 to be obtained. This indicates that one independent variable can be changed such that the same pair of phases will
be retained. A second variable must be changed to conform
to the first in order for the phase assemblage to remain
on the boundary between low and high quartz. The same
result holds for the other boundary curves in this system.
For a point C located at a triple point, a condition in
which three stability fields intersect, the phase rule (3 + F
= 1 + 2) indicates that the variance is 0. Point C is therefore
an invariant point; a change in either pressure or temperature results in the loss of one or more phases. The phase
rule also reveals that no more than three phases can stably coexist in a one-component system because additional
phases would lead to negative variance.
Binary Systems
Consider the binary system that describes the freezing and melting of the minerals titanite (CaSiTiO5) and
anorthite feldspar (CaAl2Si2O8). The melt can range in
composition from pure CaSiTiO5 to pure CaAl2Si2O8, but
the solids show no compositional substitution. All phases
therefore have the composition of CaSiTiO5, CaAl2Si2O8,
or a liquid mixture of the two. The system in the figure has
been examined at atmospheric pressure; because the pressure variable is fixed, the phase rule is expressed as P + F =
C + 1. In this form it is called the condensed phase rule, for
any gas phase is either condensed to a liquid or is present
in negligible amounts. The phase diagram shows a vertical
temperature coordinate and a horizontal compositional
coordinate (ranging from pure CaSiTiO5 at the left to pure
CaAl2Si2O8 at the right).
The phase fields contain either one or two phases. Any
point in a one-phase field corresponds to a single phase
6
whose composition is indicated directly below on the

horizontal axis. For example, point A would present a liquid whose composition is 70 percent CaAl2Si2O8 and 30
percent CaSiTiO5. The compositions of phases in a twophase field are determined by construction of a horizontal
(constant-temperature) line from the point of interest
to the extremities of the two-phase field. Thus, a sample
with composition B would consist of liquid C (43 percent
CaSiTiO5 and 57 percent CaAl2Si2O8) and solid anorthite
D. A sample at point E at a lower temperature would consist of the solids titanite (F ) and anorthite (G).
Liquid CaAl2Si2O8 cools to produce solid anorthite
at 1,550 C, whereas liquid CaSiTiO5 cools to produce
solid titanite at 1,390 C. If the batch were a mixture of
the two components, the freezing temperature of each
of these minerals would be depressed. In a melt consisting of a single component, such as CaSiTiO5, all atoms
could add to titanite nuclei to form crystals of titanite. If,
however, the melt contained 30 percent CaAl2Si2O8, the
rate of formation of titanite nuclei would be decreased,
as 30 percent of the melt could not contribute to their
formation. In order to increase the rate of formation of
titanite nuclei and promote crystallization, the temperature of the melt must be decreased below the freezing
point of pure CaSiTiO5. When cooled, liquid A does not
begin crystallization until temperature H is reached. Pure
anorthite crystals precipitate from the melt. Depletion of
CaAl2Si2O8 from the melt causes the melt composition to
become relatively enriched in CaSiTiO5, with consequent
additional depression of the anorthite freezing point.
As freezing continues, the liquid composition changes
until the minimum point is reached at I. This point is called
the eutectic. It is the lowest temperature at which a liquid
can exist in this system. At the eutectic, both anorthite
and titanite crystallize together at a fixed temperature
7
and in a fixed ratio until the remaining liquid is consumed.

All intermediate liquid compositions migrate during
crystallization to the eutectic. The melting sequence of
titanite-anorthite mixtures is exactly the opposite of the
freezing sequence (i.e., melting of any anorthite-titanite
mixture begins at the eutectic).
Depression of the freezing point of a compound by
the addition of a second component is common in both
binary and more complex systems. This usually occurs
when the solid phases either have a fixed composition or
show limited solid solution. Common examples are the
mixing of ice and salt (NaCl) or the use of ethylene glycol
(antifreeze) to depress the freezing point of water.
Chapter 2
Properties
of Gases
he remarkable feature of gases is that they appear

to have no structure at all. They have neither a definite size nor shape, whereas ordinary solids have both a
definite size and a definite shape, and liquids have a definite size, or volume, even though they adapt their shape
to that of the container in which they are placed. Gases
will completely fill any closed container; their properties
depend on the volume of a container but not on its shape.
Kinetic-Molecular Picture
Gases nevertheless do have a structure of sorts on a molecular scale. They consist of a vast number of molecules moving
chaotically in all directions and colliding with one another
and with the walls of their container. Beyond this, there is
no structurethe molecules are distributed essentially randomly in space, traveling in arbitrary directions at speeds
that are distributed randomly about an average determined
by the gas temperature. The pressure exerted by a gas is the
result of the innumerable impacts of the molecules on the
container walls and appears steady to human senses because
so many collisions occur each second on all sections of the
walls. More subtle properties such as heat conductivity, viscosity (resistance to flow), and diffusion are attributed to
the molecules themselves carrying the mechanical quantities of energy, momentum, and mass, respectively. These
are called transport properties, and the rate of transport
is dominated by the collisions between molecules, which
force their trajectories into tortuous shapes. The molecular
9
collisions are in turn controlled by the forces between the

molecules and are described by the laws of mechanics.
Thus, gases are treated as a large collection of tiny particles subject to the laws of physics. Their properties are
attributed primarily to the motion of the molecules and
can be explained by the kinetic theory of gases. It is not
obvious that this should be the case, and for many years a
static picture of gases was instead espoused, in which the
pressure, for instance, was attributed to repulsive forces
between essentially stationary particles pushing on the
container walls.
Any theory of gas behaviour based on this kinetic
model must also be a statistical one because of the enormous numbers of particles involved. The kinetic theory
of gases is now a classical part of statistical physics and
is indeed a sort of miniature display case for many of
the fundamental concepts and methods of science. Such
important modern concepts as distribution functions,
cross-sections, microscopic reversibility, and time-reversal
invariance have their historical roots in kinetic theory, as
does the entire atomistic view of matter.
Numerical Magnitudes
When considering various physical phenomena, it is helpful for one to have some idea of the numerical magnitudes
involved. In particular, there are several characteristics
whose values should be known, at least within an order of
magnitude (a factor of 10), in order for one to obtain a clear
idea of the nature of gaseous molecules. These features
include the size, average speed, and intermolecular separation at ordinary temperatures and pressures. In addition,
other important considerations are how many collisions a
typical molecule makes in one second under these conditions and how far such a typical molecule travels before
10
7 Properties of Gases
colliding with another molecule. It has been established

that molecules have sizes on the order of a few angstrom
units (1 = 108 cm) and that there are about 6 1023 molecules in one mole, which is defined as the amount of a
substance whose mass in grams is equal to its molecular
weight (e.g., 1 mole of water, H2O, is 18.0152 grams [0.6355
ounce]). With this knowledge, one could calculate at least
some of the gas values. It is interesting to see how the
answers could be estimated from simple observations and
then to compare the results to the accepted values that are
based on more precise measurements and theories.
Intermolecular Separation
and Average Speed
One of the easiest properties to work out is the average
distance between molecules compared to their diameter;
water will be used here for this purpose. Consider 1 gram
(0.04 ounce) of H2O at 100 C (212 F) and atmospheric
pressure, which are the normal boiling point conditions.
The liquid occupies a volume of 1.04 cubic cm (0.06 cubic
inch); once converted to steam it occupies a volume of
1.67 103 cubic cm. Thus, the average volume occupied
by one molecule in the gas is larger than the corresponding volume occupied in the liquid by a factor of 1.67
103/1.04, or about 1,600. Since volume varies as the cube
of distance, the ratio of the mean separation distance in
the gas to that in the liquid is roughly equal to the cube
root of 1,600, or about 12. If the molecules in the liquid
are considered to be touching each other, the ratio of the
intermolecular separation to the molecular diameter in
ordinary gases is on the order of 10 under ordinary conditions. It should be noted that the actual separation and
diameter cannot be determined in this way; only their
ratio can be calculated.
11
It is also relatively simple to estimate the average speed

of gas molecules. Consider a sound wave in a gas, which
is just the propagation of a small pressure disturbance. If
pressure is attributed to molecular impacts on a test surface, then surely a pressure disturbance cannot travel faster
than the molecules themselves. In other words, the average
molecular speed in a gas should be somewhat greater than
the speed of sound in the gas. The speed of sound in air at
ordinary temperatures is about 330 metres (1,100 feet) per
second, so the molecular speed will be estimated here to
be somewhat greater, say, about 500 metres (1,600 feet) per
second. This value depends on the particular gas and the
temperature, but it will be sufficient for the kind of estimates sought here.
Mean Free Path and Collision Rate

The average molecular speed, along with an observed rate
of the diffusion of gases, can be used to estimate the length
and tortuosity of the path traveled by a typical molecule.
If a bottle of ammonia is opened in a closed room, at least
a few minutes pass before the ammonia can be detected
at a distance of just one metre. (Ammonia, NH3, is a gas;
the familiar bottle of ammonia typically seen is actually a
solution of the gas in water.) Yet, if the ammonia molecules
traveled directly to an observer at a speed somewhat faster
than that of sound, the odour should be detectable in only
a few milliseconds. The explanation for the discrepancy
is that the ammonia molecules collide with many air molecules, and their paths are greatly distorted as a result.
For a quantitative estimate of the diffusion time, a more
controlled system must be considered, because even gentle
stray air currents in a closed room greatly speed up the
spreading of the ammonia. To eliminate the effect of such
air currents, a closed tubesay, a glass tube 1 cm (0.4 inch)
12
in diameter and 1 metre (39 inches) in lengthcan be used.

A small amount of ammonia gas is released at one end, and
both ends are then closed. In order to measure how long it
takes for the ammonia to travel to the other end, a piece of
moist red litmus paper might be used as a detector; it will
turn blue when the ammonia reaches it. This process takes
quite a long timeabout several hoursbecause diffusion occurs at such a slow rate. In this case, the time will be
taken to be approximately 3 hours, or roughly 104 seconds
(s). During this time interval, a typical ammonia molecule
actually travels a distance of (5 104 cm/s)(104 s) = 5 108
cm = 5,000 km (3,000 miles), roughly the distance across
the United States. In other words, such a molecule travels
a total distance of five million metres in order to progress a
net distance of only one metre.
The solution to a basic statistical problem can be used
to estimate the number of collisions such a typical diffusing
molecule experienced (N) and the average distance traveled between collisions (l ), called the mean free path. The
product of N and l must equal the total distance traveled
i.e., Nl = 5 108 cm. This distance can be thought of as a
chain 5,000 km long, made up of N links, each of length l.
The statistical question then is as follows: If such a chain
is randomly jumbled, how far apart will its ends be on the
average? This end-to-end distance corresponds to the
length of the diffusion tube (one metre). This is a venerable
statistical problem that recurs in many applications. One
of the more vivid ways of illustrating the concept is known
as the drunkards walk. In this scenario a drunkard takes
steps of length l but, because of inebriation, takes them in
random directions. After N steps, how far will he be from
his starting point?
The answer is that his progress is proportional not to
N but to N1/2. For example, if the drunkard takes four steps,
each of length l, he will end up at a distance of 2l from his
13
starting point. Gas molecules move in three dimensions,

whereas the drunkard moves in two dimensions; however,
the result is the same. Thus, the square root of N multiplied
by the length of the mean free path equals the length of the
diffusion tube: N1/2l = 102 cm = 1 metre. From the equations
for Nl and N1/2l, it can readily be calculated that N = 2.5
1013 collisions and l = 2.0 105 cm. The mean time between
collisions, , is found by dividing the time of the diffusion
experiment by the number of collisions during that time:
= (104)/(2.5 1013) = 4 1010 seconds between collisions, corresponding to a collision frequency of 2.5 109 collisions per
second. It is thus understandable that gases appear to be
continuous fluids on ordinary scales of time and distance.
Molecular Sizes
Molecular sizes can be estimated from the foregoing
information on the intermolecular separation, speed,
mean free path, and collision rate of gas molecules. It
would seem logical that large molecules should have a
better chance of colliding than do small molecules. The
collision frequency and mean free path must therefore be
related to molecular size.
To find this relationship, consider a single molecule in
motion. During a time interval t it will sweep out a certain
volume, hitting any other molecules present in this so-called
collision volume. If molecules are located by their centres
and each molecule has a diameter d, then the collision volume will be a long cylinder of cross-sectional area d2. The
cylinder must be sufficiently long to include enough molecules so that good statistics on the number of collisions are
obtained, but otherwise the length does not matter. If the
molecule is observed for a time t, then the length of the collision cylinder will be vt, where v is the average speed of the
molecule, and the volume of the cylinder will be (d2)(vt),
14
the product of its cross-sectional area and its length. Every

molecule in the cylinder will be struck within time t, so the
number of molecules in the collision cylinder will equal the
number of collisions that occur in time t. Each collision will
put a kink in the cylinder, but this will not affect the results
as long as the number of collisions is not too large.
If the gas is uniform, the number of molecules per volume will be consistent throughout the entire gas. Suppose
that there are N molecules in volume V; then there will be
(N/V)(d2)(vt) molecules in the collision volume; this is the
number of collisions in time t. The mean free path is equal
to the total length of the collision cylinder divided by the
number of collisions that occur in it:
Since l has been shown to be roughly 2.0 105 cm, d could

be calculated if N/V was known.
It is relatively easy to find (N/V)d3, from which
both d and N/V can be determined. Recall that the volume of one gram of steam is about 1,600 times larger
than the volume of one gram of liquid water. In other
words, there are roughly 1,600 N molecules in a volume V of liquid, and, if the molecules are just touching
(i.e., the separation distance between their centres is
one molecular diameter), the volume V of the liquid is
1,600 Nd3. When this equation for volume is combined
with the above expression for l, the following values are
obtained: d = (2.0 105)/1,600 = 3.9 10 -8 cm = 3.9 , and
N/V = 1/d2l = 1.0 1019 molecules per cubic cm. Thus,
a typical molecule is exceedingly small, and there is an
impressively large number of them in 1 cubic cm of gas.
Between collisions, a gas molecule travels a distance of
about l/d = (2.0 105)/(3.9 108) = 500 times its diameter.
15
Since it was calculated above that the average separation

between molecules is about 10 times the molecular diameter, the mean free path is approximately 50 times greater
than the mean molecular separation. Accordingly, a typical molecule passes roughly 50 other molecules before it
hits one.
Summary of Numerical Magnitudes

The following is a summary of the above estimates of
molecular quantities in a gas, with a little spread in the
numbers to allow for molecules both smaller and larger
than the typical ones used herewhich are H2O, NH3, and
the nitrogen (N2) plus oxygen (O2) mixture that is airand
to allow for the fact that some of these quantities depend
on temperature and pressure. It is important to note that
these estimates and calculations are rather simplified,
although fundamentally correct, and that there may well
be missing factors such as 3/8 or 2. The numerical estimates for gases at ordinary pressure and temperature are:
The general impression of gas molecules given by these

numbers is that they are exceedingly small, that there are
enormous numbers of them in even 1 cubic cm, that they
16
are moving very fast, and that they collide many times in
one second. Two other facts are especially important. The
first is that the lengths involved, especially the mean free
path, are minute compared with ordinary lengths, even
with the diameter of a capillary tube. This means that
gas behaviour and properties are dominated by collisions
between molecules and that collisions with walls play
only a secondary (though important) role. The second is
that the mean free path is much larger than the molecular diameter. Thus, collisions between pairs of molecules
are of paramount importance in determining ordinary gas
behaviour, while collisions that involve three or more molecules at the same time can basically be ignored.
A cautious reader might feel a bit uneasy about the
glibness of the preceding estimates, so a simple check will
be made here by calculating the number of molecules in
one mole of gas, a quantity known as Avogadros number. The number density of a gas was approximated to be
about 1.0 1019 molecules per cubic cm, and from experiment it is known that 1 mole of gas occupies a volume of
about 25 litres (2.5 104 cubic centimetres) under ordinary
conditions. Using these values, an estimate of Avogadros
number is (1.0 1019)(2.5 104) = 2.5 1023 molecules per
mole. This deviates somewhat from the accepted value of
6.022 1023 molecules per mole, but the order of magnitude is certainly correct.
In point of historical fact, a value for Avogadros number as good as this estimate was not obtained until 1865,
when Josef Loschmidt in Vienna made a calculation similar to the one here but based on gas viscosity rather than
on gas diffusion. In the older German scientific literature,
Avogadros number is often referred to as Loschmidts
number for this reason. In current English-language scientific literature, Loschmidts number is usually taken to
mean the number of gas molecules in one cubic centimetre
17
at 0 C (32 F) and one atmosphere pressure (2.687 1019

molecules per cubic centimetre).
There are other ways by which molecular sizes and
Avogadros number could have been estimated, such as
from the spreading of a surface oil film on water or from
the surface tension and the energy of evaporation of a liquid, but they will not be discussed here.
The foregoing picture of a gas as a collection of molecules dominated by binary molecular collisions is in
reality only a limited view. Two limitations of the model
are briefly discussed below.
Free-Molecule Gas
The mean free path in a gas may easily be increased by
decreasing the pressure. If the pressure is halved, the
mean free path doubles in length. Thus, at low enough
pressures the mean free path can become sufficiently
large that collisions of the gas molecules with surfaces
become more important than collisions with other gas
molecules. In such a case, the molecules can be envisioned
as moving freely through space until they encounter some
solid surface; hence, they are termed free-molecule gases.
Such gases are sometimes called Knudsen gases, after the
Danish physicist Martin Knudsen, who studied them
experimentally.
Many of their properties are strikingly different from
those of ordinary gases (also known as continuum gases). A
radiometer is a four-vaned mill that depends essentially on
free-molecule effects. A temperature difference in the freemolecule gas causes a thermomolecular pressure difference
that drives the vanes. The radiometer will stop spinning if
enough air leaks into its glass envelope. (It will also stop
spinning if all the air is removed from the envelope.) The
flight of objects at high altitudes, where the mean free path
18
is very long, is also subject to free-molecule effects. Such

effects can even occur at ordinary pressures if a significant
physical dimension becomes small enough. Important
examples are found in many chemical process industries, where reactions are forced by catalysts to proceed
at reasonable speeds. Many of these catalysts are porous
materials whose pore sizes are smaller than molecular mean
free paths. The speed of the desired chemical reaction may
be controlled by how fast the reactant gases diffuse into the
porous catalyst and by how fast the product gases can diffuse out so more reactants can enter the pores.
There is a large transition region between freemolecule behaviour and continuum behaviour, where
both molecule-molecule and molecule-surface collisions
are significant. This region is rather difficult to describe
theoretically and remains an active field of research.
Continuity of Gaseous
and Liquid States
It may be somewhat surprising to learn that there is no
fundamental distinction between a gas and a liquid. It was
noted above that a gas occupies a volume about 1,600 times
greater than that of an equal weight of liquid. The question
arises as to the behaviour of a gas that has been compressed
to 1/1,600 of its volume by application of sufficiently high
pressure. If this compression is carried out above a specific temperature called the critical temperature, which
is different for each gas, no phase change occurs, and the
resulting substance is a gas that is just as dense as a liquid.
If the compression is carried out at a fixed temperature
below the critical temperature, an astonishing phenomenon occursat a particular pressure liquid suddenly forms.
Attempts to compress the gas further simply increase the
amount of liquid present and decrease the amount of gas,
19
with the pressure remaining constant until all the gas has
been converted to liquid. The applied pressure must subsequently rise a great deal to reduce the volume further, since
liquids are much less compressible than gases.
The abrupt condensation of a gas to a liquid usually
does not seem astonishing because it is so commonplace
nearly everyone has boiled water, for example, which is
the reverse process. From the standpoint of the kineticmolecular theory of gases, however, it is something of a
mystery. Why does it occur so abruptly and only at temperatures below a critical temperature? Equations have
been written down that describe condensation, but an
explanation is still lacking in the sense that no one has
been able to show that it must occur, given only the forces
between the molecules and the fact that their motion is
described by ordinary mechanics. Condensation, which is
an example of a first-order phase transition, remains one of
the outstanding unsolved problems of statistical physics.
The critical temperature marks the separation between
an abrupt change and a continuous change. Other peculiar
phenomena occur near the critical temperature. The densities of the coexisting liquid and gas (which is usually called a
vapour in this case) become closer as the critical temperature
is approached from below, and at the critical temperature
they are identical. There is a unique point for every fluid,
called the critical point. It is described by a critical temperature, a critical volume, and a critical pressure, at which liquid
and vapour become identical. Above that temperature there
is no distinction between gas and liquid; there is only a
single fluid. Moreover, it is possible to pass continuously
from an apparently definite gas or vapour to an apparently
definite liquid with no abrupt condensation occurring. This
can be accomplished by heating the vapour above the critical temperature while keeping the volume constant, then
compressing it to a high density characteristic of a liquid,
20
and finally cooling it at constant volume to its original temperature, where it is now clearly a liquid.
In short, gases and liquids are just the extreme stages of
a fluid, with no fundamental distinction between the two.
For this reason, an arbitrary decision has been made for the
present discussion to define what is meant by the gaseous
state. The definition will be based on the number density
(i.e., molecules per unit volume): the number density of the
fluid must be low enough that only collisions between two
molecules at a time need to be considered. More specifically,
the mean free path must be much larger than the molecular
diameter. Such a fluid shall be termed a dilute gas.
A few brief historical remarks are in order before leaving the subject of the continuity of the gaseous and liquid
states. The first extensive experimental study that clearly
demonstrated the phenomena involved was performed on
carbon dioxide, CO2. (Carbon dioxide, whose solid form is
called dry ice, has a critical temperature of 31 C [88 F].)
The experiment was conducted by Thomas Andrews at
what is now the Queens University of Belfast in Northern
Ireland, and its results were summarized in 1869 in a Bakerian
lecture to the Royal Society of London entitled On the
Continuity of the Gaseous and Liquid States of Matter.
In 1873 a Dutch thesis was presented to the University of
Leiden by Johannes D. van der Waals with virtually the same
title (but in Dutch) as Andrewss lecture. In his study van
der Waals used some ingenious approximations to obtain
a simple equation relating the pressure, temperature, and
molar volume of a fluid, based on a model that considered
molecules as hard spheres with weak long-range attractive forces between them. This equation can be used to
locate the critical point of a system, and it is also consistent
with the occurrence of condensation when supplemented with a thermodynamic condition. This is possibly
one of the most-quoted but little-read theses in science.
21
Nevertheless, van der Waals started a scientific trend

that continues to the present. His pressure-volumetemperature relation, called an equation of state, is the
standard equation of state for real gases in physical chemistry, and at least one new equation of state is proposed
every year in an attempt to improve on its quantitative accuracy (which is not very good). It furnished the
impetus for the development of theories of liquids and
of solutions. The equation is compatible with a unifying
idea called the principle of corresponding states. This
principle states that, if the pressure ( p), volume (V ), and
temperature (T ) of a gas are replaced, respectively, with
the corresponding reduced variablesi.e., the pressure
divided by the critical pressure ( p/pc ), the volume divided
by the critical volume (V/Vc ), and the temperature divided
by the critical temperature (T/Tc )all gases will behave in
essentially the same manner.
The critical point has itself proved to be a rich and deep
subject. The gas-liquid critical point turns out to be only
one of many types of critical points, including those of a
magnetic variety, with the common feature that long-range
correlations develop regardless of the molecular details
of the system. That is, any small part of a system near its
critical point seems to know what quite distant parts are
doing. The mathematical description of the behaviour of a
system near its critical point also becomes rather unusual.
Behaviour and Properties

The enormous number of molecules in even a small volume of a dilute gas produces not complication, as might
be expected, but rather simplification. The reason is that
ordinarily only statistical averages are observed in the
study of the behaviour and properties of gases, and statistical methods are quite accurate when large numbers are
22
involved. Compared to the numbers of molecules involved,

there are only a few properties of gases that warrant attention here, namely, pressure, density, temperature, internal
energy, viscosity, heat conductivity, and diffusivity. (More
subtle properties can be brought into view by the application of electric and magnetic fields, but they are of minor
interest.)
It is a remarkable fact that these properties are not
independent. If two are known, the rest can be determined from them. That is to say, for a given gas, the
specification of only two propertiesusually chosen to be temperature and density or temperature and
pressurefixes all the others. Thus, if the temperature
and density of carbon dioxide are specified, the gas can
have only one possible pressure, one internal energy, one
viscosity, and so on. In order to determine the values of
these other properties, they must either be measured or
calculated from the known properties of the molecules
themselves. Such calculations are the ultimate goal of
statistical mechanics and kinetic theory, and dilute gases
constitute the case for which the most progress toward
that goal has been made.
In discussing the behaviour of gases, it is useful to separate
the equilibrium properties and the nonequilibrium transport properties. By definition, a system in equilibrium
can undergo no net change unless some external action is
performed on it (e.g., pushing in a piston or adding heat).
Its behaviour is steady with time, and no changes appear
to be occurring, even though the molecules are in ceaseless motion. In contrast, the nonequilibrium properties
describe how a system responds to some external action,
such as the imposition of a temperature or pressure
23
difference. Equilibrium behaviour is much easier to analyze, because any change that occurs on the molecular level
must be compensated by some other change or changes
on the molecular level in order for the system to remain in
equilibrium.
Ideal Gas Equation of State
Among the most obvious properties of a dilute gas, other
than its low density compared with liquids and solids, are
its great elasticity or compressibility and its large volume
expansion on heating. These properties are nearly the
same for all dilute gases, and virtually all such gases can
be described quite accurately by the following universal
equation of state:
(15)
This expression is called the ideal, or perfect, gas
equation of state, since all real gases show small deviations from it, although these deviations become less
significant as the density is decreased. Here p is the pressure, v is the volume per mole, or molar volume, r is the
universal gas constant, and t is the absolute thermodynamic temperature. To a rough degree, the expression is
accurate within a few percent if the volume is more than
10 times the critical volume; the accuracy improves as the
volume increases. The expression eventually fails at both
high and low temperatures, owing to ionization at high
temperatures and to condensation to a liquid or solid at
low temperatures.
The ideal gas equation of state is an amalgamation of
three ideal gas laws that were formulated independently.
The first is Boyles law, which refers to the elastic properties of the gas; it was described by the Anglo-Irish scientist
Robert Boyle in 1662 in his famous . . . Experiments . . .
24
Touching the Spring of the Air . . . . It states that the volume

of a gas at constant temperature is inversely proportional
to the pressure; i.e., if the pressure on a gas is doubled, for
example, its volume decreases by one-half. The second,
usually called Charless law, is concerned with the thermal
expansion of the gas. It is named in honour of the French
experimental physicist Jacques-Alexandre-Csar Charles
for the work he carried out in about 1787. The law states
that the volume of a gas at constant pressure is directly proportional to the absolute temperature; i.e., an increase of
temperature of 1 C (1.8 F) at room temperature causes the
volume to increase by about 1 part in 300, or 0.3 percent.
The third law embodied in equation (15) is based
on the 1811 hypothesis of the Italian scientist Amedeo
Avogadronamely, that equal volumes of gases at the
same temperature and pressure contain equal numbers
of particles. The number of particles (or molecules) is
proportional to the number of moles n, the constant of
proportionality being Avogadros number, N0. Thus, at
constant temperature and pressure the volume of a gas is
proportional to the number of moles. If the total volume
V contains n moles of gas, then only v = V/n appears in
the equation of state. By measuring the quantity of gas
in moles rather than grams, the constant R is made universal; if mass were measured in grams (and hence v in
volume per gram), then R would have a different value for
each gas.
The ideal gas law is easily extended to mixtures by letting n represent the total number of moles of all species
present in volume V. That is, if there are n1 moles of species 1, n2 moles of species 2, etc., in the mixture, then n =
n1 + n2 + and v = V/n as before. This result can also be
rewritten and reinterpreted in terms of the partial pressures of the different species, such that p1 = n1RT/V is the
25
robert Boyle. Hulton Archive/Getty Images
26
partial pressure of species 1 and so on. The total pressure

is then given as p = p1 + p2 + . This rule is known as
Daltons law of partial pressures in honour of the British
chemist and physicist John Dalton, who formulated it
about 1801.
A brief aside on units and temperature scales is in
order. The (metric) unit of pressure in the scientific
international system of units (known as the SI system) is
newton per square metre (N/m2), where one newton (N)
is the force that gives a mass of 1 kg an acceleration of 1
m/s2. The unit N/m2 is given the name pascal (Pa), where
one standard atmosphere is exactly 101,325 Pa (approximately 14.7 pounds per square inch). The unit of volume
in the SI system is the cubic metre (1 cubic metre = 106
cubic cm), and the unit of temperature is the kelvin (K).
The Kelvin thermodynamic temperature scale is defined
through the laws of thermodynamics so as to be absolute or universal, in the sense that its definition does not
depend on the specific properties of any particular kind
of matter. Its numerical values, however, are assigned by
defining the triple point of wateri.e., the unique temperature at which ice, liquid water, and water vapour are
all in equilibriumto be exactly 273.16 K. The freezing
point of water under one atmosphere of air then turns out
to be (by measurement) 273.1500 K. The freezing point
is 0 on the Celsius scale (or 32 on the Fahrenheit scale),
by definition. The precise thermodynamic definition of
the Kelvin scale and the rather peculiar number chosen
to define its numerical values (i.e., 273.16) are historical
choices made so that the ideal gas equation of state will
have the simple mathematical form given by the righthand side of equation (15).
The gas constant R is determined by measurement.
The best value so far obtained is that of the U.S. National
27
Institute of Standards and Technologynamely, 8.314472

J/mol . Here the unit J is one of work or energy, one
joule ( J) being equal to one newton-metre.
Internal Energy
Once the equation of state is known for an ideal gas, only
its internal energy, E, needs to be determined in order for
all other equilibrium properties to be deducible from the
laws of thermodynamics. That is to say, if the equation of
state and the internal energy of a fluid are known, then
all the other thermodynamic properties (e.g., enthalpy,
entropy, and free energy) are fixed by the condition that
it must be impossible to construct perpetual motion
machines from the fluid. Proofs of such statements are
usually rather subtle and involved and constitute a large
part of the subject of thermodynamics, but conclusions
based on thermodynamic principles are among the most
reliable results of science.
A thermodynamic result of relevance here is that the
ideal gas equation of state requires that the internal energy
depend on temperature alone, not on pressure or density.
The actual relationship between E and T must be measured or calculated from known molecular properties by
means of statistical mechanics. The internal energy is not
directly measurable, but its behaviour can be determined
from measurements of the molar heat capacity (i.e., the
specific heat) of the gas. The molar heat capacity is the
amount of energy required to raise the temperature of one
mole of a substance by one degree. Its units in the SI system are J/mol K. A system with many kinds of motion
on a molecular scale absorbs more energy than one with
only a few kinds of motion. The interpretation of the temperature dependence of E is particularly simple for dilute
gases, as shown in the discussion of the kinetic theory
28
of gases in Chapter 3. The following highlights only the

major aspects.
Every gas molecule moves in three-dimensional space,
and this translational motion contributes ( 3/2)rt (per
mole) to the internal energy e. For monatomic gases,
such as helium, neon, argon, krypton, and xenon, this is
the sole energy contribution. Gases that contain two or
more atoms per molecule also contribute additional terms
because of their internal motions:
(16)
where eint may include contributions from molecular rotations and internal vibrations and occasionally from internal
electronic excitations. Some of these internal motions
may not contribute at ordinary temperatures because of
special conditions imposed by quantum mechanics, however, so that the temperature dependence of eint can be
rather complex.
The extension to gas mixtures is straightforwardthe
total internal energy e (per mole) is the weighted sum of
the internal energies of each of the species: ne = n1e1 + n2e2
+ , where n = n1 + n2 + .
It is the task of the kinetic theory of gases to account
for these results concerning the equation of state and the
internal energy of dilute gases.
The following is a summary of the three main transport
properties: viscosity, heat conductivity, and diffusivity.
These properties correspond to the transfer of momentum, energy, and matter, respectively.
29
Viscosity
All ordinary fluids exhibit viscosity, which is a type of
internal friction. A continuous application of force is
needed to keep a fluid flowing, just as a continuous force is
needed to keep a solid body moving in the presence of friction. Consider the case of a fluid slowly flowing through a
long capillary tube. A pressure difference of p must be
maintained across the ends to keep the fluid flowing, and
the resulting flow rate is proportional to p. The rate is
inversely proportional to the viscosity () since the friction that opposes the flow increases as increases. It also
depends on the geometry of the tube, but this effect will
not be considered here. The SI units of are N s/m2 or
Pa s. An older unit of the centimetre-gram-second version of the metric system that is still often used is the
poise (1 Pa s = 10 poise). At 20 C (68 F) the viscosity of
water is 1.0 10 -3 Pa s and that of air is 1.8 10 -5 Pa s. To
a rough approximation, liquids are about 100 times more
viscous than gases.
There are three important properties of the viscosity
of dilute gases that seem to defy common sense. All can be
explained, however, by the kinetic theory. The first property is the lack of a dependence on pressure or density.
Intuition suggests that gas viscosity should increase with
increasing density, inasmuch as liquids are much more viscous than gases, but gas viscosity is actually independent
of density. This result can be illustrated by a pendulum
swinging on a solid support. It eventually slows down
owing to the viscous friction of the air. If a bell jar is placed
over the pendulum and half the air is pumped out, the air
remaining in the jar damps the pendulum just as fast as a
full jar of air would have done. Robert Boyle noted this
peculiar phenomenon in 1660, but his results were largely
either ignored or forgotten. The Scottish chemist Thomas
30
Properties of Gases
James Clerk Maxwell. Hulton Archive/Getty Images

31
Graham studied the flow of gases through long capillaries, which he called transpiration, in 1846 and 1849, but it
was not until 1877 that the German physicist O.E. Meyer
pointed out that Grahams measurements had shown the
independence of viscosity on density. Prior to Meyers
investigations, the kinetic theory had suggested the result,
so he was looking for experimental proof to support the
prediction. When James Clerk Maxwell discovered (in
1865) that his kinetic theory suggested this result, he
found it difficult to believe and attempted to check it
experimentally. He designed an oscillating disk apparatus
(which is still much copied) to verify the prediction.
The second unusual property of viscosity is its relationship with temperature. One might expect the viscosity of
a fluid to increase as the temperature is lowered, as suggested by the phrase as slow as molasses in January. The
viscosity of a dilute gas behaves in exactly the opposite
way: the viscosity increases as the temperature is raised.
The rate of increase varies approximately as T s, where s is
between and 1, and depends on the particular gas. This
behaviour was clearly established in 1849 by Graham.
The third property pertains to the viscosity of mixtures. A viscous syrup, for example, can be made less so
by the addition of a liquid with a lower viscosity, such
as water. By analogy, one would expect that a mixture
of carbon dioxide, which is fairly viscous, with a gas like
hydrogen, which is much less viscous, would have a viscosity intermediate to that of carbon dioxide and hydrogen.
Surprisingly, the viscosity of the mixture is even greater
than that of carbon dioxide. This phenomenon was also
observed by Graham in 1849.
Finally, there is no obvious correlation of gas viscosity
with molecular weight. Heavy gases are often more viscous than light gases, but there are many exceptions, and
no simple pattern is apparent.
32
Heat Conduction
If a temperature difference is maintained across a fluid,
a flow of energy through the fluid will result. The energy
flow is proportional to the temperature difference according to Fouriers law, where the constant of proportionality
(aside from the geometric factors of the apparatus) is
called the heat conductivity or thermal conductivity of the
fluid, . Mechanisms other than conduction can transport
energy, in particular convection and radiation; here it is
assumed that these can be eliminated or adjusted for. The
SI units for are J/m s K or watt per metre degree (W/m
K), but sometimes calories are used for the energy term
instead of joules (one calorie = 4.184 J). At 20 C (68 F) the
thermal conductivity of water is 0.60 W/m K, and that
of many organic liquids is roughly only one-third as large.
The thermal conductivity of air at 20 C is only about 2.5
10 -2 W/m K. To a rough approximation, liquids conduct
heat about 10 times better than do gases.
The properties of the thermal conductivity of dilute
gases parallel those of viscosity in some respects. The
most striking is the lack of dependence on pressure or
density. Based on this fact, there seems to be no advantage
to pumping out the inner chambers of thermos bottles.
As far as conduction is concerned, it does not provide any
benefits until practically all the air has been removed and
free-molecule conduction is occurring. Convection, however, does depend on density, so some degree of insulation
is provided by pumping out only some of the air.
The thermal conductivity of a dilute gas increases
with increasing temperature, much like its viscosity. In
this case, such behaviour does not seem particularly odd,
probably because most people do not have a preconceived
idea of how thermal conductivity should behave, unlike
the situation with viscosity.
33
There are some differences in the behaviour of thermal

conductivity and viscosity; one of the most notable has to
do with mixtures. At first glance the thermal conductivity of a gaseous mixture seems to be as expected, since it
falls between the conductivities of its components, but
a closer look reveals an odd regularity. The conductivity
of the mixture is always less than an average based on the
number of moles (or molecules) of each component in the
mixture. This appears to be related to the different effect
that molecular weight has on thermal conductivity and
viscosity. Light gases are usually better conductors than
are heavy gases, whereas heavy gases are often (but not
always) more viscous than are light gases. There also seems
to be some correlation between molar heat capacity and
thermal conductivity. The foregoing properties of thermal
conductivity pose more puzzles that the kinetic theory of
gases must address.
Diffusion
Diffusion in dilute gases is in some ways more complex, or
at least more subtle, than either viscosity or thermal conductivity. First, a mixture is necessarily involved, inasmuch
as a gas diffusing through itself makes no sense physically
unless the molecules are in some way distinguishable
from one another. Second, diffusion measurements are
rather sensitive to the details of the experimental conditions. This sensitivity can be illustrated by the following
considerations.
Light molecules have higher average speeds than do
heavy molecules at the same temperature. This result follows from kinetic theory, as explained in the next chapter,
but it can also be seen by noting that the speed of sound is
greater in a light gas than in a heavy gas. This is the basis
of the well-known demonstration that breathing helium
causes one to speak with a high-pitched voice. If a light and
34
a heavy gas are interdiffusing, the light molecules should

move into the heavy-gas region faster than the heavy molecules move into the light-gas region, thereby causing
the pressure to rise in the heavy-gas region. If the diffusion takes place in a closed vessel, the pressure difference
drives the heavy gas into the light-gas region at a faster
rate than it would otherwise diffuse, and a steady state is
quickly reached in which the number of heavy molecules
traveling in one direction equals, on the average, the number of light molecules traveling in the opposite direction.
This method, called equimolar countercurrent diffusion,
is the usual manner in which gaseous diffusion measurements are now carried out.
The steady-state pressure difference that develops is
almost unmeasurably small unless the diffusion occurs
through a fine capillary or a fine-grained porous material. Nevertheless, experimenters have been able to devise
clever schemes either to measure it or to prevent its development. The first to do the latter was Graham in 1831; he
kept the pressure uniform by allowing the gas mixture to
flow. The results of this work now appear in elementary
textbooks as Grahams law of diffusion. Most of these
accounts are incorrect or incomplete or both, owing to
the fact that the writers confuse the uniform-pressure
experiment either with the equal countercurrent experiment or with the phenomenon of effusion (described in
Chapter 3 on the kinetic theory of gases). Graham also
performed equal countercurrent experiments in 1863,
using a long closed-tube apparatus he devised. This sort
of apparatus is now usually called a Loschmidt diffusion
tube after Loschmidt, who used a modified version of the
tube in 1870 to make a series of accurate diffusion measurements on a number of gas pairs.
A quantitative description of diffusion follows. A
composition difference in a two-component gas mixture
35
causes a relative flow of the components that tends to

make the composition uniform. The flow of one component is proportional to its concentration difference, and
in an equal countercurrent experiment this is balanced
by an equal and opposite flow of the other component.
The constant of proportionality is the same for both
components and is called the diffusion coefficient, D12,
for that gas pair. This relationship between the flow rate
and the concentration difference is called Ficks law of
diffusion. The SI units for the diffusion coefficient are
square metres per second (m2/s). Diffusion, even in gases,
is an extremely slow process, as was pointed out above
in estimating molecular sizes and collision rates. Gaseous
diffusion coefficients at one atmosphere pressure and
ordinary temperatures lie largely in the range of 10 -5 to
10 -4 m2/s, but diffusion coefficients for liquids and solutions lie in the range of only 10 -10 to 10 -9 m2/s. To a rough
approximation, gases diffuse about 100,000 times faster
than do liquids.
Diffusion coefficients are inversely proportional to
total pressure or total molar density and are therefore
reported by convention at a standard pressure of one
atmosphere. Doubling the pressure of a diffusing mixture
halves the diffusion coefficient, but the actual rate of diffusion remains unchanged. This seemingly paradoxical
result occurs because doubling the pressure also doubles
the concentration, according to the ideal gas equation of
state, and hence doubles the concentration difference,
which is the driving force for diffusion. The two effects
exactly compensate.
Diffusion coefficients increase with increasing temperature at a rate that depends on whether the pressure or
the total molar density is held constant as the temperature
is changed. If the rate increases as T s at constant molar
density (where s usually lies between and 1), then it will
36
increase as T 1+ s at constant pressure, according to the ideal

gas equation of state.
Perhaps the most surprising property of gaseous diffusion coefficients is that they are virtually independent
of the mixtures composition, varying by at most a few
percent over the whole composition range, even for very
dissimilar gases. A trace of hydrogen, for example, diffuses
through carbon dioxide at virtually the same rate that a
trace of carbon dioxide diffuses through hydrogen. Liquid
mixtures do not behave this way, and liquid diffusion coefficients may vary by as much as a factor of 10 from one end
of the composition range to the other. The lack of composition dependence of gaseous diffusion coefficients is one
of the odder properties to be explained by kinetic theory.
Thermal Diffusion
If a temperature difference is applied to a uniform mixture of two gases, the mixture will partially separate into
its components, with the heavier, larger molecules usually
(but not invariably) concentrating at the lower temperature. This behaviour was predicted theoretically before it
was observed experimentally, but a rather elaborate explanation was required because simple theory suggests no
such phenomenon. It was predicted in 191112 by David
Enskog in Sweden and independently in 1917 by Sydney
Chapman in England, but the validity of their theoretical results was questioned until Chapman (who was an
applied mathematician) enlisted the aid of the chemist
F.W. Dootson to verify it experimentally.
Thermal diffusion can be used to separate isotopes.
The amount of separation for any reasonable temperature
difference is quite small for isotopes, but the effect can be
amplified by combining it with slow thermal convection in
a columnar arrangement devised in 1938 by Klaus Clusius
and Gerhard Dickel in Germany. While the apparatus is
37
quite simple, the theory of its operation is not: a long cylinder with a diameter of several centimetres is mounted
vertically with an electrically heated hot wire along its
central axis. The thermal diffusion occurs horizontally
between the hot wire and the cold wall of the cylinder,
and the convection takes place vertically to bring new gas
regions into contact.
There is also an effect that is the inverse of thermal
diffusion, called the diffusion thermoeffect, in which an
imposed concentration difference causes a temperature
difference to develop. That is, a diffusing gas mixture
develops small temperature differences, on the order of
1 C (0.6 F), which die out as the composition approaches
uniformity. The transport coefficient describing the diffusion thermoeffect must be equal to the coefficient
describing thermal diffusion, according to the reciprocal
relations central to the thermodynamics of irreversible
processes.
38
Chapter 3
Kinetic Theory
of Gases
he aim of kinetic theory is to account for the properties of gases in terms of the forces between the
molecules, assuming that their motions are described
by the laws of mechanics (usually classical Newtonian
mechanics, although quantum mechanics is needed in
some cases). The present discussion focuses on dilute ideal
gases, in which molecular collisions of at most two bodies
are of primary importance. Only the simplest theories are
treated here in order to avoid obscuring the fundamental
physics with complex mathematics.
Ideal Gas
The ideal gas equation of state can be deduced by calculating the pressure as caused by molecular impacts on
a container wall. The internal energy and John Daltons
law of partial pressures also emerge from this calculation,
along with some free-molecule phenomena. The calculation is significant because it is basically the same one used
to explain all dilute-gas phenomena.
Pressure
Sir Isaac Newtons second law of motion can be stated in
not-so-familiar form as impulse equals change in momentum, where impulse is force multiplied by the time during
which it acts. A molecule experiences a change in momentum when it collides with a container wall. During the
collision an impulse is imparted by the wall to the molecule
39
that is equal and opposite to the impulse imparted by the

molecule to the wall. This is required by Newtons third
law. The sum of the impulses imparted by all the molecules
to the wall is, in effect, the pressure.
Consider a system of molecules of mass m traveling
with a velocity v in an enclosed container. In order to
arrive at an expression for the pressure, a calculation will
be made of the impulse imparted to one of the walls by
a single impact, followed by a calculation of how many
impacts occur on that wall during a time t. Although the
molecules are moving in all directions, only those with a
component of velocity toward the wall can collide with it;
call this component vz, where z represents the direction
directly toward the wall. Not all molecules have the same
vz, of course; perhaps only Nz out of a total of N molecules
do. To find the total pressure, the contributions from molecules with all different values of vz must be summed. A
molecule approaches the wall with an initial momentum
mvz, and after impact it moves away from the wall with
an equal momentum in the opposite direction, -mvz. Thus,
the total change in momentum is mvz - (-mvz ) = 2mvz, which
is equal to the total impulse imparted to the wall.
The number of impacts on a small area A of the wall in
time t is equal to the number of molecules that reach the
wall in time t. Since the molecules are traveling at speed vz,
only those within a distance vz t and moving toward the wall
will reach it in that time. Thus, the molecules that are traveling toward the wall and are within a volume Avzt will strike
the area A of the wall in time t. On the average, half of the
molecules in this volume will be moving toward the wall. If
Nz molecules with speed component vz are present in the
total volume V, then (1/2)(Nz/V)(A)(vz t) molecules in the collision volume will hit, and each one contributes an impulse
of 2mvz. The total impulse in time t is therefore (1/2)(Nz/V)
(A)(vz t)(2mvz ) = (Nz/V)(mvz2)(At), which is equal to Ft, where
40
7 Kinetic Theory of Gases
F is the force on the wall due to the impacts. Equating these

two expressions, the time factor t cancels out. Since pressure is defined as the force per unit area (F/A), it follows that
the contribution to the pressure from the molecules with
speed vz is thus (Nz/V )mvz2. Because there are different values of vz2 for different molecules, the average value, denoted
vz2, is used to take into account the contributions from all
the molecules. The pressure is thus given as p = (N/V )mvz2.
Since the molecules are in random motion, this result
is independent of the choice of axis. For any choice of (x,
y, z) axes, the magnitude of the velocity is v2 = vx2 + vy2 + vz2
(which is just the Pythagorean theorem in three dimensions), and taking the average gives v2 = vx2 + vy2 + vz2. The gas
is in equilibrium, so it must appear the same in any direction, and the average velocities are therefore the same in
all directionsi.e., vx2 = vy2 = vz2; thus v2 = 3vz2. When the
value (1/3)v2 is substituted for vz2 in the expression for pressure, the following equation is obtained:
(17)
To rewrite this in molar units, N is set equal to nN0
i.e., the product of the number of moles n and Avogadros
number N0to give
(18)
where M = N0m is the molecular weight of the gas and v is
the volume per mole (V/n). Since the ideal gas equation of
state relates pressure, molar volume, and temperature as
pv = rt, the temperature t must be related to the average
kinetic energy of the molecules as
(19)
41
This expression is often written in molecular (rather

than molar) terms as (1/2)[mv2] = (3/2)kT, where k = R/N0
is called Boltzmanns constant, named after Ludwig
Boltzmann, a 19th-century Austrian physicist who substantially contributed to the foundation and development
of statistical mechanics. If the gas is a mixture, the foregoing calculation shows that the impacts of the different
species are simply added separately, and Daltons law of
partial pressures follows directly.
The energy law given as equation (16) also follows from
equation (19): the kinetic energy of translational motion
per mole is (3/2)RT. Any energy residing in the internal
motions of the individual molecules is simply carried separately without contributing to the pressure.
Average molecular speeds can be calculated from the
results of kinetic theory in terms of the so-called rootmean-square speed vrms. The vrms is the square root of the
average of the squares of the speeds of the molecules:
(v2)1/2. From equation (19) the vrms is (3RT/M)1/2. At 20 C
(68 F) the value for air (M = 29) is 502 metres (1,647 feet)
per second, a result very close to the rough estimate of 500
metres per second given above.
Molecule-molecule collisions were not considered
in the calculation of the expression for pressure even
though many such collisions occur. Such collisions could
be ignored because they are elastic; i.e., linear momentum
is conserved in the collision, provided that no external
forces act. Two molecules therefore continue to carry the
same momentum to the wall even if they collide with one
another before striking it. The ideal gas equation of state
remains valid as the density is decreased, even holding for a
free-molecule gas. The equation eventually fails as the density is increased, however, because other molecules exert
forces and change the rate of collisions with the walls.
42
It was not until the mid- to late 19th century that

kinetic theory was successfully applied to such calculations as gas pressure. Such notable scientists as Newton
and Dalton had believed that gas pressure was caused by
repulsions between molecules that pushed them against
the container walls. For many reasons, the kinetic theory
had overshadowed such static theories (and others such
as vortex theories) by about 1860. It was not until 1875,
however, that James Clerk Maxwell actually proved that a
static theory was in conflict with experiment.
Effusion
Consider the system described above in the calculation of gas pressure, but with the area A in the container
wall replaced with a small hole. The number of molecules that escape through the hole in time t is equal to
(1/2)(N/V)vz(At). In this case, collisions between molecules are significant, and the result holds only for tiny
holes in very thin walls (as compared to the mean free
path), so that a molecule that approaches near the hole
will get through without colliding with another molecule
and being deflected away. The relationship between vz and
the average speed v is rather straightforward: vz = (1/2)v.
If the rates for two different gases effusing through
the same hole are compared, starting with the same gas
density each time, it is found that much more light gas
escapes than heavy gas and that more gas escapes at a
high temperature than at a low temperature, other things
being equal. In particular,
(20)
43
The last step follows from the energy formula,

(1/2)mv2 = (3/2)kt, where (v2)1/2 is approximated to be v, even
though v2 and (v)2 actually differ by a numerical factor near
unity (namely, 3/8). This result was discovered experimentally in 1846 by Graham for the case of constant temperature
and is known as Grahams law of effusion. It can be used to
measure molecular weights, to measure the vapour pressure
of a material with a low vapour pressure, or to calculate the
rate of evaporation of molecules from a liquid or solid surface.
Thermal Transpiration
Suppose that two containers of the same gas but at different temperatures are connected by a tiny hole and that
the gas is brought to a steady state. If the hole is small
enough and the gas density is low enough that only effusion occurs, the equilibrium pressure will be greater on the
high-temperature side. But, if the initial pressures on both
sides are equal, gas will flow from the low-temperature
side to the high-temperature side to cause the hightemperature pressure to increase. The latter situation is
called thermal transpiration, and the steady-state result
is called the thermomolecular pressure difference. These
results follow simply from the effusion formula if the ideal
gas law is used to replace N/V with p/t;
(21)
When a steady state is reached, the effusion rates are
equal, and thus
(22)
44
This phenomenon was first investigated experimentally by Osborne Reynolds in 1879 in Manchester, England.
Errors can result if a gas pressure is measured in a vessel
at very low or very high temperature by connecting it via
a fine tube to a manometer at room temperature. A continuous circulation of gas can be produced by connecting
the two containers with another tube whose diameter is
large compared with the mean free path. The pressure difference drives gas through this tube by viscous flow. A heat
engine based on this circulating flow unfortunately has a
low efficiency.
Viscosity
The kinetic-theory explanation of viscosity can be simplified by examining it in qualitative terms. Viscosity is
caused by the transfer of momentum between two planes
sliding parallel to one another but at different rates,
and this momentum is transferred by molecules moving between the planes. Molecules from the faster plane
move to the slower plane and tend to speed it up, while
molecules from the slower plane travel to the faster plane
and tend to slow it down. This is the mechanism by which
one plane experiences the drag of the other. A simple analogy is two mail trains passing each other, with workers
throwing mailbags between the trains. Every time a mailbag from the fast-moving train lands on the slow one, it
imparts its momentum to the slow train, speeding it up a
little; likewise each mailbag from the slow train that lands
on the fast one slows it down a bit.
If the trains are too far apart, the mailbags cannot be
passed between them. Similarly, the planes of a gas must
be only about a mean free path apart in order for molecules to pass between them without being deflected by
45
collisions. If one uses this approach, a simple calculation

can be carried out, much as in the case of the gas pressure,
with the result that
(23)
where a is a numerical constant of order unity, the term
(N/V)vl is a measure of the number of molecules contained in a small counting cylinder, and the mass m is a
measure of the momentum carried between the sliding
planes. The cross-sectional area of the counting cylinder
and the relative speed of the sliding planes do not appear
in the equation because they cancel one another when the
drag force is divided by the area and speed of the planes in
order to find .
It can now be seen why is independent of gas density
or pressure. The term (N/V ) in equation (23) is the number
of carriers of momentum, but l measures the number of
collisions that interfere with these carriers and is inversely
proportional to (N/V ). The two effects exactly cancel
each other. Viscosity increases with temperature because
the average velocity v does; that is, momentum is carried
more quickly when the molecules move faster. Although v
increases as t1/2, increases somewhat faster because the
mean free path also increases with temperature, since it
is harder to deflect a fast molecule than a slow one. This
feature depends explicitly on the forces between the molecules and is difficult to calculate accurately, as is the value
of the constant a, which turns out to be close to 1/2.
The behaviour of the viscosity of a mixture can also
be explained by the foregoing calculation. In a mixture
of a light gas and a viscous heavy gas, both types of molecules have the same average energy. However, most of the
momentum is carried by the heavy molecules, which are
46
therefore the main contributors to the viscosity. The light

molecules are rather ineffective in deflecting the heavy
molecules, so that the latter continue to carry virtually as
much momentum as they would in the absence of light
molecules. The addition of a light gas to a heavy gas therefore does not reduce the viscosity substantially and may
in fact increase it because of the small extra momentum
carried by the light molecules. The viscosity will eventually decrease when there are only a few heavy molecules
remaining in a large sea of light molecules.
The main dependence of on the molecular mass is
through the product vm in equation (23), which varies
as m1/2 since v varies as 1/m1/2. Owing to this effect, heavy
gases tend to be more viscous than light gases, but this
tendency is compensated for to some degree by the behaviour of l, which tends to be smaller for heavy molecules
because they are usually larger than light molecules and
therefore more likely to collide. The often confusing connection between viscosity and molecular weight can thus
be accounted for by equation (23).
Finally, in a free-molecule gas there are no collisions
with other molecules to impede the transport of momentum, and the viscosity thus increases linearly with pressure
or density until the number of collisions becomes great
enough so that the viscosity assumes the constant value
given by equation (23). The nonideal behaviour of the gas
that accompanies further increases in density eventually
leads to an increase in viscosity, and the viscosity of an
extremely dense gas becomes much like that of a liquid.
The kinetic-theory explanation of heat conduction is
similar to that for viscosity, but in this case the molecules
47
carry net energy from a region of higher energy (i.e., temperature) to one of lower energy (temperature). Internal
molecular motions must be accounted for because, though
they do not transport momentum, they do transport
energy. Monatomic gases, which carry only their kinetic
energy of translational motion, are the simplest case. The
resulting expression for thermal conductivity is
(24)
which has the same basic form as equation (23) for viscosity, with (3k/2) replacing m. The (3k/2) is the heat capacity
per molecule and is the conversion factor from an energy
difference to a temperature difference.
It can be shown from equation (24) that the independence of density and the increase with temperature is the
same for thermal conductivity as it is for viscosity. The
dependence on molecular mass is different, however, with
varying as 1/m1/2 owing to the factor v. Thus, light gases tend
to be better conductors of heat than are heavy gases, and
this tendency is usually augmented by the behaviour of l.
The behaviour of the thermal conductivity of mixtures may be qualitatively explained. Adding heavy gas
to light gas reduces the thermal conductivity because the
heavy molecules carry less energy and also interfere with
the energy transport of the light molecules.
The similar behaviour of and suggests that their
ratio might provide information about the constants a
and a. The ratio of a/a is given as
(25)
Although simple theory suggests that this ratio should
be about one, both experiment and more refined theory
48
give a value close to 5/2. This means that molecules do not

forget their past history in every collision, but some persistence of their precollision velocities occurs. Molecules
transport both energy and momentum from a somewhat
greater distance than just one mean free path, but this
distance is greater for energy than for momentum. This
is plausible, for molecules with higher kinetic energies
might be expected to have greater persistences.
Attempts to calculate the constants a and a by tracing
collision histories to find the persistence of velocities
have not met with much success. The molecular memory fades slowly, too many previous collisions have to be
traced, and the calculations become almost hopelessly
complicated. A different theoretical approach is needed,
which was supplied about 191617 independently by David
Enskog and Sydney Chapman. Their theory also shows
that the same value of l applies to both and , a fact that is
not obvious in the simple theory described here.
The thermal conductivity of polyatomic molecules is
accounted for by simply adding on a contribution for the
energy carried by the internal molecular motions:
(26)
where cint is the contribution of the internal motions to
the heat capacity (per molecule) and is easily found by
subtracting (3k/2) from the total measured heat capacity.
As might be expected, the constant a is only about half
as large as a.
The pressure or density dependence of must be
similar to that of an initial linear increase in the freemolecule region, followed by a constant value in the
dilute-gas region and finally an increase in the densefluid region.
49
Diffusion and Thermal Diffusion

Both of these properties present difficulties for the simple
mean free path version of kinetic theory. In the case of diffusion it must be argued that collisions of the molecules
of species 1 with other species 1 molecules do not inhibit
the interdiffusion of species 1 and 2, and similarly for 22
collisions. If this is not assumed, the calculated value of
the diffusion coefficient for the 12 gas pair, D12, depends
strongly on the mixture composition instead of being virtually independent of it, as is shown by experiment. The
neglect of 11 and 22 collisions can be rationalized by
noting that the flow of momentum is not disturbed by
such like-molecule collisions owing to the conservation of
momentum, but it can be contended that the argument
was simply invented to make the theory agree with experiment. A more charitable view is that the experimental
results demonstrate that collisions between like molecules have little affect on D12. It is one of the triumphs of
the accurate kinetic theory of Enskog and Chapman that
this result clearly emerges.
If 11 and 22 collisions are ignored, a simple calculation gives a result much like those for and :
(27)
where a12 is a numerical constant, v12 is an average relative
speed for 12 collisions given by v122 = (1/2)(v12 + v22), and
l12 is a mean free path for 12 collisions that is inversely
proportional to the total molecular number density, (N1 +
N2)/V. Thus, D12 is inversely proportional to gas density or
pressure, unlike and , but the concentration difference
is proportional to pressure, with the two effects canceling one another, as pointed out previously. The actual
50
transport of molecules is therefore independent of pressure. The numerical value of a12, as obtained by refined
calculations, is close to 3/5.
The pressure dependence of pD12 should be qualitatively similar to that of and an initial linear increase
in the free-molecule region, a constant value in the
dilute-gas region, and finally an increase in the densefluid region.
Thermal diffusion presents special difficulties for
kinetic theory. The transport coefficients , , and
D12 are always positive regardless of the nature of the
intermolecular forces that produce the collisions
the mere existence of collisions suffices to account for
their important features. The transport coefficient that
describes thermal diffusion, however, depends critically on the nature of the intermolecular forces and the
collisions and can be positive, negative, or zero. Its
dependence on composition is also rather complicated.
There have been a number of attempts to explain thermal diffusion with a simple mean free path model, but
none has been satisfactory. No simple physical explanation of thermal diffusion has been devised, and recourse
to the accurate, but complicated, kinetic theory is
necessary.
Boltzmann Equation
The simple mean free path description of gas transport
coefficients accounts for the major observed phenomena, but it is quantitatively unsatisfactory with respect to
two major points: the values of numerical constants such
as a, a, a, and a12, and the description of the molecular
collisions that define a mean free path. Indeed, collisions
remain a somewhat vague concept except when they are
51
considered to take place between molecules modeled

as hard spheres. Improvement has required a different,
somewhat indirect, and more mathematical approach
through a quantity called the velocity distribution function. This function describes how molecular velocities
are distributed on the average: a few very slow molecules,
a few very fast ones, and most near some average value
namely, vrms = (v2)1/2 = (3kT/2)1/2. If this function is known,
all gas properties can be calculated by using it to obtain
various averages. For example, the average momentum
carried in a certain direction would give the viscosity.
The velocity distribution for a gas at equilibrium was
suggested by Maxwell in 1859 and is represented by the
familiar bell-shaped curve that describes the normal, or
Gaussian, distribution of random variables in large populations. Attempts to support more definitively this result
and to extend it to nonequilibrium gases led to the formulation of the Boltzmann equation, which describes how
collisions and external forces cause the velocity distribution to change. This equation is difficult to solve in any
general sense, but some progress can be made by assuming that the deviations from the equilibrium distribution
are small and are proportional to the external influences
that cause the deviations, such as temperature, pressure,
and composition differences.
Even the resulting simpler equations remained
unsolved for nearly 50 years until the work of Enskog and
Chapman, with a single notable exception. The one case
that was solvable dealt with molecules that interact with
forces that fall off as the fifth power of their separation
(i.e., as 1/r5), for which Maxwell found an exact solution.
Unfortunately, thermal diffusion happens to be exactly
zero for molecules subject to this force law, so that phenomenon was missed.
52
It was later discovered that it is possible to use the

solutions for the 1/r5 Maxwell model as a starting point
and then calculate successive corrections for more general
interactions. Although the calculations quickly increase in
complexity, the improvement in accuracy is rapid, unlike
the persistence-of-velocities corrections applied in mean
free path theory. This refined version of kinetic theory is
now highly developed, but it is quite mathematical and is
not described here.
Deviations from the

Ideal Model
Deviations from ideal gas behaviour occur both at low
densities, where molecule-surface collisions become
important, and at high densities, where a description in
terms of only two-body collisions becomes inadequate. The
low-density case can be handled in principle by including
both molecule-surface and molecule-molecule collisions in
the Boltzmann equation. Since this branch of the subject
is now quite advanced and mathematical in character, only
the high-density case will be discussed here.
Equation of State
To a first approximation, molecule-molecule collisions do
not affect the ideal gas equation of state, pv = RT, but real
gases at nonzero densities show deviations from this equation that are due to interactions among the molecules.
Ever since the great advance made by van der Waals in
1873, an accurate universal formula relating p, v, and T has
been sought. No completely satisfactory equation of state
has been found, though important advances occurred in
the 1970s and 80s. The only rigorous theoretical result
53
available is an infinite-series expansion in powers of 1/v,

known as the virial equation of state:
(28)
where B(t ), C(t ), . . . are called the second, third, . . . virial
coefficients and depend only on the temperature and the
particular gas. The virtue of this equation is that there is
a rigorous connection between the virial coefficients and
intermolecular forces, and experimental values of B(t )
were an early source (and still a useful one) of quantitative information on intermolecular forces. The drawback
of the virial equation of state is that it is an infinite series
and becomes essentially useless at high densities, which in
practice are those greater than about the critical density.
Also, the equation is wanting in that it does not predict
condensation.
The most practical approaches to the equation of state
for real fluids remain the versions of the principle of corresponding states first proposed by van der Waals.
Despite many attempts, there is still no satisfactory
theory of the transport properties of dense fluids. Even
the extension of the Boltzmann equation to include collisions of more than two bodies is not entirely clear. An
important advance was made in 1921 by Enskog, but it is
restricted to hard spheres and has not been extended to
real molecules except in an empirical way to fit experimental measurements.
Attempts to develop a virial type of expansion in 1/v
for the transport coefficients have failed in a surprising
54
way. A formal theory was formulated, but, when the virial

coefficients were evaluated for the tractable case of hard
spheres, an infinite result was obtained for the coefficient
of the 1/v2 term. This is a signal that a virial expansion is
not accurate in a mathematical sense, and subsequent
research showed that the error arose from a neglected
term of the form (1/v2)ln(1/v). It remains unknown how
many similar problematic mathematical terms exist in
the theory. Transport coefficients of dense fluids are usually described by some empirical extension of the Enskog
hard-sphere theory or more commonly by some version
of a principle of corresponding states. Much work clearly
remains to be done.
55
Chapter 4
Properties
of Liquids
he most obvious physical properties of a liquid are

its retention of volume and its conformation to the
shape of its container. When a liquid substance is poured
into a vessel, it takes the shape of the vessel, and, as long as
the substance stays in the liquid state, it will remain inside
the vessel. Furthermore, when a liquid is poured from one
vessel to another, it retains its volume (as long as there
is no vaporization or change in temperature) but not its
shape. These properties serve as convenient criteria for
distinguishing the liquid state from the solid and gaseous
states. Gases, for example, expand to fill their container
so that the volume they occupy is the same as that of the
container. Solids retain both their shape and volume when
moved from one container to another.
On Earth, water is the most abundant liquid, although
much of the water with which organisms come into contact is not in pure form but is a mixture in which various
substances are dissolved. Such mixtures include those fluids essential to lifeblood, for examplebeverages, and
seawater. Seawater is a liquid mixture in which a variety
of salts have been dissolved in water. Even though in pure
form these salts are solids, in oceans they are part of the
liquid phase. Thus, liquid mixtures contain substances
that in their pure form may themselves be liquids, solids,
or even gases.
The liquid state sometimes is described simply as the
state that occurs between the solid and gaseous states,
and for simple molecules this distinction is unambiguous.
However, clear distinction between the liquid, gaseous,
56
7 Properties of Liquids
and solid states holds only for those substances whose

molecules are composed of a small number of atoms.
When the number exceeds about 20, the liquid may often
be cooled below the true melting point to form a glass,
which has many of the mechanical properties of a solid but
lacks crystalline order. If the number of atoms in the molecule exceeds about 100200, the classification into solid,
liquid, and gas ceases to be useful. At low temperatures
such substances are usually glasses or amorphous solids,
and their rigidity falls with increasing temperaturei.e.,
they do not have fixed melting points; some may, however,
form true liquids. With these large molecules, the gaseous
state is not attainable, because they decompose chemically before the temperature is high enough for the liquid
to evaporate. Synthetic and natural high polymers (e.g.,
nylon and rubber) behave in this way.
If the molecules are large, rigid, and either roughly planar or linear, as in cholesteryl acetate or p-azoxyanisole, the
solid may melt to an anisotropic liquid (i.e., one that is not
uniform in all directions) in which the molecules are free
to move about but have great difficulty in rotating. Such a
state is called a liquid crystal, and the anisotropy produces
changes of the refractive index (a measure of the change
in direction of light when it passes from one medium into
another) with the direction of the incident light and hence
leads to unusual optical effects. Liquid crystals have found
widespread applications in temperature-sensing devices
and in displays for watches and calculators. However,
no inorganic compounds and only about 5 percent of
the known organic compounds form liquid crystals. The
theory of normal liquids is, therefore, predominantly the
theory of the behaviour of substances consisting of simple
molecules.
A liquid lacks both the strong spatial order of a solid,
though it has the high density of solids, and the absence
57
of order of a gas that results from the low density of

gasesi.e., gas molecules are relatively free of each others
influence. The combination of high density and of partial
order in liquids has led to difficulties in developing quantitatively acceptable theories of liquids. Understanding of
the liquid state, as of all states of matter, came with the
kinetic molecular theory, which stated that matter consisted of particles in constant motion and that this motion
was the manifestation of thermal energy. The greater the
thermal energy of the particle, the faster it moved.
Transitions Between
States of Matter
In very general terms, the particles that constitute matter include molecules, atoms, ions, and electrons. In a
gas these particles are far enough from one another and
are moving fast enough to escape each others influence, which may be of various kindssuch as attraction
or repulsion due to electrical charges and specific forces
of attraction that involve the electrons orbiting around
atomic nuclei. The motion of particles is in a straight line,
and the collisions that result occur with no loss of energy,
although an exchange of energies may result between colliding particles. When a gas is cooled, its particles move
more slowly, and those slow enough to linger in each others vicinity will coalesce, because a force of attraction will
overcome their lowered kinetic energy and, by definition,
thermal energy.
Each particle, when it joins others in the liquid state,
gives up a measure of heat called the latent heat of liquefaction, but each continues to move at the same speed
within the liquid as long as the temperature remains at
the condensation point. The distances that the particles
58
can travel in a liquid without colliding are on the order of

molecular diameters. As the liquid is cooled, the particles
move more slowly still, until at the freezing temperature the attractive energy produces so high a density that
the liquid freezes into the solid state. They continue to
vibrate, however, at the same speed as long as the temperature remains at the freezing point, and their latent heat
of fusion is released in the freezing process.
Heating a solid provides the particles with the heat
of fusion necessary to allow them to escape one anothers
influence enough to move about in the liquid state. Further
heating provides the liquid particles with their heat of
evaporation, which enables them to escape one another
completely and enter the vapour, or gaseous, state.
This starkly simplified view of the states of matter
ignores many complicating factors, the most important
being the fact that no two particles need be moving at the
same speed in a gas, liquid, or solid and the related fact
that even in a solid some particles may have acquired the
energy necessary to exist as gas particles, while even in
a gas some particles may be practically motionless for a
brief time. It is the average kinetic energy of the particles
that must be considered, together with the fact that the
motion is random. At the interface between liquid and gas
and between liquid and solid, an exchange of particles is
always taking place; slow gas molecules condensing at the
liquid surface and fast liquid molecules escaping into the
gas. An equilibrium state is reached in any closed system,
so that the number of exchanges in either direction is the
same. Because the kinetic energy of particles in the liquid state can be defined only in statistical terms (i.e., every
possible value can be found), discussion of the liquid (as
well as the gaseous) state at the molecular level involves
formulations in terms of probability functions.
59
behaViour oF Pure liquids

Liquids may be divided into two general categories: pure
liquids and liquid mixtures. Liquid mixtures can contain substances in the gas and solid phase and thus have
somewhat different behaviour than the pure liquids discussed below.
Phase Diagram of a Pure Substance

When the temperature and pressure of a pure substance
are fixed, the equilibrium state of the substance is also
fixed. Consider the phase diagram for pure argon. In this
diagram a single phase is shown as an area, two as a line,
and three as the intersection of the lines at the triple
point, t. Along a line tC, called the vapour-pressure
curve, liquid and vapour exist in equilibrium. The liquid
region exists to the left and above this line while the gas,
or vapour, region exists below it. At the upper extreme,
this curve ends at the critical point, C. If line tC is crossed
by moving directly from point P to S, there is a distinct
phase change accompanied by abrupt changes in the
physical properties of the substance (e.g., density, heat
capacity, viscosity, and dielectric constant) because the
vapour and liquid phases have distinctly different properties. At the critical point, however, the vapour and liquid
phases become identical, and above the critical point, the
two phases are no longer distinct. Thus, if the substance
moves from point P to S by the path PQrS so that no
phase-change lines are crossed, the change in properties
will be smooth and continuous, and the specific moment
when the substance converts from a liquid to a gas is not
clearly defined.
In fact, the path PQrS demonstrates the essential
continuity of state between liquid and gas, which differ
60
Phase diagram of argon. Copyright Encyclopdia Britannica; rendering

for this edition by Rosen Educational Services
in degree but which together constitute the single fluid

state. Strictly speaking, the term liquid should be applied
only to the denser of the two phases on the line tC, but
it is generally extended to any dense fluid state at low
temperaturesi.e., to the area lying within the angle CtM.
The extension of line tC below the triple point is
called the sublimation curve. It represents the equilibrium between solid and gas, and when the sublimation
curve is crossed, the substance changes directly from solid
to gas. This conversion occurs when dry ice (solid carbon
dioxide) vaporizes at atmospheric pressure to form gaseous carbon dioxide because the triple-point pressure for
carbon dioxide is greater than atmospheric pressure. Line
tM is the melting curve and represents an equilibrium
between solid and liquid. When this curve is crossed from
left to right, solid changes to liquid with the associated
abrupt change in properties.
61
The melting curve is initially much steeper than the

vapour-pressure curve; hence, as the pressure is changed,
the temperature does not change much, and the melting
temperature is little affected by pressure. No substance
has been found to have a critical point on this line, and
there are theoretical reasons for supposing that it continues indefinitely to high temperatures and pressures,
until the substance is so compressed that the molecules
break up into atoms, ions, and electrons. At pressures
above 106 bars (one bar is equal to 0.987 atmosphere,
where one atmosphere is the pressure exerted by the air
at sea level), it is believed that most substances pass into
a metallic state.
It is possible to cool a gas at constant pressure to a
temperature lower than that of the vapour-pressure line
without producing immediate condensation, since the liquid phase forms readily only in the presence of suitable
nuclei (e.g., dust particles or ions) about which the drops
can grow. Unless the gas is scrupulously cleaned, such
nuclei remain; a subcooled vapour is unstable and will
ultimately condense. It is similarly possible to superheat a
liquid to a temperature where, though still a liquid, the gas
is the stable phase. Again, this occurs most readily with
clean liquids heated in smooth vessels, because bubble
formation occurs around foreign particles or sharp points.
When the superheated liquid changes to gas, it does so
with almost explosive violence. A liquid also may be subcooled to below its freezing temperature.
Representative Values of PhaseDiagram Parameters

To a certain extent the behaviour of all substances is similar in that the parameters that vary from substance to
substance are the particular values of the triple-point and
62
critical-point temperature and pressure, the size of the

various regions, and the slopes of the lines. Triple-point
temperatures range from 14 K (259 C [434 F]) for hydrogen to temperatures too high for accurate measurement.
Triple-point pressures are generally low, that of carbon
dioxide at 5.2 bars being one of the highest. Most are around
10 -3 bar, and those of some hydrocarbons are as low as 10 -7
bar. The normal melting point of a substance is defined as
the melting temperature at a pressure of one atmosphere
(equivalent to 1.01325 bars); it differs little from the triplepoint temperature, because of the steepness of melting
lines. Critical temperatures (the maximum temperature at
which a gas can be liquefied by pressure) range from 5.2 K
(268 C [450.3 F]), for helium, to temperatures too high
to measure. Critical pressures (the vapour pressure at the
critical temperature) are generally about 40100 bars.
The normal boiling point is the temperature at which the
vapour pressure reaches one atmosphere. The normal liquid range is defined as the temperature interval between
the normal melting point and the normal boiling point,
but such a restriction is artificial, the true liquid range
being from triple point to critical point. Substances whose
triple-point pressures are above atmospheric (e.g., carbon
dioxide) have no normal liquid range but sublime at atmospheric pressure.
Each of the three two-phase lines in a phase diagram
canbe described by the Clapeyron equation:
(1)
In this equation, dp/dt is the slope of the curve under
considerationi.e., either the melting, sublimation, or
vapour-pressure curve. h is the latent heat required for
the phase change, and V is the change in volume associated with the phase change. Thus, for the sublimation and
63
vapour-pressure curves, since H and V are both positive (i.e., heat is required for vaporization, and the volume
increases on vaporization), the slope is always positive. The slope of the sublimation curve immediately
below the triple point is greater than the slope of the
vapour-pressure curve immediately above it, so that
the vapour-pressure curve is not continuous through the
triple point. This is consistent with equation (1) because
the heat of sublimation for a substance is somewhat larger
than its heat of vaporization.
The slope of the melting line is usually positive, but
there are a few substances, such as water and bismuth,
for which the melting-line slope is negative. The negative
melting-line slope is consistent with equation (1) because,
for these two substances, the density of the solid is less
than the density of the liquid. This is the reason ice floats.
For water, this negative volume change (i.e., shrinking)
persists to 2.1 kilobars and 22 C (8 F), at which point the
normal form of ice changes to a denser form, and thereafter the change in volume on melting is positive.
Behaviour of Substances Near

Critical and Triple Points
At the critical point the liquid is identical to the vapour
phase, and near the critical point the liquid behaviour is
somewhat similar to vapour-phase behaviour. While the
particular values of the critical temperature and pressure
vary from substance to substance, the nature of the behaviour in the vicinity of the critical point is similar for all
compounds. This fact has led to a method that is commonly
referred to as the law of corresponding states. Roughly
speaking, this approach presumes that, if the phase diagram is plotted using reduced variables, the behaviour
64
of all substances will be more or less the same. Reduced

variables are defined by dividing the actual variable by its
associated critical constant; the reduced temperature, Tr,
equals T/Tc, and the reduced pressure, pr, equals p/pc. Then,
for all substances, the critical point occurs at a value of Tr
and pr equal to unity.
This approach has been used successfully to develop
equations to correlate and predict a number of liquidphase properties including vapour pressures, saturated
and compressed liquid densities, heat capacities, and
latent heats of vaporization. The corresponding states
approach works remarkably well at temperatures between
the normal boiling point and the critical point for many
compounds but tends to break down near and below the
triple-point temperature. At these temperatures the liquid is influenced more by the behaviour of the solid, which
has not been successfully correlated by corresponding
states methods.
Many of the properties of a liquid near its triple point
are closer to those of the solid than to those of the gas.
It has a high density (typically 0.51.5 grams per cubic
cm [0.020.05 pound per cubic inch]), a high refractive
index (which varies from 1.3 to 1.8 for liquids), a high
heat capacity at constant pressure (24 joules per gram
per kelvin, 1 joule being equal to 0.239 calorie), and a low
compressibility (0.51 104 per bar). The compressibility falls to values characteristic of a solid (0.1 104 per
bar or less) as the pressure increases. A simple and widely
used equation describes the change of specific volume
with pressure. If V( p) is the volume at pressure p,V(0)
is volume at zero pressure, and A and B are positive
parameters (constants whose values may be arbitrarily
assigned), then the difference in volume resulting from a
change in pressure equals the product of A, the pressure,
65
and the volume at zero pressure, divided by the sum of B

and the pressure. This is written:
(2)
The pressure parameter B is close to the pressure at which
the compressibility has fallen to half its initial value and
is generally about 500 bars for liquids near their triple
points. It falls rapidly with increasing temperature.
As a liquid is heated along its vapour-pressure
curve, tC, its density falls and its compressibility rises.
Conversely, the density of the saturated vapour in equilibrium with the liquid rises; i.e., the number of gas molecules
in a fixed space above the liquid increases. Liquid and gas
states approach each other with increasing rapidity as
the temperature approaches C, until at this point they
become identical and have a density about one-third that
of the liquid at point t. The change of saturated-gas density ( g ) and liquid density ( l ) with temperature t can be
expressed by a simple equation when the temperature is
close to critical. If c is the density at the critical temperature tc, then the difference between densities equals the
difference between temperatures raised to a factor called
beta, :
(3)
where is about 0.34. The compressibility and the heat
capacity of the gas at constant pressure (Cp ) become infinite as t approaches tc from above along the path of
constant density. The infinite compressibility implies that
the pressure no longer restrains local fluctuations of density. The fluctuations grow to such an extent that their
size is comparable with the wavelength of light, which is
therefore strongly scattered. Hence, at the critical point,
66
a normally transparent liquid is almost opaque and usually dark brown in colour. The classical description of the
critical point and the results of modern measurement do
not agree in detail, but recent considerations of thermodynamic stability show that there are certain regularities
in behaviour that are common to all substances.
Surface Tension
Between a liquid and its corresponding vapour there is a
dividing surface that has a measurable tension; work must
be done to increase the area of the surface at constant temperature. Hence, in the absence of gravity or during free
fall, the equilibrium shape of a volume of liquid is one that
has a minimum areai.e., a sphere. In Earths field this
shape is found only for small drops, for which the gravitational forces, since they are proportional to the volume,
are negligible compared with surface forces, which are
proportional to the area. The surface tension falls with rising temperature and vanishes at the critical point. There
is a similar dividing surface between two immiscible liquids, but this usually has lower tension. It is believed that
there is a tension also between a liquid and a solid, though
it is not directly measurable because of the rigidity of the
solid; it may be inferred, however, under certain assumptions, from the angle of contact between the liquid and
the solid (i.e., the angle at which the liquids surface meets
the solid). If this angle is zero, the liquid surface is parallel
to the solid surface and is said to wet the solid completely.
Molecular Structure of Liquids

For a complete understanding of the liquid state of matter, an understanding of behaviour on the molecular
level is necessary. Such behaviour is characterized by two
67
quantities called the intermolecular pair potential function, u, and the radial distribution function, g. The pair
potential gives information about the energy due to the
interaction of a pair of molecules and is a function of the
distance r between their centres. Information about the
structure or the distances between pairs of molecules is
contained in the radial distribution function. If g and u
are known for a substance, macroscopic properties can be
calculated.
In an ideal gaswhere there are no forces between
molecules, and the volume of the molecules is negligible
g is unity, which means that the chance of encountering a
second molecule when moving away from a central molecule is independent of position. In a solid, g takes on
discrete values at distances that correspond to the locations associated with the solids crystal structure. Liquids
radial distribution function for a dense liquid. Copyright Encyclopdia

Britannica; rendering for this edition by Rosen Educational Services
68
possess neither the completely ordered structure of a

solid crystal nor the complete randomness of an ideal
gas. The structure in a liquid is intermediate to these two
extremesi.e., the molecules in a liquid are free to move
about, but there is some order because they remain relatively close to one another.
Although there are an infinite number of possible positions one molecule may assume with respect to another,
some are more likely than others. In the radial distribution function for the dense packing typical of liquids,
g is a measure of the probability of finding the centre of
one molecule at a distance r from the centre of a second
molecule. For values of r less than those of the molecular
diameter, d, g goes to zero. This is consistent with the fact
that two molecules cannot occupy the same space. The
most likely location for a second molecule with respect
to a central molecule is slightly more than one molecular
diameter away, which reflects the fact that in liquids the
molecules are packed almost against one another. The second most likely location is a little more than two molecular
diameters away, but beyond the third layer preferred locations damp out, and the chance of finding the centre of a
molecule becomes independent of position.
The pair potential function, u, is a large positive number for r less than d, assumes a minimum value at the most
preferred location, and damps out to zero as r approaches
infinity. The large positive value of u corresponds to a
strong repulsion, while the minimum corresponds to the
net result of repulsive and attractive forces.
There are two methods of measuring the radial distribution function g: first, by X-ray or neutron diffraction
from simple fluids and, second, by computer simulation
of the molecular structure and motions in a liquid. In the
first, the liquid is exposed to a specific, single wavelength
69
(monochromatic) radiation, and the observed results are

then subjected to a mathematical treatment known as a
Fourier transform.
The second method of obtaining the radial distribution function g supposes that the energy of interaction,
u, for the liquid under study is known. A computer
model of a liquid is set up in which thousands of molecules are contained within a cube. There are now two
methods of proceeding, by Monte Carlo calculation or
by what is called molecular dynamics; only the latter is
discussed here.
Each molecule is assigned a random position and
velocity, and Newtons equations of motion are solved to
calculate the path of each molecule in the changing field
of all the others. A molecule that leaves the cell is deemed
to be replaced by a new one with equal velocity entering
through the corresponding point on the opposite wall.
After a few collisions per molecule, the distribution of
velocities conforms with equations worked out by the
Scottish physicist James Clerk Maxwell, and after a longer time the mean positions are those appropriate to the
density and mean kinetic energy (i.e., temperature) of
the liquid. Functions such as the radial distribution function g can now be evaluated by taking suitable averages
as the system evolves in time. Since 1958 such computer
experiments have added more to the knowledge of the
molecular structure of simple liquids than all the theoretical work of the previous century and continue to be an
active area of research for not only pure liquids but liquid
mixtures as well.
Speed of Sound and Electric Properties

A sound wave is a series of longitudinal compressions
and expansions that travels through a liquid at a speed of
70
about 1 km (0.62 mile) per second, or about three times

the speed of sound in air. If the frequency is not too high,
the compressions and expansions are adiabatic (i.e., the
changes take place without transfer of heat) and reversible. Conduction of energy from the hot (compressed)
to the cold (expanded) regions of the liquid introduces
irreversible effects, which are dissipative, and thus such
conduction leads to the absorption of the sound. A longitudinal compression (in the direction of the wave) is a
combination of a uniform compression and a shearing
stress (a force that causes one plane of a substance to glide
past an adjacent plane). Hence, both bulk and shear viscosity also govern the propagation of sound in a liquid.
If a liquid is placed in a static electric field, the field
exerts a force on any free carriers of electric charge in the
liquid, and the liquid, therefore, conducts electricity. Such
carriers are of two kinds: mobile electrons and ions. The
former are present in abundance in liquid metals, which
have conductivities that are generally about one-third of
the conductivity of the corresponding solid. The decrease
in conductivity upon melting arises from the greater disorder of the positive ions in the liquid and hence their
greater ability to scatter electrons. The contribution of
the ions is small, less than 5 percent in most liquid metals, but it is the sole cause of conductivity in molten salts
and in their aqueous solutions. Such conductivities vary
widely but are much lower than those of liquid metals.
Nonionic liquids (those composed of molecules that
do not dissociate into ions) have negligible conductivities,
but they are polarized by an electric field; that is, the liquid develops positive and negative poles and also a dipole
moment (which is the product of the pole strength and the
distance between the poles) that is oriented against the
field, from which the liquid acquires energy. This polarization is of three kinds: electron, atomic, and orientation.
71
In electron polarization the electrons in each atom

are displaced from their usual positions, giving each molecule a small dipole moment. The contribution of electron
polarization to the dielectric constant of the liquid is
numerically equal to the square root of its refractive index.
The second effect, atomic polarization, arises because
there is a relative change in the mean positions of the
atomic nuclei within the molecules. This generally small
effect is observed at radio frequencies but not at optical,
and so it is missing from the refractive index.
The third effect, orientation polarization, occurs with
molecules that have permanent dipole moments. These
molecules are partially aligned by the field and contribute
heavily to the polarization. Thus, the dielectric constant
of a nonpolar liquid, such as a hydrocarbon, is about 2,
that of a weakly polar liquid, such as chloroform or ethyl
ether, about 5, while those of highly polar liquids, such as
ethanol and water, range from 25 to 80.
72
Chapter 5
Liquid Solutions
and Solubility
he ability of liquids to dissolve solids, other liquids,

or gases has long been recognized as one of the fundamental phenomena of nature encountered in daily life.
The practical importance of solutions and the need to
understand their properties have challenged numerous
writers since the Ionian philosophers and Aristotle. Many
physicists and chemists have devoted themselves to a
study of solutions.
A solution is a mixture of two or more chemically distinct substances that is said to be homogeneous on the
molecular scalethe composition at any one point in the
mixture is the same as that at any other point. This is in
contrast to a suspension (or slurry), in which small discontinuous particles are surrounded by a continuous fluid.
Although the word solution is commonly applied to the
liquid state of matter, solutions of solids and gases are also
possible. Brass, for example, is a solution of copper and
zinc, and air is a solution primarily of oxygen and nitrogen
with a few other gases present in relatively small amounts.
The ability of one substance to dissolve another
depends always on the chemical nature of the substances,
frequently on the temperature, and occasionally on the
pressure. Water, for example, readily dissolves methyl
alcohol but does not dissolve mercury; it barely dissolves
benzene at room temperature but does so increasingly
as the temperature rises. While the solubility in water of
the gases present in air is extremely small at atmospheric
pressure, it becomes appreciable at high pressures where,
in many cases, the solubility of a gas is (approximately)
73
proportional to its pressure. Thus, a diver breathes air

(four-fifths nitrogen) at a pressure corresponding to the
pressure around him, and, as he goes deeper, more air dissolves in his blood. If he ascends rapidly, the solubility of
the gases decreases so that they leave his blood suddenly,
forming bubbles in the blood vessels. This condition
(known as the bends) is extremely painful and may cause
death; it can be alleviated by breathing, instead of air, a
mixture of helium and oxygen because the solubility of
helium in blood is much lower than that of nitrogen.
The solubility of one fluid in another may be complete or partial. Thus, at room temperature water and
methyl alcohol mix in all proportions, but 100 grams (3.5
ounces) of water dissolve only 0.07 gram (0.002 ounce)
of benzene. Though it is generally supposed that all gases
are completely misciblei.e., mutually soluble in all
proportionsthis is true only at normal pressures. At high
pressures pairs of chemically unlike gases may exhibit only
limited miscibility. For example, at 20 C (68 F) helium
and xenon are completely miscible at pressures below 200
atmospheres but become increasingly immiscible as the
pressure rises.
The ability of a liquid to dissolve selectively forms the
basis of common separation operations in chemical and
related industries. A mixture of two gases, carbon dioxide
and nitrogen, can be separated by bringing it into contact
with ethanolamine, a liquid solvent that readily dissolves
carbon dioxide but barely dissolves nitrogen. In this process, called absorption, the dissolved carbon dioxide is later
recovered, and the solvent is made usable again by heating
the carbon dioxide-rich solvent, since the solubility of a
gas in a liquid usually (but not always) decreases with rising
temperature. A similar absorption operation can remove a
pollutant such as sulfur dioxide from smokestack gases in
a plant using sulfur-containing coal or petroleum as fuel.
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7 Liquid Solutions and Solubility
The process wherein a dissolved substance is transferred from one liquid to another is called extraction.
As an example, phenolic pollutants (organic compounds
of the types known as phenol, cresol, and resorcinol) are
frequently found in industrial aqueous waste streams,
and, since these phenolics are damaging to marine life,
it is important to remove them before sending the waste
stream back to a lake or river. One such removal technique is to bring the waste stream into contact with a
water-insoluble solvent (e.g., an organic liquid such as a
high-boiling hydrocarbon) that has a strong affinity for the
phenolic pollutant. The solubility of the phenolic in the
solvent divided by that in water is called the distribution
coefficient, and it is clear that for an efficient extraction
process it is desirable to have as large a distribution coefficient as possible.
Classes of Solutions
Broadly speaking, liquid mixtures can be classified as
either solutions of electrolytes or solutions of nonelectrolytes. They can also be divided into endothermic and
exothermic solutions based on their chemical reactions.
Electrolytes and Nonelectrolytes

Electrolytes are substances that can dissociate into electrically charged particles called ions, while nonelectrolytes
consist of molecules that bear no net electric charge.
Thus, when ordinary salt (sodium chloride, formula NaCl)
is dissolved in water, it forms an electrolytic solution,
dissociating into positive sodium ions (Na+) and negative chloride ions (Cl-), whereas sugar dissolved in water
maintains its molecular integrity and does not dissociate.
Because of its omnipresence, water is the most common
75
solvent for electrolytes; the ocean is a solution of electrolytes. Electrolyte solutions, however, are also formed by
other solvents (such as ammonia and sulfur dioxide) that
have a large dielectric constant (a measure of the ability of
a fluid to decrease the forces of attraction and repulsion
between charged particles). The energy required to separate an ion pair (i.e., one ion of positive charge and one
ion of negative charge) varies inversely with the dielectric
constant, and, therefore, appreciable dissociation into
separate ions occurs only in solvents with large dielectric
constants.
Most electrolytes (for example, salts) are nonvolatile,
which means that they have essentially no tendency to
enter the vapour phase. There are, however, some notable
exceptions, such as hydrogen chloride (HCl), which is
readily soluble in water, where it forms hydrogen ions (H+)
and chloride ions (Cl-). At normal temperature and pressure, pure hydrogen chloride is a gas, and, in the absence
of water or some other ionizing solvent, hydrogen chloride exists in molecular, rather than ionic, form.
Solutions of electrolytes readily conduct electricity,
whereas nonelectrolyte solutions do not. A dilute solution of hydrogen chloride in water is a good electrical
conductor, but a dilute solution of hydrogen chloride in
a hydrocarbon is a good insulator. Because of the large
difference in dielectric constants, hydrogen chloride is
ionized in water but not in hydrocarbons.
Weak Electrolytes
While classification under the heading electrolytesolution or nonelectrolyte-solution is often useful, some
solutions have properties near the boundary between
these two broad classes. Although such substances
as ordinary salt and hydrogen chloride are strong
76
electrolytesi.e., they dissociate completely in an ionizing solventthere are many substances, called weak
electrolytes, that dissociate to only a small extent in ionizing solvents. For example, in aqueous solution, acetic
acid can dissociate into a positive hydrogen ion and a
negative acetate ion (CH3COO-), but it does so to a limited extent; in an aqueous solution containing 50 grams
(1.8 ounces) acetic acid and 1,000 grams (2.2 pounds)
water, less than 1 percent of the acetic acid molecules are
dissociated into ions. Therefore, a solution of acetic acid
in water exhibits some properties associated with electrolyte solutions (e.g., it is a fair conductor of electricity),
but in general terms it is more properly classified as a
nonelectrolyte solution. By similar reasoning, an aqueous
solution of carbon dioxide is also considered a nonelectrolyte solution even though carbon dioxide and water
have a slight tendency to form carbonic acid, which, in
turn, dissociates to a small extent to hydrogen ions and
bicarbonate ions (HCO3-).
Endothermic and Exothermic Solutions

When two substances mix to form a solution, heat is
either evolved (an exothermic process) or absorbed
(an endothermic process); only in the special case of an
ideal solution do substances mix without any heat effect.
Most simple molecules mix with a small endothermic
heat of solution, while exothermic heats of solution are
observed when the components interact strongly with
one another. An extreme example of an exothermic heat
of mixing is provided by adding an aqueous solution of
sodium hydroxide, a powerful base, to an aqueous solution of hydrogen chloride, a powerful acid; the hydroxide
ions (OH-) of the base combine with the hydrogen ions
of the acid to form water, a highly exothermic reaction
77
that yields 75,300 calories per 100 grams (3.5 ounces) of

water formed. In nonelectrolyte solutions, heat effects
are usually endothermic and much smaller, often about
100 calories, when roughly equal parts are mixed to form
100 grams of mixture.
Formation of a solution usually is accompanied by
a small change in volume. If equal parts of benzene and
stannic chloride are mixed, the temperature drops; if the
mixture is then heated slightly to bring its temperature
back to that of the unmixed liquids, the volume increases
by about 2 percent. On the other hand, mixing roughly
equal parts of acetone and chloroform produces a small
decrease in volume, about 0.2 percent. It frequently happens that mixtures with endothermic heats of mixing
expandi.e., show small increases in volumewhile mixtures with exothermic heats of mixing tend to contract.
A large decrease in volume occurs when a gas is
dissolved in a liquid. For example, at 0 C (32 F) and
atmospheric pressure, the volume of 28 grams (1 ounce)
of nitrogen gas is 22,400 cubic cm (0.79 cubic feet).
When these 28 grams of nitrogen are dissolved in an
excess of water, the volume of the water increases only
40 cubic cm (2.4 cubic inches); the decrease in volume
accompanying the dissolution of 28 grams of nitrogen in
water is therefore 22,360 cubic cm. In this case, it is said
that the nitrogen gas has been condensed into a liquid,
the word condense meaning to make densei.e., to
decrease the volume.
Properties of Solutions
The properties of liquid solutions have been the subject
of thorough study. For instance, the composition of a solution and the proportions of the dissolved and dissolving
substances play key roles in a mixtures properties.
78
Composition Ratios
The composition of a liquid solution means the composition of that solution in the bulkthat is, of that part that
is not near the surface. The interface between the liquid
solution and some other phase (for example, a gas such as
air) has a composition that differs, sometimes very much,
from that of the bulk. The environment at an interface is
significantly different from that throughout the bulk of
the liquid, and in a solution the molecules of a particular
component may prefer one environment over the other.
If the molecules of one component in the solution prefer
to be at the interface as opposed to the bulk, it is said that
this component is positively adsorbed at the interface.
In aqueous solutions of organic liquids, the organic
component is usually positively adsorbed at the solutionair interface; as a result, it is often possible to separate
a mixture of an organic solute from water by a process
called froth separation. Air is bubbled vigorously into the
solution, and a froth is formed. The composition of the
froth differs from that of the bulk because the organic
solute concentrates at the interfacial region. The froth is
mechanically removed and collapsed, and, if further separation is desired, a new froth is generated. The tendency
of some dissolved molecules to congregate at the surface
has been utilized in water conservation. A certain type of
alcohol, when added to water, concentrates at the surface
to form a barrier to evaporating water molecules. In warm
climates, therefore, water loss by evaporation from lakes
can be significantly reduced by introducing a solute that
adsorbs positively at the lake-air interface.
The composition of a solution can be expressed in a
variety of ways, the simplest of which is the weight fraction,
or weight percent; for example, the salt content of seawater
is about 3.5 weight percenti.e., of 100 grams (3.5 ounces)
79
of seawater, 3.5 grams (0.1 ounce) is salt. For a fundamental

understanding of solution properties, however, it is often
useful to express composition in terms of molecular units
such as molecular concentration, molality, or mole fraction.
To understand these terms, it is necessary to define
atomic and molecular weights. The atomic weight of elements is a relative figure, with one atom of the carbon-12
isotope being assigned the atomic weight of 12; the atomic
weight of hydrogen is then approximately 1, of oxygen
approximately 16, and the molecular weight of water (H2O)
18. The atomic and molecular theory of matter asserts that
the atomic weight of any element in grams must contain
the same number of atoms as the atomic weight in grams
(the gram-atomic weight) of any other element. Thus, two
grams of molecular hydrogen (H2 )its gram-molecular
weightcontain the same number of molecules as 18 grams
(0.6 ounce) of water or 32 grams (1.1 ounces) of oxygen molecules (O2 ). Further, a specified volume of any gas (at low
pressure) contains the same number of molecules as the
same volume of any other gas at the same temperature and
pressure. At standard temperature and pressure (0 C [32
F] and one atmosphere) the volume of one gram-molecular
weight of any gas has been determined experimentally to
be approximately 22.4 litres (23.7 quarts). The number of
molecules in this volume of gas, or in the gram-molecular
weight of any compound, is called Avogadros number.
Molarity
Molecular concentration is the number of molecules of
a particular component per unit volume. Since the number of molecules in a litre or even a cubic centimetre is
enormous, it has become common practice to use what
are called molar, rather than molecular, quantities. A mole
is the gram-molecular weight of a substance and, therefore, also Avogadros number of molecules (6.02 1023).
80
Thus, the number of moles in a sample is the weight of the

sample divided by the molecular weight of the substance;
it is also the number of molecules in the sample divided
by Avogadros number. Instead of using molecular concentration, it is more convenient to use molar concentration;
instead of saying, for example, that the concentration is
12.04 1023 molecules per litre, it is simpler to say that it is
two moles per litre. Concentration in moles per litre (i.e.,
molarity) is usually designated by the letter M.
Molality
In electrolyte solutions it is common to distinguish
between the solvent (usually water) and the dissolved substance, or solute, which dissociates into ions. For these
solutions it is useful to express composition in terms of
molality, designated as m, a unit proportional to the number of undissociated solute molecules (or, alternatively, to
the number of ions) per 1,000 grams of solvent. The number of molecules or ions in 1,000 grams of solvent usually
is very large, so molality is defined as the number of moles
per 1,000 grams (2.2 pounds) of solvent.
Formality
Many compounds do not exist in molecular form, either
as pure substances or in their solutions. The particles that
make up sodium chloride (NaCl), for example, are sodium
ions (Na+) and chloride ions (Cl-), and, although equal
numbers of these two ions are present in any sample of
sodium chloride, no Na+ ion is associated with a particular
Cl- ion to form a neutral molecule having the composition
implied by the formula. Therefore, even though the compositions of such compounds are well defined, it would
be erroneous to express concentrations of their solutions
in terms of molecular weights. A useful concept in cases
of this kind is that of the formula weight, defined as the
81
sum of the weights of the atoms in the formula of the

compound; thus, the formula weight of sodium chloride
is the sum of the atomic weights of sodium and chlorine,
23 plus 35.5, or 58.5, and a solution containing 58.5 grams
(2.1 ounces) of sodium chloride per litre is said to have a
concentration of one formal, or 1 F.
Mole Fraction and Mole Percentage
It often is useful to express the composition of nonelectrolyte solutions in terms of mole fraction or mole
percentage. In a binary mixturei.e., a mixture of two
components, 1 and 2there are two mole fractions, x1 and
x2, which satisfy the relation x1 + x2 = 1. The mole fraction x1
is the fraction of molecules of species 1 in the solution, and
x2 is the fraction of molecules of species 2 in the solution.
(Mole percentage is the mole fraction multiplied by 100.)
Volume Fraction
The composition of a nonelectrolyte solution containing very large molecules, known as polymers, is most
conveniently expressed by the volume fraction ()i.e., the
volume of polymer used to prepare the solution divided by
the sum of that volume of polymer and the volume of the
solvent.
A quantitative description of liquid-solution properties
when the system is in equilibrium is provided by relating
the vapour pressure of the solution to its composition. The
vapour pressure of a liquid, pure or mixed, is the pressure
exerted by those molecules that escape from the liquid to
form a separate vapour phase above the liquid. If a quantity
of liquid is placed in an evacuated, closed container the volume of which is slightly larger than that of the liquid, most
82
of the container is filled with the liquid, but, immediately

above the liquid surface, a vapour phase forms, consisting of
molecules that have passed through the liquid surface from
liquid to gas; the pressure exerted by that vapour phase is
called the vapour (or saturation) pressure. For a pure liquid,
this pressure depends only on the temperature, the bestknown example being the normal boiling point, which is
that temperature at which the vapour pressure is equal to
the pressure of the atmosphere. The vapour pressure is one
atmosphere at 100 C (212 F) for water, at 78.5 C (173.3 F)
for ethyl alcohol, and at 125.7 C (258.3 F) for octane. In
a liquid solution, the component with the higher vapour
pressure is called the light component, and that with the
lower vapour pressure is called the heavy component.
In a liquid mixture, the vapour pressure depends not
only on the temperature but also on the composition, and
the key problem in understanding the properties of solutions lies in determining this composition dependence.
The simplest approximation is to assume that, at constant
temperature, the vapour pressure of a solution is a linear
function of its composition (i.e., as one increases, so does
the other in such proportion that, when the values are
plotted, the resulting graph is a straight line). A mixture
following this approximation is called an ideal solution.
Fugacity
In a pure liquid, the vapour generated by its escaping molecules necessarily has the same composition as that of
the liquid. In a mixture, however, the composition of the
vapour is not the same as that of the liquid; the vapour is
richer in that component whose molecules have greater
tendency to escape from the liquid phase. This tendency
is measured by fugacity, a term derived from the Latin
fugere (to escape, to fly away). The fugacity of a component in a mixture is (essentially) the pressure that the
83
component exerts in the vapour phase when the vapour is

in equilibrium with the liquid mixture. (A state of equilibrium is attained when all the properties remain constant
in time and there is no net transfer of energy or matter
between the vapour and the liquid.) If the vapour phase
can be considered to be an ideal gas (i.e., the molecules
in the gas phase are assumed to act independently and
without any influence on each other), then the fugacity
of a component, i, is equal to its partial pressure, which
is defined as the product of the total vapour pressure, P,
and the vapour-phase mole fraction, yi. Assuming ideal
gas behaviour for the vapour phase, the fugacity (yi P)
equals the product of the liquid-phase mole fraction, xi,
the vapour pressure of pure liquid at the same temperature as that of the mixture, Pi, and the activity coefficient,
i. The real concentration of a substance may not be an
accurate measure of its effectiveness, because of physical
and chemical interactions, in which case an effective concentration must be used, called the activity. The activity is
given by the product of the mole fraction xi and the activity coefficient i. The equation is:
(4)
Raoults Law
In a real solution, the activity coefficient, i, depends on
both temperature and composition, but, in an ideal solution, i equals 1 for all components in the mixture. For an
ideal binary mixture then, the above equation becomes,
for components 1 and 2, y1P = x1 P1 and y2 P = x2 P2, respectively. Upon adding these equationsrecalling that x1 +
x2 = 1 and y1 + y2 = 1the total pressure, P, is shown to be
expressed by the equation P = x1P1 + x2P2 = x1[P1 - P2] + P2,
which is a linear function of x1.
84
Assuming 1 = 2 = 1, equations for y1 P and y2 P express

what is commonly known as Raoults law, which states that
at constant temperature the partial pressure of a component in a liquid mixture is proportional to its mole fraction
in that mixture (i.e., each component exerts a pressure that
depends directly on the number of its molecules present).
It is unfortunate that the word law is associated with this
relation, because only very few mixtures behave according
to the equations for ideal binary mixtures. In most cases
the activity coefficient, i, is not equal to unity. When i is
greater than 1, there are positive deviations from Raoults
law; when i is less than 1, there are negative deviations
from Raoults law.
When the vapour in equilibrium with a liquid mixture
has a composition identical to that of the liquid, the mixture is called an azeotrope. It is not possible to separate
an azeotropic mixture by fractional distillation because
no change in composition is achieved by a series of vaporizations and condensations. Azeotropic mixtures are
common. At the azeotropic composition, the total pressure (at constant temperature) is always either a maximum
or a minimum with respect to composition, and the boiling temperature (at constant pressure) is always either a
minimum or a maximum temperature.
Partial Miscibility
Only pairs of liquids that are completely miscible have been
considered so far. Many pairs of liquids, however, are only
partially miscible in one another, the degree of miscibility
often depending strongly on temperature. In most cases,
rising temperature produces enhanced solubility, but this is
not always so. For example, at 50 C (122 F) the solubility
(weight percent) of n-butyl alcohol in water is 6.5 percent,
whereas that of water in n-butyl alcohol is 22.4 percent. At
127 C (261 F), the upper consolute temperature, complete
85
miscibility is attained: above 127 C the two liquids mix in

all proportions, but below 127 C they show a miscibility
gap. Thus, if n-butyl alcohol is added to water at 50 C, there
is only one liquid phase until 6.5 weight percent of the mixture is alcohol; when more alcohol is added, a second liquid
phase appears the composition of which is 22.4 weight
percent water. When sufficient alcohol is present to make
the overall composition 77.6 weight percent alcohol, the
first phase disappears, and only one liquid phase remains.
A qualitatively different example is the system watertriethylamine, which has a lower consolute temperature
at 17 C (63 F). Below 17 C the two liquids are completely
miscible, but at higher temperatures they are only partially
miscible. Finally, it is possible, although rare, for a binary
system to exhibit both upper and lower consolute temperatures. Above 128 C (262 F) and below 49 C (120 F) butyl
glycol and water are completely miscible, but between these
temperatures they do not mix in all proportions.
Colligative Properties
Colligative properties depend only on the concentration
of the solute, not on the identity of the solute molecules.
The concept of an ideal solution, as expressed by Raoults
law, was already well-known during the last quarter of the
19th century, and it provided the early physical chemists with a powerful technique for measuring molecular
weights. (Reliable measurements of molecular weights, in
turn, provided important evidence for the modern atomic
and molecular theory of matter.)
Rise in Boiling Point
It was observed that, whenever one component in a binary
solution is present in large excess, the partial pressure of
that component is correctly predicted by Raoults law,
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even though the solution may exhibit departures from

ideal behaviour in other respects. When Raoults law is
applied to the solvent of a very dilute solution containing a
nonvolatile solute, it is possible to calculate the mole fraction of the solute from an experimental determination of
the rise in boiling point that results when the solute is dissolved in the solvent. Since the separate weights of solute
and solvent are readily measured, the procedure provides
a simple experimental method for the determination of
molecular weight. If a weighed amount of a nonvolatile
substance, w2, is dissolved in a weighed amount of a solvent, w1, at constant pressure, the increase in the boiling
temperature, tb1, the gas constant, r (derived from the
gas laws), the heat of vaporization of the pure solvent per
unit weight, l1vap, and the boiling temperature of pure solvent, tb1, are related in a simple product of ratios equal to
the molecular weight of the solute, M2. The equation is:
(5)
The essence of this technique follows from the observation that, in a dilute solution of a nonvolatile solute, the
rise in boiling point is proportional to the number of solute molecules, regardless of their size and mass.
Decrease in Freezing Point
Another colligative property of solutions is the decrease
in the freezing temperature of a solvent that is observed
when a small amount of solute is dissolved in that solvent.
By reasoning similar to that leading to equation (5), the
freezing-point depression, tf , the freezing temperature
of pure solvent, tf 1, the heat of fusion (also called the heat
of melting ) of pure solvent per unit weight, l1fusion, and
the weights of solute and solvent in the solution, w2 and
87
w1, respectively, are so related as to equal the molecular

weight of solute, M2, in the equation
(6)
A well-known practical application of freezing-point
depression is provided by adding antifreeze to the cooling
water in an automobiles radiator. Water alone freezes at
0 C (32 F), but the freezing temperature decreases appreciably when ethylene glycol is mixed with water.
Osmotic Pressure
A third colligative property, osmotic pressure, helped to
establish the fundamentals of modern physical chemistry
and played a particularly important role in the early days of
solution theory. Osmosis is especially important in medicine
and biology, but in recent years it has also been applied industrially to problems such as the concentration of fruit juices,
the desalting of seawater, and the purification of municipal sewage. Osmosis occurs whenever a liquid solution is
in contact with a semipermeable membranei.e., a thin,
porous wall whose porosity is such that some, but not all, of
the components in the liquid mixture can pass through the
wall. A semipermeable membrane is a selective barrier, and
many such barriers are found in plants and animals. Osmosis
gives rise to what is known as osmotic pressure in which a
container at uniform temperature is divided into two parts
by a semipermeable membrane that allows only molecules
of component A to pass from the left to the right side; the
selective membrane does not allow molecules of component B to pass. Example compounds for A and B might be
water and sodium chloride (table salt), respectively.
Molecules of component A are free to pass back and
forth through the membrane, but, at equilibrium, when
88
Osmotic pressure caused by a membrane that allows A to pass but not B.

A representative system could consist of water (A) and salt (B). Copyright
Encyclopdia Britannica; rendering for this edition by Rosen
Educational Services
the fugacity (escaping tendency) of A in the right-hand

side is the same as that in the left-hand side, there is no
net transfer of A from one side to the other. On the left
side, the presence of B molecules lowers the fugacity of A,
and, therefore, to achieve equal fugacities for A on both
sides, some compensating effect is needed on the left side.
This compensating effect is an enhanced pressure, designated by and called osmotic pressure. At equilibrium
the pressure in the left side of the container is larger than
that in the right side; the difference in pressure is . In the
simplest case, when the concentration of B is small (i.e.,
A is in excess), the osmotic pressure is the product of the
gas constant (r), the absolute temperature (t ), and the
concentration of B (cB ) in the solution expressed in moles
of B per unit volume: = rtcB. Since the osmotic pressure
89
for a dilute solution is proportional to the number of solute molecules, it is a colligative property, and, as a result,
osmotic-pressure measurements are often used to determine molecular weights, especially for large molecules
such as polymers. When wB grams of solute B are added to
a large amount of solvent A at temperature t, and V is the
volume of liquid solvent A in the left side of the container,
then the molecular weight of B, MB, is given by
(7)
For sodium chloride in water, cB is the concentration of the ions, which is twice the concentration of
the salt owing to the dissociation of the salt (NaCl) into
sodium ions (Na+) and chloride ions (Cl-). Thus, for a 3.5
percent sodium chloride solution at 25 C (77 F), is 29
atmospheres, which is the minimum pressure at which a
desalination reverse osmosis process can operate.
Transport Properties in Solutions

Pure fluids have two transport properties that are of primary importance: viscosity and thermal conductivity.
Transport properties differ from equilibrium properties in
that they reflect not what happens at equilibrium but the
speed at which equilibrium is attained. In solutions these
two transport properties are also important. In addition,
there is a third one, called diffusivity.
Viscosity
The viscosity of a fluid (pure or not) is a measure of its
ability to resist deformation. If water is poured into a
thin vertical tube with a funnel at the top, it flows easily through the tube, but salad oil is difficult to force into
the tube. If the oil is heated, however, its flow through
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the tube is much facilitated. The intrinsic property

that is responsible for these phenomena is the viscosity
(the thickness) of the fluid, a property which is often
strongly affected by temperature. All fluids (liquid or gas)
exhibit viscous behaviour (i.e., all fluids resist deformation
to some degree), but the range of viscosity is enormous:
the viscosity of air is extremely small, while that of glass is
essentially infinite. The viscosity of a solution depends not
only on temperature but also on composition. By varying
the composition of a petroleum mixture, it is possible to
attain a desired viscosity at a particular temperature. This
is precisely what the oil companies do when they sell oil to
a motorist: in winter, they recommend an oil with lower
viscosity than that used in summer, because otherwise, on
a cold morning, the viscosity of the lubricating oil may be
so high that the cars battery will not be powerful enough
to move the lubricated piston.
The thermal conductivity of a material reflects its ability to transfer heat by conduction. In practical situations
both viscosity and thermal conductivity are important, as
is illustrated by the contrast between an air mattress and
a water bed. Because of its low viscosity, air yields rapidly
to an imposed load, and thus the air mattress responds
quickly when someone lying on it changes position. Water,
because of its higher viscosity, noticeably resists deformation, and someone lying on a water bed experiences a
caressing response whenever position is changed. At the
same time, since the thermal conductivity as well as the
viscosity of water are larger than those of air, the user of a
water bed rapidly gets cold unless a heater keeps the water
warm. No heater is required by the user of an air mattress
because stagnant air is inefficient in removing heat from
a warm body.
91
Composition and temperature affect the thermal conductivity of a solution but, in typical liquid mixtures, the
effect on viscosity is much larger than that on thermal
conductivity.
Diffusivity
While viscosity is concerned with the transfer of momentum and thermal conductivity with the transfer of heat,
diffusivity is concerned with the transport of molecules in
a mixture. If a lump of sugar is put into a cup of coffee, the
sugar molecules travel from the surface of the lump into
the coffee at a speed determined by the temperature and
by the pertinent intermolecular forces. The characteristic
property that determines this speed is called diffusivity
i.e., the ability of a molecule to diffuse through a sea of
other molecules. Diffusivities in solids are extremely small,
and those in liquids are much smaller than those in gases.
For this reason, a spoon is used to stir the coffee to speed up
the motion of the sugar molecules, but, if the odour of cigarette smoke fills a room, little effort is needed to clear the
airopening the windows for a few minutes is sufficient.
In order to define diffusivity, it is necessary to consider
a binary fluid mixture in which the concentration of solute
molecules is c1 at position 1 and c2 at position 2, which is l
centimetres from position 1; if c1 is larger than c2, then the
concentration gradient (change with respect to distance),
given by (c2 - c1)/l, is a negative number, indicating that molecules of solute spontaneously diffuse from position 1 to
position 2. The number of solute molecules that pass through
an area of 1 square cm perpendicular to l, per second, is called
the flux J (expressed in molecules per second per square
centimetre). The diffusivity D is given by the formula
(8)
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The leading minus sign is introduced because, when

the gradient is positive, J is negative, and, by convention,
D is a positive number. In binary gaseous mixtures, diffusivity depends only weakly on the composition, and,
therefore, to a good approximation, the diffusivity of gas
A in gas B is the same as that of gas B in gas A. In liquid
systems, however, the diffusivity of solute A in solvent
B may be significantly different from that of solute B in
solvent A. In a very viscous fluid, molecules cannot rapidly move from one place to another. Therefore, in liquid
systems, the diffusivity of solute A depends strongly
on the viscosity of solvent B and vice versa. While the
letter D is always used for diffusivity, viscosity is commonly given the symbol : in many liquid solutions it is
observed that, as the composition changes (as long as the
temperature remains constant), the product D remains
nearly the same.
Thermodynamics
and Intermolecular
Forces in Solutions
The properties of solutions depend, essentially, on two
characteristics: first, the manner in which the molecules
arrange themselves (that is, the geometric array in which
the molecules occupy space) and, second, the nature and
strength of the forces operating between the molecules.
Energy Considerations
The first characteristic is reflected primarily in the
thermodynamic quantity S, called entropy, which is
a measure of disorder, and the second characteristic
is reflected in the thermodynamic quantity H, called
enthalpy, which is a measure of potential energyi.e.,
93
the energy that must be supplied to separate all the molecules from one another. Enthalpy minus the product of
the absolute temperature t and entropy equals a thermodynamic quantity G, called Gibbs energy (also called
free energy):
(9)
From the second law of thermodynamics, it can be
shown that, at constant temperature and pressure, any
spontaneous process is accompanied by a decrease in
Gibbs energy. The change in G that results from mixing
is designated by G, which, in turn, is related to changes
in h and S at constant temperature by the equation
(10)
At a fixed temperature and pressure, two substances
mix spontaneously whenever G is negative; that is,
mixing (either partial or complete) occurs whenever the
Gibbs energy of the substances after mixing is less than
that before mixing.
The two characteristics that determine solution
behaviour, structure and intermolecular forces, are,
unfortunately, not independent, because the structure is
influenced by the intermolecular forces and because the
potential energy of the mixture depends on the structure.
Only in limiting cases is it possible, on the one hand, to
calculate S (the entropy change upon mixing) from structural considerations alone and, on the other, to calculate
h (the enthalpy change of mixing) exclusively from relations describing intermolecular forces. Nevertheless, such
calculations have proved to be useful for establishing models that approximate solution behaviour and that serve
94
as guides in interpreting experimental measurements.

Solutions for which structural considerations are dominant are called athermal solutions, and those for which
the effects of intermolecular forces are more important
than those of structure are called regular solutions (see
Theories of Solutions: Regular and Athermal Solutions).
Effects of Molecular Structure

A variety of forces operate between molecules, and there
is a qualitative relation between the properties of a solution and the types of intermolecular forces that operate
within it. The volume occupied by a solution is determined
primarily by repulsive forces. When two molecules are
extremely close to one another, they must necessarily exert
a repulsive force on each other since two molecules of finite
dimensions cannot occupy the same space; two molecules
in very close proximity resist attempts to shorten the distance between them.
At larger distances of separation, molecules may attract
or repel each other depending on the sign (plus or minus)
and distribution of their electrical charge. Two ions attract
one another if the charge on one is positive and that on
the other is negative; they repel when both carry charges
of the same sign. Forces between ions are called Coulomb
forces and are characterized by their long range; the force
(F ) between two ions is inversely proportional to the
square of the distance between them; i.e., F varies as 1/r2.
Noncoulombic physical forces between molecules decay
more rapidly with distance; i.e., in general F varies as 1/rn,
n being larger than 2 for intermolecular forces other than
those between ions.
The Coulomb force (F ) equals the product of the magnitude of the charge on one ion (e1) and that on the other
95
(e2) divided by the product of the distance squared (r2) and

the dielectric constant ():
(11)
If both e1 and e2 are positive, F is positive and the force is
repulsive. If either e1 or e2 is positive while the other is negative, F is negative and the force is attractive. Coulomb
forces are dominant in electrolyte solutions.
Molecular Structure and

Charge Distribution
If a molecule has no net electrical charge, its negative charge
is equal to its positive charge. The forces experienced by
such molecules depend on how the positive and negative
charges are arranged in space. If the arrangement is spherically symmetric, the molecule is said to be nonpolar; if there
is an excess of positive charge on one end of the molecule
and an excess of negative charge on the other, the molecule
has a dipole moment (i.e., a measurable tendency to rotate
in an electric or magnetic field) and is therefore called polar.
The dipole moment ( ) is defined as the product of the
magnitude of the charge, e, and the distance separating the
positive and negative charges, l: = el. Electrical charge is
measured in electrostatic units (esu), and the typical charge
at one end of a molecule is of the order of 10 -10 esu; the distance between charges is of the order of 10 -8 cm. Dipole
moments, therefore, usually are measured in debyes (one
debye is 10 -18 esu-cm). For nonpolar molecules, = 0.
Polar Molecules
The force F between two polar molecules is directly proportional to the product of the two dipole moments ( 1 and
2) and inversely proportional to the fourth power of the
96
distance between them (r4): that is, F varies as 12/r4. The

equation for this relationship contains a constant of proportionality (F = k12/r4), the sign and magnitude of which
depend on the mutual orientation of the two dipoles. If the
positive end of one faces the negative end of the other, the
constant of proportionality is negative (meaning that an
attractive force exists), while it is positive (meaning that a
repulsive force exists) when the positive end of one faces
the positive end of the other. When polar molecules are
free to rotate, they tend to favour those orientations that
lead to attractive forces. To a first approximation, the force
(averaged over all orientations) is inversely proportional to
the temperature and to the seventh power of the distance
of separation. Mixtures of polar molecules often exhibit
only mild deviations from ideality, but mixtures containing
polar and nonpolar molecules are frequently strongly nonideal. Because of the qualitative and quantitative differences
in intermolecular forces, the molecules segregate: the polar
molecules prefer to be with each other, and so do the nonpolar ones. Only at higher temperatures, such that the thermal
energy of the molecules offsets the cohesion between identical molecules, do the two liquids mix in all proportions. In
mixtures containing both polar and nonpolar components,
deviations from Raoults law diminish as temperature rises.
Nonpolar Molecules
A nonpolar molecule is one whose charge distribution is
spherically symmetric when averaged over time; since the
charges oscillate, a temporary dipole moment exists at any
given instant in a so-called nonpolar molecule. These temporary dipole moments fluctuate rapidly in magnitude and
direction, giving rise to intermolecular forces of attraction called London (or dispersion) forces. All molecules,
charged or not, polar or not, interact by London forces.
To a first approximation, the London force between two
97
molecules is inversely proportional to the seventh power

of the distance of separation; it is therefore short-range,
decreasing rapidly as one molecule moves away from
the other. The London theory indicates that for simple
molecules positive deviations from Raoults law may be
expected (i.e., the activity coefficient i is greater than 1, as
explained previously). Since the London theory suggests
that the attractive forces between unlike simple molecules
are smaller than those corresponding to an ideal solution, the escaping tendency of the molecules in solution is
larger than that calculated by Raoults law. As a result, mixing of small nonpolar molecules is endothermic (absorbing
heat from the surroundings) and the volume occupied
by the liquid solution often exceeds that of the unmixed
componentsthat is, the components expand on mixing.
In addition to the forces listed above, there are so-called
induction forces set up when a charged or polar molecule
induces a dipole in another molecule; the electric field of
the inducing molecule distorts the charge distribution in
the other. When a charged molecule induces a dipole in
another, the force is always attractive and is inversely proportional to the fifth power of the distance of separation.
When a polar molecule induces a dipole in another molecule, the force is also attractive and is inversely proportional
to the seventh power of separation. Induction forces are
usually small but may make a significant contribution to the
energy of a mixture of molecules that are strongly dissimilar.
Effects of Chemical Interactions

In many cases the properties of a mixture are determined
primarily by forces that are more properly classified as
chemical rather than as physical. For example, when dinitrogen pentoxide is dissolved in water, a new substance,
nitric acid, is formed; and it is necessary to interpret the
98
behaviour of such a solution in terms of its chemical properties, which, in this case, are more important than its
physical properties. This example is an extreme one, and
there are many solutions for which the chemical effect is
less severe but nevertheless dominant.
Hydrogen Bonding: Association
This dominance is especially important in those solutions
that involve hydrogen bonding. Whenever a solution
contains molecules with an electropositive hydrogen
atom and with an electronegative atom (such as nitrogen, oxygen, sulfur, or fluorine), hydrogen bonding may
occur and, when it does, the properties of the solution are
affected profoundly. Hydrogen bonds may form between
identical molecules or between dissimilar molecules.
For example, methanol (CH3OH) has an electropositive
(electron-attracting) hydrogen atom and also an electronegative (electron-donating) oxygen atom, and therefore
two methanol molecules may hydrogen-bond (represented by the dashed line) singly to form the structure
or in chains to form
Hydrogen bonding between identical molecules is often

called association.
99
Hydrogen Bonding: Solvation

In a mixture of methanol and, say, pyridine (C5H5N),
hydrogen bonds can also form between the electropositive hydrogen atom in methanol and the electronegative
nitrogen atom in pyridine. Hydrogen bonding between
dissimilar molecules is an example of a type of interaction known as solvation. Since the extent of association
or solvation or both depends on the concentrations of
the solutions components, the partial pressure of a component is not even approximately proportional to its
mole fraction as given by Raoults law; therefore, large
deviations from Raoults law are commonly observed in
solutions in which hydrogen bonding is extensive. Broadly
speaking, association of one component, but not the
other, tends to produce positive deviations from Raoults
law, because the associating component hydrogen-bonds
to a smaller extent when it is surrounded by other molecules than it does in the pure state. On the other hand,
solvation between dissimilar molecules tends to produce
negative deviations from Raoults law.
Theories of Solutions
The following section treats solutions in a more theoretical manner. Much of the theory of solutions deals with the
activity coefficients mentioned above in the discussion of
Raoults law.
Activity Coefficients and Excess Functions

As has been explained previously, when actual concentrations do not give simple linear relations for the behaviour
of a solution, activity coefficients, symbolized by i, are
used in expressing deviations from Raoults law. Activity
100
coefficients are directly related to excess functions, and,

in attempting to understand solution behaviour, it is convenient to characterize nonelectrolyte solutions in terms
of these functions. In particular, it is useful to distinguish
between two types of limiting behaviour: one corresponds
to that of a regular solution; the other, to that of an athermal solution (i.e., when components are mixed, no heat is
generated or absorbed).
In a binary mixture with mole fractions x1 and x2 and
activity coefficients 1 and 2, these quantities can be
related to a thermodynamic function designated by GE,
called the excess Gibbs (or free) energy. The significance
of the word excess lies in the fact that GE is the Gibbs
energy of a solution in excess of what it would be if it
were ideal.
In a binary solution the two activity coefficients are
not independent but are related by an exact differential
equation called the Gibbs-Duhem relation. If experimental data at constant temperature are available for 1 and 2
as a function of composition, it is possible to apply this
equation to check the data for thermodynamic consistency: the data are said to be consistent only if they satisfy
the Gibbs-Duhem relation. Experimental data that do
not satisfy this relation are thermodynamically inconsistent and therefore must be erroneous.
To establish a theory of solutions, it is necessary to
construct a theoretical (or semitheoretical) equation for
the excess Gibbs energy as a function of absolute temperature (T ) and the mole fractions x1 and x2. After such
an equation has been established, the individual activity
coefficients can readily be calculated.
Gibbs energy, by definition, consists of two parts: one
part is the enthalpy, which reflects the intermolecular
forces between the molecules, which, in turn, are responsible for the heat effects that accompany the mixing
101
process (enthalpy is, in a general sense, a measure of the

heat content of a substance); and the other part is the
entropy, which reflects the state of disorder (a measure
of the random behaviour of particles) in the mixture. The
excess Gibbs energy Ge is given by the equation
(12)
where he is the excess enthalpy and Se is the excess entropy.
The word excess means in excess of that which would prevail if the solution were ideal. In the simplest case, both
he and Se are zero; in that case the solution is ideal and
1 = 2 = 1. In the general case, neither he nor Se is zero, but
two types of semi-ideal solutions can be designated: in the
first, Se is zero but he is not; this is called a regular solution. In the second, he is zero but Se is not; this is called
an athermal solution. An ideal solution is both regular and
athermal.
Regular Solutions
The word regular implies that the molecules mix in a completely random manner, which means that there is no
segregation or preference; a given molecule chooses its
neighbours with no regard for chemical identity (species
1 or 2). In a regular solution of composition x1 and x2, the
probability that the neighbour of a given molecule is of
species 1 is given by the mole fraction x1, and the probability that it is of species 2 is given by x2.
Two liquids form a solution that is approximately regular when the molecules of the two liquids do not differ
appreciably in size and there are no strong orienting forces
caused by dipoles or hydrogen bonding. In that event, the
mixing process can be represented by a lattice model with
102
Physical significance of interchange energy. the energy absorbed in the process above is 2. Copyright Encyclopdia Britannica; rendering for
this edition by Rosen Educational Services
two pure liquids, 1 and 2, and the central molecule of liquid 1 is then interchanged with the central molecule of
liquid 2. Before interchange, the potential energy between
central molecule 1 and one of its immediate neighbours
is 11, and that between central molecule 2 and one of its
immediate neighbours is 22. After interchange, the potential energy between molecule 1 and one of its immediate
neighbours is 12, and that between molecule 2 and one of
its immediate neighbours is also 12. The change in energy
that accompanies this mixing process is equal to twice
103
the interchange energy (), which is equal to the potential

energy after mixing less one-half the sum of the potential energies before mixing, the whole multiplied by
the number of immediate neighbours, called the coordination number (z), surrounding the two shifted molecules:
(13)
In this lattice model, z equals 4; but, in three dimensions, z varies between 6 and 12, depending on the lattice
geometry. In this simple lattice model, the interchange
process occurs without change of volume; thus, in this
particular case, the excess enthalpy is the same as the
energy change upon mixing. Assuming regular-solution
behaviour (i.e., Se = 0), an equation may be derived
relating Gibbs energy, Avogadros number, interchange
energy, and mole fractions. In principle, the interchange
energy () may be positive or negative, but, for simple
molecules, for which only London forces of attraction
are important, is positive. The equation obtained from
the simple lattice model can be extended semiempirically to apply to mixtures of molecules whose sizes are
not nearly the same by using volume fractions instead
of mole fractions to express the effect of composition
and by introducing the concept of cohesive energy density, which is defined as the potential energy of a liquid
divided by its volume. The adjective cohesive is well
chosen because it indicates that this energy is associated
with the forces that keep the molecules close together in
a condensed state. Again restricting attention to nonpolar molecules and assuming a completely random mixture
(Se = 0), an equation may be derived that requires only
pure-component properties to predict the excess Gibbs
energy (and hence the activity coefficients) of binary
104
mixtures. Because of many simplifying assumptions, this

equation does not give consistently accurate results, but
in many cases it provides good semiquantitative estimates. The form of the equation is such that the excess
Gibbs energy is larger than zero; hence, the equation is
not applicable to mixtures that have negative deviations
from Raoults law.
Athermal Solutions
In a solution in which the molecules of one component are
much larger than those of the other, the assumption that
the solution is regular (i.e., that SE = 0) no longer provides
a reasonable approximation even if the effect of intermolecular forces is neglected. A large flexible molecule (e.g.,
a chain molecule such as polyethylene) can attain many
more configurations when it is surrounded by small molecules than it can when surrounded by other large flexible
molecules; the state of disorder in such a solution is
therefore much larger than that of a regular solution
in which SE = 0. A solution of very large molecules (i.e.,
polymers) in an ordinary liquid solvent is analogous to a
mixture of cooked spaghetti (representing the polymers)
and tomato sauce (the solvent). When there is a large
amount of sauce and relatively little spaghetti, each piece
of spaghetti is free to exist in many different shapes; this
freedom, however, becomes restricted as the number
of spaghetti pieces rises and the amount of sauce available for each strand declines. The excess entropy then is
determined primarily by the freedom that the spaghetti
has in the tomato sauce mixture relative to the freedom
it has in the absence of sauce.
Regular solutions and athermal solutions represent
limiting cases; real solutions are neither regular nor
105
athermal. For real solutions it has been proposed to calculate GE by combining the equations derived separately
for regular solutions and for athermal solutions, but, in
view of the restrictive and mutually inconsistent assumptions that were made in deriving these two equations, the
proposal has met with only limited success.
Associated and Solvated Solutions

For those solutions in which there are strong intermolecular forces due to large dipole moments, hydrogen bonding,
or complex formation, equations based on fundamental
molecular theory cannot be applied, but it is frequently
useful to apply a chemical treatmenti.e., to describe
the liquid mixture in terms of association and solvation,
by assuming the existence of a variety of distinct chemical species in chemical equilibrium with one another. For
example, there is much experimental evidence for association in acetic acid, in which most of the molecules dimerize;
i.e., two single acetic acid molecules, called monomers,
combine to form a new molecule, called a dimer, through
hydrogen bonding. When acetic acid is dissolved in a solvent such as benzene, the extent of dimerization of acetic
acid depends on the temperature and on the total concentration of acetic acid in the solution. The escaping tendency
(vapour pressure) of a monomer is much greater than that
of a dimer, and it is thus possible to explain the variation
of activity coefficient with composition for acetic acid in
benzene; the activity coefficient of acetic acid in an excess
of benzene is large because, under these conditions, acetic acid is primarily in the monomeric state, whereas pure
acetic acid is almost completely dimerized. In the acetic
acidbenzene system, association of acetic acid molecules
produces positive deviations from Raoults law.
106
When a solvent and a solute molecule link together

with weak bonds, the process is called solvation. For
example, in the system acetone-chloroform, a hydrogen
bond is formed between the hydrogen atom in chloroform and the oxygen atom in acetone. In this case,
hydrogen bonding depresses the escaping tendencies of
both components, producing negative deviations from
Raoults law.
While hydrogen bonding is frequently encountered
in solutions, there are many other examples of weak
chemical-bond formation between dissimilar molecules.
The formation of such weak bonds is called complex
formationthat is, formation of a new chemical species, called a complex, which is held together by weak
forces that are chemical in nature rather than physical.
Such complexes usually exist only in solution; because
of their low stability, they cannot, in general, be isolated.
The ability of molecules to form complexes has a strong
effect on solution behaviour. For example, the solubility of a sparingly soluble species can be much increased
by complex formation: the solubility of silver chloride
in water is extremely small since silver chloride dissociates only slightly to silver ion and chloride ion; however,
when a small quantity of ammonia is added, solubility
rises dramatically because of the reaction of six molecules
of ammonia with one silver ion to form the complex ion
Ag(NH3)6+. By tying up silver ions and forcing extensive
dissociation of molecular silver chloride, the ammonia
pulls silver chloride into aqueous solution.
In recent years there has been much interest in the
use of computers to generate theoretical expressions
for the activity coefficients of solutions. In many cases
the calculations have been restricted to model systems,
in particular to mixtures of hard-sphere (envisioned as
107
billiard balls) moleculesi.e., idealized molecules that

have finite size but no forces of attraction. These calculations have produced a better understanding of the
structure of simple liquid solutions since the manner in
which nonpolar and non-hydrogen-bonding molecules
arrange themselves in space is determined primarily by
their size and shape and only secondarily by their attractive intermolecular forces. The results obtained for
hard-sphere molecules can be extended to real molecules
by applying corrections required for attractive forces and
for the softness of the moleculesi.e., the ability of
molecules to interpenetrate (overlap) at high temperatures. While practical results are still severely limited
and while the amount of required computer calculation
is large even for simple binary systems, there is good reason to believe that advances in the theory of solution will
increasingly depend on computerized, as opposed to analytical, models.
Solutions of Electrolytes
Near the end of the 19th century, the properties of electrolyte solutions were investigated extensively by the
early workers in physical chemistry. A suggestion of
Svante August Arrhenius, a Swedish chemist, that salts of
strong acids and bases (for example, sodium chloride) are
completely dissociated into ions when in aqueous solution received strong support from electrical-conductivity
measurements and from molecular-weight studies
(freezing-point depression, boiling-point elevation, and
osmotic pressure). These studies showed that the number
of solute particles was larger than it would be if no dissociation occurred. For example, a 0.001 molal solution
of a uni-univalent electrolyte (one in which each ion has
108
a valence, or charge, of 1, and, when dissociated, two ions

are produced) such as sodium chloride, Na+Cl-, exhibits
colligative properties corresponding to a nonelectrolyte
solution whose molality is 0.002. The colligative properties of a 0.001 molal solution of a univalent-divalent
electrolyte (yielding three ions) such as magnesium bromide, Mg2+Br2-, correspond to those of a nonelectrolyte
solution with a molality of 0.003.
At somewhat higher concentrations the experimental data showed some inconsistencies with Arrheniuss
dissociation theory, and initially these were ascribed to
incomplete, or partial, dissociation. In the years 192030,
however, it was shown that these inconsistencies could be
explained by electrostatic interactions (Coulomb forces)
of the ions in solution. The current view of electrolyte
solutions is that, in water at normal temperatures, the
salts of strong acids and strong bases are completely dissociated into ions at all concentrations up to the solubility
limit. At high concentrations Coulombic interactions
may cause the formation of ion pairs, which implies that
the ions are not dispersed uniformly in the solution but
have a tendency to form two-ion aggregates in which a
positive ion seeks the close proximity of a negative ion
and vice versa. While the theory of dilute electrolyte
solutions is well advanced, no adequate theory exists for
concentrated electrolyte solutions primarily because of
the long-range Coulomb forces that dominate in ionic
solutions.
The equilibrium properties of electrolyte solutions can be studied experimentally by electrochemical
measurements, freezing-point depressions, solubility
determinations, osmotic pressures, or measurements of
vapour pressure. Most electrolytes, such as salts, are nonvolatile at ordinary temperature, and, in that event, the
109
vapour pressure exerted by the solution is the same as the

partial pressure of the solvent. The activity coefficient of
the solvent can, therefore, be found from total-pressure
measurements, and, using the Gibbs-Duhem equation, it
is then possible to calculate the activity coefficient of the
electrolyte solute. This activity coefficient is designated
by to indicate that it is a mean activity coefficient for
the positive and negative ions. Since it is impossible to
isolate positive ions and negative ions into separate containers, it is not possible to determine individual activity
coefficients for the positive ions and for the negative
ions. The mean activity coefficient is so defined that it
approaches a value of unity at very low molality where the
ions are so far apart that they exert negligible influence on
one another.
For small concentrations of electrolyte, the theory of
Peter Debye, a Dutch-born American physical chemist,
and Erich Hckel, a German chemist, relates to the
ionic strength, which is the sum of the products of the concentration of each ion (in moles per litre) and the square
of its charge. The equation predicts that decreases with
rising ionic strength in agreement with experiment at very
low ionic strength. At higher ionic strength, however,
rises, and in some cases is greater than 1. The derivation
of the Debye-Hckel theory clearly shows that it is limited
to low concentrations. Many attempts have been made to
extend the Debye-Hckel equation to higher electrolyte
concentrations. One of the more successful attempts is
based on the idea that the ions are solvated, which means
that every ion is surrounded by a tight-fitting shell of solvent molecules.
The concept of solvation is often used to explain
properties of aqueous solutions; one well-known property is the salting-out effect, in which the solubility of a
nonelectrolyte in water is decreased when electrolyte is
110
added. For example, the solubility of ethyl ether in water

at 25 C (77 F) is 0.91 mole percent, but, in an aqueous
solution containing 15 weight percent sodium chloride, it
is only 0.13 mole percent. This decrease in solubility can
be explained by postulating that some of the water molecules cannot participate in the dissolution of the ether
because they are tightly held (solvated) by sodium and
chloride ions.
Electrolyte solutions have long been of interest in
industry since many common inorganic chemicals are
directly obtained, or else separated, by crystallization
from aqueous solution. Further, many important chemical
and metallurgical products (e.g., aluminum) are obtained
or refined by electrochemical processes that occur in
liquid solution. In recent years there has been renewed
interest in electrolyte solutions because of their relevance
to fuel cells as a possible source of power for automobiles.
The properties of electrolyte solutions also have large
importance in physiology. Many molecules that occur in
biological systems bear electric charges; a large molecule
that has a positive electric charge at one end and a negative charge at the other is called a zwitterion. Very large
molecules, such as those of proteins, may have numerous
positive and negative charges; such molecules are called
polyelectrolytes. In solution, the conformation (i.e., the
three-dimensional structure) of a large, charged molecule
is strongly dependent on the ionic strength of the dissolving medium. For example, depending on the nature
and concentration of salts present in the solvent, a polyelectrolyte molecule may coagulate into a ball, it may
stretch out like a rod, or it may form a coil or helix. The
conformation, in turn, is closely related to the molecules
physiological function. As a result, improved understanding of the properties of electrolyte solutions has direct
consequences in molecular biology and medicine.
111
Solubilities of Solids and Gases

Since the dissolution of one substance in another can
occur only if there is a decrease in the Gibbs energy,
it follows that, generally speaking, gases and solids do
not dissolve in liquids as readily as do other liquids. To
understand this, the dissolution of a solid can be visualized as occurring in two steps. In the first, the pure
solid is melted at constant temperature to a pure liquid. In the second, that liquid is dissolved at constant
temperature in the solvent. Similarly, the dissolution
of a gas can be divided at some fixed pressure into two
parts, the first corresponding to constant-temperature
condensation of the pure gas to a liquid and the second to constant-temperature mixing of that liquid with
solvent. In many cases, the pure liquids (obtained by
melting or by condensation) may be hypothetical (i.e.,
unstable and, therefore, physically unobtainable), but
usually their properties can be estimated by reasonable
extrapolations.
It is found that the change in Gibbs energy corresponding to the first step is positive and, hence, in opposition to
the change needed for dissolution. For example, at 10 C
(14 F), ice is more stable than water, and, at 110 C (230
F) and one atmosphere, steam is more stable than water.
Therefore, the Gibbs energy of melting ice at 10 C is
positive, and the Gibbs energy of condensing steam at
one atmosphere and 110 C is also positive. For the second
step, however, the change in Gibbs energy is negative; its
magnitude depends on the equilibrium composition of the
mixture. Owing to the positive Gibbs energy change that
accompanies the first step, there is a barrier that makes
it more difficult to dissolve solids and gases as compared
with liquids.
112
For gases at normal pressures, the positive Gibbs energy

of condensation increases with rising temperature, but, for
solids, the positive Gibbs energy of melting decreases with
rising temperature. For example, the change in energy, G,
of condensing steam at one atmosphere is larger at 120 C
(248 F) than it is at 110 C, while the change in energy of
melting ice at 5 C (23 F) is smaller than it is at 10 C.
Thus, as temperature rises, the barrier becomes larger for
gases but lower for solids, and therefore, with few exceptions, the solubility of a solid rises while the solubility of a
gas falls as the temperature is raised.
For solids, the positive Gibbs energy barrier depends
on the melting temperature. If the melting temperature
is much higher than the temperature of the solution, the
barrier is large, shrinking to zero when the melting temperature and solution temperature become identical.
The solubilities of the common gases hydrogen, nitrogen, methane, and carbon dioxide, as well as the solubility
of (solid) naphthalene in a few typical solvents, illustrate
the qualitative rule that like dissolves like; thus naphthalene, an aromatic hydrocarbon, dissolves more readily
in another aromatic hydrocarbon such as benzene than it
does in a chlorinated solvent such as carbon tetrachloride
or in a hydrogen-bonded solvent such as methyl alcohol.
By similar reasoning, the gas methane, a paraffinic hydrocarbon, dissolves more readily in another paraffin such as
hexane than it does in water. In all three solvents, the gas
hydrogen (which boils at 252.5 C [422.5 F]) is less soluble than nitrogen (which boils at a higher temperature,
195.8 C [320.4 F]).
While exceptions may occur at very high pressures,
the solubility of a gas in a liquid generally rises as the pressure of that gas increases. When the pressure of the gas is
much larger than the vapour pressure of the solvent, the
113
solubility is often proportional to the pressure. This proportionality is consistent with Henrys law, which states
that, if the gas phase is ideal, the solubility x2 of gas 2 in
solvent 1 is equal to the partial pressure (the vapour-phase
mole fraction y2 times the total pressure Pi.e., y2P)
divided by a temperature-dependent constant, h2,1 (called
Henrys constant), which is determined to a large extent by
the intermolecular forces between solute 2 and solvent 1:
When the vapour pressure of solvent 1 is small compared with the total pressure, the vapour-phase mole
fraction of gas 2 is approximately one, and the solubility
of the gas is proportional to the total pressure.
114
Chapter 6
Crystalline Solids
and Liquid Crystals
olids are one of the three basic states of matter, the

others being liquids and gases. (Sometimes plasmas, or
ionized gases, are considered a fourth state of matter.) A
solid forms from liquid or gas because the energy of atoms
decreases when the atoms take up a relatively ordered,
three-dimensional structure.
Solids exhibit certain characteristics that distinguish
them from liquids and gases. All solids have, for example,
the ability to resist forces applied either perpendicular or
parallel to a surface (i.e., normal or shear loads, respectively). Such properties depend on the properties of the
atoms that form the solid, on the way those atoms are
arranged, and on the forces between them.
Solids are generally divided into three broad
classescrystalline, noncrystalline (amorphous), and
quasicrystalline. Crystalline solids have a very high degree
of order in a periodic atomic arrangement. Practically all
metals and many other minerals, such as common table
salt (sodium chloride), belong to this class. Noncrystalline
solids are those in which atoms and molecules are not
organized in a definite lattice pattern. They include
glasses, plastics, and gels. Quasicrystalline solids display
novel symmetries in which the atoms are arranged in quasiperiodic fashioni.e., in patterns that do not repeat at
regular intervals. They exhibit symmetries, such as fivefold symmetry, that are forbidden in ordinary crystals.
Quasicrystal structures are common in alloys in which
aluminum is combined with another metal, such as iron,
cobalt, or nickel.
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Some molecules may exist in the liquid crystal state,

which is intermediate to the crystalline solid and liquid
states. Liquid crystals flow like liquids yet display a certain
degree of the symmetry characteristic of crystalline solids.
Four principal types of atomic bonds are found in
crystalline solids: metallic, ionic, covalent, and molecular.
Metals and their alloys are characterized in the main by
their high electrical and thermal conductivity, which arise
from the migration of free electrons; free electrons also
influence how the atoms bond. Ionic crystals are aggregates of charged ions. These salts commonly exhibit ionic
conductivity, which increases with temperature. Covalent
crystals are hard, frequently brittle materials such as
diamond, silicon, and silicon carbide. In the simpler, monatomic types (e.g., diamond), each atom is surrounded by
a number of atoms equal to its valence. Molecular crystals
are substances that have relatively weak intermolecular
binding, such as dry ice (solidified carbon dioxide), solid
forms of the rare gases (e.g., argon, krypton, and xenon),
and crystals of numerous organic compounds.
Various alloys, salts, covalent crystals, and molecular crystals that are good electrical insulators at low
temperature become conductors at elevated temperatures, conductivity increasing rapidly with temperature.
Materials of this type are called semiconductors. Their
electrical conductivity is generally low when compared
with that of such metals as copper, silver, or aluminum.
Basic Units of Solids

The definition of a solid appears obvious; a solid is generally thought of as being hard and firm. Upon inspection,
however, the definition becomes less straightforward. A
cube of butter, for example, is hard after being stored in
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7 Crystalline Solids and Liquid Crystals 7
a refrigerator and is clearly a solid. After remaining on the

kitchen counter for a day, the same cube becomes quite
soft, and it is unclear if the butter should still be considered a solid. Many crystals behave like butter in that they
are hard at low temperatures but soft at higher temperatures. They are called solids at all temperatures below
their melting point. A possible definition of a solid is an
object that retains its shape if left undisturbed. The pertinent issue is how long the object keeps its shape. A highly
viscous fluid retains its shape for an hour but not a year. A
solid must keep its shape longer than that.
The basic units of solids are either atoms or atoms
that have combined into molecules. The electrons of an
atom move in orbits that form a shell structure around
the nucleus. The shells are filled in a systematic order,
with each shell accommodating only a small number of
electrons. Different atoms have different numbers of electrons, which are distributed in a characteristic electronic
structure of filled and partially filled shells. The arrangement of an atoms electrons determines its chemical
properties. The properties of solids are usually predictable from the properties of their constituent atoms and
molecules, and the different shell structures of atoms are
therefore responsible for the diversity of solids.
All occupied shells of the argon (Ar) atom, for
example, are filled, resulting in a spherical atomic shape.
In solid argon the atoms are arranged according to the
closest packing of these spheres. The iron (Fe) atom, in
contrast, has one electron shell that is only partially filled,
giving the atom a net magnetic moment. Thus, crystalline iron is a magnet. The covalent bond between two
carbon (C) atoms is the strongest bond found in nature.
This strong bond is responsible for making diamond the
hardest solid.
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Long- and Short-Range Order

A solid is crystalline if it has long-range order. Once the
positions of an atom and its neighbours are known at one
point, the place of each atom is known precisely throughout the crystal. Most liquids lack long-range order, although
many have short-range order. Short range is defined as the
first- or second-nearest neighbours of an atom. In many
liquids the first-neighbour atoms are arranged in the same
structure as in the corresponding solid phase. At distances
that are many atoms away, however, the positions of the
atoms become uncorrelated. These fluids, such as water,
have short-range order but lack long-range order. Certain
liquids may have short-range order in one direction and
long-range order in another direction; these special substances are called liquid crystals. Solid crystals have both
short-range order and long-range order.
Solids that have short-range order but lack long-range
order are called amorphous. Almost any material can be
made amorphous by rapid solidification from the melt
(molten state). This condition is unstable, and the solid
will crystallize in time. If the timescale for crystallization
is years, then the amorphous state appears stable. Glasses
are an example of amorphous solids. In crystalline silicon
(Si) each atom is tetrahedrally bonded to four neighbours.
In amorphous silicon (a-Si) the same short-range order
exists, but the bond directions become changed at distances farther away from any atom. Amorphous silicon is
a type of glass. Quasicrystals are another type of solid that
lack long-range order.
Most solid materials found in nature exist in polycrystalline form rather than as a single crystal. They are
actually composed of millions of grains (small crystals)
packed together to fill all space. Each individual grain
has a different orientation from its neighbours. Although
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long-range order exists within one grain, at the boundary

between grains, the ordering changes direction. A typical piece of iron or copper (Cu) is polycrystalline. Single
crystals of metals are soft and malleable, while polycrystalline metals are harder and stronger and are more useful
industrially. Most polycrystalline materials can be made
into large single crystals after extended heat treatment.
In the past blacksmiths would heat a piece of metal to
make it malleable: heat makes a few grains grow large by
incorporating smaller ones. The smiths would bend the
softened metal into shape and then pound it awhile; the
pounding would make it polycrystalline again, increasing
its strength.
Categories of Crystals
Crystals are classified in general categories, such as insulators, metals, semiconductors, and molecular solids. A
single crystal of an insulator is usually transparent and
resembles a piece of glass. Metals are shiny unless they
have rusted. Semiconductors are sometimes shiny and
sometimes transparent but are never rusty. Many crystals
can be classified as a single type of solid, while others have
intermediate behaviour. Cadmium sulfide (CdS) can be
prepared in pure form and is an excellent insulator; when
impurities are added to cadmium sulfide, it becomes an
interesting semiconductor. Bismuth (Bi) appears to be a
metal, but the number of electrons available for electrical
conduction is similar to that of semiconductors. In fact,
bismuth is called a semimetal. Molecular solids are usually crystals formed from molecules or polymers. They can
be insulating, semiconducting, or metallic, depending on
the type of molecules in the crystal. New molecules are
continuously being synthesized, and many are made into
crystals. The number of different crystals is enormous.
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struCture
Crystals can be grown under moderate conditions from all
92 naturally occurring elements except helium, and helium
can be crystallized at low temperatures by using 25 atmospheres of pressure. Binary crystals are composed of two
elements. There are thousands of binary crystals; some
examples are sodium chloride (NaCl), alumina (Al2O3),
and ice (H2O). Crystals can also be formed with three or
more elements.
The Unit Cell

A basic concept in crystal structures is the unit cell. It is the
smallest unit of volume that permits identical cells to be
stacked together to fill all space. By repeating the pattern
of the unit cell over and over in all directions, the entire
crystal lattice can be constructed. A cube is the simplest
Unit cells for face-centred and body-centred cubic lattices. Copyright

120
example of a unit cell. Two other examples are the facecentred cubic lattice and the body-centred cubic lattice.
There are only a few different unit-cell shapes, so many
different crystals share a single unit-cell type. An important characteristic of a unit cell is the number of atoms
it contains. The total number of atoms in the entire crystal is the number in each cell multiplied by the number of
unit cells. Copper and aluminum (Al) each have one atom
per unit cell, while zinc (Zn) and sodium chloride have
two. Most crystals have only a few atoms per unit cell,
but there are some exceptions. Crystals of polymers, for
example, have thousands of atoms in each unit cell.
Structures of Metals
The elements are found in a variety of crystal packing
arrangements. The most common lattice structures for
metals are those obtained by stacking the atomic spheres
into the most compact arrangement. There are two such
possible periodic arrangements. In each, the first layer has
the atoms packed into a plane-triangular lattice in which
every atom has six immediate neighbours. The second
layer has the same plane-triangular structure; the atoms
sit in the holes formed by the first layer. The first layer
has two equivalent sets of holes, but the atoms of the second layer can occupy only one set. The third layer, labeled
C, has the same structure, but there are two choices for
selecting the holes that the atoms will occupy. The third
layer can be placed over the atoms of the first layer, generating an alternate layer sequence ABABAB . . . , which
is called the hexagonal closest-packed (hcp) structure.
Cadmium and zinc crystallize with this structure.
The second possibility is to place the atoms of the third
layer over those of neither of the first two but instead over
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Stacking of spheres in closest-packed arrangements. Copyright

the set of holes in the first layer that remains unoccupied.

The fourth layer is placed over the first, and so there is a
three-layer repetition ABCABCABC . . . , which is called
the face-centred cubic (fcc), or cubic-closest-packed, lattice. Copper, silver (Ag), and gold (Au) crystallize in fcc
lattices. In the hcp and the fcc structures the spheres fill 74
percent of the volume, which represents the closest possible packing of spheres. Each atom has 12 neighbours. The
number of atoms in a unit cell is two for hcp structures and
one for fcc. There are 32 metals that have the hcp lattice
and 26 with the fcc. Another possible arrangement is the
body-centred cubic (bcc) lattice, in which each atom has
eight neighbours arranged at the corners of a cube. For
example, the cesium chloride (CsCl) structure is a cubic
arrangement. If all atoms in this structure are of the same
species, it is a bcc lattice. The spheres occupy 68 percent of
the volume. There are 23 metals with the bcc arrangement.
The sum of these three numbers (32 + 26 + 23) exceeds the
number of elements that form metals (63), since some elements are found in two or three of these structures.
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The fcc structure is also found for crystals of the rare

gas solids neon (Ne), argon (Ar), krypton (Kr), and xenon
(Xe). Their melting temperatures at atmospheric pressure
are: Ne, 24.6 K (248.5 C, or 415.4 F); Ar, 83.8 K (189.4 C,
or 308.8 F); Kr, 115.8 K (157.4 C, or 251.2 F); and Xe,
161.4 K (111.8 C, or 169.2 F).
Structures of Nonmetallic Elements

The elements in the fourth row of the periodic table
carbon, silicon, germanium (Ge), and -tin (-Sn)prefer
covalent bonding. Carbon has several possible crystal
structures. Each atom in the covalent bond has four firstneighbours, which are at the corners of a tetrahedron.
This arrangement is called the diamond lattice. There
are two atoms in a unit cell, which is fcc. Large crystals
of diamond are valuable gemstones. The crystal has other
interesting properties; it has the highest sound velocity
of any solid and is the best conductor of heat. Besides
diamond, the other common form of carbon is graphite,
which is a layered material. Each carbon atom has three
coplanar near neighbours, forming an arrangement called
the honeycomb lattice. Three-dimensional graphite crystals are obtained by stacking similar layers.
Another form of crystalline carbon is based on a molecule with 60 carbon atoms called buckminsterfullerene
(C60 ). The molecular shape is spherical. Each carbon is
bonded to three neighbours, as in graphite, and the spherical shape is achieved by a mixture of 12 rings with five
sides and 20 rings with six sides. Similar structures were
first visualized by the American architect R. Buckminster
Fuller for geodesic domes. The C60 molecules, also called
buckyballs, are quite strong and almost incompressible.
Crystals are formed such that the balls are arranged in
an fcc lattice with a one-nanometre spacing between the
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centres of adjacent balls. The similar C70 molecule has

the shape of a rugby ball; C70 molecules also form an fcc
crystal when stacked together. The solid fullerenes form
molecular crystals, with weak bindingprovided by van
der Waals interactionsbetween the molecules.
Many elements form diatomic gases: hydrogen (H),
oxygen (O), nitrogen (N), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). When cooled to low temperature,
they form solids of diatomic molecules. Nitrogen has the
hcp structure, while oxygen has a more complex structure.
The most interesting crystal structures are those of
elements that are neither metallic, covalent, nor diatomic.
Although boron (B) and sulfur (S) have several different
crystal structures, each has one arrangement in which it
is usually found. Twelve boron atoms form a molecule in
the shape of an icosahedron. Crystals are formed by stacking the molecules. The -rhombohedral structure of boron
the icosahedral arrangement of a boron molecule. Copyright

124
has seven of these icosahedral molecules in each unit cell,

giving a total of 84 atoms. Molecules of sulfur are usually
arranged in rings; the most common ring has eight atoms.
The typical structure is -sulfur, which has 16 molecules
per unit cell, or 128 atoms. In the common crystals of
selenium (Se) and tellurium (Te), the atoms are arranged
in helical chains, which stack like cordwood. However,
selenium also makes eight-atom rings, similar to sulfur,
and forms crystals from them. Sulfur also makes helical
chains, similar to selenium, and stacks them together
into crystals.
Structures of Binary Crystals

Binary crystals are found in many structures. Some pairs
of elements form more than one structure. At room
temperature, cadmium sulfide may crystallize either in
the zinc blende or wurtzite structure. Alumina also has
two possible structures at room temperature, -alumina
(corundum) and -alumina. Other binary crystals exhibit
different structures at different temperatures. Among
the most complex crystals are those of silicon dioxide
(SiO2), which has seven different structures at various
temperatures and pressures; the most common of these
structures is quartz. Some pairs of elements form several
different crystals in which the ions have different chemical valences. Cadmium (Cd) and phosphorus (P) form the
crystals Cd3P2, CdP2, CdP4, Cd7P10, and Cd6P7. Only in
the first case are the ions assigned the expected chemical
valences of Cd2+ and P3-.
Among the binary crystals, the easiest structures to
visualize are those with equal numbers of the two types
of atoms. The structure of sodium chloride is based on a
cube. To construct the lattice, the sodium and chlorine
atoms are placed on alternate corners of a cube, and the
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(A)
(B)
(C)
(D)
Crystal structures. there is an equal number of the two types of ions in

the unit cell of the (A) cesium chloride, (B) sodium chloride, and (D) zinc
blende arrangements. the diamond arrangement is shown in (C). If both
atoms are identical in (A), the structure is body-centred cubic. Copyright
structure is repeated. The structure of the sodium atoms

alone, or the chlorine atoms alone, is fcc and defines the
unit cell. The sodium chloride structure thus is made up
of two interpenetrating fcc lattices. The cesium chloride
lattice is based on the bcc structure; every other atom is
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cesium or chlorine. In this case, the unit cell is a cube. The

third important structure for AB (binary) lattices is zinc
blende. It is based on the diamond structure, where every
other atom is A or B. Many binary semiconductors have
this structure, including those with one atom from the
third (boron, aluminum, gallium [Ga], or indium [In]) and
one from the fifth (nitrogen, phosphorus, arsenic [As], or
antimony [Sb]) column of the periodic table (GaAs, InP,
etc.). Most of the chalcogenides (O, S, Se, Te) of cadmium
and zinc (CdTe, ZnSe, ZnTe, etc.) also have the zinc blende
structure. The mineral zinc blende is ZnS; its unit cell is
also fcc. The wurtzite structure is based on the hcp lattice,
where every other atom is A or B. These four structures
comprise most of the binary crystals with equal numbers
of cations and anions.
The fullerene molecule forms binary crystals MxC60
with alkali atoms, where M is potassium (K), rubidium
(Rb), or cesium (Cs). The fullerene molecules retain their
spherical shape, and the alkali atoms sit between them.
The subscript x can take on several values. A compound
with x = 6 (e.g., K6C60) is an insulator with the fullerenes in
a bcc structure. The case x = 4 is an insulator with the bodycentred tetragonal structure, while the case x = 3 is a metal
with the fullerenes in an fcc structure. K3C60, Rb3C60, and
Cs3C60 are superconductors at low temperatures.
Alloys
Alloys are solid mixtures of atoms with metallic properties.
The definition includes both amorphous and crystalline
solids. Although many pairs of elements will mix together
as solids, many pairs will not. Almost all chemical entities
can be mixed in liquid form. But cooling a liquid to form
a solid often results in phase separation; a polycrystalline
material is obtained in which each grain is purely one atom
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or the other. Extremely rapid cooling can produce an amorphous alloy. Some pairs of elements form alloys that are
metallic crystals. They have useful properties that differ
from those exhibited by the pure elements. For example,
alloying makes a metal stronger; for this reason alloys of
gold, rather than the pure metal, are used in jewelry.
Atoms tend to form crystalline alloys when they are
of similar size. The sizes of atoms are not easy to define,
however, because atoms are not rigid objects with sharp
boundaries. The outer part of an atom is composed of
electrons in bound orbits; the average number of electrons decreases gradually with increasing distance from
the nucleus. There is no point that can be assigned as the
precise radius of the atom. Scientists have discovered,
however, that each atom in a solid has a characteristic
radius that determines its preferred separation from
neighbouring atoms. For most types of atom this radius
is constant, even in different solids. An empirical radius is
assigned to each atom for bonding considerations, which
leads to the concept of atomic size. Atoms readily make
crystalline alloys when the radii of the two types of atoms
agree to within roughly 15 percent.
Two kinds of ordering are found in crystalline
alloys. Most alloys at low temperature are binary crystals with perfect ordering. An example is the alloy of
copper and zinc. Copper is fcc, whereas zinc is hcp. A
50-percent-zinc50-percent-copper alloy has a different structure-brass. At low temperatures it has the
cesium chloride structure: a bcc lattice with alternating
atoms of copper and zinc and a cubic unit cell. If the temperature is raised above 470 C (878 F), however, a phase
transition to another crystalline state occurs. The ordering at high temperature is also bcc, but now each site has
equal probability of having a copper or zinc atom. The
two types of atoms randomly occupy each site, but there
128
is still long-range order. At all temperatures, thousands of

atoms away from a site, the location of the atom site can
be predicted with certainty. At temperatures below 470
C one also knows whether that site will be occupied by a
copper or zinc atom, while above 470 C there is an equal
likelihood of finding either atom. The high-temperature
phase is crystalline but disordered. The disorder phase is
obtained through a partial melting, not into a liquid state
but into a less ordered one. This behaviour is typical of
metal alloys. Other common alloys are steel, an alloy of
iron and carbon; stainless steel, an alloy of iron, nickel
(Ni), and chromium (Cr); pewter and solder, alloys of tin
and lead (Pb); and britannia metal, an alloy of tin, antimony, and copper.
Crystal Defects
A crystal is never perfect; a variety of imperfections can
mar the ordering. A defect is a small imperfection affecting a few atoms. The simplest type of defect is a missing
atom and is called a vacancy. Since all atoms occupy space,
extra atoms cannot be located at the lattice sites of other
atoms, but they can be found between them; such atoms
are called interstitials. Thermal vibrations may cause
an atom to leave its original crystal site and move into a
nearby interstitial site, creating a vacancy-interstitial pair.
Vacancies and interstitials are the types of defects found
in a pure crystal. In another defect, called an impurity,
an atom is present that is different from the host crystal
atoms. Impurities may either occupy interstitial spaces or
substitute for a host atom in its lattice site.
There is no sharp distinction between an alloy and a
crystal with many impurities. An alloy results when a sufficient number of impurities are added that are soluble in
the host metal. However, most elements are not soluble in
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most crystals. Crystals generally can tolerate a few impurities per million host atoms. If too many impurities of the
insoluble variety are added, they coalesce to form their
own small crystallite. These inclusions are called precipitates and constitute a large defect.
Germanium is a common impurity in silicon. It prefers the same tetrahedral bonding as silicon and readily
substitutes for silicon atoms. Similarly, silicon is a common impurity in germanium. No large crystal can be made
without impurities; the purest large crystal ever grown
was made of germanium. It had about 1010 impurities in
each cubic centimetre of material, which is less than one
impurity for each trillion atoms.
Impurities often make crystals more useful. In the
absence of impurities, -alumina is colourless. Iron and
titanium impurities impart to it a blue colour, and the
resulting gem-quality mineral is known as sapphire.
Chromium impurities are responsible for the red colour
characteristic of rubies, the other gem of -alumina. Pure
semiconductors rarely conduct electricity well at room
temperatures. Their ability to conduct electricity is caused
by impurities. Such impurities are deliberately added to
silicon in the manufacture of integrated circuits. In fluorescent lamps the visible light is emitted by impurities in
the phosphors (luminescent materials).
Other imperfections in crystals involve many atoms.
Twinning is a special type of grain boundary defect, in
which a crystal is joined to its mirror image. Another kind
of imperfection is a dislocation, which is a line defect that
may run the length of the crystal. One of the many types
of dislocations is due to an extra plane of atoms that is
inserted somewhere in the crystal structure. Another type
is called an edge dislocation. This line defect occurs when
there is a missing row of atoms. In the figure the crystal
arrangement is perfect on the top and on the bottom. The
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Crystalline lattice defect. An edge dislocation occurs when there is a missing row of atoms as shown in region b. region a is strained. Copyright
defect is the row of atoms missing from region b. This mistake runs in a line that is perpendicular to the page and
places a strain on region a.
Dislocations are formed when a crystal is grown, and
great care must be taken to produce a crystal free of them.
Dislocations are stable and will exist for years. They relieve
mechanical stress. If one presses on a crystal, it will accommodate the induced stress by growing dislocations at the
surface, which gradually move inward. Dislocations make
a crystal mechanically harder. When a metal bar is coldworked by rolling or hammering, dislocations and grain
boundaries are introduced; this causes the hardening.
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Determination of Crystal Structures

Crystal structures are determined by scattering experiments using a portion of the crystal as the target. A beam
of particles is sent toward the target, and upon impact
some of the particles scatter from the crystal and ricochet
in various directions. A measurement of the scattered
particles provides raw data, which is then computerprocessed to give a picture of the atomic arrangements.
The positions are then inferred from the computeranalyzed data.
Incident rays (1 and 2) at angle on the planes of atoms in a crystal. rays

reinforce if their difference in path length (AB + BC) is an integer times the
wavelength of the X ray. Copyright Encyclopdia Britannica; rendering
for this edition by Rosen Educational Services
132
Max von Laue first suggested in 1912 that this

measurement could be done using X rays, which are
electromagnetic radiation of very high frequency. High
frequencies are needed because these waves have a
short wavelength. Von Laue realized that atoms have a
spacing of only a few angstroms (1 angstrom [] is 1010
metre, or 3.94 109 inch). In order to measure atomic
arrangements, the particles scattering from the target must also have a wavelength of a few angstroms. X
rays are required when the beam consists of electromagnetic radiation. The X rays only scatter in certain
directions, and there are many X rays associated with
each direction. The scattered particles appear in spots
corresponding to locations where the scattering from
each identical atom produces an outgoing wave that
has all the wavelengths in phase. The scattering from
an atom A2 further in the crystal has a longer path than
that from atom A1. If this additional path has a length
(AB + BC) that is an exact multiple of the wavelength,
then the two outgoing waves are in phase and reinforce
each other. If the scattering angle is changed slightly,
the waves no longer add coherently and begin to cancel one another. Combining the scattered radiation
from all the atoms in the crystal causes all the outgoing
waves to add coherently in certain directions and produce a strong signal in the scattered wave. If the extra
path length (AB + BC) is five wavelengths, for example,
the spot appears in one place. If it is six wavelengths,
the spot is elsewhere. Thus, the different spots correspond to the different multiples of the wavelength
of the X ray. The measurement produces two types of
information: the directions of the spots and their intensity. This information is insufficient to deduce the exact
crystal structure, however, as there is no algorithm by
which the computer can go directly from the data to the
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structure. The crystallographer must propose various structures and compute how they would scatter the X rays. The
theoretical results are compared with the measured one,
and the theoretical arrangement is chosen that best fits the
data. Although this procedure is fast when there are only
a few atoms in a unit cell, it may take months or years for
complex structures. Some protein molecules, for instance,
have hundreds of atoms. Crystals of the proteins are grown,
and X rays are used to measure the structure. The goal is to
determine how the atoms are arranged in the protein, rather
than how the proteins are arranged in the crystal.
Beams of neutrons may also be used to measure crystal
structure. The beam of neutrons is obtained by drilling a
hole in the side of a nuclear reactor. The energetic neutrons created in nuclear fission escape through the hole.
The motion of elementary particles is governed by quantum, or wave, mechanics. Each neutron has a wavelength
that depends on its momentum. The scattering directions
are determined by the wavelength, as is the case with X
rays. The wavelengths for neutrons from a reactor are suitable for measuring crystal structures.
X rays and neutrons provide the basis for two competing technologies in crystallography. Although they are
similar in principle, the two methods have some differences. X rays scatter from the electrons in the atoms so
that more electrons result in more scattering. X rays easily detect atoms of high atomic number, which have many
electrons, but cannot readily locate atoms with few electrons. In hydrogen-bonded crystals, X rays do not detect
the protons at all. Neutrons, on the other hand, scatter
from the atomic nucleus. They scatter readily from protons and are excellent for determining the structure of
hydrogen-bonded solids. One drawback to this method is
that some nuclei absorb neutrons completely, and there is
little scattering from these targets.
134
Beams of electrons can also be used to measure crystal

structure, because energetic electrons have a wavelength
that is suitable for such measurements. The problem with
electrons is that they scatter strongly from atoms. Proper
interpretation of the experimental results requires that an
electron scatter only from one atom and leave the crystal without scattering again. Low-energy electrons scatter
many times, and the interpretation must reflect this. Lowenergy electron diffraction (LEED) is a technique in
which a beam of electrons is directed toward the surface.
The scattered electrons that reflect backward from the
surface are measured. They scatter many times before
leaving backward but mainly leave in a few directions that
appear as spots in the measurements. An analysis of the
varied spots gives information on the crystalline arrangement. Because the electrons are scattered strongly by the
atoms in the first few layers of the surface, the measurement gives only the arrangements of atoms in these layers.
It is assumed that the same structure is repeated throughout the crystal. Another scattering experiment involves
electrons of extremely high energy. The scattering rate
decreases as the energy of the electron increases, so that
very energetic electrons usually scatter only once. Various
electron microscopes are constructed on this principle.
Types of Bonds
The properties of a solid can usually be predicted from the
valence and bonding preferences of its constituent atoms.
Four main bonding types are discussed here: ionic, covalent, metallic, and molecular. Hydrogen-bonded solids,
such as ice, make up another category that is important in
a few crystals. There are many examples of solids that have
a single bonding type, while other solids have a mixture of
types, such as covalent and metallic or covalent and ionic.
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Ionic Bonds
Sodium chloride exhibits ionic bonding. The sodium atom
has a single electron in its outermost shell, while chlorine
needs one electron to fill its outer shell. Sodium donates
one electron to chlorine, forming a sodium ion (Na+) and
a chlorine ion (Cl). Each ion thus attains a closed outer
shell of electrons and takes on a spherical shape. In addition to having filled shells and a spherical shape, the ions
of an ionic solid have integer valence. An ion with positive
valence is called a cation. In an ionic solid the cations are
surrounded by ions with negative valence, called anions.
Similarly, each anion is surrounded by cations. Since
opposite charges attract, the preferred bonding occurs
when each ion has as many neighbours as possible, consistent with the ion radii. Six or eight nearest neighbours
are typical; the number depends on the size of the ions
and not on the bond angles. The alkali halide crystals are
binaries of the AH type, where A is an alkali ion (lithium
[Li], sodium, potassium, rubidium, or cesium) and H is a
halide ion (fluorine, chlorine, bromine, or iodine). The
crystals have ionic bonding, and each ion has six or eight
neighbours. Metal ions in the alkaline earth series (magnesium [Mg], calcium [Ca], barium [Ba], and strontium
[Sr]) have two electrons in their outer shells and form
divalent cations in ionic crystals. The chalcogenides (oxygen, sulfur, selenium, and tellurium) need two electrons
to fill their outer p-shell. (Electron shells are divided into
subshells, designated as s, p, d, f, g, and so forth. Each subshell is divided further into orbitals.) Two electrons are
transferred from the cations to the anions, leaving each
with a closed shell. The alkaline earth chalcogenides form
ionic binary crystals such as barium oxide (BaO), calcium
sulfide (CaS), barium selenide (BaSe), or strontium oxide
(SrO). They have the same structure as sodium chloride,
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with each atom having six neighbours. Oxygen can be

combined with various cations to form a large number of
ionically bonded solids.
Covalent Bonds
Silicon, carbon, germanium, and a few other elements form
covalently bonded solids. In these elements there are four
electrons in the outer sp-shell, which is half filled. (The spshell is a hybrid formed from one s and one p subshell.) In
the covalent bond an atom shares one valence (outer-shell)
electron with each of its four nearest neighbour atoms.
The bonds are highly directional and prefer a tetrahedral
arrangement. A covalent bond is formed by two electrons
one from each atomlocated in orbitals between the ions.
Insulators, in contrast, have all their electrons within shells
inside the atoms.
The perpetual spin of an electron is an important
aspect of the covalent bond. From a vantage point above
the spinning particle, counterclockwise rotation is designated spin-up, while clockwise rotation is spin-down. A
fundamental law of quantum physics is the Pauli exclusion
principle, which states that no two electrons can occupy
the same point in space at the same time with the same
direction of spin. In a covalent bond two electrons occupy
the same small volume of space (i.e., the same orbital) at
all times, so they must have opposite spin: one up and one
down. The exclusion principle is then satisfied, and the
resulting bond is strong.
In graphite the carbon atoms are arranged in parallel sheets, and each atom has only three near neighbours.
The covalent bonds between adjacent carbons within each
layer are quite strong and are called bonds. The fourth
valence electron in carbon has its orbital perpendicular
to the plane. This orbital bonds weakly with the similar
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orbitals on all three neighbours, forming bonds. The four

bonds for each carbon atom in the graphite structure are
not arranged in a tetrahedron; three are in a plane. The planar arrangement results in strong bonding, although not as
strong as the bonding in the diamond configuration. The
bonding between layers is quite weak and arises from the
van der Waals interaction; there is much slippage parallel
to the layers. Diamond and graphite form an interesting
contrast: diamond is the hardest material in nature and is
used as an abrasive, while graphite is used as a lubricant.
Besides the elemental semiconductors, such as silicon and germanium, some binary crystals are covalently
bonded. Gallium has three electrons in the outer shell,
while arsenic lacks three. Gallium arsenide (GaAs) could
be formed as an insulator by transferring three electrons
from gallium to arsenic; however, this does not occur.
Instead, the bonding is more covalent, and gallium arsenide is a covalent semiconductor. The outer shells of the
gallium atoms contribute three electrons, and those of the
arsenic atoms contribute five, providing the eight electrons needed for four covalent bonds. The centres of the
bonds are not at the midpoint between the ions but are
shifted slightly toward the arsenic. Such bonding is typical of the IIIV semiconductorsi.e., those consisting of
one element from the third column of the periodic table
and one from the fifth column. Elements from the third
column (boron, aluminum, gallium, and indium) contribute three electrons, while the fifth-column elements
(nitrogen, phosphorus, arsenic, and antimony) contribute
five electrons. All IIIV semiconductors are covalently
bonded and typically have the zinc blende structure with
four neighbours per atom. Most common semiconductors
favour this arrangement.
The factor that determines whether a binary crystal
will act as an insulator or a semiconductor is the valence
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of its constituent atoms. Ions that donate or accept one

or two valence electrons form insulators. Those that
have three to five valence electrons tend to have covalent
bonds and form semiconductors. There are exceptions to
these rules, however, as is the case with the IVVI semiconductors such as lead sulfide. Heavier elements from
the fourth column of the periodic table (germanium, tin,
and lead) combine with the chalcogenides from the sixth
row to form good binary semiconductors such as germanium telluride (GeTe) or tin sulfide (SnS). They have the
sodium chloride structure, where each atom has six neighbours. Although not tetrahedrally bonded, they are good
semiconductors.
Filled atomic shells with d-orbitals have an important
role in covalent bonding. Electrons in atomic orbits have
angular momentum (L), which is quantized in integer (n)
multiples of Plancks constant h: L = nh. Electron orbitals
with n = 0 are called s-states, with n = 1 are p-states, and with
n = 2 are d-states. Silver and copper ions have one valence
electron outside their closed shells. The outermost filled
shell is a d-state and affects the bonding. Eight binary crystals are formed from the copper and silver halides. Three
(AgF, AgCl, AgBr) have the sodium chloride structure
with six neighbours. The other five (AgI, CuF, CuCl, CuBr,
CuI) have the zinc blende structure with four neighbours.
The bonding in this group of solids is on the borderline
between covalent and ionic, since the crystals prefer both
types of bonds. The alkali metal halides exhibit somewhat
different behaviour. The alkali metals are also monovalent
cations, but their halides are strictly ionic. The difference
in bonding between the alkali metals on the one hand and
silver and copper on the other hand is that silver and copper have filled d-shells while the alkalis have filled p-shells.
Since the d-shells are filled, they do not covalently bond.
This group of electrons is, however, highly polarizable,
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which influences the bonding of the valence electrons.

Similar behaviour is found for zinc and cadmium, which
have two valence electrons outside a filled d-shell. They
form binary crystals with the chalcogenides, which have
tetrahedral bonding. In this case the covalent bonding
seems to be preferred over the ionic bond. In contrast,
the alkaline earth chalcogenides, which are also divalent,
have outer p-shells and are ionic. The zinc and cadmium
chalcogenides are covalent, as the outer d-shell electrons
of the two cations favour covalent bonding.
Metallic Bonds
Metallic bonds fall into two categories. The first is the case
in which the valence electrons are from the sp-shells of the
metal ions; this bonding is quite weak. In the second category the valence electrons are from partially filled d-shells,
and this bonding is quite strong. The d-bonds dominate
when both types of bonding are present.
The simple metals are bonded with sp-electrons. The
electrons of these metal atoms are in filled atomic shells
except for a few electrons that are in unfilled sp-shells.
The electrons from the unfilled shells are detached from
the metal ion and are free to wander throughout the
crystal. They are called conduction electrons, since they
are responsible for the electrical conductivity of metals.
Although the conduction electrons may roam anywhere
in the crystal, they are distributed uniformly throughout
the entire solid. Any large imbalance of charge is prevented by the strong electrical attraction between the
negative electrons and the positive ions, plus the strong
repulsion between electrons. The phrase electron correlation describes the correlated movements of the electrons;
the motion of each electron depends on the positions of
neighbouring electrons. Electrons have strong short-range
140
order with one another. Correlation ensures that each unit

cell in the crystal has, on the average, the number of electrons needed to cancel the positive charge of the cation so
that the unit cell is electrically neutral.
Cohesive energy is the energy gained by arranging
the atoms in a crystalline state, as compared with the gas
state. Insulators and semiconductors have large cohesive
energies; these solids are bound together strongly and
have good mechanical strength. Metals with electrons in
sp-bonds have very small cohesive energies. This type of
metallic bond is weak; the crystals are barely held together.
Single crystals of simple metals such as sodium are
mechanically weak. At room temperature the crystals have
the mechanical consistency of warm butter. Special care
must be used in handling these crystals, because they are
easily distorted. Metals such as magnesium or aluminum
must be alloyed or polycrystalline to have any mechanical
strength. Although the simple metals are found in a variety
of structures, most are in one of the three closest-packed
structures: fcc, bcc, and hcp. Theoretical calculations
show that the cohesive energy of a given metal is almost
the same in each of the different crystal arrangements;
therefore, crystal arrangements are unimportant in metals bound with electrons from sp-shells.
A different type of metallic bonding is found in
transition metals, which are metals whose atoms are characterized by unfilled d-shells. The d-orbitals are more
tightly bound to an ion than the sp-orbitals. Electrons in
d-shells do not wander away from the ion. The d-orbitals
form a covalent bond with the d-orbitals on the neighbouring atoms. The bonding of d-orbitals does not occur in a
tetrahedral arrangement but has a different directional
preference. In metals the bonds from d-orbitals are not
completely filled with electrons. This situation is different
from the tetrahedral bonds in semiconductors, which are
141
filled with eight electrons. In transition metals the covalent bonds formed with the d-electrons are much stronger
than the weak bonds made with the sp-electrons of simple
metals. The cohesive energy is much larger in transition
metals. Titanium, iron, and tungsten, for example, have
exceptional mechanical strength. Crystal arrangements
are important in the behaviour of the transition metals and
occur in the close-packed fcc, bcc, or hcp arrangements.
Molecular Binding
The Dutch physicist Johannes D. van der Waals first proposed the force that binds molecular solids. Any two atoms
or molecules have a force of attraction (F) that varies according to the inverse seventh power of the distance R between
the centres of the atoms or molecules: F = C/R7, where C
is a constant. The force, known as the van der Waals force,
declines rapidly with the distance R and is quite weak. If
the atoms or molecules have a net charge, there is a strong
force whose strength varies according to Coulombs law
as the inverse second power of the separation distance:
F = C/R2, where C is a constant. This force provides the
binding in ionic crystals and some of the binding in metals.
Coulombs law does not apply to atoms or molecules without a net charge. Molecules with a dipole moment, such as
water, have a strong attractive force owing to the interactions between the dipoles. For atoms and molecules with
neither net charges nor dipole moments, the van der Waals
force provides the crystal binding. The force of gravity also
acts between neutral atoms and molecules, but it is far too
weak to bind molecules into crystals.
The van der Waals force is caused by quantum fluctuations. Two neighbouring atoms that are each fluctuating
can lower their joint energy by correlating their fluctuations. The van der Waals force arises from correlations
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in their dipole fluctuations. Electrons bound in atomic

orbits are in constant motion around the nucleus, and the
distribution of charges in the atom changes constantly as
the electrons move, owing to quantum fluctuations. One
fluctuation might produce a momentary electric dipole
moment (i.e., a separation of charges) on an atom if a
majority of its electrons are on one side of the nucleus. The
dipole moment creates an electric field on a neighbouring
atom; this field will induce a dipole moment on the second
atom. The two dipoles attract one another via the van der
Waals interaction. Since the force depends on the inverse
seventh power of the distance, it declines rapidly with
increasing distance. Atoms have a typical radius of one to
three angstroms. The van der Waals force binds atoms and
molecules within a few angstroms of each other; beyond
that distance the force is negligible. Although weak, the
van der Waals force is always present and is important in
cases where the other forces are absent.
Hydrogen is rarely found as a single atom. Instead
it forms diatomic molecules (H2), which are gaseous at
room temperature. At lower temperatures the hydrogen
becomes a liquid and at about 20 K turns into a solid. The
molecule retains its identity in the liquid and solid states.
The solid exists as a molecular crystal of covalently bound
H2 molecules. The molecules attract one another by
van der Waals forces, which provide the crystal binding.
Helium, the second element in the periodic table, has two
electrons, which constitute a filled atomic shell. In its liquid and solid states, the helium atoms are bound together
by van der Waals forces. In fact, all the rare gases (helium,
neon, argon, krypton, and xenon) are molecular crystals
with the binding provided by van der Waals forces.
Many organic molecules form crystals where the molecules are bound by van der Waals forces. In methane (CH4),
a central carbon makes a covalent bond with each hydrogen
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atom, forming a tetrahedron. In crystalline methane the

molecules are arranged in the fcc structure. Benzene (C6H6)
has the carbon atoms in a hexagonal ring; each carbon has
three coplanar bonds, as in graphite, where two bonds are
with neighbouring carbon atoms and the third bond is with
a hydrogen atom. Crystalline benzene has four molecules
per unit cell in a complex arrangement. Fullerene and the
rare gas atoms are spherical, and the crystalline arrangement corresponds to the closest packing of spheres. Most
organic molecules, however, are not spherical and display
irregular shapes. For odd-shaped molecules, the van der
Waals interaction depends on the rotational orientation
of the two molecules. In order to maximize the force, the
molecules in the crystal have unusual arrangements, as in
the case of benzene.
Hydrogen Bonding
Hydrogen bonding is important in a few crystals, notably in ice. With its lone electron, a hydrogen atom usually
forms a single covalent bond with an electronegative atom.
In the hydrogen bond the atom is ionized to a proton. The
proton sits between two anions and joins them. Hydrogen
bonding occurs with only the most electronegative ions:
nitrogen, oxygen, and fluorine. In water the hydrogen
links pairs of oxygen ions. Water is found in many different crystal structures, but they all have the feature that
the hydrogen atoms sit between pairs of oxygen. Another
hydrogen-bonded solid is hydrogen fluoride (HF), in
which the hydrogen atom (proton) links pairs of fluorines.
Crystal Growth
The earliest crystal grower was nature. Many excellent
crystals of minerals formed in the geologic past are found
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in mines and caves throughout the world. Most precious

and semiprecious stones are well-formed crystals. Early
efforts to produce synthetic crystals were concentrated
on making gems. Synthetic ruby was grown by the French
scientist Marc Antoine Augustin Gaudin in 1873. Since
about 1950 scientists have learned to grow in the laboratory crystals of quality equal or superior to those found in
nature. New techniques for growth are continually being
developed, and crystals with three or more atoms per unit
cell are continually being discovered.
Vapour Growth
Crystals can be grown from a vapour when the molecules of the gas attach themselves to a surface and
move into the crystal arrangement. Several important
conditions must be met for this to occur. At constant
temperature and equilibrium conditions, the average
number of molecules in the gas and solid states is constant; molecules leave the gas and attach to the surface
at the same rate that they leave the surface to become
gas molecules. For crystals to grow, the gas-solid chemical system must be in a nonequilibrium state such that
there are too many gaseous molecules for the conditions
of pressure and temperature. This state is called supersaturation. Molecules are more prone to leave the gas
than to rejoin it, so they become deposited on the surface of the container. Supersaturation can be induced by
maintaining the crystal at a lower temperature than the
gas. A critical stage in the growth of a crystal is seeding,
in which a small piece of crystal of the proper structure and orientation, called a seed, is introduced into
the container. The gas molecules find the seed a more
favourable surface than the walls and preferentially
deposit there. Once the molecule is on the surface of the
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seed, it wanders around this surface to find the preferred

site for attachment. Growth proceeds one molecule at
a time and one layer at a time. The process is slow; it
takes days to grow a small crystal. Crystals are grown
at temperatures well below the melting point to reduce
the density of defects. The advantage of vapour growth
is that very pure crystals can be grown by this method,
while the disadvantage is that it is slow.
Most clouds in the atmosphere are ice crystals that
form by vapour growth from water molecules. Most raindrops are crystals as they begin descending but thaw during
their fall to Earth. Seeding for rainaccomplished by
dropping silver iodide crystals from airplanesis known
to induce precipitation. In the laboratory, vapour growth
is usually accomplished by flowing a supersaturated gas
over a seed crystal. Quite often a chemical reaction at the
surface is needed to deposit the atoms. Crystals of silicon
can be grown by flowing chlorosilane (SiCl4) and hydrogen (H2) over a seed crystal of silicon. Hydrogen acts as
the buffer gas by controlling the temperature and rate of
flow. The molecules dissociate on the surface in a chemical
reaction that forms hydrogen chloride (HCl) molecules.
Hydrogen chloride molecules leave the surface, while silicon atoms remain to grow into a crystal. Binary crystals
such as gallium arsenide (GaAs) are grown by a similar
method. One process employs gallium chloride (GaCl)
as the gallium carrier. Arsenic is provided by molecules
such as arsenous chloride (AsCl3), arsine (AsH3), or As4
(yellow arsenic). These molecules, with hydrogen as the
buffer gas, grow crystals of gallium arsenide while forming gas molecules such as gallium trichloride (GaCl3)
and hydrogen chloride. Trimethylgallium, (CH3)3Ga, is
another molecule that can be used to deliver gallium to
the surface.
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Growth from Solution

Large single crystals may be grown from solution. In this
technique the seed crystal is immersed in a solvent that
contains typically about 1030 percent of the desired
solute. The choice of solvent usually depends on the solubility of the solute. The temperature and pH (a measure of
acidity or basicity) of the solution must be well controlled.
The method is faster than vapour growth, because there
is a higher concentration of molecules at the surface in a
liquid as compared to a gas, but it is still relatively slow.
Growth from the Melt

This method is the most basic. A gas is cooled until it
becomes a liquid, which is then cooled further until it
becomes a solid. Polycrystalline solids are typically
produced by this method unless special techniques are
employed. In any case, the temperature must be controlled carefully. Large crystals can be grown rapidly from
the liquid elements using a popular method invented in
1918 by the Polish scientist Jan Czochralski and called
crystal pulling. One attaches a seed crystal to the bottom
of a vertical arm such that the seed is barely in contact
with the material at the surface of the melt. The arm
is raised slowly, and a crystal grows underneath at the
interface between the crystal and the melt. Usually the
crystal is rotated slowly, so that inhomogeneities in the
liquid are not replicated in the crystal. Large-diameter
crystals of silicon are grown in this way for use as computer chips. Based on measurements of the weight of the
crystal during the pulling process, computer-controlled
apparatuses can vary the pulling rate to produce any
desired diameter.
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7 The Britannica Guide to Matter 7
Crystal pulling using the Czochralski method. A schematic view of a modern

apparatus. Copyright Encyclopdia Britannica; rendering for this edition by Rosen Educational Services
148
Crystal pulling is the least expensive way to grow

large amounts of pure crystal. The original seed is on the
right tip. Binary crystals can also be pulled; for example,
synthetic sapphire crystals can be pulled from molten alumina. Special care is required to grow binary and other
multicomponent crystals; the temperature must be precisely controlled because such crystals may be grown only
at a single, extremely high temperature. The melt has a
tendency to be inhomogeneous, since the two liquids may
try to separate by gravity.
The Bridgman method (named after the American
scientist Percy Williams Bridgman) is also widely used for
growing large single crystals. The molten material is put into
a crucible, often of silica, which has a cylindrical shape with
a conical lower end. Heaters maintain the molten state. As
the crucible is slowly lowered into a cooler region, a crystal
starts growing in the conical tip. The crucible is lowered at
a rate that matches the growth of the crystal, so that the
interface between crystal and melt is always at the same
temperature. The rate of moving the crucible depends on
the temperature and the material. When done successfully,
the entire molten material in the crucible grows into a single
large crystal. One disadvantage of the method is that excess
impurities are pushed out of the crystal during growth. A
layer of impurities grows at the interface between melt and
solid as this surface moves up the melt, and the impurities
become concentrated in the higher part of the crystal.
Epitaxy is the technique of growing a crystal, layer by
layer, on the atomically flat surface of another crystal. In
homoepitaxy a crystal is grown on a substrate of the same
material. Silicon layers of different impurity content, for
example, are grown on silicon substrates in the manufacture of computer chips. Heteroepitaxy, on the other hand,
is the growth of one crystal on the substrate of another.
Silicon substrates are often used since they are readily
149
available in atomically smooth form. Many different semiconductor crystals can be grown on silicon, such as gallium
arsenide, germanium, cadmium telluride (CdTe), and lead
telluride (PbTe). Any flat substrate can be used for epitaxy,
however, and insulators such as rock salt (NaCl) and magnesium oxide (MgO) are also used.
Molecular-beam epitaxy, commonly abbreviated as
MBE, is a form of vapour growth. The field began when
the American scientist John Read Arthur reported in 1968
that gallium arsenide could be grown by sending a beam
of gallium atoms and arsenic molecules toward the flat
surface of a crystal of the molecule. The amount of gas
molecules can be controlled to grow just one layer, or just
two, or any desired amount. This method is slow, since
molecular beams have low densities of atoms. Chemical
vapour deposition (CVD) is another form of epitaxy that
makes use of the vapour growth technique. Also known
as vapour-phase epitaxy (VPE), it is much faster than
MBE since the atoms are delivered in a flowing gas rather
than in a molecular beam. Synthetic diamonds are grown
by CVD. Rapid growth occurs when methane (CH4) is
mixed with atomic hydrogen gas, which serves as a catalyst. Methane dissociates on a heated surface of diamond.
The carbon remains on the surface, and the hydrogen
leaves as a molecule. Growth rates are several micrometres (1 micrometre is equal to 0.00004 inch) per hour.
At that rate, a stone 1 cm (0.4 inch) thick is grown in 18
weeks. CVD diamonds are of poor quality as gemstones
but are important electronic materials. Because hydrogen is found in nature as a molecule rather than as a single
atom, making atomic hydrogen gas is the major expense
in growing CVD diamonds. Liquid-phase epitaxy (LPE)
uses the solution method to grow crystals on a substrate.
The substrate is placed in a solution with a saturated concentration of solute. This technique is used to grow many
150
crystals employed in modern electronics and optoelectronic devices, such as gallium arsenide, gallium aluminum
arsenide, and gallium phosphide.
An important concern in successful epitaxy is matching lattice distances. If the spacing between atoms in the
substrate is close to that of the top crystal, then that crystal
will grow well; a small difference in lattice distance can be
accommodated as the top crystal grows. When the lattice
distances are different, however, the top crystal becomes
deformed, since structural defects such as dislocations
appear. Although few crystals share the same lattice
distance, a number of examples are known. Aluminum
arsenide and gallium arsenide have the same crystal structure and the same lattice parameters to within 0.1 percent;
they grow excellent crystals on one another. Such materials, known as superlattices, have a repeated structure of n
layers of GaAs, m layers of AlAs, n layers of GaAs, m layers
of AlAs, and so forth. Superlattices represent artificially
created structures that are thermodynamically stable;
they have many applications in the modern electronics industry. Another lattice-matched epitaxial system is
mercury telluride (HgTe) and cadmium telluride (CdTe).
These two semiconductors form a continuous semiconductor alloy CdxHg1 xTe, where x is any number between 0
and 1. This alloy is used as a detector of infrared radiation
and is incorporated in particular in night-vision goggles.
Dendritic Growth
At slow rates of crystal growth, the interface between
melt and solid remains planar, and growth occurs uniformly across the surface. At faster rates of crystal growth,
instabilities are more likely to occur; this leads to dendritic growth. Solidification releases excess energy in the
form of heat at the interface between solid and melt. At
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slow growth rates, the heat leaves the surface by diffusion. Rapid growth creates more heat, which is dissipated
by convection (liquid flow) when diffusion is too slow.
Convection breaks the planar symmetry so that crystal
growth develops along columns, or fingers, rather than
along planes. Each crystal has certain directions in which
growth is fastest, and dendrites grow in these directions.
As the columns grow larger, their surfaces become flatter
and more unstable. This feather or tree structure is characteristic of dendritic growth. Snowflakes are an example of
crystals that result from dendritic growth.
Liquid Crystals
Liquid crystals blend the structures and properties of
the normally disparate liquid and crystalline solid states.
Liquids can flow, for example, while solids cannot, and
crystalline solids possess special symmetry properties
that liquids lack. Ordinary solids melt into ordinary liquids as the temperature increasese.g., ice melts into
liquid water. Some solids actually melt twice or more as
temperature rises. Between the crystalline solid at low
temperatures and the ordinary liquid state at high temperatures lies an intermediate state, the liquid crystal.
Liquid crystals share with liquids the ability to flow but
also display symmetries inherited from crystalline solids.
The resulting combination of liquid and solid properties
allows important applications of liquid crystals in the displays of such devices as wristwatches, calculators, portable
computers, and flat-screen televisions.

Crystals exhibit special symmetries when they slide in
certain directions or rotate through certain angles. These
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symmetries can be compared to those encountered when

walking in a straight line through empty space. Regardless
of the direction or distance of each step, the view remains
the same, as there are no landmarks by which to measure
ones progress. This is called continuous translational symmetry because all positions look identical. A crystal lattice
breaks the continuous translational symmetry of free
space; starting at one molecule there is a finite distance to
travel before reaching the next. Some translational symmetry is present, however, because, by moving the proper
distance in the proper direction, one is guaranteed to
locate additional molecules on repeated excursions. This
property is called discrete translational periodicity. Real,
three-dimensional crystals display translational periodicity in three independent directions.
Rotational symmetries can be considered in a similar
fashion. From one point in empty space, the view is the
same regardless of which direction one looks. There is continuous rotational symmetrynamely, the symmetry of a
perfect sphere. In a crystal, however, the distance to the
nearest molecule from any given molecule depends on the
direction taken. Furthermore, the molecules themselves
may have shapes that are less symmetric than a sphere. A
crystal possesses a certain discrete set of angles of rotation
that leave the appearance unchanged. The continuous
rotational symmetry of empty space is broken, and only
a discrete symmetry exists. Broken rotational symmetry
influences many important properties of crystals. Their
resistance to compression, for example, may vary according to the direction along which one squeezes the crystal.
Transparent crystals, such as quartz, may exhibit an optical
property known as birefringence. When a light ray passes
through a birefringent crystal, it is bent, or refracted, at an
angle depending on the direction of the light and also its
polarization, so that the single ray is broken up into two
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Arrangements of molecules. Copyright Encyclopdia Britannica; rendering for this edition by Rosen Educational Services
polarized rays. This is why one sees a double image when

looking through such crystals.
In a liquid, all the molecules sit in random positions
with random orientations. This does not mean that there
is less symmetry than in the crystal, however. All positions
are actually equivalent to one another, and likewise all orientations are equivalent, because in a liquid the molecules
are in constant motion. At one instant the molecules in
the liquid may occupy specific positions and orientations,
but a moment later the molecules will move to previously
empty points in space. Likewise, at one instant a molecule
points in one direction, and the next instant it points
in another. Liquids share the homogeneity and isotropy
of empty space; they have continuous translational and
rotational symmetries. No form of matter has greater
symmetry.
As a general rule, molecules solidify into crystal lattices
with low symmetry at low temperatures. Both translational and rotational symmetries are discrete. At high
temperatures, after melting, liquids have high symmetry.
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Translational and rotational symmetries are continuous.

High temperatures provide molecules with the energy
needed for motion. The mobility disorders the crystal
and raises its symmetry. Low temperatures limit motion
and the possible molecular arrangements. As a result,
molecules remain relatively immobile in low-energy, lowsymmetry configurations.
Symmetries of Liquid Crystals
Liquid crystals, sometimes called mesophases, occupy the
middle ground between crystalline solids and ordinary
liquids with regard to symmetry, energy, and properties.
Not all molecules have liquid crystal phases. Water molecules, for example, melt directly from solid crystalline ice
into liquid water. The most widely studied liquid-crystalforming molecules are elongated, rodlike molecules,
rather like grains of rice in shape (but far smaller in size).
A popular example is the molecule p-azoxyanisole (PAA):
Typical liquid crystal structures include the smectic

and the nematic (this nomenclature was invented in the
1920s by the French scientist Georges Friedel). The smectic phase differs from the solid phase in that translational
symmetry is discrete in one direction and continuous in
the remaining two.
In the nematic phase all translational symmetries are
continuous. The molecule positions are disordered in all
directions. Their orientations are all alike, however, so that
the rotational symmetry remains discrete. The orientation
of the long axis of a nematic molecule is called its director.
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It was noted earlier that, as temperature decreases,

matter tends to evolve from highly disordered states with
continuous symmetries toward ordered states with discrete symmetries. This can occur through a sequence of
symmetry-breaking phase transitions. As a substance in
the liquid state is reduced in temperature, rotational symmetry breaking creates the nematic liquid crystal state in
which molecules are aligned along a common axis. Their
directors are all nearly parallel. At lower temperatures
continuous translational symmetries break into discrete
symmetries. There are three independent directions for
translational symmetry. When continuous translational
symmetry is broken along only one direction, the smectic
liquid crystal is obtained. At temperatures sufficiently low
to break continuous translational symmetry in all directions, the ordinary crystal is formed.
The mechanism by which liquid crystalline order is
favoured can be illustrated through an analogy between
molecules and grains of rice. Collisions of molecules
require energy, so the greater the energy, the greater the
tolerance for collisions. If rice grains are poured into a
pan, they fall at random positions and orientations and
tend to jam up against their neighbours. This is similar
to the liquid state. After the pan is shaken to allow the
rice grains to readjust their positions, the neighbouring grains tend to line up. The alignment is not perfect
across the sample owing to defects, which also can occur
in nematic liquid crystals. When all grains align, they
have greater freedom to move before hitting a neighbour
than they have when they are disordered. This produces
the nematic phase. The freedom to move is primarily in the direction of molecular alignment, as sideways
motion quickly results in collision with a neighbour.
Layering the grains enhances sideways motion. This
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produces the smectic phase. In the smectic phase some

molecules have ample free volume to move in, while
others are tightly packed. The lowest-energy arrangement shares the free volume equitably among molecules.
Each molecular environment matches all others, and the
structure is a crystal.
There is a great variety of liquid crystalline structures
known in addition to those described so far. Continuous
in-plane rotational symmetry, present within smectic-A
layers, is broken in the hexatic-B phase, but a proliferation of dislocations maintains continuous translational
symmetry within its layers. A similar relationship
holds between smectic-C and smectic-F. Crystal-B and
crystal-G have molecular positions on regular crystal lattice sites, with long axes of molecules (directors) aligned,
but allow rotation of molecules about their directors.
These are the so-called plastic crystals. There also are
crystals in the discotic phase, consisting of disk-shaped
molecules, and the columnar phases, in which translational symmetry is broken in not one but two spatial
directions, leaving liquidlike order only along columns.
In general, crystals in the isotropic liquid and nematic
phases are expected at high temperatures, while many
of the other phases mentioned here are expected at low
temperatures.
Liquid Crystal Compounds
Liquid-crystal-forming compounds are widespread and
quite diverse. Soap can form a type of smectic known as
a lamellar phase, also called neat soap. In this case it is
important to recognize that soap molecules have a dual
chemical nature. One end of the molecule (the hydrocarbon tail) is attracted to oil, while the other end (the
polar head) attaches itself to water. When soap is placed
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in water, the hydrocarbon tails cluster together, while

the polar heads adjoin the water. Small numbers of soap
molecules form spherical or rodlike micelles, which float
freely in the water, while concentrated solutions create bilayers, which stack along some direction just like
smectic layers. Indeed, the name smectic is derived from
the Greek word for soap. The slippery feeling caused by
soap reflects the ease with which the layers slide across
one another.
Many biological materials form liquid crystals. Myelin,
a fatty material extracted from nerve cells, was the first
intensively studied liquid crystal. The tobacco mosaic
virus, with its rodlike shape, forms a nematic phase. In
cholesterol the nematic phase is modified to a cholesteric
phase characterized by continuous rotation of the direction of molecular alignment. An intrinsic twist of the
cholesterol molecule, rather like the twist of the threads
of a screw, causes this rotation. Since the molecular orientation rotates steadily, there is a characteristic distance
after which the orientation repeats itself. This distance is
frequently comparable to the wavelength of visible light,
so brilliant colour effects result from the diffraction of
light by these materials.
Perhaps the first description of a liquid crystal occurred
in the story The Narrative of Arthur Gordon Pym, by Edgar
Allan Poe:
I am at a loss to give a distinct idea of the nature of this liquid,
and cannot do so without many words. Although it flowed
with rapidity in all declivities where common water would do
so, yet never, except when falling in a cascade, had it the customary appearance of limpidity. . . . At first sight, and especially
in cases where little declivity was found, it bore resemblance,
as regards consistency, to a thick infusion of gum Arabic in
common water. But this was only the least remarkable of its
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extraordinary qualities. It was not colourless, nor was it of any

one uniform colourpresenting to the eye, as it flowed, every
possible shade of purple, like the hues of a changeable silk. . . .
Upon collecting a basinful, and allowing it to settle thoroughly,
we perceived that the whole mass of liquid was made up of a
number of distinct veins, each of a distinct hue; that these veins
did not commingle; and that their cohesion was perfect in
regard to their own particles among themselves, and imperfect
in regard to neighbouring veins. Upon passing the blade of a
knife athwart the veins, the water closed over it immediately,
as with us, and also, in withdrawing it, all traces of the passage
of the knife were instantly obliterated. If, however, the blade
was passed down accurately between two veins, a perfect separation was effected, which the power of cohesion did not
immediately rectify.
The liquid described in this passage is human blood.

In its usual state within the human body, blood is an ordinary disordered isotropic fluid. The disklike shape of red
blood cells, however, favours liquid crystallinity at certain
concentrations and temperatures.
Optical Properties
An understanding of the principal technological applications of liquid crystals requires a knowledge of their
optical properties. In particular, liquid crystals alter the
polarization of light passing through them.
Effect of Liquid Crystals on Polarized Light
Light waves are actually waves in electric and magnetic
fields. The direction of the electric field is the polarization of the light wave. A polarizing filter selects a single
component of polarized light to pass through while
absorbing all other components of incoming waves. If a
159
second polarizing filter is placed above the first but with

its polarization axis rotated by 90, no light can pass
through because the polarization passed by the first filter
is precisely the polarization blocked by the second filter.
When optically active materials, such as liquid crystals,
are placed between polarizing filters crossed in this manner, some light may get through, because the intervening
material changes the polarization of the light. If the nematic director is not aligned with either of the polarizing
filters, polarized light passing through the first filter
becomes partially polarized along the nematic director.
This component of light in turn possesses a component
Spatial variation of the director causing threadlike images. Copyright

160
aligned with the top polarizing filter, so a fraction of the

incoming light passes through the entire assembly. The
amount of light passing through is largest when the nematic director is positioned at a 45 angle from both filters.
The light is fully blocked when the director lies parallel to
one filter or the other.
During the last decades of the 19th century, pioneering
investigators of liquid crystals, such as the German physicist Otto Lehmann and the Austrian botanist Friedrich
Reinitzer, equipped ordinary microscopes with pairs of
polarizing filters to obtain images of nematic and smectic
phases. Spatial variation in the alignment of the nematic
director causes spatial variation in light intensity. Since the
nematic is defined by having all directors nearly parallel to
one another, the images arise from defects in the nematic
structure. The directors may rotate or bend around defect
lines. The resulting threadlike images inspired the name
nematic, which is based on the Greek word for thread.
The layered smectic structure causes layering of defects.
Nonuniformity in director alignment may be induced
artificially. The surfaces of a glass container can be coated
with a material that, when rubbed in the proper direction,
forces the director to lie perpendicular or parallel to the wall
adjacent to a nematic liquid crystal. The orientation forced
by one wall need not be consistent with that forced by
another wall; this situation causes the director orientation
to vary in between the walls. The nematic must compromise
its preference for all directors to be parallel to one another
with the inconsistent orienting forces of the container
walls. In doing so, the liquid crystal may take on a twisted
alignment across the container. Electric or magnetic fields
provide an alternate means of influencing the orientation of
the nematic directors. Molecules may prefer to align so that
their director is, say, parallel to an applied electric field.
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Use of Liquid Crystals as

Optoelectronic Displays
Optical behaviour and orienting fields underlie the important contemporary use of liquid crystals as optoelectronic
displays. Consider, for example, the twisted-nematic cell.
The polarizer surfaces are coated and rubbed so that the
nematic will align with the polarizing axis. The two polarizers are crossed, forcing the nematic to rotate between
them. The rotation is slow and smooth, assuming a 90
twist across the cell. Light passing through the first polarizer is aligned with the bottom of the nematic layer. As
the nematic twists, it rotates the polarization of the light
so that, as the light leaves the top of the nematic layer,
its polarization is rotated by 90 from that at the bottom.
The new polarization is just right for passing through the
top filter, and so light travels unhindered through the
assembly.
A twisted-nematic cell. (A) the assembly is transparent to light in the absence

of an electric field. (B) An applied field destroys the twist of the nematic,
rendering the assembly opaque. Copyright Encyclopdia Britannica; rendering for this edition by Rosen Educational Services
162
If an electric field is applied in the direction of light

propagation, the liquid crystal directors align with the
orienting field, so they are no longer parallel to the light
passing though the bottom polarizer. They are no longer capable of rotating this polarization through the 90
needed to allow the light to emerge from the top polarizer. Although this assembly is transparent when no field
is applied, it becomes opaque when the field is present.
A grid of such assemblies placed side by side may be
used to display images. If one turns on the electric field
attached to the parts of the grid that lie where the image
is to appear, these points will turn black while the remaining points of the grid stay white. The resulting patchwork
of dark and light creates the image on the display. In a
wristwatch, calculator, or computer these may be simply
numbers or letters, and in a television the images may be
detailed pictures. Switching the electric fields on or off
will cause the picture to move, just as ordinary television
pictures display an ever-changing stream of electrically
encoded images.
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Chapter 7
Amorphous Solids
and Quasicrystals
morphous solids are any noncrystalline solid in

which the atoms and molecules are not organized in
a definite lattice pattern. Such solids include glass, plastic,
and gel.
Quasicrystals are matter formed atomically in a manner somewhere between the amorphous solids of glasses
(special forms of metals and other minerals, as well as
common glass) and the precise pattern of crystals. Like
crystals, quasicrystals contain an ordered structure, but
the patterns are subtle and do not recur at precisely regular intervals. Rather, quasicrystals appear to be formed
from two different structures assembled in a nonrepeating array, the three-dimensional equivalent of a tile floor
made from two shapes of tile and having an orientational
order but no repetition.
Amorphous Solids
Solids and liquids are both forms of condensed matter;
both are composed of atoms in close proximity to each
other. But their properties are, of course, enormously
different. While a solid material has both a well-defined
volume and a well-defined shape, a liquid has a welldefined volume but a shape that depends on the shape of
the container. Stated differently, a solid exhibits resistance
to shear stress while a liquid does not. Externally applied
forces can twist or bend or distort a solids shape, but (provided the forces have not exceeded the solids elastic limit)
it springs back to its original shape when the forces are
164
Amorphous Solids and Quasicrystals
removed. A liquid flows under the action of an external

force; it does not hold its shape. These macroscopic characteristics constitute the essential distinctions: a liquid
flows, lacks a definite shape (though its volume is definite),
and cannot withstand a shear stress; a solid does not flow,
has a definite shape, and exhibits elastic stiffness against
shear stress.
On an atomic level, these macroscopic distinctions
arise from a basic difference in the nature of the atomic
motion. Atoms in a solid are not mobile. Each atom stays
close to one point in space, although the atom is not stationary but instead oscillates rapidly about this fixed
point (the higher the temperature, the faster it oscillates).
The fixed point can be viewed as a time-averaged centre
of gravity of the rapidly jiggling atom. The spatial arrangement of these fixed points constitutes the solids durable
atomic-scale structure. In contrast, a liquid possesses no
enduring arrangement of atoms. Atoms in a liquid are
mobile and continually wander throughout the material.
Distinction Between Crystalline

and Amorphous Solids
There are two main classes of solids: crystalline and amorphous. What distinguishes them from one another is the
nature of their atomic-scale structure. Atomic positions
in a crystal exhibit a property called long-range order or
translational periodicity; positions repeat in space in a
regular array. In an amorphous solid, translational periodicity is absent. There is no long-range order. The atoms
are not randomly distributed in space, however, as they
are in the gas. In certain glasses, for example, each atom
has three nearest-neighbour atoms at the same distance
(called the chemical bond length) from it, just as in a corresponding crystal.
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the atomic arrangements in (A) a crystalline solid, (B) an amorphous solid,

and (C) a gas. Copyright Encyclopdia Britannica; rendering for this
edition by Rosen Educational Services
All solids, both crystalline and amorphous, exhibit

short-range (atomic-scale) order. Thus, the term amorphous, literally without form or structure, is actually
a misnomer in the context of the standard expression
amorphous solid. The well-defined short-range order is
a consequence of the chemical bonding between atoms,
which is responsible for holding the solid together.
In addition to the terms amorphous solid and glass, other
terms in use include noncrystalline solid and vitreous solid.
Amorphous solid and noncrystalline solid are more general
terms, while glass and vitreous solid have historically been
reserved for an amorphous solid prepared by rapid cooling
(quenching) of a melt.
There are two types of scenarios that can occur
when cooling causes a given number of atoms to condense from the gas phase into the liquid phase and then
into the solid phase. In the discussion that follows, the
temperature tb is the boiling point, tf is the freezing (or
melting) point, and tg is the glass transition temperature.
In scenario 1 the liquid freezes at tf into a crystalline
solid, with an abrupt discontinuity in volume. When
cooling occurs slowly, this is usually what happens. At
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sufficiently high cooling rates, however, most materials

display a different behaviour and follow scenario 2 to the
solid state. tf is bypassed, and the liquid state persists
until the lower temperature tg is reached and the second
solidification scenario is realized. In a narrow temperature range near tg , the glass transition occurs: the liquid
freezes into an amorphous solid with no abrupt discontinuity in volume.
the two general cooling paths by which a group of atoms can condense.
route 1 is the path to the crystalline state; route 2 is the rapid-quench path
to the amorphous solid state. Copyright Encyclopdia Britannica;
rendering for this edition by Rosen Educational Services
167
The glass transition temperature Tg is not as sharply

defined as Tf ;Tg shifts downward slightly when the cooling rate is reduced. The reason for this phenomenon is the
steep temperature dependence of the molecular response
time. When the temperature is lowered below Tg , the
response time for molecular rearrangement becomes
much larger than experimentally accessible times, so that
liquidlike mobility disappears and the atomic configuration becomes frozen into a set of fixed positions to which
the atoms are tied.
Some textbooks erroneously describe glasses as undercooled viscous liquids, but this is actually incorrect. In
scenario 2, it is the portion lying between Tf and Tg that is
correctly associated with the description of the material
as an undercooled liquid (undercooled meaning that its
temperature is below Tf ). But below Tg , in the glass phase,
it is a bona fide solid (exhibiting such properties as elastic
stiffness against shear).
Preparation of Amorphous Solids

It was once thought that relatively few materials could
be prepared as amorphous solids, and such materials
(notably, oxide glasses and organic polymers) were called
glass-forming solids. It is now known that the amorphous
solid state is almost a universal property of condensable
matter. The glass transition temperatures of every class of
chemical bonding type span a wide range.
Glass formation is a matter of bypassing crystallization. The channel to the crystalline state is evaded by
quickly crossing the temperature interval between Tf and
Tg. Nearly all materials can, if cooled quickly enough, be
prepared as amorphous solids. The definition of quickly
enough varies enormously from material to material. The
four techniques for preparing amorphous solidsslow
168
cooling, moderate quenching, rapid splat quenching, and

condensation from the gas phaseare not fundamentally
different from those used for preparing crystalline solids;
the key is simply to quench the sample quickly enough to
form the glass, rather than slowly enough to form the crystal. The quench rate increases greatly from left to right in
the figure.
Melt Quenching
Preparation of metallic glasses requires a quite rapid
quench. The technique called splat quenching can quench
a droplet of a molten metal roughly 1,000 C (1,800 F) in
one millisecond, producing a thin film of metal that is an
amorphous solid. In enormous contrast to this, the silicate
glass that forms the rigid ribbed disk of the Hale telescope
of the Palomar Observatory near San Diego, California,
was prepared by cooling (over a comparable temperature
drop) during a time interval of eight months. The great
difference in the quench rates needed for arriving at the
amorphous solid state (the quench rates here differ by a
factor of 3 1010) is a dramatic demonstration of the difference in the glass-forming tendency of silicate glasses (very
high) and metallic glasses (very low).
The required quench rate for glass formation can vary
significantly within a family of related materials that differ
from one another in chemical composition. Consider the
representative behaviour for a binary (two-component)
system, gold-silicon. Here x specifies the fraction of
atoms that are silicon atoms, and Au1 - xSix denotes a particular material in this family of materials. (Au is the
chemical symbol for gold, Si is the symbol for silicon,
and, for example, Au0.8Si0.2 denotes a material containing
20 percent silicon atoms and 80 percent gold atoms.) In
a diagram of the composition dependence of the freezing
point Tf , there is a deep cusp near the composition x = 0.2.
169
Near this special composition, as at a in the figure, a liquid

is much more readily quenched than is a liquid at a distant
composition such as b. To reach the glass phase, the liquid
must be cooled from above Tf to below the glass transition
temperature Tg without crystallizing. Throughout the
temperature interval from Tf down to Tg, the liquid is at
risk vis--vis crystallization. Since this dangerous interval
is much longer at b than at a, a faster quench rate is needed
for glass formation at b than at a.
Similar diagrams exist for many binary systems. For
example, in the oxide system CaO-Al2O3, in which the
two end-member compositions (x = 0 and x = 1) correspond to pure calcium oxide (CaO) and pure aluminum
oxide (Al2O3), there is a deep minimum in the Tf-versus-x
curve near the middle of the composition range. Although
neither calcium oxide nor aluminum oxide readily forms a
glass, glasses are easily formed from mixed compositions;
for reasons related to this, many oxide glasses have complex chemical compositions.
Vapour Condensation Techniques
In the gold-silicon system, at compositions far from the
cusp, glasses cannot be formed by melt quenchingeven
by the rapid splat-quench technique. Amorphous solids
can still be prepared by dispensing with the liquid phase
completely and constructing a thin solid film in atomby-atom fashion from the gas phase. In the simplest of
these vapour-condensation techniques, a vapour stream,
formed within a vacuum chamber by thermal evaporation of a sample of the material to be deposited, impinges
on the surface of a cold substrate. The atoms condense
on the cold surface and, under a range of conditions
(usually a high rate of deposition and a low substrate
temperature), an amorphous solid is formed as a thin
170
film. Pure silicon can be prepared as an amorphous solid

in this manner. Variations of the method include using
an electron beam to vapourize the source or using the
plasma-induced decomposition of a molecular species.
The latter technique is used to deposit amorphous silicon from gaseous silane (SiH4). Among the amorphous
solids those that normally require vapour-condensation
methods for their preparation are silicon (Si), germanium
(Ge), water (H2O), and the elemental metallic glasses iron
(Fe), cobalt (Co), and bismuth (Bi).
Other Preparation Techniques
Numerous other methods exist for preparing amorphous
solids, and new methods are continually invented. In melt
spinning, a jet of molten metal is propelled against the
moving surface of a cold, rotating copper cylinder. A solid
film of metallic glass is spun off as a continuous ribbon
at a speed that can exceed 1 km per minute. In laser glazing, a brief intense laser pulse melts a tiny spot, which is
swiftly quenched by the surrounding material into a glass.
In sol-gel synthesis, small molecules in a liquid solution
chemically link up with each other, forming a disordered
network. It is possible to take a crystalline solid and convert it into an amorphous solid by bombarding it with
high-kinetic-energy ions. Under certain conditions of
composition and temperature, interdiffusion (mixing on
an atomic scale) between crystalline layers can produce
an amorphous phase. Pyrolysis and electrolysis are other
methods that can be used.
Atomic-Scale Structure
The absence of long-range order is the defining characteristic of the atomic arrangement in amorphous solids.
171
However, because of the absence in glasses of long parallel rows and flat parallel planes of atoms, it is extremely
difficult to determine details of the atomic arrangement
with the structure-probing techniques (such as X-ray diffraction) that are so successful for crystals. For glasses
the information obtained from such structure-probing
experiments is contained in a curve called the radial distribution function (RDF).
The Radial Distribution Function
The significance of the RDF is that it gives the probability
of neighbouring atoms being located at various distances
from an average atom. Imagine an RDF graph, with the
horizontal axis specifying the distance from a given atom
and the vertical axis proportional to the average number
of atoms found at each distance. (The distance scale is
expressed in angstrom units; one angstrom equals 10 -8 cm.)
The curve for crystalline germanium (c-Ge) would display
sharp peaks over the full range shown, corresponding to
well-defined shells of neighbouring atoms at specific distances, which arise from the long-range regularity of the
crystals atomic arrangement. Amorphous germanium
(a-Ge) would exhibit a close-in sharp peak corresponding to the nearest-neighbour atoms (there are four nearest
neighbours in both c-Ge and a-Ge), but at larger distances
the undulations in the RDF curve would become washed
out owing to the absence of long-range order. The first,
sharp, nearest-neighbour peak in a-Ge would be identical to the corresponding peak in c-Ge, showing that the
short-range order in the amorphous form of solid germanium is as well-defined as it is in the crystalline form.
The detailed shape of the a-Ge RDF curve is the input
used in the difficult task of developing a model for the
atomic arrangement in amorphous germanium. The normal procedure is to construct a model of the structure
172
and then to calculate from the models atomic positions

a theoretical RDF curve. This calculated RDF is then
compared to the experimental curve (which provides the
definitive test of the validity of the model). Computerassisted refinements are then made in the model in order
to improve the agreement between the model-dependent
theoretical RDF and the experimentally observed RDF.
This program has been successfully carried out for many
amorphous solids, so there is now much that is known
about their atomic-scale structure. In contrast to the
complete information available for crystals, however, the
structural knowledge of glasses still contains gaps.
Models of Atomic Scale Structures
Amorphous solids, like crystalline solids, exhibit a wide
variety of atomic-scale structures. Most of these can be
recognized as falling within one or another of three broad
classes of structure associated with the following models:
(1) the continuous random-network model, applicable to
covalently bonded glasses, such as amorphous silicon and
the oxide glasses, (2) the random-coil model, applicable to
the many polymer-chain organic glasses, such as polystyrene, and (3) the random close-packing model, applicable
to metallic glasses, such as Au0.8Si0.2 gold-silicon. These are
the names in conventional use for the models. Although
each of them contains the word random, the well-defined
short-range order means that they are not random in the
sense that the structure of a gas is random.
The continuous random-network model clearly demonstrates how short-range order for an amorphous solid
like glass is compatible with the absence of long-range
order. At the bridging oxygen atoms, the bond angles have
some flexibility, so it is easy to continue the network.
Common oxide glasses are chemically more complex
than SiO2. Chemical species such as phosphorus and
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7 The Britannica Guide to Matter 7
two basic models for the atomic-scale structure of amorphous solids.

Copyright Encyclopdia Britannica; rendering for this edition by
Rosen Educational Services
germanium, which (like silicon) enter into the structure of

the network by forming strong chemical bonds with oxygen atoms, are called network formers. Chemical species
such as sodium and calcium, which do not bond directly
to the network but which simply sit (in ionic form) within
its interstitial holes, are called network modifiers.
A large fraction of the everyday materials called
plastics are amorphous solids composed of long-chain
molecules known as polymers. Each polymer chain has
a backbone consisting of a string of many (up to roughly
100,000) carbon atoms bonded to each other. These
organic polymeric glasses are present in innumerable
familiar molded products (e.g., pens, tires, toys, appliance
bodies, building materials, and automobile and airplane
parts). The random-coil model, first proposed in 1949 by
P.J. Flory (who later received a Nobel Prize in Chemistry
for his pioneering work on polymers), is the established
structural model for this important class of amorphous
solids. As schematically sketched in the figure, the structure consists of intermeshed, entangled polymer chains.
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The chain configurations are well-defined, statistically, by

a mathematical trajectory called a three-dimensional random walk.
The third important structural model, the random
close-packing model for metallic glasses, is difficult to
illustrate with a simple diagram. Roughly speaking, it is
similar to the structure that arises when a bunch of marbles are swiftly scrunched together in a paper bag.
Properties of Oxide Glasses

The wide range of the properties of glasses depends on
their composition, and special effects result from the
presence of various modifying agents in certain basic
glass-forming materials.
One of the most important glass formers is silica
(SiO2). Pure crystalline silica melts at 1,710 C (1,980 F). In
pure form, silica glass exhibits such properties as low thermal expansion, high softening temperatures, and excellent
chemical and electrical resistance. In pure form it is relatively transparent over a wide range of wavelengths to
visible and ultraviolet light and to ultrasonic waves.
The high viscosity and melting temperature of silica
glass are affected by the presence or absence of other
materials. For example, if certain materials called fluxes
are added, the most important being soda (Na2O), both
viscosity and melting temperature can be reduced. If too
much soda is added, the resulting glass is readily attacked
by water, but, if there are suitable amounts of stabilizing oxides, such as lime (CaO) and magnesia (MgO),
the glass becomes more durable. Most commercial glass
has a soda-lime-silica composition and is produced in
vast quantities for plate and sheet glass, containers, and
lightbulbs.
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In soda-lime-silica glasses, if lime is replaced by lead

oxide (PbO) and if potash (K2O) is used as a partial replacement for soda, lead-alkali-silicate glasses result that have
lower softening points than lime glasses. The refractive
indices, dispersive powers, and electrical resistance of
these glasses are generally much greater than those of
soda-lime-silica glasses.
Boric oxide (B2O3), itself a glass former, acts as a flux
(i.e., lowers the working temperature) when present in
silica and forms borosilicate glass, and the substitution
of small percentages of alkali and alumina increases
the chemical stability. It also exhibits low thermal
expansion, high dielectric strength, and high softening
temperature.
Aluminosilicate glasses find applications similar to
those of borosilicates, but the former can stand higher
operating temperatures; glasses with relatively high
alumina contents and no boric oxide are exceptionally
resistant to alkalies.
The above glasses all have silica as the glass former.
With other glass formers, glasses have special properties.
For example, if boric oxide is present, X rays are transmitted and rare-earth glasses will exhibit low dispersion and
a high refractive index. Phosphate glasses (used as optical
glasses) based on phosphorus pentoxide (P2O5) are highly
resistant to hydrofluoric acid and act as efficient heat
absorbers when iron oxide is added.
Properties and Applications

of Amorphous Solids
The following sections discuss technological applications
of amorphous solids in connection with the properties
that make those applications possible. It is important to
176
understand that, although differences do exist between

the properties of amorphous and crystalline solids, it is
nevertheless broadly true that amorphous solids exhibit
essentially the full range of properties and phenomena
exhibited by crystalline solids. There are amorphoussolid metals, semiconductors, and insulators; there are
transparent glasses and opaque glasses; and there are
superconducting amorphous solids and ferromagnetic
amorphous solids.
Some of the general differences between the properties
of crystals and glasses, in addition to the fundamental one
of the glass transition, are noted here. The atomic-scale
disorder present in a metallic glass causes its electrical
conductivity to be lower than the conductivity of the corresponding crystalline metal, because the structural disorder
impedes the motion of the mobile electrons that make up
the electrical current. (This lower electrical conductivity
for the amorphous metal can be an advantage in some situations.) For a similar reason, the thermal conductivity of
an insulating glass is lower than that of the corresponding crystalline insulator; glasses thus make good thermal
insulators. Crystals and glasses also differ systematically in
their optical spectra, which are the curves that describe the
wavelength dependence of the degree to which the solid
absorbs infrared, visible, or ultraviolet light. Although the
overall spectra are often similar, crystal spectra typically
exhibit sharp peaks and other features that specifically
arise as a consequence of the long-range order of the
crystals atomic-scale structure. These sharp features are
absent in the optical spectra of amorphous solids.
The continuous liquid-to-solid transition near Tg, the
glass transition, has a profound significance in connection
with classical applications of glasses. While crystallization abruptly transforms a mobile, low-viscosity liquid to a
177
crystalline solid at Tf, near Tg the liquid viscosity increases

continuously through a large range in the transformation to
an amorphous solid. Viscosity, expressed in units of poise,
is often used to specify characteristic working temperatures in the processing of the liquid precursors of various
oxide glasses. A poise is the centimetre-gram-second (cgs)
unit of viscosity. It expresses the force needed to maintain a unit velocity difference between parallel plates
separated by 1 cm of fluid: 1 poise equals 1 dyne-second
per square cm. Molten glass may have a viscosity of 1013
poise (similar to honey on a cold day), and it quickly gets
stiffer when cooled since the viscosity steeply increases
with decreasing temperature. The ability to tune the viscosity of the melt (by changing temperature) allows glass
to be conveniently processed and worked into desired
shapes; glassblowing is a classic example of the usefulness
of this widely exploited property.
Some amorphous solids have important technological uses. Window glass is a centuries-old technology, but
others blossomed during the second half of the 20th century. A significant theme in the uses of amorphous solids
is their role in applications calling for large-area sheets
or films. Amorphous solids often have great advantages
over crystalline solids in such applications, since their use
avoids the functional problems associated with polycrystallinity or the expense of preparing large single crystals.
Thus, while it would be prohibitively expensive to fabricate large windows out of crystalline SiO2 (quartz), it is
practical to do so using SiO2-based silicate glasses.
Transparent Glasses
The terms glass and window glass are often used interchangeably in everyday language, so familiar is this ancient
architectural application of amorphous solids. Not only
are oxide glasses, such as those used for window glass and
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fibre-optic waveguides, excellent for letting light in, they

are also good for keeping cold out, because (as mentioned
above) they are efficient thermal insulators.
Another technological application of amorphous solids represents a modern development that carries the
property of optical transparency to a phenomenal level.
The transparency of the extraordinarily pure glasses that
have been developed for fibre-optic telecommunications
is so great that, at certain wavelengths, light can pass
through 1 km (0.6 mile) of glass and still retain 95 percent
of its original intensity.
Glass fibres (transmitting optical signals) are now
doing what copper wires (transmitting electrical signals)
once did and are doing it more efficiently: carrying telephone messages around the planet. Digital electrical
pulses produced by encoding of the voice-driven electrical
signal are converted into light pulses by a semiconductor
laser coupled to one end of the optical fibre. The signal is
then transmitted over a long length of fibre as a stream of
light pulses. At the far end it is converted back into electrical pulses and then into sound.
The glass fibre is somewhat thinner than a human
hair. The simplest type has a central core of ultratransparent glass surrounded by a coaxial cladding of a glass
having a lower refractive index, n. This ensures that light
rays propagating within the core, at small angles relative to the fibre axis, do not leak out but instead are 100
percent reflected at the core-cladding interface by the
optical effect known as total internal reflection.
The great advantage provided by the substitution of
light-transmitting fibres of ultratransparent oxide glass
for electricity-transmitting wires of crystalline copper
is that a single optical fibre can carry many more simultaneous conversations than can a thick cable packed
with copper wires. This is the case because light waves
179
oscillate at enormously high frequencies (about 2 1014

cycles per second for the infrared light generally used
for fibre-optic telecommunications). This allows the
light-wave signal carrier to be modulated at very high
frequencies and to transmit a high volume of information traffic. Fibre-optic communications have greatly
expanded the information-transmitting capacity of the
worlds telecommunications networks.
Polymeric Structural Materials
Polystyrene is a prototypical example of a polymeric glass.
These glasses make up a broad class of lightweight structural materials important in the automotive, aerospace,
and construction industries. These materials are also ubiquitous in everyday experience as plastic molded objects.
The quantity of polymer materials produced each year,
measured in terms of volume, exceeds the quantity of steel
produced.
Polystyrene is among the most important of the thermoplastic materials that, when heated (to the vicinity of
the glass transition temperature), soften and flow controllably, enabling them to be processed at high speeds and on
a large scale in the manufacture of molded products. The
chemical formula of a polystyrene chain may be written as
(CH2CHC6H5)N. The building block (inside the parentheses) consists of two backbone carbon atoms to which three
hydrogen atoms and one phenyl (C6H5) ring are bonded as
side groups. The polymerization index N reaches values
above 105. Polystyrene is a purely hydrocarbon polymer
(i.e., it contains only hydrogen and carbon); most organic
polymers contain additional chemical components.
Amorphous Semiconductors in Electronics
Amorphous semiconductors, in the form of thin films,
are important in applications requiring large areas of
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electronically active material. The first electronic application of amorphous semiconductors to occur on a large scale
was in xerography (or electrostatic imaging), the process
that provides the basis of plain-paper copiers. Amorphous
selenium (Se) and, later, amorphous arsenic selenide
(As2Se3) were used to form the thin-film, large-area photoconducting element that lies at the heart of the xerographic
process. The photoconductor, which is an electrical insulator in the absence of light but which conducts electricity
when illuminated, is exposed to an image of the document
to be copied. Throughout the worldin offices, libraries,
schools, and so forththe xerographic process makes billions of copies every day. This process is also widely used in
laser printers, in which the photoconductor is exposed to
a digitally controlled on-and-off laser beam that is raster
scanned (like the electron beam in a television tube) over
the photoconductor surface.
Although still in use, selenium and arsenic selenide
have been joined by other amorphous materials in this
important technology. Polymeric organic glasses, in the
form of thin films, are now used in multilayer photoconductor configurations in which the light is absorbed in one
layer and electrical charge is transported through an adjacent layer. Both layers are formed of amorphous polymer
films, and these photoreceptors can be made in the form
of flexible belts.
Amorphous silicon thin films are used in solar cells that
power handheld calculators. This important amorphous
semiconductor is also used as the image sensor in facsimile (fax) machines, and it serves as the photoreceptor in
some xerographic copiers. All these applications exploit
the ability of amorphous silicon to be vapour-deposited
in the form of large-area thin films. The practical form
of this amorphous semiconductor is not pure silicon but
a silicon-hydrogen alloy containing 10 percent hydrogen.
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The key role played by hydrogen, in what is now called

hydrogenated amorphous silicon, emerged in a scientific
puzzle that took years to solve. Stated briefly, hydrogen
eliminates the electronic defects that are intrinsic to pure
amorphous silicon.
Hydrogenated amorphous silicon also is used in highresolution flat-panel displays for computer monitors and
for television screens. In such applications the large-area
amorphous-semiconductor thin film is etched into an
array of many tiny units, each of which forms the active
element of a transistor that electronically turns on or off
a small pixel (picture element) of a liquid-crystal display.
Magnetic Glasses
Some metallic glasses have magnetic properties. These are
typically iron-rich amorphous solids with compositions
such as Fe0.8B0.2 iron-boron and Fe0.8B0.1Si0.1 iron-boronsilicon. They are readily formed as long metallic glass
ribbons by melt spinning or as wide sheets by planar flow
casting. Ferromagnetic glasses are mechanically hard
materials, but they are magnetically soft, meaning that
they are easily magnetized by small magnetic fields. Also,
because of their disordered atomic-scale structure, they
have higher electrical resistance than conventional (crystalline) magnetic materials.
The three attributes of ease of manufacture, magnetic
softness, and high electrical resistance make magnetic
glasses extremely suitable for use in the magnetic cores of
electrical power transformers. High electrical resistance
(which arises here as a direct consequence of amorphicity)
is a crucial property in this application, because it minimizes unwanted electrical eddy currents and cuts down
on power losses. For these reasons, sheets of iron-based
magnetic glasses are used as transformer-core laminations
in electrical power applications.
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Thin films of magnetic glass are finding use in many

other applications. These include magnetic recording media
for audio and video digital recording, as well as recording
heads used with magnetic disks.
Quasicrystals
Although when first discovered such structures surprised
the scientific community, it now appears that quasicrystals
rank among the most common structures in alloys of aluminum with such metals as iron, cobalt, or nickel. While
no major commercial applications yet exploit properties
of the quasicrystalline state directly, quasicrystals form in
compounds noted for their high strength and light weight,
suggesting potential applications in aerospace and other
industries.

Dan Shechtman, a researcher from Technion, a part of the
Israel Institute of Technology, and his colleagues at the
National Bureau of Standards (now the National Institute
of Standards and Technology) in Gaithersburg, Maryland,
discovered quasicrystals in 1984. A research program of
the U.S. Air Force sponsored their investigation of the
metallurgical properties of aluminum-iron and aluminummanganese alloys. Shechtman and his coworkers mixed
aluminum and manganese in a roughly six-to-one proportion and heated the mixture until it melted. The mixture
was then rapidly cooled back into the solid state by dropping the liquid onto a cold spinning wheel, a process
known as melt spinning. When the solidified alloy was
examined using an electron microscope, a novel structure
was revealed. It exhibited fivefold symmetry, which is forbidden in crystals, and long-range order, which is lacking
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in amorphous solids. Its order, therefore, was neither

amorphous nor crystalline. Many other alloys with these
same features have subsequently been produced.
Microscopic Images of
Quasicrystalline Structures
The electron microscope has played a significant role in the
investigation of quasicrystals. It is a versatile tool that can
probe many important aspects of the structure of matter.
Low-resolution scanning electron microscopy magnifies
the shapes of individual grains. Symmetries of solid grains
often reflect the internal symmetries of the underlying
atomic positions. Grains of salt, for example, take cubical
shapes consistent with the cubic symmetries of their crystal lattices. Quasicrystalline aluminum-copper-iron has
been imaged using a scanning electron microscope, revealing the pentagonal dodecahedral shape of the grains. Its 12
faces are regular pentagons, with axes of fivefold rotational
symmetry passing through them. That is to say, rotations
about this axis by 72 leave the appearance of the grain
unchanged. In a full 360 rotation the grain will repeat
itself in appearance five times, once every 72. There are
also axes of twofold rotational symmetry passing through
the edges and axes of threefold rotational symmetry passing through the vertices. This is also known as icosahedral
symmetry because the icosahedron is the geometric dual of
the pentagonal dodecahedron. At the centre of each face
on an icosahedron, the dodecahedron places a vertex, and
vice versa. The symmetry of a pentagonal dodecahedron
or icosahedron is not among the symmetries of any crystal
structure, yet this is the symmetry that was revealed in the
electron microscope image of the aluminum-manganese
alloy produced by Shechtman and his colleagues.
High-resolution electron microscopy magnifies to
such a great degree that patterns of atomic positions
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may be determined. In ordinary crystals such a lattice

image reveals regularly spaced rows of atoms. Regular
spacing implies spatial periodicity in the placement of
atoms. The angles between rows indicate rotational symmetries of the atomic positions. In a high-resolution
electron microscope image of quasicrystalline aluminummanganese-silicon, parallel rows occur in five sets,
rotated from one another by 72, confirming that the fivefold symmetry suggested by the shape of the pentagonal
dodecahedron grain reflects a fivefold symmetry in the
actual placement of atoms.
Translational Periodicity and Symmetry
Fivefold symmetry axes are forbidden in ordinary crystals,
while other axes, such as sixfold axes, are allowed. The reason is that translational periodicity, which is characteristic
hexagonal lattice of atomic sites. Copyright Encyclopdia Britannica;

185
of crystal lattices, cannot be present in structures with

fivefold symmetry. A triangular array of atoms has axes of
sixfold rotational symmetry passing through each atomic
position. Arrows drawn from a specific atom can represent
the translational symmetries of this crystalline structure.
That is, if the entire array of atoms is displaced along one
of these arrows, all new atomic positions coincide with
the locations of other atoms prior to the displacement.
Such a displacement of atoms that leaves atomic positions invariant is called a symmetry of the crystal. If two
different symmetries are combined such that the structure is first displaced along arrow a and then along arrow b,
the net result is equivalent to a displacement along arrow
c, which itself must be a symmetry of the structure. Again,
atomic sites coincide before and after the displacement.
Repeated displacements along the same arrow demonstrate the translational periodicity of the crystal.
A pentagonal atomic arrangement exhibits fivefold
rotational symmetry but lacks the translational symmetries that must be present in a crystalline structure. Now,
Pentagonal arrangement of atoms. Copyright Encyclopdia Britannica;

186
as before, consider the combinations of two symmetries

a and b with the net result c. The length of c is smaller
than either a or b by a factor = (5 + 1)/2, which is known
as the golden mean. The new atomic position does not
coincide with a previous atomic position, indicating that
the structure does not exhibit translational periodicity.
Therefore, an array of atoms may not simultaneously
display fivefold rotational symmetry and translational
periodicity, for, if it did, there would be no lower limit to
the spacing between atoms.
In fact, the compatibility of translational periodicity
with sixfold rotational symmetry is a remarkable accident, for translational periodicity is not possible with
most rotational symmetries. The only allowed symmetry axes in periodic crystals are twofold, threefold,
fourfold, and sixfold. All others are forbidden owing to
the lack of minimum interatomic separation. In particular, fivefold, eightfold, tenfold, and twelvefold axes
cannot exist in crystals. These symmetries are mentioned in particular because they have been reported in
quasicrystalline alloys.
Since a high-resolution electron microscope image of
aluminum-manganese-silicon quasicrystal clearly reveals
an axis of fivefold symmetry, it may be concluded that
the arrangement of atoms lacks translational periodicity.
That, in itself, is no great surprise, for many materials lack
translational periodicity. Amorphous metals, for example,
are frequently produced by the same melt-spinning process that was employed in the discovery of quasicrystals.
Amorphous metals have no discrete rotational symmetries,
however, and high-resolution electron microscope images
reveal no rows of atoms. The arrangement of atoms in a
quasicrystal displays a property called long-range order,
which is lacking in amorphous metals. Long-range order
permits rows of atoms to span the image and maintains
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agreement of row orientations. Ordinary crystal structures display long-range order. Strict rules govern the
relative placement of atoms at remote locations in solids
with long-range order.
Electron diffraction confirms the presence of longrange order in both crystals and quasicrystals. Quantum
mechanics predicts that particles such as electrons move
through space as if they were waves, in the same manner
that light travels. When light waves strike a diffraction
grating, they are diffracted. White light breaks up into a
rainbow, while monochromatic light breaks up into discrete sharp spots. Similarly, when electrons strike evenly
spaced rows of atoms within a crystalline solid, they break
up into a set of bright spots known as Bragg diffraction
peaks. Symmetrical arrangements of spots reveal axes of
rotational symmetry in the crystal, and spacings between
the discrete spots relate inversely to translational periodicities. Amorphous metals contain only diffuse rings in their
diffraction patterns since long-range coherence in atomic
positions is required to achieve sharp diffraction spots.
The electron diffraction pattern of quasicrystalline
aluminum-manganese published by Shechtman and his
coworkers has the following features: rings of 10 bright
spots indicate axes of fivefold symmetry, and rings of
six bright spots indicate axes of threefold symmetry.
The twofold symmetry axes are self-evident. The angles
between these axes, indicated on the figure, agree with
the geometry of the icosahedron. The very existence of
spots at all indicates long-range order in atomic positions. Recalling the earlier result that fivefold symmetry
axes are forbidden in crystalline materials, a paradox is
presented by quasicrystals. They have long-range order
in their atomic positions, but they must lack spatial
periodicity.
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three views of the icosahedral symmetry of quasicrystalline aluminummanganese. top view is along the fivefold symmetry axis. the centre view,
rotating by 37.38, reveals the threefold axis, and (bottom left) rotating by
58.29 reveals the twofold axis. Copyright Encyclopdia Britannica;
189
Quasiperiodicity
Dov Levine and Paul Steinhardt, physicists at the
University of Pennsylvania, proposed a resolution of this
apparent conflict. They suggested that the translational
order of atoms in quasicrystalline alloys might be quasiperiodic rather than periodic. Quasiperiodic patterns
share certain characteristics with periodic patterns. In
particular, both are deterministicthat is, rules exist
that specify the entire pattern. These rules create longrange order. Both periodic and quasiperiodic patterns
have diffraction patterns consisting entirely of Bragg
peaks. The difference between quasiperiodicity and
periodicity is that a quasiperiodic pattern never repeats
itself. There are no translational symmetries, and, consequently, there is no minimum spacing between Bragg
peaks. Although the peaks are discrete, they fill the diffraction pattern densely.
The most well-known quasiperiodic pattern may be
the Fibonacci sequence, discovered during the Middle
Ages in the course of studies conducted on rabbit reproduction. Consider the following rules for birth and
maturation of rabbits. Start with a single mature rabbit
(denoted by the symbol L for large) and a baby
rabbit (denoted by S for small). In each generation every
L rabbit gives birth to a new S rabbit, while each preexisting S rabbit matures into an L rabbit. A table of rabbit
sequences may be established as follows. Start with an
L and an S side by side along a line. Replace the L with LS
and the S with L to obtain LSL and repeat the procedure.
The numbers of rabbits present after each generation are
the Fibonacci numbers. The population grows exponentially over time, with the population of each generation
approaching (the golden mean) multiplied by the
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population of the previous generation. The sequence of

L and S symbols forms a quasiperiodic pattern. It has
no subunit that repeats itself periodically. In contrast,
a periodic sequence such as LSLLSLLSLLSLLSL . . .
has a fundamental unit (LSL) that is precisely repeated
at equal intervals. In crystallography such a repeated
unit is called a unit cell. Quasiperiodic sequences have
no unit cell of finite size. Any portion of the Fibonacci
sequence is repeated infinitely often, but at intervals
that are not periodic. These intervals themselves form a
Fibonacci sequence.
An example of a two-dimensional pattern that combines fivefold rotational symmetry with quasiperiodic
translational order is the Penrose pattern, discovered by
the English mathematical physicist Roger Penrose. The
diffraction pattern of such a sequence closely resembles
those of quasicrystalline aluminum-manganese. The
rhombic tiles are arranged in sets of parallel rows; the
shaded tiles represent one such set, or family. Five families
of parallel rows are present in the figure, with 72 angles
A Penrose tiling. Copyright Encyclopdia Britannica; rendering for

this edition by Rosen Educational Services
191
between the families, although only one of the five has

been shaded. Within a family the spacings between rows
are either large (L) or small (S), as labeled in the margin.
The ratio of widths of the large rows to the small rows is
equal to the golden mean , and the quasiperiodic sequence
of large and small follows the Fibonacci sequence.
Levines and Steinhardts proposal that quasicrystals possess quasiperiodic translational order can be
examined in terms of a high-resolution electron micrograph. The rows of bright spots are separated by small
and large intervals. As in the Penrose pattern, the length
of the large interval divided by the length of the small
one equals the golden mean, and the sequence of large
and small reproduces the Fibonacci sequence. Levines
and Steinhardts proposal appears consistent with the
electron diffraction results. The origin of the name quasicrystals arises from the fact that these materials have
quasiperiodic translational order, as opposed to the periodic order of ordinary crystals.
Symmetries Observed in Quasicrystals
Consider quasicrystals with the symmetry of an icosahedron. Icosahedral quasicrystals occur in many intermetallic
compounds, including aluminum-copper-iron, aluminummanganese-palladium, aluminum-magnesium-zinc, and
aluminum-copper-lithium. Other crystallographically
forbidden symmetries have been observed as well. These
include decagonal symmetry, which exhibits tenfold
rotational symmetry within two-dimensional atomic layers but ordinary translational periodicity perpendicular
to these layers. Decagonal symmetry has been found in
the compounds aluminum-copper-cobalt and aluminumnickel-cobalt. Structures that are periodic in two
dimensions but follow a Fibonacci sequence in the remaining third dimension occur in aluminum-copper-nickel.
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All the compounds named thus far contain aluminum.

Indeed, it appears that aluminum is unusually prone to
quasicrystal formation, but there do exist icosahedral quasicrystals without it. Some, like gallium-magnesium-zinc,
simply substitute the chemically similar element gallium
for aluminum. Others, like titanium-manganese, appear
chemically unrelated to aluminum-based compounds.
Furthermore, some quasicrystals such as chromium-nickelsilicon and vanadium-nickel-silicon display octagonal
and dodecagonal structures with eightfold or twelvefold
symmetry, respectively, within layers and translational
periodicity perpendicular to the layers.
The Origin of Quasicrystalline Order
The origin of quasicrystalline order remains in question.
No proven explanation clarifies why a material favours
crystallographically forbidden rotational symmetry and
translational quasiperiodicity when at nearby compositions it forms more conventional crystal structures.
The American chemist Linus Pauling noted that these
related crystalline structures frequently contain icosahedral motifs within their unit cells, which are then
repeated periodically. Pauling proposed that quasicrystals are really ordinary crystalline materials caught out
of equilibrium by a type of crystal defect called twinning, in which unit cells are attached at angles defined
by these icosahedral motifs. While this may be a reasonable model for rapidly cooled alloys such as Shechtmans
original aluminum-manganese, other compounds, such
as aluminum-copper-iron, possess quasicrystalline structures in thermodynamic equilibrium. These quasicrystals
can be grown slowly and carefully using techniques for
growth of high-quality conventional crystals. The more
slowly the quasicrystal grows, the more perfect will be
its rotational symmetry and quasiperiodicity. Measuring
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the sharpness of diffraction pattern spots shows perfect

ordering on length scales of at least 30,000 angstroms in
these carefully prepared quasicrystals. Twinning cannot
account for such long-range order.
Levine and Steinhardt proposed that matching rules,
such as those Penrose discovered to determine proper
placement of his tiles to fill the plane quasiperiodically,
may force the atoms into predefined, low-energy locations.
Such a mechanism cannot be the complete explanation,
though, since the compound forms ordinary crystalline
structures at nearby compositions and temperatures.
Indeed, it appears that, when quasicrystals are thermodynamically stable phases, it is only over a limited range
of temperatures close to the melting point. At lower temperatures they transform into ordinary crystal structures.
Thermodynamics predicts that the stable structure is the
one that minimizes the free energy, defined as the ordinary energy minus the product of the temperature and the
entropy. It is likely that entropy (a measure of fluctuations
around an ideal structure) must be considered in addition
to energy to explain stability of quasicrystals.
Properties
Along with their novel structures and symmetries, quasicrystals are expected to exhibit unusual properties. Both
their elastic and their electronic behaviour distinguish
quasicrystals from ordinary crystalline metals. Elastic
response may be studied by measuring the speed of sound
waves propagating through the metal. Sound speeds
usually vary depending on the direction of propagation
relative to axes of high rotational symmetry. Because the
icosahedron has such high symmetryit is closer to a
sphere than is, for instance, a cubethe sound speeds turn
out to be independent of the direction of propagation.
194
Longitudinal sound waves (with displacements parallel to

the direction of propagation) have speeds different from
transverse waves (with displacements perpendicular to
the direction of propagation), as is the case for all matter. Because the sound speeds do not depend on direction
of propagation, only two elastic constants are required to
specify acoustic properties of icosahedral quasicrystals.
In contrast, cubic crystals require three elastic constants,
and lower-symmetry crystals require up to 21 constants.
Elastic Properties
As a consequence of the translational quasiperiodicity,
there exists a second type of elastic deformation beyond
the ordinary sound wave, or phonon. Known as phasons,
these elastic deformations correspond to rearrangements
of the relative atomic positions. Removal of a phason
requires adjusting positions of all atoms within a row of
atoms in a quasicrystalline structure. At low temperatures
motion of atoms within the solid is difficult, and phason
strain may be easily frozen into the quasicrystal, limiting
its perfection. At high temperatures, close to the melting point, phasons continually fluctuate, and atoms jump
from place to place.
Electric Properties
The electric properties of quasicrystals have proved to
be rather unusual. Unlike their constituent elements,
which tend to be good electrical conductors, quasicrystals
conduct electricity poorly. For alloys of aluminum-copperruthenium these conductivities differ by as much as a
factor of 100. As the perfection of the quasicrystalline
order grows, the conductivity drops. Such behaviour is
consistent with the appearance of a gap in the electronic
density of states at the Fermi surface, which is the energy
level separating filled electronic states from empty ones.
195
Since it is only Fermi-surface electrons that carry current, a vanishingly small density of such electronic states
leads to low electrical conductivities in semiconductors
and insulators. Such a gap in the density of states may also
play a role in explaining the formation of quasicrystalline
structures. This is known as the Hume-Rothery rule for
alloy formation. Since the Fermi-surface electrons are the
highest-energy electrons, diminishing the number of such
electrons may lower the overall energy.
Mechanical Properties
The mechanical properties of quasicrystals are especially
significant because the desire to develop a material that
exhibited these properties motivated the investigators
who discovered quasicrystals. Mechanical properties
also relate to their first potential practical applications.
Quasicrystals are exceptionally brittle. They have few
dislocations, and those present have low mobility. Since
metals bend by creating and moving dislocations, the
near absence of dislocation motion causes brittleness.
On the positive side, the difficulty of moving dislocations
makes quasicrystals extremely hard. They strongly resist
deformation. This makes them excellent candidates for
high-strength surface coatings. Indeed, the first successful application of quasicrystals was as a surface treatment
for aluminum frying pans.
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Chapter 8
Plasma
plasma is an electrically conducting medium in which

there are roughly equal numbers of positively and
negatively charged particles, produced when the atoms in
a gas become ionized. It is sometimes referred to as the
fourth state of matter, distinct from the solid, liquid, and
gaseous states.
The negative charge is usually carried by electrons,
each of which has one unit of negative charge. The positive charge is typically carried by atoms or molecules that
are missing those same electrons. In some rare but interesting cases, electrons missing from one type of atom
or molecule become attached to another component,
resulting in a plasma containing both positive and negative ions. The most extreme case of this type occurs when
small but macroscopic dust particles become charged in a
state referred to as a dusty plasma. The uniqueness of the
plasma state is due to the importance of electric and magnetic forces that act on a plasma in addition to such forces
as gravity that affect all forms of matter. Since these electromagnetic forces can act at large distances, a plasma will
act collectively much like a fluid even when the particles
seldom collide with one another.
Nearly all the visible matter in the universe exists in
the plasma state, occurring predominantly in this form
in the Sun and stars and in interplanetary and interstellar
space. Auroras, lightning, and welding arcs are also plasmas; plasmas exist in neon and fluorescent tubes, in the
crystal structure of metallic solids, and in many other phenomena and objects. Earth itself is immersed in a tenuous
197
plasma called the solar wind and is surrounded by a

dense plasma called the ionosphere.
A plasma may be produced in the laboratory by heating a gas to an extremely high temperature, which causes
such vigorous collisions between its atoms and molecules
that electrons are ripped free, yielding the requisite electrons and ions. A similar process occurs inside stars. In
space the dominant plasma formation process is photoionization, wherein photons from sunlight or starlight
are absorbed by an existing gas, causing electrons to be
emitted. Since the Sun and stars shine continuously, virtually all the matter becomes ionized in such cases, and
the plasma is said to be fully ionized. This need not be the
case, however, for a plasma may be only partially ionized.
A completely ionized hydrogen plasma, consisting solely
of electrons and protons (hydrogen nuclei), is the most
elementary plasma.
The Development of
Plasma Physics
The modern concept of the plasma state is of recent
origin, dating back only to the early 1950s. Its history is
interwoven with many disciplines. Three basic fields of
study made unique early contributions to the development of plasma physics as a discipline: electric discharges,
magnetohydrodynamics (in which a conducting fluid such
as mercury is studied), and kinetic theory.
Interest in electric-discharge phenomena may be
traced back to the beginning of the 18th century, with
three English physicistsMichael Faraday in the 1830s
and Joseph John Thomson and John Sealy Edward
Townsend at the turn of the 19th centurylaying the
foundations of the present understanding of the phenomena. Irving Langmuir introduced the term plasma in
198
Plasma
1923 while investigating electric discharges. In 1929 he

and Lewi Tonks, another physicist working in the United
States, used the term to designate those regions of a
discharge in which certain periodic variations of the negatively charged electrons could occur. They called these
oscillations plasma oscillations, their behaviour suggesting that of a jellylike substance. Not until 1952, however,
when two other American physicists, David Bohm and
David Pines, first considered the collective behaviour of
electrons in metals as distinct from that in ionized gases,
was the general applicability of the concept of a plasma
fully appreciated.
The collective behaviour of charged particles in magnetic fields and the concept of a conducting fluid are
implicit in magnetohydrodynamic studies, the foundations of which were laid in the early and middle 1800s by
Faraday and Andr-Marie Ampre of France. Not until
the 1930s, however, when new solar and geophysical phenomena were being discovered, were many of the basic
problems of the mutual interaction between ionized gases
and magnetic fields considered. In 1942 Hannes Alfvn,
a Swedish physicist, introduced the concept of magnetohydrodynamic waves. This contribution, along with his
further studies of space plasmas, led to Alfvns receipt of
the Nobel Prize for Physics in 1970.
These two separate approachesthe study of electric
discharges and the study of the behaviour of conducting
fluids in magnetic fieldswere unified by the introduction of the kinetic theory of the plasma state. This theory
states that plasma, like gas, consists of particles in random
motion, whose interactions can be through long-range
electromagnetic forces as well as via collisions. In 1905
the Dutch physicist Hendrik Antoon Lorentz applied the
kinetic equation for atoms (the formulation by the Austrian
physicist Ludwig Eduard Boltzmann) to the behaviour of
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David Bohm. Keystone/Hulton Archive/Getty Images

200
Plasma
electrons in metals. Various physicists and mathematicians

in the 1930s and 40s further developed the plasma kinetic
theory to a high degree of sophistication. Since the early
1950s interest has increasingly focused on the plasma state
itself. Space exploration, the development of electronic
devices, a growing awareness of the importance of magnetic fields in astrophysical phenomena, and the quest for
controlled thermonuclear (nuclear fusion) power reactors
all have stimulated such interest. Many problems remain
unsolved in space plasma physics research, owing to the
complexity of the phenomena. For example, descriptions
of the solar wind must include not only equations dealing with the effects of gravity, temperature, and pressure
as needed in atmospheric science but also the equations
of the Scottish physicist James Clerk Maxwell, which are
needed to describe the electromagnetic field.
Plasma Oscillations
and Parameters
Just as a lightweight cork in water will bob up and down
about its rest position, any general displacement of light
electrons as a group with respect to the positive ions
in a plasma leads to the oscillation of the electrons as
a whole about an equilibrium state. In the case of the
cork, the restoring force is provided by gravity; in plasma
oscillations, it is provided by the electric force. These
movements are the plasma oscillations that were studied
by Langmuir and Tonks. Analogously, just as buoyancy
effects guide water waves, plasma oscillations are related
to waves in the electron component of the plasma called
Langmuir waves. Wavelike phenomena play a critical role
in the behaviour of plasmas.
The time required for an oscillation of this type is
the most important temporal parameter in a plasma. The
201
main spatial parameter is the Debye length, h, which is the

distance traveled by the average thermal electron in time
/2. A plasma can be defined in terms of these parameters
as a partially or fully ionized gas that satisfies the following criteria: (1) a constituent electron may complete many
plasma oscillations before it collides with either an ion or
one of the other heavy constituents, (2) inside each sphere
with a radius equal to the Debye length, there are many
particles, and (3) the plasma itself is much larger than the
Debye length in every dimension.
Another important temporal parameter is the time
between collisions of particles. In any gas, separate collision frequencies are defined for collisions between all
different particle types. The total collision frequency
for a particular species is the weighted sum of all the
separate frequencies. Two basic types of collision may
occur: elastic and inelastic. In an elastic collision, the
total kinetic energy of all the particles participating in
the collision is the same before and after the event. In
an inelastic collision, a fraction of the kinetic energy is
transferred to the internal energy of the colliding particles. In an atom, for example, the electrons have certain
allowed (discrete) energies and are said to be bound.
During a collision, a bound electron may be excited
that is, raised from a low to a high energy state. This
can occur, however, only by the expenditure of kinetic
energy and only if the kinetic energy exceeds the difference between the two energy states. If the energy is
sufficient, a bound electron may be excited to such a
high level that it becomes a free electron, and the atom
is said to be ionized; the minimum, or threshold, energy
required to free an electron is called the ionization
energy. Inelastic collisions may also occur with positive
ions unless all the electrons have been stripped away. In
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Plasma
general, only collisions of electrons and photons (quanta

of electromagnetic radiation) with atoms and ions are
significant in these inelastic collisions; ionization by a
photon is called photoionization.
A molecule has additional discrete energy states,
which may be excited by particle or photon collisions. At
sufficiently high energies of interaction, the molecule can
dissociate into atoms or into atoms and atomic ions. As in
the case of atoms, collision of electrons and photons with
molecules may cause ionization, producing molecular
ions. In general, the reaction rate for inelastic collisions
is similar to that of chemical reactions. At sufficiently
high temperatures, the atoms are stripped of all electrons
and become bare atomic nuclei. Finally, at temperatures
of about 1,000,000 K or greater, nuclear reactions can
occuranother form of inelastic collisions. When such
reactions lead to the formation of heavier elements, the
process is called thermonuclear fusion; mass is transmuted, and kinetic energy is gained instead of lost.
All sources of energy now existing on the Earth can be
traced in one way or another to the nuclear fusion reactions inside the Sun or some long-extinct star. In such
energy sources, gravity controls and confines the fusion
process. The high temperatures required for the nuclear
fusion reactions that take place in a hydrogen, or thermonuclear, bomb are attained by first igniting an atomic
bomb, which produces a fission chain reaction. One of
the great challenges of humankind is to create these high
temperatures in a controlled manner and to harness the
energy of nuclear fusion. This is the great practical goal of
plasma physicsto produce nuclear fusion on the Earth.
Confinement schemes devised by scientists use magnetic
fields or the inertia of an implosion to guide and control
the hot plasma.
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Basic Plasma Physics

Apart from solid-state plasmas, such as those in metallic crystals, plasmas do not usually occur naturally at the
surface of the Earth. For laboratory experiments and
technological applications, plasmas therefore must be
produced artificially. Because the atoms of such alkalies
as potassium, sodium, and cesium possess low ionization
energies, plasmas may be produced from these by the
direct application of heat at temperatures of about 3,000
K. In most gases, however, before any significant degree
of ionization is achieved, temperatures in the neighbourhood of 10,000 K are required. A convenient unit for
measuring temperature in the study of plasmas is the electron volt (eV), which is the energy gained by an electron
in vacuum when it is accelerated across one volt of electric
potential. The temperature, W, measured in electron volts
is given by W = T/12,000 when T is expressed in kelvins.
The temperatures required for self-ionization thus range
from 2.5 to 8 electron volts, since such values are typical of
the energy needed to remove one electron from an atom
or molecule.
Plasma Formation
Because all substances melt at temperatures far below
that level, no container yet built can withstand an external application of the heat necessary to form a plasma;
therefore, any heating must be supplied internally. One
technique is to apply an electric field to the gas to accelerate and scatter any free electrons, thereby heating
the plasma. This type of ohmic heating is similar to the
method in which free electrons in the heating element
of an electric oven heat the coil. Because of their small
energy loss in elastic collisions, electrons can be raised
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Plasma
to much higher temperatures than other particles. For

plasma formation a sufficiently high electric field must
be applied, its exact value depending on geometry and
the gas pressure. The electric field may be set up via electrodes or by transformer action, in which the electric
field is induced by a changing magnetic field. Laboratory
temperatures of about 10 million K, or 8 kiloelectron
volts (keV), with electron densities of about 1019 per
cubic metre have been achieved by the transformer
method. The temperature is eventually limited by energy
losses to the outside environment. Extremely high temperatures, but relatively low-density plasmas, have been
produced by the separate injection of ions and electrons
into a mirror system (a plasma device using a particular
arrangement of magnetic fields for containment). Other
methods have used the high temperatures that develop
behind a wave that is moving much faster than sound
to produce what is called a shock front; lasers have also
been employed.
Natural plasma heating and ionization occur in analogous ways. In a lightning-induced plasma, the electric
current carried by the stroke heats the atmosphere in the
same manner as in the ohmic heating technique described
above. In solar and stellar plasmas the heating is internal
and caused by nuclear fusion reactions. In the solar corona,
the heating occurs because of waves that propagate from
the surface into the Suns atmosphere, heating the plasma
much like shock-wave heating in laboratory plasmas. In
the ionosphere, ionization is accomplished not through
heating of the plasma but rather by the flux of energetic
photons from the Sun. Far-ultraviolet rays and X rays from
the Sun have enough energy to ionize atoms in Earths
atmosphere. Some of the energy also goes into heating the
gas, with the result that the upper atmosphere, called the
thermosphere, is quite hot.
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Lightning flashes over a high-rise building in Kuala Lumpur. Plasma is

produced when the electric current in a lightning bolt heats the atmosphere.
Saeed Khan/AFP/Getty Images
These processes protect Earth from energetic photons much as the ozone layer protects terrestrial life-forms
from lower-energy ultraviolet light. The typical temperature 300 km (200 miles) above Earths surface is 1,200 K
(900 C, or 1,700 F), or about 0.1 eV. Although it is quite
warm compared with the surface of the Earth, this temperature is too low to create self-ionization. When the
Sun sets with respect to the ionosphere, the source of ionization ceases, and the lower portion of the ionosphere
reverts to its nonplasma state. Some ions, in particular
singly charged oxygen (O+), live long enough that some
plasma remains until the next sunrise. In the case of an
aurora, a plasma is created in the nighttime or daytime
atmosphere when beams of electrons are accelerated to
hundreds or thousands of electron volts and smash into
the atmosphere.
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Plasma
Methods of Describing Plasma Phenomena

The behaviour of a plasma may be described at different
levels. If collisions are relatively infrequent, it is useful to
consider the motions of individual particles. In most plasmas of interest, a magnetic field exerts a force on a charged
particle only if the particle is moving, the force being at
right angles to both the direction of the field and the direction of particle motion. In a uniform magnetic field (B), a
charged particle gyrates about a line of force. The centre
of the orbit is called the guiding centre. The particle may
also have a component of velocity parallel to the magnetic
field and so traces out a helix in a uniform magnetic field.
If a uniform electric field (e) is applied at right angles to
the direction of the magnetic field, the guiding centre
drifts with a uniform velocity of magnitude equal to the
ratio of the electric to the magnetic field (e/B), at right
angles to both the electric and magnetic fields. A particle
starting from rest in such fields follows the same cycloidal
path a dot on the rim of a rolling wheel follows. Although
the wheel radius and its sense of rotation vary for different particles, the guiding centre moves at the same e/B
velocity, independent of the particles charge and mass.
Should the electric field change with time, the problem
would become even more complex. If, however, such an
alternating electric field varies at the same frequency as
the cyclotron frequency (i.e., the rate of gyration), the
guiding centre will remain stationary, and the particle will
be forced to travel in an ever-expanding orbit. This phenomenon is called cyclotron resonance and is the basis of
the cyclotron particle accelerator.
The motion of a particle about its guiding centre constitutes a circular current. As such, the motion produces a
dipole magnetic field not unlike that produced by a simple
bar magnet. Thus, a moving charge not only interacts with
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magnetic fields but also produces them. The direction of

the magnetic field produced by a moving particle, however, depends both on whether the particle is positively
or negatively charged and on the direction of its motion.
If the motion of the charged particles is completely random, the net associated magnetic field is zero. On the
other hand, if charges of different sign have an average
relative velocity (i.e., if an electric current flows), then a
net magnetic field over and above any externally applied
field exists. The magnetic interaction between charged
particles is therefore of a collective, rather than of an individual, particle nature.
At a higher level of description than that of the single
particle, kinetic equations of the Boltzmann type are
used. Such equations essentially describe the behaviour of
those particles about a point in a small-volume element,
the particle velocities lying within a small range about
a given value. The interactions with all other velocity
groups, volume elements, and any externally applied electric and magnetic fields are taken into account. In many
cases, equations of a fluid type may be derived from the
kinetic equations; they express the conservation of mass,
momentum, and energy per unit volume, with one such
set of equations for each particle type.
Determination of Plasma Variables

The basic variables useful in the study of plasma are number densities, temperatures, electric and magnetic field
strengths, and particle velocities. In the laboratory and
in space, both electrostatic (charged) and magnetic types
of sensory devices called probes help determine the magnitudes of such variables. With the electrostatic probe,
ion densities, electron and ion temperatures, and electrostatic potential differences can be determined. Small
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Plasma
search coils and other types of magnetic probes yield

values for the magnetic field; and from Maxwells electromagnetic equations the current and charge densities
and the induced component of the electric field may be
found. Interplanetary spacecraft have carried such probes
to nearly every planet in the solar system, revealing to scientists such plasma phenomena as lightning on Jupiter
and the sounds of Saturns rings and radiation belts. In the
early 1990s, signals were being relayed to the Earth from
several spacecraft approaching the edge of the plasma
boundary to the solar system, the heliopause.
In the laboratory the absorption, scattering, and excitation of neutral and high-energy ion beams are helpful in
determining electron temperatures and densities; in general, the refraction, reflection, absorption, scattering, and
interference of electromagnetic waves also provide ways
to determine these same variables. This technique has also
been employed to remotely measure the properties of the
plasmas in the near-space regions of Earth using the incoherent scatter radar method. The largest single antenna
is at the National Astronomy and Ionosphere Center at
Arecibo in Puerto Rico. It has a circumference of 305
metres and was completed in 1963. It is still used to probe
space plasmas to distances of 3,000 km (2,000 miles). The
method works by bouncing radio waves from small irregularities in the electron gas that occur owing to random
thermal motions of the particles. The returning signal is
shifted slightly from the transmitted onebecause of the
Doppler-shift effectand the velocity of the plasma can
be determined in a manner similar to the way in which the
police detect a speeding car. Using this method, the wind
speed in space can be found, along with the temperature,
density, electric field, and even the types of ions present. In geospace the appropriate radar frequencies are in
the range of 50 to 1,000 megahertz (MHz), while in the
209
laboratory, where the plasma densities and plasma frequencies are higher, microwaves and lasers must be used.
Aside from the above methods, much can be learned
from the radiation generated and emitted by the plasma
itself; in fact, this is the only means of studying cosmic
plasma beyond the solar system. The various spectroscopic
techniques covering the entire continuous radiation
spectrum determine temperatures and identify such nonthermal sources as those pulses producing synchrotron
radiations.
Waves in Plasmas
The waves most familiar to people are the buoyancy waves
that propagate on the surfaces of lakes and oceans and
break onto the worlds beaches. Equally familiar, although
not necessarily recognized as waves, are the disturbances
in the atmosphere that create what is referred to as the
weather. Wave phenomena are particularly important
in the behaviour of plasmas. In fact, one of the three
criteria for the existence of a plasma is that the particleparticle collision rate be less than the plasma-oscillation
frequency. This in turn implies that the collective interactions that control the plasma gas depend on the electric
and magnetic field effects as much as, or more so than,
simple collisions. Since waves are able to propagate, the
possibility exists for force fields to act at large distances
from the point where they originated.
Ordinary fluids can support the propagation of sound
(acoustic) waves, which involve pressure, temperature, and
velocity variations. Electromagnetic waves can propagate
even in a vacuum but are slowed down in most cases by
the interaction of the electric fields in the waves with the
charged particles bound in the atoms or molecules of the
gas. Although it is important for a complete description
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Plasma
of electromagnetic waves, such an interaction is not very

strong. In a plasma, however, the particles react in concert
with any electromagnetic field (e.g., as in an electromagnetic wave) as well as with any pressure or velocity field
(e.g., as in a sound wave). In fact, in a plasma sound wave
the electrons and ions become slightly separated owing
to their difference in mass, and an electric field builds up
to bring them back together. The result is called an ion
acoustic wave. This is just one of the many types of waves
that can exist in a plasma. The brief discussion that follows touches on the main types in order of increasing
wave-oscillation frequency.
Low-Frequency Waves
At the lowest frequency are Alfvn waves, which require
the presence of a magnetic field to exist. In fact, except
for ion acoustic waves, the existence of a background
magnetic field is required for any wave with a frequency
less than the plasma frequency to occur in a plasma. Most
natural plasmas are threaded by a magnetic field, and laboratory plasmas often use a magnetic field for confinement,
so this requirement is usually met, and all types of waves
can occur.
Alfvn waves are analogous to the waves that occur on
the stretched string of a guitar. In this case, the string represents a magnetic field line. When a small magnetic field
disturbance takes place, the field is bent slightly, and the
disturbance propagates in the direction of the magnetic
field. Since any changing magnetic field creates an electric
field, an electromagnetic wave results. Such waves are the
slowest and have the lowest frequencies of any known electromagnetic waves. For example, the solar wind streams
out from the Sun with a speed greater than either electromagnetic (Alfvn) or sound waves. This means that, when
the solar wind hits Earths outermost magnetic field lines,
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a shock wave results to inform the incoming plasma

that an obstacle exists, much like the shock wave associated with a supersonic airplane. The shock wave travels
toward the Sun at the same speed but in the opposite
direction as the solar wind, so it appears to stand still with
respect to Earth. Because there are almost no particleparticle collisions, this type of collisionless shock wave is
of great interest to space plasma physicists who postulate
that similar shocks occur around supernovas and in other
astrophysical plasmas. On Earths side of the shock wave,
the heated and slowed solar wind interacts with Earths
atmosphere via Alfvn waves propagating along the magnetic field lines.
The turbulent surface of the Sun radiates largeamplitude Alfvn waves, which are thought to be
responsible for heating the corona to 1,000,000 K. Such
waves can also produce fluctuations in the solar wind, and,
as they propagate through it to Earth, they seem to control the occurrence of magnetic storms and auroras that
are capable of disrupting communication systems and
power grids on the planet.
Two fundamental types of wave motion can occur:
longitudinal, like a sound or ion acoustic wave, in which
particle oscillation is in a direction parallel to the direction of wave propagation; and transverse, like a surface
water wave, in which particle oscillation is in a plane perpendicular to the direction of wave propagation. In all
cases, a wave may be characterized by a speed of propagation (u), a wavelength (), and a frequency () related by an
expression in which the velocity is equal to the product of
the wavelength and frequency, namely, u = . The Alfvn
wave is a transverse wave and propagates with a velocity
that depends on the particle density and the magnetic
field strength. The velocity is equal to the magnetic flux
density (B) divided by the square root of the mass density
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Plasma
() times the permeability of free space ( 0)that is to say,

B/0. The ion acoustic wave is a longitudinal wave and
also propagates parallel to the magnetic field at a speed
roughly equal to the average thermal velocity of the ions.
Perpendicular to the magnetic field a different type of
longitudinal wave called a magnetosonic wave can occur.
Higher Frequency Waves
In these waves the plasma behaves as a whole, and the
velocity is independent of wave frequency. At higher frequencies, however, the separate behaviour of ions and
electrons causes the wave velocities to vary with direction
and frequency. The Alfvn wave splits into two components, referred to as the fast and slow Alfvn waves, which
propagate at different frequency-dependent speeds. At
still higher frequencies these two waves (called the electron cyclotron and ion cyclotron waves, respectively)
cause electron and cyclotron resonances (synchronization) at the appropriate resonance frequencies. Beyond
these resonances, transverse wave propagation does not
occur at all until frequencies comparable to and above the
plasma frequency are reached.
At frequencies between the ion and electron gyrofrequencies lies a wave mode called a whistler. This name
comes from the study of plasma waves generated by lightning. When early researchers listened to natural radio
waves by attaching an antenna to an audio amplifier, they
heard a strange whistling sound. The whistle occurs when
the electrical signal from lightning in one hemisphere
travels along the Earths magnetic field lines to the other
hemisphere. The trip is so long that some waves (those at
higher frequencies) arrive first, resulting in the generation of a whistlelike sound. These natural waves were used
to probe the region of space around Earth before spacecraft became available. Such a frequency-dependent wave
213
velocity is called wave dispersion because the various frequencies disperse with distance.
The speed of an ion acoustic wave also becomes dispersive at high frequencies, and a resonance similar to
electron plasma oscillations occurs at a frequency determined by electrostatic oscillations of the ions. Beyond this
frequency no sonic wave propagates parallel to a magnetic
field until the frequency reaches the plasma frequency,
above which electroacoustic waves occur. The wavelength
of these waves at the critical frequency (p) is infinite, the
electron behaviour at this frequency taking the form of the
plasma oscillations of Langmuir and Tonks. Even without
particle collisions, waves shorter than the Debye length
are heavily dampedi.e., their amplitude decreases rapidly with time. This phenomenon, called Landau damping,
arises because some electrons have the same velocity as
the wave. As they move with the wave, they are accelerated much like a surfer on a water wave and thus extract
energy from the wave, damping it in the process.
Containment
Magnetic fields are used to contain high-density, hightemperature plasmas because such fields exert pressures
and tensile forces on the plasma. An equilibrium configuration is reached only when at all points in the plasma
these pressures and tensions exactly balance the pressure
from the motion of the particles. A well-known example
of this is the pinch effect observed in specially designed
equipment. If an external electric current is imposed on
a cylindrically shaped plasma and flows parallel to the
plasma axis, the magnetic forces act inward and cause the
plasma to constrict, or pinch. An equilibrium condition is
reached in which the temperature is proportional to the
square of the electric current. This result suggests that any
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Plasma
temperature may be achieved by making the electric current sufficiently large, the heating resulting from currents
and compression. In practice, however, since no plasma can
be infinitely long, serious energy losses occur at the ends
of the cylinder; also, major instabilities develop in such a
simple configuration. Suppression of such instabilities has
been one of the major efforts in laboratory plasma physics
and in the quest to control the nuclear fusion reaction.
A useful way of describing the confinement of a plasma
by a magnetic field is by measuring containment time (c),
or the average time for a charged particle to diffuse out of
the plasma; this time is different for each type of configuration. Various types of instabilities can occur in plasma.
These lead to a loss of plasma and a catastrophic decrease
in containment time. The most important of these is
called magnetohydrodynamic instability. Although an
equilibrium state may exist, it may not correspond to
the lowest possible energy. The plasma, therefore, seeks
a state of lower potential energy, just as a ball at rest on
top of a hill (representing an equilibrium state) rolls down
to the bottom if perturbed; the lower energy state of the
plasma corresponds to a ball at the bottom of a valley.
In seeking the lower energy state, turbulence develops,
leading to enhanced diffusion, increased electrical resistivity, and large heat losses. In toroidal geometry, circular
plasma currents must be kept below a critical value called
the Kruskal-Shafranov limit, otherwise a particularly violent instability consisting of a series of kinks may occur.
Although a completely stable system appears to be virtually impossible, considerable progress has been made in
devising systems that eliminate the major instabilities.
Temperatures on the order of 10,000,000 K at densities
of 1019 particles per cubic metre and containment times as
high as 150 of a second have been achieved.
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Applications of Plasmas
The most important practical applications of plasmas lie
in the future, largely in the field of power production. The
major method of generating electric power has been to
use heat sources to convert water to steam, which drives
turbogenerators. Such heat sources depend on the combustion of fossil fuels, such as coal, oil, and natural gas, and
fission processes in nuclear reactors. A potential source of
heat might be supplied by a fusion reactor, with a basic
element of deuterium-tritium plasma; nuclear fusion collisions between those isotopes of hydrogen would release
large amounts of energy to the kinetic energy of the reaction products (the neutrons and the nuclei of hydrogen
and helium atoms). By absorbing those products in a
surrounding medium, a powerful heat source could be created. To realize a net power output from such a generating
stationallowing for plasma radiation and particle losses
and for the somewhat inefficient conversion of heat to
electricityplasma temperatures of about 100,000,000
K and a product of particle density times containment
time of about 1020 seconds per cubic metre are necessary.
For example, at a density of 1020 particles per metre cubed,
the containment time must be one second. Such figures are
yet to be reached, although there has been much progress.
In general, there are two basic methods of eliminating or minimizing end losses from an artificially created
plasma: the production of toroidal plasmas and the use
of magnetic mirrors. A toroidal plasma is essentially one
in which a plasma of cylindrical cross section is bent in
a circle so as to close on itself. For such plasmas to be in
equilibrium and stable, however, special magnetic fields
are required, the largest component of which is a circular
field parallel to the axis of the plasma. In addition, a number of turbulent plasma processes must be controlled to
216
Plasma
keep the system stable. In 1991 a machine called the JET

( Joint European Torus) was able to generate 1.7 million
watts of fusion power for almost 2 seconds after researchers injected titrium into the JETs magnetically confined
plasma. It was the first successful controlled production
of fusion power in such a confined medium.
Besides generating power, a fusion reactor might desalinate seawater. Approximately two-thirds of the worlds
land surface is uninhabited, with one-half of this area
being arid. The use of both giant fission and fusion reactors in the large-scale evaporation of seawater could make
irrigation of such areas economically feasible. Another
possibility in power production is the elimination of the
heatsteammechanical energy chain. One suggestion
depends on the dynamo effect. If a plasma moves perpendicular to a magnetic field, an electromotive force,
according to Faradays law, is generated in a direction perpendicular to both the direction of flow of the plasma and
the magnetic field. This dynamo effect can drive a current in an external circuit connected to electrodes in the
plasma, and thus electric power may be produced without the need for steam-driven rotating machinery. This
process is referred to as magnetohydrodynamic (MHD)
power generation and has been proposed as a method
of extracting power from certain types of fission reactors. Such a generator powers the auroras as the Earths
magnetic field lines tap electrical current from the MHD
generator in the solar wind.
The inverse of the dynamo effect, called the motor
effect, may be used to accelerate plasma. By pulsing cuspshaped magnetic fields in a plasma, for example, it is
possible to achieve thrusts proportional to the square of
the magnetic field. Motors based on such a technique have
been proposed for the propulsion of craft in deep space.
They have the advantage of being capable of achieving
217
large exhaust velocities, thus minimizing the amount of

fuel carried.
A practical application of plasma involves the glow discharge that occurs between two electrodes at pressures of
one-thousandth of an atmosphere or thereabouts. Such
glow discharges are responsible for the light given off by
neon tubes and such other light sources as fluorescent
lamps, which operate by virtue of the plasmas they produce in electric discharge. The degree of ionization in
such plasmas is usually low, but electron densities of 1016
to 1018 electrons per cubic metre can be achieved with
an electron temperature of 100,000 K. The electrons
responsible for current flow are produced by ionization in
a region near the cathode, with most of the potential difference between the two electrodes occurring there. This
region does not contain a plasma, but the region between
it and the anode (i.e., the positive electrode) does.
Other applications of the glow discharge include electronic switching devices; it and similar plasmas produced
by radio-frequency techniques can be used to provide
ions for particle accelerators and act as generators of
laser beams. As the current is increased through a glow
discharge, a stage is reached when the energy generated
at the cathode is sufficient to provide all the conduction
electrons directly from the cathode surface, rather than
from gas between the electrodes. Under this condition
the large cathode potential difference disappears, and the
plasma column contracts. This new state of electric discharge is called an arc. Compared with the glow discharge,
it is a high-density plasma and will operate over a large
range of pressures. Arcs are used as light sources for welding, in electronic switching, for rectification of alternating
currents, and in high-temperature chemistry. Running an
arc between concentric electrodes and injecting gas into
such a region causes a hot, high-density plasma mixture
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Plasma
called a plasma jet to be ejected. It has many chemical and

metallurgical applications.
Natural Plasmas
It has been suggested that the universe originated as a
violent explosion about 10 billion years ago and initially
consisted of a fireball of completely ionized hydrogen
plasma. Irrespective of the truth of this, there is little matter in the universe now that does not exist in the plasma
state. The observed stars are composed of plasmas, as are
interstellar and interplanetary media and the outer atmospheres of planets. Scientific knowledge of the universe has
come primarily from studies of electromagnetic radiation
emitted by plasmas and transmitted through them and,
since the 1960s, from space probes within the solar system.
Extraterrestrial Forms
In a star the plasma is bound together by gravitational
forces, and the enormous energy it emits originates in
thermonuclear fusion reactions within the interior. Heat
is transferred from the interior to the exterior by radiation
in the outer layers, where convection is of greater importance. In the vicinity of a hot star, the interstellar medium
consists almost entirely of completely ionized hydrogen,
ionized by the stars ultraviolet radiation. Such regions are
referred to as H II regions. The greater proportion by far
of interstellar medium, however, exists in the form of neutral hydrogen clouds referred to as H I regions. Because
the heavy atoms in such clouds are ionized by ultraviolet
radiation (or photoionized), they also are considered to
be plasmas, although the degree of ionization is probably
only one part in 10,000. Other components of the interstellar medium are grains of dust and cosmic rays, the latter
219
consisting of very high-energy atomic nuclei completely

stripped of electrons. The almost isotropic velocity distribution of the cosmic rays may stem from interactions
with waves of the background plasma.
Throughout this universe of plasma there are magnetic fields. In interstellar space magnetic fields are about
5 10 -6 gauss (a unit of magnetic field strength) and in
interplanetary space 5 10 -5 gauss, whereas in intergalactic
space they could be as low as 10 -9 gauss. These values are
exceedingly small compared with Earths surface field of
about 5 101 gauss. Although small in an absolute sense,
these fields are nevertheless gigantic, considering the
scales involved. For example, to simulate interstellar phenomena in the laboratory, fields of about 1015 gauss would
be necessary. Thus, these fields play a major role in nearly
all astrophysical phenomena. On the Sun the average surface field is in the vicinity of 1 to 2 gauss, but magnetic
disturbances arise, such as sunspots, in which fields of
between 10 and 1,000 gauss occur. Many other stars are
also known to have magnetic fields. Field strengths of 10 3
gauss are associated with various extragalactic nebulae
from which synchrotron radiation has been observed.
Solar-Terrestrial Forms
The most notable natural plasmas are those that occur in
the space environment around Earth. Some of these plasmas create currents that have caused power outages on
Earths surface.
Regions of the Sun
The visible region of the Sun is the photosphere, with its
radiation being about the same as the continuum radiation
from a 5,800 K blackbody. Lying above the photosphere is
the chromosphere, which is observed by the emission of
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Plasma
line radiation from various atoms and ions. Outside the

chromosphere, the corona expands into the ever-blowing
solar wind), which on passing through the planetary system eventually encounters the interstellar medium. The
corona can be seen in spectacular fashion when the Moon
eclipses the bright photosphere. During the times in
which sunspots are greatest in number (called the sunspot
maximum), the corona is very extended and the solar wind
is fierce. Sunspot activity waxes and wanes with roughly
an 11-year cycle. During the mid-1600s and early 1700s,
sunspots virtually disappeared for a period known as the
Maunder minimum. This time coincided with the Little
Ice Age in Europe, and much conjecture has arisen about
the possible effect of sunspots on climate. Periodic variations similar to that of sunspots have been observed in
tree rings and lake-bed sedimentation. If real, such an
effect is important because it implies that the Earths climate is fragile.
In 1958 the American astrophysicist Eugene Parker
showed that the equations describing the flow of plasma in
the Suns gravitational field had one solution that allowed
the gas to become supersonic and to escape the Suns pull.
The solution was much like the description of a rocket
nozzle in which the constriction in the flow is analogous
to the effect of gravity. Parker predicted the Suns atmosphere would behave just as this particular solar-wind
solution predicts rather than according to the solar-breeze
solutions suggested by others. The interplanetary satellite
probes of the 1960s proved his solution to be correct.
Interaction of the Solar Wind
and the Magnetosphere
The solar wind is a collisionless plasma made up primarily
of electrons and protons and carries an outflow of matter moving at supersonic and super-Alfvnic speed. The
221
wind takes with it an extension of the Suns magnetic field,

which is frozen into the highly conducting fluid. In the
region of Earth, the wind has an average speed of 400 km
(250 miles) per second; and, when it encounters the planets magnetic field, a shock front develops, the pressures
acting to compress the field on the side toward the Sun
and elongate it on the nightside (in Earths lee away from
the Sun). Earths magnetic field is therefore confined to
a cavity called the magnetosphere, into which the direct
entry of the solar wind is prohibited. This cavity extends
for about 10 Earth radii on the Suns side and about 1,000
Earth radii on the nightside.
Inside this vast magnetic field a region of circulating
plasma is driven by the transfer of momentum from the
solar wind. Plasma flows parallel to the solar wind on the
edges of this region and back toward Earth in its interior.
The resulting system acts as a secondary magnetohydrodynamic generator (the primary one being the solar wind
itself ). Both generators produce potential on the order of
100,000 volts. The solar-wind potential appears across the
polar caps of Earth, while the magnetospheric potential
appears across the auroral oval. The latter is the region of
the Earth where energetic electrons and ions precipitate
into the planets atmosphere, creating a spectacular light
show. This particle flux is energetic enough to act as a new
source of plasmas even when the Sun is no longer shining. The auroral oval becomes a good conductor; and large
electric currents flow along it, driven by the potential difference across the system. These currents commonly are
on the order of 1,000,000 amperes.
The plasma inside the magnetosphere is extremely hot
(110 million K) and very tenuous (110 particles per cubic
cm). The particles are heated by a number of interesting
plasma effects, the most curious of which is the auroral
acceleration process itself. A particle accelerator that may
222
Plasma
be the prototype for cosmic accelerators throughout the

universe is located roughly 1 Earth radius above the auroral oval and linked to it by all-important magnetic field
lines. In this region the auroral electrons are boosted by
a potential difference on the order of 36 kilovolts, most
likely created by an electric field parallel to the magnetic
field lines and directed away from Earth. Such a field is
difficult to explain because magnetic field lines usually act
like nearly perfect conductors. The auroras occur on magnetic field lines thatif it were not for the distortion of
Earths dipole fieldwould cross the equatorial plane at a
distance of 610 Earth radii.
Closer to Earth, within about 4 Earth radii, the planet
wrests control of the system away from the solar wind.
Inside this region the plasma rotates with Earth, just
as its atmosphere rotates with it. This system can also
be thought of as a magnetohydrodynamic generator in
which the rotation of the atmosphere and the ionospheric
plasma in it create an electric field that puts the inner
magnetosphere in rotation about Earths axis. Since this
inner region is in contact with the dayside of Earth where
the Sun creates copious amounts of plasma in the ionosphere, the inner zone fills up with dense, cool plasma to
form the plasmasphere. On a planet such as Jupiter, which
has both a larger magnetic field and a higher rotation rate
than Earth, planetary control extends much farther from
the surface.
The Ionosphere and Upper Atmosphere
At altitudes below about 2,000 km (1,200 miles), the
plasma is referred to as the ionosphere. Thousands of
rocket probes have helped chart the vertical structure of
this region of the atmosphere, and numerous satellites
have provided latitudinal and longitudinal information.
The ionosphere was discovered in the early 1900s when
223
radio waves were found to propagate over the horizon.

If radio waves have frequencies near or below the plasma
frequency, they cannot propagate throughout the plasma
of the ionosphere and thus do not escape into space; they
are instead either reflected or absorbed. At night the
absorption is low since little plasma exists at the height of
roughly 100 km (60 miles) where absorption is greatest.
Thus, the ionosphere acts as an effective mirror, as does
the Earths surface, and waves can be reflected around the
entire planet much as in a waveguide. A great communications revolution was initiated by the wireless, which relied
on radio waves to transmit audio signals. Development
continues to this day with satellite systems that must
propagate through the ionospheric plasma. In this case,
the wave frequency must be higher than the highest
plasma frequency in the ionosphere so that the waves will
not be reflected away from the Earth.
The dominant ion in the upper atmosphere is atomic
oxygen, while below about 200 km (120 miles) molecular oxygen and nitric oxide are most prevalent. Meteor
showers also provide large numbers of metallic atoms
of elements such as iron, silicon, and magnesium, which
become ionized in sunlight and last for long periods of
time. These form vast ion clouds, which are responsible
for much of the fading in and out of radio stations at night.
The Lower Atmosphere and Surface of Earth
A more normal type of cloud forms at the base of Earths
plasma blanket in the summer polar mesosphere regions.
Located at an altitude of 85 km (50 miles), such a cloud is
the highest on Earth and can be seen only when darkness
has just set in on the planet. Hence, clouds of this kind
have been called noctilucent clouds. They are thought to
be composed of charged and possibly dusty ice crystals
that form in the coldest portion of the atmosphere at a
224
Plasma
temperature of 120 K (150 C, or 240 F). This unusual

medium has much in common with dusty plasmas in planetary rings and other cosmic systems. Noctilucent clouds
have been increasing in frequency throughout the 20th
century and may be a forerunner of global change.
High-energy particles also exist in the magnetosphere.
At about 1.5 and 3.5 Earth radii from the centre of the
planet, two regions contain high-energy particles. These
regions are the Van Allen radiation belts, named after the
American scientist James Van Allen, who discovered them
using radiation detectors aboard early spacecraft. The
charged particles in the belts are trapped in the mirror
system formed by Earths magnetic dipole field.
Plasma can exist briefly in the lowest regions of the
Earths atmosphere. In a lightning stroke an oxygennitrogen plasma is heated at approximately 20,000 K with
an ionization of about 20 percent, similar to that of a laboratory arc. Although the stroke is only a few centimetres
thick and lasts only a fraction of a second, tremendous
energies are dissipated. A lightning flash between the
ground and a cloud, on the average, consists of four such
strokes in rapid succession. At all times, lightning is occurring somewhere on Earth, charging the surface negatively
with respect to the ionosphere by roughly 200,000 volts,
even far from the nearest thunderstorm. If lightning
ceased everywhere for even one hour, Earth would discharge. An associated phenomenon is ball lightning. There
are authenticated reports of glowing, floating, stable balls
of light several tens of centimetres in diameter occurring
at times of intense electrical activity in the atmosphere.
On contact with an object, these balls release large amounts
of energy. Although lightning balls are probably plasmas,
so far no adequate explanation of them has been given.
Considering the origins of plasma physics and the fact
that the universe is little more than a vast sea of plasma, it
225
is ironic that the only naturally occurring plasmas at the

surface of Earth besides lightning are those to be found in
ordinary matter. The free electrons responsible for electrical conduction in a metal constitute a plasma. Ions are
fixed in position at lattice points, and so plasma behaviour
in metals is limited to such phenomena as plasma oscillations and electron cyclotron waves (called helicon waves)
in which the electron component behaves separately from
the ion component. In semiconductors, on the other
hand, the current carriers are electrons and positive holes,
the latter behaving in the material as free positive charges
of finite mass. By proper preparation, the number of electrons and holes can be made approximately equal so that
the full range of plasma behaviour can be observed.
Magnetic Fields
The importance of magnetic fields in astrophysical phenomena has already been noted. It is believed that these
fields are produced by self-generating dynamos, although
the exact details are still not fully understood. In the case
of Earth, differential rotation in its liquid conducting core
causes the external magnetic dipole field (manifest as the
North and South poles). Cyclonic turbulence in the liquid,
generated by heat conduction and Coriolis forces (apparent forces accompanying all rotating systems, including
the heavenly bodies), generates the dipole field from
these loops. Over geologic time, Earths field occasionally becomes small and then changes direction, the North
Pole becoming the South Pole and vice versa. During the
times in which the magnetic field is small, cosmic rays can
more easily reach Earths surface and may affect life forms
by increasing the rate at which genetic mutations occur.
Similar magnetic-field generation processes are
believed to occur in both the Sun and the Milky Way
Galaxy. In the Sun the circular internal magnetic field is
226
Plasma
made observable by lines of force apparently breaking the

solar surface to form exposed loops; entry and departure
points are what are observed as sunspots. Although the
exterior magnetic field of Earth is that of a dipole, this
is further modified by currents in both the ionosphere
and magnetosphere. Lunar and solar tides in the ionosphere lead to motions across Earths field that produce
currents, like a dynamo, that modify the initial field. The
auroral oval current systems discussed earlier create even
larger magnetic-field fluctuations. The intensity of these
currents is modulated by the intensity of the solar wind,
which also induces or produces other currents in the magnetosphere. Such currents taken together constitute the
essence of a magnetic storm.
227
Chapter 9
Clusters
toms and molecules are the smallest forms of matter

typically encountered under normal conditions and
are in that sense the basic building blocks of the material
world. There are phenomena, such as lightning and electric discharges of other kinds, that allow free electrons to
be observed, but these are exceptional occurrences. It is
of course in its gaseous state that matter is encountered at
its atomic or molecular level; in gases each molecule is an
independent entity, only occasionally and briefly colliding
with another molecule or with a confining wall.
In contrast to the free-molecule character of gases,
the condensed phases of matteras liquids, crystalline
solids, and glasses are calleddepend for their properties
on the constant proximity of all their constituent atoms.
The extent to which the identities of the molecular constituents are maintained varies widely in these condensed
forms of matter. Weakly bound solids, such as solid carbon dioxide (dry ice), or their liquid counterparts, such
as liquid air or liquid nitrogen, are made up of molecules
whose properties differ only slightly from the properties
of the same molecules in gaseous form; such solids or liquids are simply molecules packed tightly enough to be in
constant contact. These are called van der Waals solids
or liquids, after Johannes D. van der Waals, the Dutch
physicist who described the weak forces that just manage
to hold these materials together if they are cold enough.
In other solids, like diamond, graphite, silicon, or quartz,
the individual atoms retain their identity, but there are
228
7 Clusters
no identifiable molecules in their structures. The forces

between the constituent atoms are roughly as strong as
the forces that hold atoms together in the strongly bound
covalent molecules that make up most common substances. Negatively charged electrons act as a glue to
hold the positively charged nuclei together and are more
or less confined to the vicinity of the so-called home-base
nuclei with which they are associated; they are not free
to roam through the entire solid or liquid. These materials are said to be covalently bound and are electrical
insulators. They are best described as neutral atoms held
together by covalent bonds and are essentially one giant
molecule.
Another kind of bonding found in condensed matter is
exhibited by sodium chloride, ordinary table salt, which is
composed of positive sodium ions (Na+) and negative chloride ions (Cl-). Such ionic compounds are held together
by the mutual attraction of the oppositely charged ions;
because of their locations, these attractions are stronger
than the repulsions of the ions with like charges. Each ion
in an ionic crystal is surrounded by nearest neighbours
of opposite charge. The consequence is that the binding energies of ionic compounds are large, comparable to
those of strongly bound covalent substances.
Metallic bonding is another type of binding found in
condensed matter. Electrons moving between the positive
atomic cores (i.e., the nuclei plus inner-shell, tightly bound
electrons) form an electron cloud; the attractions between
the positive cores and the negative charges that make up
the cloud hold metals together. Metals differ from covalently bound insulators in that those electrons responsible
for the cohesion of the metals move freely throughout the
metal when given the slightest extra energy. For example,
under the influence of the electric field produced in a
229
copper wire when its ends are connected to the terminals

of a battery, electrons move through the wire from the
end connected to the batterys negative pole toward
the end connected to its positive pole. An electric field
applied to a metal generates an electric current, but the
same electric field applied to a covalent insulator does
not. The net binding forces between electrons and atomic
cores of a metal are comparable in strength to those that
hold ionic compounds together.
As mentioned previously, liquids constitute a condensed or dense phase of matter, but their atomic
arrangement differs from that of solids. In a liquid the constituent atoms are only slightly farther apart than they are
in a solid, but that small difference is significant enough
to allow the atoms or molecules that constitute a liquid
to move around and to assume a full range of geometric
configurations. Atoms of the same kind can trade places
and can wander through the liquid by the random-walk
process called diffusion. In general, materials that can
form solids can also form liquids, but some, such as carbon dioxide, can only enter the liquid state under excess
pressure. At least one substance, helium, can form a liquid
while having no known solid form.
Materials that form solids and liquids can exhibit
another form, one that may be solidlike or liquidlike but
that has properties somewhat different from those of
the bulk. This is the form of matter consisting of exceedingly small particles that are called clusters. Clusters
are aggregates of atoms, molecules, or ions that adhere
together under forces like those that bind the atoms,
ions, or molecules of bulk matter; because of the manner
in which they are prepared, clusters remain as tiny particles at least during the course of an experiment. There
are clusters held together by van der Waals forces, by
230
7 Clusters
ionic forces, by covalent bonds, and by metallic bonds.

Despite the similarity of the forces that bind both clusters and bulk matter, one of the fascinating aspects of
clusters is that their properties differ from those of the
corresponding bulk material; that characteristic affords
the opportunity to learn about the properties of bulk
matter by studying how, as the number of constituent
particles increases, the properties of clusters evolve into
those of bulk matter. For example, a cluster of 20 or 30
atoms typically has a melting point far lower than that
of the corresponding bulk. The electrical properties of
clusters also differ in some instances from those of the
bulk matter: clusters of only a few atoms of mercury are
insulators, held together by weak van der Waals forces,
but clusters of hundreds of mercury atoms are metallic.
One of the puzzles posed by clusters is the question of
how properties of small clusters evolve with size into
properties of bulk matter.
Comparison with Bulk Matter

Several characteristics differentiate clusters from molecules and bulk matter. They differ from bulk matter,
first and foremost, in size; whether three particles bound
together constitute a cluster is a matter of choice and
convention, but an aggregate of four or more atoms or
molecules certainly comprises a cluster. Such a small cluster would differ markedly from bulk matter in almost all
its properties. A second difference between clusters and
bulk matter is the variability of the properties of clusters with the number of their constituent particles. The
properties of a lump of bulk matter remain unchanged
by the addition or subtraction of a few atoms or molecules, whereas the properties of a small cluster vary
231
significantly and, in general, neither uniformly nor even

in the same direction with a change in the number of
constituent particles. Medium-size clusters have properties that vary smoothly with the number of constituent
particles (denoted N), but their properties, such as the
melting point, differ significantly from those of the corresponding bulk. Large clusters have properties that vary
smoothly with N and clearly merge into those of their
bulk counterparts. This distinction, while not extremely
precise, is quite useful. For example, the average binding energiesthat is, the average energy per constituent
atom or molecule required to separate the particles from
each othervary widely with N for small clusters. The
reason for this wide range is that clusters of certain values of N, known as magic numbers, can take on unusually
stable geometric structures that yield large binding energies, while others with different small values of N have no
especially stable forms and therefore only relatively low
binding energies. The binding energies of medium-size
clusters vary rather smoothly with N, but they are in general considerably lower than the binding energies of bulk
matter. The most important reason for this trend is that
in a body of bulk matter almost all the particles are in the
interior, while in a cluster most of the particles are on the
surface. In a cluster of 13 atoms of copper or argon, for
example, 12 of the atoms are on the surface. In a cluster
of 55 argon atoms, 42 atoms are on the surface, and, in a
cluster of 137 argon atoms, 82 are on the surface. Surface
atoms are bonded only to atoms in their own layer and
to those directly beneath them, so they have fewer atoms
holding them to the main body of matter, whether cluster
or bulk, than do atoms in the interior. Hence, the average
binding energies of atoms in clusters are normally considerably less than those of bulk matter.
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7 Clusters
An important difference between clusters, in particular small- and medium-size clusters, and bulk solids is the
structure that is assumed by their most stable form. Most
bulk solids are crystalline. This means that their atomic
structures consist of periodic latticesi.e., structures that
repeat over and over so that every unit composed of a few
neighbouring atoms is indistinguishable from other groups
of atoms that have exactly the same arrangement. In a simple
cubic crystal, for example, all the atoms lie at the corners of
cubes (in fact at a point common to eight equivalent cubes),
and all these lattice points are identical. Such structures are
called periodic. Most clusters, by contrast, have structures
that are not periodic; many have the form of icosahedrons,
incomplete icosahedrons, or other polyhedral structures
that cannot grow into periodic lattices. One of the challenging puzzles of cluster science is to explain how, as an
aggregate grows, it transforms from a polyhedral clustertype structure into a crystalline lattice-type structure.
Furthermore, some properties of clusters reflect their
small size in more subtle ways that depend on quantum
mechanical phenomena. These are generally much more
pronounced in exceedingly small systems than in bulk or
macroscopic samples. One such property is the nature of
the energy levels occupied by the electrons. In a macroscopic sample the energies of the states available to an
electron are, in principle, discrete but are merged into
bands consisting of many energy levels. Within each band
the intervals of energy between those discrete levels are
too tiny to be discerned; only the gaps between the bands
are large enough to be important because they correspond
to ranges of energy that are forbidden to the electrons. In
fact, it is the contrast in the mobility of electrons that differentiates insulators from electrical conductors. In even
a very cold metal, only an infinitesimal amount of excess
233
energy is required to promote a few electrons into the previously empty energy levels in which they can move freely
throughout the material. If an electric field is applied
to the metal, the negatively charged electrons move
toward the positive pole of the field so that a net current
flows in the metal. It is the motion of these electrons,
driven by an applied field, that makes metals conductors of electricity. In an insulator the electrons fill all the
energy levels up to the top of the highest-energy occupied
band. This means that at least the full energy of the forbidden interval, called the band gap, must be imparted
to any electron to promote it to an allowed state where it
may travel readily through the material. In an insulator
this is far more energy than is normally available, and so
no electrons are in states that allow them to move freely;
such materials cannot conduct electric currents.
Clusters containing only a small number of metal
atoms have so few available quantum states for their electrons that these states must be considered discrete, not
as components of a dense band of available states. In this
sense, small clusters of metal atoms are like conventional
molecules rather than like bulk metals. Medium-size clusters of metal atoms have electronic energy states that are
close enough together to be treated like the bands of bulk
metals, but the conducting properties of these clusters
are different from those of the bulk. Electrons driven by a
constant electric field in a bulk metal can travel distances
that are extremely long compared with atomic dimensions
before they encounter any boundaries at the edges of the
metal. Electrons in metal clusters encounter the boundaries of their cluster in a much shorter distance. Hence,
metal clusters do not conduct electricity like bulk metals;
if they are subjected to rapidly oscillating electric fields,
such as those of visible, infrared, or microwave radiation,
234
7 Clusters
their free electrons are driven first one way and then
back in the opposite direction over distances smaller than
the dimensions of the cluster. If they are subjected to constant or low-frequency electric fields, such as the common
60-hertz fields that drive ordinary household currents,
the electrons reach the boundaries of their clusters and
can go no farther. Thus, the equivalent of conduction is
not seen at low frequencies.
Comparison with Molecules

The manner in which clusters differ from molecules is
more of a categorical nature than one of physical properties. Molecules have a definite composition and geometry;
with few exceptions clusters can be made of any number
of particles and may have any of several geometries. For
example, the 13-atom cluster has the form of a regular icosahedron of 12 argon atoms around a central atom and is
particularly stable.
Despite their multiplicity of structures, small clusters
of fixed size, undergoing vibrations of small amplitude
around a single geometry, are in most respects indistinguishable from molecules. If such clusters are given energy
that is not great enough in magnitude to break them into
separate parts, they may assume other geometries, alternating among these structural forms. This phenomenon
is rarely seen with conventional molecules, but it is not
unknown for energized molecules to exhibit more than
one structure and to pass among them.
All in all, small clusters are much like molecules and
are often considered to be molecules, while very large
clusters are quite similar to bulk matter. The properties
of clusters whose size is between these extremes may be
like either or like neither.
235
the four lowest-energy structures of the 13-atom cluster of argon. Copyright

methods oF study
Clusters can be studied by experiment, by theoretical
analysis, and by simulation with computer-generated
models. For several reasons they cannot be studied in the
same manner as bulk matter. First, if individual clusters
236
7 Clusters
are allowed to coalesce into a mass, they will actually turn

into bulk matter, so they must be kept separated. Second,
it is desirable (but not always possible) to conduct experiments that distinguish the size and structure of each kind
of cluster under observation. Because of these two considerations, experiments with clusters are usually more
difficult than those with either specific molecules or bulk
matter. Most of the difficulties arise from the same properties that make clusters interesting: the ease with which
their sizes and compositions are varied and the variety of
structures available for clusters of almost any given size.
Preparation of Clusters
Because of these difficulties, most experiments on clusters have been carried out with the clusters isolated in the
gas phase; a few studies have been done with them in solution or in frozen matrices. Clusters can be prepared in the
gas phase and then either studied in that form or captured
into solvents or matrices or onto surfaces. They may be
made by condensation of atoms or molecules or by direct
blasting of matter from solids. In the most generally used
method, a gas containing the gaseous cluster material is
cooled by passing it under high pressure through a fine hole
or slot. The expansion cools the gas rapidly from its initial
temperatureusually room temperature but much higher
if the cluster material is solid at room temperatureto a
temperature not far above absolute zero. If, for example,
argon gas is expanded in this way, it condenses into clusters if the pressure is not too high and the aperture is not
too small; if the conditions are too extreme, the argon
instead turns to snow and condenses.
Inert gases are often used as the medium by which
other materials, in a gaseous or vaporous state, are transported from the ovens or other sources where they have
237
been gasified and through the jets that cool them and turn
them into clusters. One especially popular and interesting
method in which solids are vaporized is by the action of
intense laser beams on solid surfaces. Often called ablation, this process is an effective means of vaporizing even
highly refractory materials like solid carbon. The ablated
material is then carried through the cooling jet by an inert
gas such as helium or argon.
Ionization and Sorting of Clusters

Once the clusters have been formed, they can be studied
in a variety of ways. One of the first techniques was simply to ionize the clusters, either with ultraviolet radiation
(usually from a laser) or by electron impact. The gaseous
ionized clusters are accelerated by an electric field and
then analyzed according to their masses; these results
immediately reveal the number of atoms or molecules in
the cluster. The analysis yields the distribution of the relative abundances of clusters of different sizes in the beam.
If the experiment is done with considerable care, the
abundance distribution corresponds to the true relative
stabilities of the clusters of different sizes. However, like
many experiments with clusters, these can either provide
results consistent with the equilibrium conditions that
reflect those relative stabilities, or they can give results
that reflect the rates of the cluster-forming processes
rather than the equilibrium characteristics, as the latter
may take far longer to reach than the time required to
form clusters.
Because of the conditions under which clusters are
formed, their distributions contain many different sizes
and, in some instances, different shapes. Because chemists
seek to characterize clusters of a single size and geometry, the clusters must first be sorted on that basis. If the
238
7 Clusters
clusters carry charge, they can be separated according to

size with a mass spectrometer that sorts charged particles
with approximately the same energy according to their
masses. This is usually done by deflecting the charged clusters or ions with an electric or magnetic field; the smaller
the mass, the greater is the deflection. This is one of the
most effective ways of preparing a beam of clusters of only
a single selected mass. It does not eliminate the problem
of multiple structures, however.
A technique that can sometimes be used to sort clusters according to their size and structure is a two-step
process in which one cluster species at a time is excited
with the light from a laser and is then ionized with light
from a second laser. This process, called resonant twophoton ionization, is highly selective if the clusters being
separated have moderately different absorption spectra.
Since this is frequently the case, the method is quite powerful. As the experimenter varies the wavelength of the first
exciting laser, a spectrum is produced that includes those
wavelengths of light that excite the cluster. If the wavelength of the second ionizing laser is varied, the method
also yields the ionization potential, which is the minimum
energy that the photon in the ionizing beam must possess
in order to knock an electron out of the cluster. Such data
help to reveal the forces that bind the cluster together and
give some indication of how the cluster will react with
atoms, molecules, or other clusters.
Computer Simulation of Cluster Behaviour

A powerful tool for studying clusters is computer simulation of their behaviour. If the nature of the forces between
the individual atoms or molecules in a cluster is known,
then one can construct a computer model that represents
the behaviour of those atoms or molecules by solving the
239
equations of motion of the cluster. To describe the cluster

in terms of classical mechanics, the Newtonian equations
of motion are solved repeatedlynamely, force equals
mass times acceleration, in which the forces depend on
the instantaneous positions of all the particles. Hence,
these equations are simultaneous, interlinked equations;
there is one set of three (for the three instantaneous coordinates of each particle) for each atom or molecule. The
results can take one of three forms: (1) the positions and
coordinates of the atoms, given in tables, (2) the average
properties of the entire cluster, or (3) animations. Tables
are too cumbersome for most purposes, and specific average properties are frequently what the investigator seeks.
Animated sequences show the same content as the tables
but far more efficiently than extensive tables do. In fact,
animations sometimes reveal considerably more than is
expected by scientists.
It is also possible to construct computer models of
clusters based on quantum mechanics instead of Newtons
classical mechanics. This is especially appropriate for clusters of hydrogen and helium, because the small masses of
their constituent atoms make them very quantumlike in
the sense that they reveal the wavelike character that all
matter exhibits according to quantum mechanics. The
same kinds of data and inferences can be extracted from
quantum mechanical calculations as from classical ones,
but the preparation and visualization of animations for
such clusters are much more demanding than their classical mechanical counterparts.
struCture
The abundance distributions for several kinds of clusters
show that there are certain sizes of clusters with exceptional stability, analogous to the exceptional stability of
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7 Clusters
the atoms of the inert gases helium, neon, argon, krypton,

and xenon and of the so-called magic number nucleii.e.,
the sequence of unusually stable atomic nuclei beginning
with the -particle, or helium nucleus. Such unusual stability suggests that its interpretation should be associated
with the closing of some kind of shell, or energy level. The
overall structure that determines the clusters stability is
generally called its shell structure.
Clusters with Icosahedral Structures

Clusters of atoms bound by van der Waals forces or by other
simple forces that depend only on the distance between
each pair of atoms have unusual stability when the cluster
has exactly the number of atoms needed to form a regular icosahedron. The first three clusters in this series have,
respectively, 13, 55, and 147 atoms. In the 13-atom cluster, all but one of the atoms occupy equivalent sites. The
55-atom cluster in this series consists of a corewhich is
just the 13-atom icosahedronplus 12 more atoms atop
the first three complete icosahedral structures of 13, 55, and 147 particles. these
are the structures taken on by clusters of 13, 55, and 147 atoms of neon, argon,
krypton, and xenon, for example. Copyright Encyclopdia Britannica;
241
the 12 vertices of the icosahedron and 30 more atoms, one

in the centre of each of the 30 edges of the icosahedron.
The 147-atom cluster consists of a 55-atom icosahedral
core, 12 more atoms at the vertices of the outermost shell,
one atom in the centre of each of the 20 faces, and two
atoms along each of the 30 edges between the vertices.
The shell structure that provides special stabilities in this
class of clusters is determined by the individual stabilities
of the shells of the atoms themselves.
Clusters of Simple Metal Atoms

A different kind of extraordinary stability manifests itself
in clusters of simple metal atoms. The shell structure for
this class of clusters is determined by the electrons and the
filling of those shells that have energy states available to
the electrons. The numbers of electrons corresponding to
closed electron shells in metal clusters are 8, 20, 40, 58, . . . .
The electron structure can be modeled by supposing that
the positively charged cores consisting of the protons and
inner-shell electrons of all the clusters atoms are smeared
out into a continuous, attractive background, while the
valence, or outer-shell, electrons are delocalized (i.e.,
shared among all atoms in the cluster). The electron environment is much like a well or pit with a flat bottom and
a moderately steep wall. The determination of the energy
states available for electrons in such a simplified model
system is relatively easy and gives a good description of
clusters of more than about eight or nine alkali atoms
i.e., lithium, sodium, potassium, rubidium, or cesium. The
single valence, or outer-shell, electron of each alkali atom
is treated explicitly, while all the others are considered
part of the smeared-out core. Since each alkali atom has
only one valence electron, the unusually stable clusters
242
7 Clusters
of alkalis consist of 8, 20, 40, . . . atoms, corresponding

to major shell closings. This model is not as successful in
treating metals such as aluminum, which have more than
one valence electron.
Network Structures
Still another kind of particularly stable closed shell occurs
in clusters sometimes called network structures. The
best-known of these is C60, the 60-atom cluster of carbon
atoms. In this cluster the atoms occupy the sites of the 60
equivalent vertices of the soccer ball structure, which can
be constructed by cutting off the 12 vertices of the icosahedron to make 12 regular 5-sided (regular pentagonal)
faces. The icosahedron itself has 20 triangular faces; when
its vertices are sliced off, the triangles become hexagons.
The 12 pentagons share their edges with these 20 hexagonal faces. No two pentagons have any common edge in
this molecule or cluster (C60 may be considered either).
The resulting high-symmetry structure has been named
buckminsterfullerene, after R. Buckminster Fuller, who
advocated using such geometric structures in architectural design.
Other network compounds of carbon are also known.
To form a closed-shell structure, a network compound
of carbon must have exactly 12 rings of 5 carbon atoms,
but the number of rings of 6 carbon atoms is variable.
Shells smaller than C60 have been discovered, but some
of their constituent pentagons must share edges; this
makes the smaller network compounds less stable than
C60. Shells larger than C60, such as C70, C76, and C84, are
known and are relatively stable. Even tubes and onions
of concentric layers of carbon shells have been reported
in observations made with modern electron microscopes
243
the structure of C60, buckminsterfullerene. Copyright Encyclopdia

Britannica; rendering for this edition by Rosen Educational Services
known as scanning tunneling microscopes. These devices

are powerful enough to reveal images of extremely small
clusters and even individual foreign atoms deposited on
clean surfaces.
The network compounds of carbon, which make up
the class called fullerenes, form compounds with alkali
244
7 Clusters
and other metals. Some of these compounds of fullerenes

combined with metals, such as K3C60, become superconductors at low temperatures; that is to say, they lose all
resistance to electric current flow when they are cooled
sufficiently. The class of network compounds as a group
had been imagined from time to time, but only in the late
1980s were they realized in the laboratory and shown to
have closed-shell network structures.
PhysiCal ProPerties
Clusters share some of the physical properties of bulk
matter, a few of which are rather surprising. Clusters of
all substances except helium and possibly hydrogen are
solidlike at low temperatures as expected. The atoms
or molecules of a cluster remain close to their equilibrium positions, vibrating around these positions in
moderately regular motions of small amplitude. This is
characteristic of all solids; their atoms are constrained
to stay roughly in the same position at all times. In a liquid or a gas, the atoms or molecules are free to wander
through the space accessible to the substance. A gas or
vapour has so much empty space relative to the volume
occupied by the particles that the particles move almost
unhindered, colliding only occasionally with other particles or with the walls of the container. A liquid is typically
almost as dense as a solid but has some empty spaces into
which the atoms or molecules can easily move. Hence,
the particles of a liquid can diffuse with moderate ease.
(Water is an exception; its density as a liquid is higher
than its density as ice, because ice has an unusually open
structure in comparison with most solids, and this open
structure collapses when ice turns to water.) Clusters can
be liquidlike if they are warm enough, but typically the
245
temperatures at which clusters can become liquid are

much lower than the melting points of the corresponding
bulk solids. If temperatures are measured on the Kelvin
scale, small clusters become liquidlike at temperatures of
roughly half the bulk melting temperatures. For example,
solid argon melts at approximately 80 K (190 C,
or 320 F), while small clusters of argon become liquid at
about 40 K (230 C, or 390 F).
Liquid and Solid Phases

Some clusters are expected to show a gradual transition from solidlike to liquidlike, appearing slushy in the
temperature range between their solidlike and liquidlike
zones. Other clusters are expected to show, as seen in
computer simulations, distinct solidlike and liquidlike
forms that qualitatively resemble bulk solids and liquids
in virtually every aspect, even though they may exhibit
quantitative differences from the bulk. Solid clusters,
for example, show virtually no diffusion, but the particles of a liquid cluster can and do diffuse. The forces
that hold a particle in place in a solid cluster are strong,
comparable to those of a bulk solid; but those in a liquid cluster include, in addition to forces comparable in
strength to those in solids, some forces weak enough to
allow a particle to wander far from its home base and find
new equilibrium positions. Those same weak forces are
responsible for making a liquid cluster compliant; that
is, weak forces allow the liquid to accommodate any new
force, say, a finger inserted into water. Ice will not yield
to such an intruding force, but when a finger is placed
into liquid water, the water molecules move aside under
the force of the finger. This is much like the behaviour
of a bulk liquid. The greatest differences between bulk
246
7 Clusters
solids and liquids and solid and liquid clusters arise from
the fact that a large fraction of the particles of a cluster
are on its surface. As a result, the particle mobility that
characterizes liquids and enables them to exhibit diffusion and physical compliance is enhanced in a cluster,
for the cluster can easily expand by enlarging the spaces
between particles and can also transfer particles from
its interior to its surface, leaving vacancies that enhance
the mobility of the interior particles. The large surface
area, together with the curved shape of the clusters
surface, make it easier for particles to leave a cluster
than to leave the flat surface of a bulk liquid or solid.
An important consequence is that the vapour pressure
of a cluster is higher than the vapour pressure of the
corresponding bulk, and accordingly the boiling point
of a liquid clusteri.e., the temperature at which the
vapour pressure of a liquid is equal to the pressure of the
surrounding atmosphereis lower than that of the corresponding bulk liquid. The vapour pressure of clusters
decreases with increasing cluster size, while the boiling
point increases.
Perhaps the greatest difference between clusters and
bulk matter with regard to their transformation between
solid and liquid is the nature of the equilibrium between
two phases. Bulk solids can be in equilibrium with their
liquid forms at only a single temperature for any given
pressure or at only a single pressure for any given temperature. A graph of the temperatures and pressures
along which the solid and liquid forms of any given substance are in equilibrium is called a coexistence curve.
One point on the coexistence curve for ice and liquid
water is 0 C (32 F) and one atmosphere of pressure. A
similar curve can be drawn for the coexistence of any two
bulk phases, such as liquid and vapour; a point on the
247
coexistence curve for liquid water and steam is 100 C

(212 F) and one atmosphere of pressure. Clusters differ
sharply from bulk matter in that solid and liquid clusters of the same composition are capable of coexisting
within a band of temperatures and pressures. At any chosen pressure, the proportion of liquid clusters to solid
clusters increases with temperature. At low temperatures the clusters are solid, as described above. As the
temperature is increased, some clusters transform from
solid to liquid. If the temperature is raised further, the
proportion of liquid clusters increases, passing through
50 percent, so that the mixture becomes predominantly
liquid clusters. At sufficiently high temperatures all the
clusters are liquid.
No cluster remains solid or liquid all the time; liquidlike clusters occasionally transform spontaneously into
solidlike clusters and vice versa. The fraction of time that
a particular cluster spends as a liquid is precisely the same
as the fraction of clusters of that same type within a large
collection that are liquid at a given instant. That is to say,
the time average behaviour gives the same result as the
ensemble average, which is the average over a large collection of identical objects. This equivalence is not limited
to clusters; it is the well-known ergodic property that is
expected of all but the simplest real systems.
Electric, Magnetic, and Optical Properties

Other significant physical properties of clusters are their
electric, magnetic, and optical properties. The electric
properties of clusters, such as their conductivity and
metallic or insulating character, depend on the substance
and the size of the cluster. Quantum theory attributes
wavelike character to matter, a behaviour that is detectable
248
7 Clusters
only when matter is examined on the scale of atoms and

electrons. At a scale of millimetres or even millionths of
millimetres, the wavelengths of matter are too short to
be observed. Clusters are often much smaller than that,
with the important consequence that many are so small
that when examined their electrons and electronic states
can exhibit the wavelike properties of matter. In fact,
quantum properties may play an important role in determining the electrical character of the cluster. In particular,
as described previously, if a cluster is extremely small, the
energy levels or quantum states of its electrons are not
close enough together to permit the cluster to conduct
electricity.
Moreover, an alternative way to view this situation is
to recognize that a constant electric force (i.e., the kind
that drives a direct current) and an alternating force (the
kind that generates alternating current) can behave quite
differently in a cluster. Direct current cannot flow in an
isolated cluster and probably cannot occur in a small cluster even if it is sandwiched between slabs of metal. The
current flow is prohibited both because the electrons that
carry the current encounter the boundaries of the cluster
and because there are no quantum states readily available
at energies just above those of the occupied states, which
are the states that must be achieved to allow the electrons
to move. However, if a field of alternating electric force
is applied with a frequency of alternation so high that
the electrons are made to reverse their paths before they
encounter the boundaries of the cluster, then the equivalent of conduction will take place. Ordinary 60-cycle
(60-hertz) alternating voltage and even alternations at
radio-wave frequencies switch direction far too slowly to
produce this behaviour in clusters; microwave frequencies
are required.
249
Magnetic properties of clusters, in contrast, appear

to be rather similar to those of bulk matter. They are not
identical, because clusters contain only small numbers of
electrons, which are the particles whose magnetic character makes clusters and bulk matter magnetic. As a result,
the differences between magnetic properties of clusters
and of bulk matter are more a matter of degree than of
kind. Clusters of substances magnetic in the bulk also tend
to be magnetic. The larger the cluster, the more nearly
will the magnetic character per atom approach that of the
bulk. The degree of this magnetic character depends on
how strongly the individual electron magnets couple to
each other to become aligned in the same direction; the
larger the cluster, the stronger is this coupling.
The optical properties of weakly bound clusters are
much like those of their component atoms or molecules;
the small differences are frequently useful diagnostics of
how the cluster is bound and what its structure may be.
Optical properties of metal clusters are more like those of
the corresponding bulk metals than like those of the constituent atoms. These properties reveal which cluster sizes
are unusually stable and therefore correspond to magicnumber sizes. Optical properties of covalently bound
clusters are in most casese.g., fullerenesunlike those
of either the component atoms or the bulk but are important clues to the structure and bonding of the cluster.
Chemical Properties
The chemical properties of clusters are a combination
of the properties of bulk and molecular matter. Several
kinds of clusters, particularly those of the metallic variety, induce certain molecules to dissociate. For example,
hydrogen molecules, H2, spontaneously break into two
250
7 Clusters
hydrogen atoms when they attach themselves to a cluster of iron atoms. Ammonia likewise dissociates when
attaching itself to an iron cluster. Similar reactions occur
with bulk matter, but the rate at which such gases react
with bulk metals depends only on how much gaseous reactant is present and how much surface area the bulk metal
presents to the gas. Metal powders react much faster
than dense solids with the same total mass because they
have much more surface area. Small and medium-size
clusters, on the other hand, show different reactivities
for every size, although these reactivities do not vary
smoothly with size. Furthermore, there are instances,
such as reactions of hydrogen with iron, in which two
different geometric forms of clusters of a single size have
different reaction rates, just as two different molecules
with the same elemental composition, called chemical
isomers, may have different reaction rates with the same
reactant partner. In the case of molecules, this is not surprising, because different isomers typically have quite
different structures, physical properties, and reactivities
and do not normally transform readily into one another.
Isomers of clusters of a specific chemical composition,
however, may well transform into one another with moderate ease and with no excessive increase in energy above
the amount present when they formed. If the reaction
releases energy (i.e., it is exothermic) in sufficient quantity to transform the cluster from solid to liquid, a cluster
may melt as it reacts.
Some of the interesting chemistry of clusters is set in
motion by light. For example, light of sufficiently short
wavelength can dissociate molecules that are captured
in the middle of a cluster of nonreactive atoms or molecules. A common question is whether the surrounding
molecules or atoms form a cage strong enough to prevent
251
the fragment atoms from flying apart and from leaving

the cluster. The answer is that, if there are only a few surrounding atoms or molecules, the fragments escape their
initial cage, and, if the energy of the light is high enough,
at least one of the fragments escapes. On the other hand,
if there are enough nonreacting cage atoms or molecules
in the cluster to form at least one complete shell around
the molecule that breaks up, the cage usually holds the
fragments close together until they eventually recombine.
A related sort of reaction, another example of competition between a particles attempt to escape from a
cluster and some other process, occurs if light is used to
detach an excess electron from a negative ion in the middle of an inert cluster. If, for example, light knocks the
extra electron off a free, negatively charged bromine molecule, Br2-, the electron of course escapes. If the charged
molecule is surrounded by a few inert molecules of carbon
dioxide (CO2), the electron escapes almost as readily. If 10
or 15 CO2 molecules encase the Br2-, the electron does not
escape; instead, it loses its energy to the surrounding molecules of CO2, some of which boil off, and then eventually
recombines with the now neutral bromine molecule to
re-form the original Br2-.
The chemical properties of fullerenes and other network compounds have become a subject of their own,
bridging molecular and cluster chemistry. These compounds typically react with a specific number of other
atoms or molecules to form new species with definite
compositions and structures. Compounds such as K3C60
mentioned previously have the three potassium atoms
outside the C60 cage, all as singly charged ions, K+, and
the ball of 60 carbon atoms carries three negative charges
to make the entire compound electrically neutral. Other
compounds of C60, such as that made with the metal
252
7 Clusters
lanthanum, contain the metal inside the carbon cage,

forming a new kind of substance. It is possible to add or
take away hydrogen atoms from C60 and its larger relatives, much as hydrogen atoms can be added or removed
from some kinds of hydrocarbons; in this way some of
the chemistry of this class of clusters is similar to classical
organic chemistry.
One of the goals of cluster science is the creation of
new kinds of materials. The possible preparation of diamond films is one such application; another example is
the proposal to make so-called superatoms that consist of
an electron donor atom in the centre of a cluster of electron acceptors; the fullerene clusters containing a metal
ion inside the cage seem to be just such a species but with
much more open structures than had been previously
envisioned. Molecular electronics is another goal; in this
technology clusters would be constructed with electrical
properties much like those of transistors and could be
packed together to make microcircuits far smaller than
any now produced. These applications are still theoretical, however, and have not yet been realized.
Clusters do indeed form a bridge between bulk and
molecular matter. Their physical and chemical properties
are in many instances unique to their finely divided state.
Some examples of clusters, such as the network clusters
of carbon, are new forms of matter. Nevertheless, such
clusters, particularly the small and middle-size ones, not
only exhibit behaviours of their own but also provide new
insights into the molecular origins of the properties of
bulk matter. They may yield other new materialse.g.,
possibly far more disordered, amorphous glasslike substances than the glasses now in common useand at the
same time give rise to deeper understanding of why and
how glasses form at all.
253
Conclusion
Although basic ideas about matter trace back to Newton
and even earlier to Aristotles natural philosophy, further
understanding of matter, along with new puzzles, began
emerging in the early 20th century. Einsteins theory of
special relativity (1905) shows that matter (as mass) and
energy can be converted into each other according to the
famous equation E=mc2, where E is energy, m is mass, and
c is the speed of light. This transformation occurs, for
instance, during nuclear fission, in which the nucleus of a
heavy element such as uranium splits into two fragments
of smaller total mass, with the mass difference released as
energy. Einsteins theory of gravitation, also known as his
theory of general relativity (1916), takes as a central postulate the experimentally observed equivalence of inertial
mass and gravitational mass and shows how gravity arises
from the distortions that matter introduces into the surrounding space-time continuum.
The concept of matter is further complicated by quantum mechanics, whose roots go back to Max Plancks
explanation in 1900 of the properties of electromagnetic
radiation emitted by a hot body. In the quantum view,
elementary particles behave both like tiny balls and like
waves that spread out in spacea seeming paradox that
has yet to be fully resolved. Additional complexity in the
meaning of matter comes from astronomical observations
that began in the 1930s and that show that a large fraction
of the universe consists of dark matter. This invisible
material does not affect light and can be detected only
through its gravitational effects. Its detailed nature has
yet to be determined, but it may be an as yet undiscovered
elementary particle.
On the other hand, through the contemporary search
for a unified field theory, which would place three of the
254
7 Clusters
four types of interactions between elementary particles

(the strong force, the weak force, and the electromagnetic
force, excluding only gravity) within a single conceptual
framework, physicists may be on the verge of explaining
the origin of mass. Although a fully satisfactory grand unified theory (GUT) of physics has yet to be derived, one
component the electroweak theory of Sheldon Glashow,
Abdus Salam, and Steven Weinberg (who shared the 1979
Nobel Prize for Physics for this work)predicts that an
elementary subatomic particle known as the Higgs boson
imparts mass to all known elementary particles. There
is as yet no experimental evidence that the Higgs boson
exists, however, and physicists are eager to search for it,
using the Large Hadron Collider, which is the most powerful particle accelerator available.
255
Glossary
amorphous solid Any noncrystalline solid in which the
atoms and molecules are not organized in a definite
lattice pattern.
aqueous Made from, with, or by water.
coefficient Any of the factors of a product considered in relation to a specific factor; specifically, a
constant factor of a term as distinguished from a
variable.
colligative Depending on the number of particles (as
molecules) and not on the nature of the particles.
colloid A substance that consists of particles dispersed
throughout another substance but whose particles
are incapable of passing through a semipermeable
membrane.
covalent bond The interatomic linkage that results
from the sharing of an electron pair between two
atoms, arising from the electrostatic attraction of
their nuclei for the same electrons.
critical point The set of conditions under which a liquid
and its vapour become identical.
diffusion coefficient The constant of proportionality
between the flow of a material and the gradient of its
concentration.
diffusion thermoeffect The physics effect in which an
imposed concentration difference causes a temperature difference to develop.
dipole A pair of equal and opposite electric charges
or magnetic poles of opposite sign separated by a
distance.
256
7 Glossary
eutectic The one mixture of a set of substances able to

dissolve in one another as liquids that, of all such mixtures, liquefies at the lowest temperature.
fugacity A measure of the tendency of a component
of a liquid mixture to escape, or vaporize, from the
mixture.
immiscible Incapable of mixing or attaining
homogeneity.
lepton Any member of a class of subatomic particles
that respond only to electromagnetic, weak, and gravitational forces, but not by strong force.
manometer An instrument for measuring the pressure
of gases and vapors.
mole A standard scientific unit for measuring large quantities of very small entities such as atoms, molecules,
or other specified particles.
osmosis The diffusion of a solvent through a semipermeable membrane.
polymer A chemical compound or mixture of compounds formed by polymerization and consisting
essentially of repeating structural units.
radiometer A four-vaned mill that spins when light is
absorbed by the vanes.
thermal transpiration The situation in which, given
equal initial pressure, gas will flow from the lowtemperature side to the high-temperature side,
causing the high-temperature pressure to increase.
thermodynamics The science of the relationship
between heat, work, temperature, and energy.
viscosity A matter transport property characterized by
the resistance to flow.
257
Bibliography
Phases
Gerhard L. Salinger and Francis Weston Sears,
Thermodynamics, Kinetic Theory, and Statistical
Thermodynamics (1975), is a classic introduction. A
detailed application of thermodynamic principles to
phases, phase changes, and phase diagrams is given in
Mats Hillert, Phase Equilibria, Phase Diagrams, and Phase
Transformations: Their Thermodynamic Basis (1998).
Works focusing on phase equilibria in geology and
petrology include W.G. Ernst, Petrologic Phase Equilibria
(1976), a concise introduction to phase equilibria that
assumes some knowledge of thermodynamics; Ernest G.
Ehlers and Harvey Blatt, Petrology: Igneous, Sedimentary,
and Metamorphic (1982), an introduction to phase equilibria of petrologic systems; and Ernest G. Ehlers, The
Interpretation of Geological Phase Diagrams (1972, reprinted
1987), which provides step-by-step nonmathematical procedures for understanding phase diagrams. A more recent
work is Thomas M. Will, Phase Equilibria in Metamorphic
Rocks: Thermodynamic Background and Petrological
Applications (1998).
Gases
Three excellent introductions to the kinetic theory of
gases at an elementary level are Joel H. Hildebrand,
An Introduction to Molecular Kinetic Theory (1963, reissued 1966); Sidney Golden, Elements of the Theory of
258
Bibliography
Gases (1964); and Gerhard L. Salinger and Francis W.

Sears, Thermodynamics, Kinetic Theory, and Statistical
Thermodynamics (1975). An accessible popular work that
touches some of these issues is Hans Christian von
Baeyer, Warmth Disperses and Time Passes: A History of
Heat (1999; originally published as Maxwells Demon: Why
Warmth Disperses and Time Passes, 1998).
Books that focus on historical development include
Stephen Brush (ed.), Kinetic Theory, 3 vol. (196572), a
set of famous historical papers along with introductory
commentaries and summaries by the editor; Stephen
Brush, The Kind of Motion We Call Heat: A History of the
Kinetic Theory of Gases in the 19th Century, 2 vol. (1976, reissued 1986), a thorough historical account without much
mathematics, and Statistical Physics and the Atomic Theory
of Matter: From Boyle and Newton to Landau and Onsager
(1983), which requires a thorough scientific background;
Elizabeth Garber, Stephen Brush, and C.W.F. Everitt
(eds.), Maxwell on Molecules and Gases (1986), a compilation of early writings on the kinetic theory of gases
by the English physicist James Clerk Maxwell; and J.S.
Rowlinson (ed.), J.D. van der Waals: On the Continuity of
the Gaseous and Liquid States (1988), a translation of the
seminal 1873 thesis by the Dutch physicist J.D. van der
Waals, with an excellent introduction by the editor that
surveys modern developments in the theory of liquids
and solutions.
Liquids
A classic survey of the liquid state by a pioneer in the
field is given in J.S. Rowlinson (ed.), J.D. van der Waals:
On the Continuity of the Gaseous and Liquid States (1988),
with an extensive bibliography. J.N. Murrell and E.A.
Boucher, Properties of Liquids and Solutions, 2nd ed. (1994),
259
is a short introduction to the physics and chemistry

of the liquid state. A general approach to the chemical thermodynamics of pure substances and solutions
is given in the classic text Gilbert Newton Lewis and
Merle Randall, Thermodynamics, 2nd ed., rev. by Kenneth
S. Pitzer and Leo Brewer (1961). J.S. Rowlinson and F.L.
Swinton, Liquids and Liquid Mixtures, 3rd ed. (1982), gives
a thorough treatment of the physics of fluids and of the
statistical mechanics of the equilibrium properties of
simple pure liquids and liquid mixtures; the work also
contains a data bibliography and is primarily for researchoriented readers.
More specialized books include John P. OConnell,
John M. Prausnitz, and Bruce E. Poling, The Properties
of Gases and Liquids, 5th ed. (2001), which focuses on the
vapour-liquid transition and evaluates techniques for estimating and correlating properties of gases and liquids,
as well as tabulating the properties of 600 compounds;
and John M. Prausnitz, Ruediger N. Lichtenthaler, and
Edmundo Gomes de Azevedo, Molecular Thermodynamics
of Fluid-Phase Equilibria, 3rd ed. (1998), which is written
from a chemical-engineering point of view.
Those interested in the properties of water from
the physical and chemical standpoint, and in terms of
biological function, will find accessible introductory
descriptions in Sidney Perkowitz, The Rarest Element,
The Sciences, 39:(1): 3438 (Jan./Feb. 1999); and Mark W.
Denny, Air and Water: The Biology and Physics of Lifes
Media (1993).
Crystals
Works on solids in general include Lawrence H. Van
Vlack, Elements of Materials Science and Engineering, 6th
ed. (1989), an elementary textbook; Charles Kittel,
260
Bibliography
Introduction to Solid State Physics, 8th ed. (2005), a standard

college textbook; and Linus Pauling, The Nature of the
Chemical Bond and the Structure of Molecules and Crystals,
3rd ed. (1960, reissued 1989), a classic work on chemical
bonding.
For crystalline solids in particular, Alan Holden and
Phylis Morrison, Crystals and Crystal Growing (1960, reissued 1982), is a readable illustrated treatment; Richard
P. Feynman, The Feynman Lectures on Physics: From Crystal
Structure to Magnetism, vol. 3 (1999), is also highly accessible as a sound recording.
Richard Dalven, Introduction to Applied Solid State
Physics, 2nd ed. (1990), is an intermediate-level textbook
on semiconductors and semiconducting devices.
Books on magnetism include David Jiles, Introduction
to Magnetism and Magnetic Materials, 2nd. ed. (1998);
and Robert C. OHandley, Modern Magnetic Materials:
Principles and Applications (2000).
Fullerenes are reviewed in Wanda Andreoni, The
Physics of Fullerene-Based and Fullerene-Related Materials
(2000); and Mildred S. Dresselhaus, Gene Dresselhaus,
and Phaedon Avouris (eds.), Carbon Nanotubes: Synthesis,
Structure, Properties, and Applications (2001)
Liquid crystals
ed. (1989), an elementary textbook; Charles A. Wert and
Robb M. Thomson, Physics of Solids, 2nd ed. (1970), an
intermediate-level text; Charles Kittel, Introduction to
Solid State Physics, 6th ed. (1986), the standard college
textbook; Neil W. Ashcroft and N. David Mermin, Solid
State Physics (1976), an advanced textbook; George E.
Bacon, The Architecture of Solids (1981), an introduction to
261
bonding and structure; and Linus Pauling, The Nature of

the Chemical Bond and the Structure of Molecules and Crystals,
3rd ed. (1960, reissued 1989), the classic reference work
on chemical bonding.
The history of liquid crystals in particular is surveyed by H. Kelker, History of Liquid Crystals,
Molecular Crystals and Liquid Crystals, 21(1 and 2):148
(May 1973). The Nobel Prize acceptance lecture by P.G.
de Gennes, Soft Matter, Reviews of Modern Physics,
64(3):645648 ( July 1992), sets liquid crystals in a
broader scientific context. Discussions of special topics in liquid crystals, frequently at a level close to this
book, may be found in the periodical Condensed Matter
News (bimonthly). More technical presentations are
given in P.G. de Gennes, The Physics of Liquid Crystals
(1974); S. Chandrasekhar, Liquid Crystals, 2nd ed. (1992);
and P.S. Pershan, Structure of Liquid Crystal Phases
(1988). Applications of liquid crystals are described
in E. Kaneko, Liquid Crystal TV Displays (1987); and
J. Funfschilling, Liquid Crystals and Liquid Crystal
Displays, Condensed Matter News, 1:1216 (1991).
Amorphous solids
262
Bibliography

On amorphous solids in particular, a lucid introductory text accessible to a nontechnical reader is Richard
Zallen, The Physics of Amorphous Solids (1983), with coverage of structural models for the various classes of
amorphous solids as well as percolation theory, a modern
paradigm for disordered systems. A classic advanced
work is N.F. Mott and E.A. Davis, Electronic Processes in
Non-crystalline Materials, 2nd ed. (1979), which features
many of the theoretical contributions of Nobel Laureate
coauthor Mott. A text providing a thorough treatment
of oxide glasses is J. Zarzycki, Glasses and the Vitreous
State (1991; originally published in French, 1982). A reference work with wide coverage of recent research topics,
including detailed treatment of chalcogenide glasses,
is S.R. Elliott, Physics of Amorphous Materials, 2nd ed.
(1990). A comprehensive collection of detailed reviews
is contained in R.W. Cahn, P. Haassen, and E.J. Kramer
(eds.), Materials Science and Technology, vol. 6, Glasses and
Amorphous Materials, ed. by J. Zarzycki (1991), including
coverage of glass technology, formation, and structure,
oxide glasses, chalcogenide glasses, metallic glasses,
polymeric glasses, and the optical, electric, and mechanical properties of glasses. Amorphous silicon is treated
in detail in another work, R.A. Street, Hydrogenated
Amorphous Silicon (1991).
Quasicrystals
263

Introductions to quasicrystals in particular are
available in David R. Nelson, Quasicrystals, Scientific
American, 255(2):4351 (August 1986); Peter W. Stephens
and Alan I. Goldman, The Structure of Quasicrystals,
Scientific American, 264(4): 4447, 5053 (April 1991);
and P.J. Steinhardt, Icosahedral Solids: A New Phase
of Matter?, Science, 238(4831): 124247 (Nov. 27, 1987).
Martin Gardner, Mathematical Games, Scientific
American, 236(1):110112, 115121 (January 1977), discusses
Penrose tilings and their remarkable properties. More
technically detailed works are D.P. DiVencenzo and P.J.
Steinhardt (eds.), Quasicrystals: The State of the Art (1991);
and the series Aperiodicity and Order, ed. by Marko V. Jari
(1988 ).
Plasma
Yaffa Eliezer and Shalom Eliezer, The Fourth State of
Matter: An Introduction to the Physics of Plasma, 2nd ed.
(2001), is a useful starting point for general readers.
More advanced texts, some with applications in nuclear
fusion and in terrestrial plasmas, include Francis F. Chen,
Introduction to Plasma Physics and Controlled Fusion (1984);
Michael C. Kelley and Rodney A. Heelis, The Earths
Ionosphere: Plasma Physics and Electrodynamics (1989); R.J.
Goldston and P.H. Rutherford, Introduction to Plasma
264
Bibliography
Physics (1995, reissued 2000); and Masahiro Wakatani and

Kyoji Nishikawa, Plasma Physics: Basic Theory with Fusion
Applications, 3rd rev. ed. (2000), which begins at an introductory level.
Overviews of nuclear fusion efforts involving plasmas include Ruth Howes and Anthony Fainberg (eds.),
The Energy Sourcebook: A Guide to Technology, Resources,
and Policy (1991); and National Research Council (U.S.),
Fusion Science Assessment Committee, An Assessment
of the Department of Energys Office of Fusion Energy
Sciences Program (2001). An accessible description of one
approach to fusion energy production is Gerald Yonas,
Fusion and the Z Pinch, Scientific American, 279(2):
4045 (August 1998).
Robert H. Eather, Majestic Lights: The Aurora in
Science, History, and the Arts (1980), is a broad treatment
of the aurora, with numerous illustrations. An accessible
account of research on the solar plasma is given in Robert
Irion, Our Tortured Star, New Scientist, 162(2184): 4448
(May 1, 1999).
Clusters
Michael A. Duncan and Dennis H. Roubray,
Microclusters, Scientific American, 261(6):110115
(December 1989), provides a general introduction and
survey for nonscientists. Works presenting the results
of recent research include R. Stephen Berry, When
the Melting and Freezing Points Are Not the Same,
Scientific American, 263(2): 6872, 74 (August 1990), written for nonscientists, a description of the melting and
freezing of clusters and their relation to bulk melting
and freezing; and several collections of conference proceedings: P. Jena, B.K. Rao, and S.N. Khanna (eds.),
265
Physics and Chemistry of Small Clusters (1987), covering a

wide variety of topics within cluster science; S. Sugano,
Y. Nishina, and S. Ohnishi (eds.), Microclusters (1987); G.
Scoles (ed.), The Chemical Physics of Atomic and Molecular
Clusters (1990), at the graduate-student level; S. Sugano,
Microcluster Physics (1991), accessible to scientifically literate readers; and Zeitschrift fr Physik, part D, vol. 19 and
20 (1991) and vol. 26 (1993), the proceedings of the international conferences on small particles and inorganic
clusters held in 1990 and 1992, respectively.
266
Index
A
ablation, 238
absorption, explanation of, 74
activity, 84
activity coefficients, 84, 85, 98,
100102, 104, 106, 107, 110
Alfvn, Hannes, 199
Alfvn waves, 211, 212, 213
alloys, explanation of, 127129
amorphous/noncrystalline solids
atomic-scale structure of,
171175
and distinction between
crystalline solids, 165168
preparation of, 168171
properties and applications of,
176183
Ampre, Andr-Marie, 199
Andrews, Thomas, 21
anions, 127, 136, 144
anisotropy, 57
Arrhenius, Svante August,
108, 109
Arthur, John Read, 150
associated and solvated solutions,
explanation of, 106108
athermal solutions, explanation
of, 95, 105106
atomic polarization, 71, 72
atomic weight, explanation of, 80
Avogadro, Amedeo, 25
Avogadros number, 17, 18, 25, 80,

81, 104
azeotrope, 85
B
binary crystals, 120, 125127, 128,
138139, 140, 146, 149
binary systems, 5, 68
birefringence, 153
Bohm, David, 199
boiling point, explanation of,
63, 83
Boltzmann, Ludwig, 42
Boltzmann equation, 52, 53, 54
Boltzmanns constant, 42
Boyle, Robert, 2425, 30
Boyles law, 2425
Bragg diffraction peaks, 188, 190
Bridgman, Percy Williams, 149
Bridgman method, 149
buckminsterfullerene, 243
C
cations, 127, 136, 137, 139, 140, 141
Chapman, Sydney, 37, 49, 50, 52
Charles, Jacques-AlexandreCsar, 25
Charless law, 25
chemical vapour deposition, 150
chromosphere, 220221
267
Clapeyron equation, 6364

Clusius, Klaus, 37
clusters
chemical properties of, 250253
comparison with bulk matter,
231235, 246248, 250
comparison with molecules, 235
computer simulation of
behaviour, 239240
electric, magnetic, and optical
properties of, 248250
explanation of, 2, 230231
with icosahedral structures,
241242
ionization and sorting of,
238239
liquid and solid phases, 246248
network structures, 243245
preparation of, 237238
of simple metal atoms, 242243
coexistence curve, 247248
cohesive energy, 141, 142
colligative properties of solutions, 8690, 109
collision rate of gas molecules,
1314
composition ratios of solutions,
7982
condensation, 6, 20, 21, 24, 54,
58, 62, 78, 85, 112, 113, 166,
169, 170, 237
condensed phase rule, 6
conduction electrons, 140
continuous rotational symmetry, 153
continuum gases, 18, 19
corona, 205, 212, 221
corresponding states, principle
of, 22, 64
Coulomb forces, 9596, 109
covalent bonds, 116, 117, 123, 135,

137140, 141, 142, 144, 229,
230, 231
covalent crystals, 116
critical point, 20, 21, 22, 60, 62,
63, 6467
critical temperature, 19, 20, 21,
22, 63, 64, 66
crystalline solids/crystals
categories of, 119
defects in, 129131
and distinction between
amorphous/noncrystalline
solids, 165168
explanation of, 115
growth of, 144152
structure of, 120135
types of atomic bonds found
in, 116, 135144
crystal pulling, 147149
cyclotron resonance, 207
Czochralski, Jan, 147
D
Dalton, John, 27, 39, 43
Daltons law of partial pressures,
27, 39, 42
Debye, Peter, 110
Debye-Hckel theory, 110
Debye length, 202, 214
dendritic growth, 152
Dickel, Gerhard, 37
diffusion coefficient, 3637
diffusion of gases, 13, 29, 3437,
5051
diffusion thermoeffect, 38
diffusivity of solutions, 90, 9293
dislocation, 130131, 151, 157, 196
distribution coefficient, 75
268
7 Index
Dootson, F.W., 37
drunkards walk concept, 1314
E
effusion, 35, 4344
Einstein, Albert, 1, 254
electrical charge distribution of
solutions, 9698
electrical properties of liquids,
7172
electrolyte solutions, 7577, 81,
108111
electron correlation, 140141
electron cyclotron wave, 213, 226
electron polarization, 71, 72
endothermic solutions, 7778
Enskog, David, 37, 49, 50, 52, 54, 55
enthalpy, 9395, 102, 104
entropy, 9395, 102, 105
epitaxy, 149151
equilibrium properties
of gases, 2329
of solutions, 8286, 109
equimolar countercurrent
diffusion, 35
eutectic, 78
evaporation, 18, 44, 59, 79
excess functions, 100102
exothermic solutions, 7778
extraction, explanation of, 75
F
Faraday, Michael, 198, 199
Faradays law, 217
Fibonacci sequence, 190191, 192
fibre-optic telecommunications,
179180
Ficks law of diffusion, 36
Flory, P.J., 174

formality, 8182
formula weight, explanation of,
8182
free-molecule gases, 1819, 39, 47
Friedel, Georges, 155
froth separation, 79
fugacity, 8384, 89
Fuller, R. Buckminster, 123, 243
fullerenes, 124, 127, 144, 244, 245,
250, 252, 253
G
gases
average speed of molecules,
10, 12, 14, 34, 42, 43
collision rate of molecules, 1314
diffusion of, 13, 29, 3437, 5051
effusion of, 35, 4344
equilibrium properties of, 2329
heat conductivity of, 29, 3334,
4749
intermolecular separation of
molecules, 11, 14, 16
internal energy of, 2829
kinetic theory of, 10, 20,
2829, 30, 32, 34, 37, 3955
mean free path, 1213, 14, 15,
16, 17, 1819, 21, 49, 50, 51, 53
molecular sizes, 1416, 18
thermal diffusion of, 3738, 51, 52
thermal transpiration of, 4445
transport properties of, 9,
2938, 5455
viscosity of, 29, 3032, 33, 34,
4547, 48, 52
Gibbs, J. Willard, 3
Gibbs-Duhem relation/equation, 101, 110
269
internal energy of gases, 2829

interstitials, 129
ion acoustic wave, 211, 213, 214
ionic bonds, 116, 135, 136137, 139,
140, 229, 230, 231
ionic crystals, 116
ionosphere, 198, 205, 206,
223224, 225, 227
Gibbs energy, 94, 101102, 104,

105, 112113
glassblowing, 178
Graham, Thomas, 3032, 35, 44
Grahams law of diffusion, 35, 44
H
heat/thermal conductivity
of gases, 29, 3334, 4749
of metals and alloys, 116
heat/thermal conductivity of
solutions, 90, 9192
Henrys law, 114
heteroepitaxy, 149
homoepitaxy, 149
Hckel, Erich, 110
Hume-Rothery rule, 196
hydrogenated amorphous
silicon, 182
hydrogen bonding
in solutions, 99100, 102,
106, 107
in solids/crystals, 135, 144
J
JET (Joint European Torus), 217
K
Kelvin temperature scale, 27
kinetic theory of gases, 10, 20,
2829, 30, 32, 34, 37, 3955
Knudsen, Martin, 18
Knudsen gases, 18
I
ideal gas equation of state,
2428, 36, 37, 39, 41, 42, 53
ideal solution, explanation of,
83, 102
impurities, 119, 129130, 149
induction forces, 98
insulators, 76, 116, 119, 127, 137,
138139, 141, 150, 177, 179, 181,
196, 229, 230, 231, 233, 234
intermolecular pair potential
function, 68, 69
intermolecular separation of gas
molecules, 11, 14, 16
Landau damping, 214

Langmuir, Irving, 198199, 201, 214
Langmuir waves, 201
latent heat, 58, 59, 63, 65
Laue, Max von, 133
Lehmann, Otto, 161
Levine, Dov, 190, 192, 194
liquid crystals
compounds, 157159
effect of on polarized light,
159161
explanation of, 57, 116, 152
structure and symmetry of,
152157
use of as optoelectronic
displays, 162163
liquid-phase epitaxy, 150151
270
7 Index
liquids
electrical properties of, 7172
molecular structure of, 6770
speed of sound in, 7071
surface tension of, 18, 67
London forces, 9798, 104
long-range order, 118119, 129,
165, 171, 172, 173, 177, 183184,
187188, 190, 194
Lorentz, Hendrik Antoon, 199
Loschmidt, Josef, 17, 35
Loschmidt diffusion tube, 35
Loschmidts number, 1718
mole, explanation of, 11, 80

molecular-beam epitaxy, 150
molecular bonds, 116, 135,
142144
molecular crystals, 116, 124, 143
molecular structure
of liquids, 6770
of solutions, 9598
molecular weight, explanation
of, 80
mole fraction/mole percentage,
80, 82, 84, 85, 87, 101, 104,
111, 114
magnetic glasses, 182183

magnetohydrodynamic instability, 215
magnetohydrodynamic power
generation, 217, 222, 223
magnetosonic wave, 213
magnetosphere, 222, 223, 225, 227
Maxwell, James Clerk, 32, 43, 52,
53, 70, 201, 209
mean free path, 1213, 14, 15, 16,
17, 1819, 21, 49, 50, 51, 53
melting curve, 61, 62, 63
melting point, explanation of, 63
metallic bonds, 116, 135, 140142,
229230, 231
metals
clusters of simple atoms, 242243
and electrical conduction, 71,
116, 140, 226, 230, 234, 248
structures of, 121123
Meyer, O.E., 32
molality, 80, 81, 109, 110
molar heat capacity, 28, 34
molarity, 8081
Narrative of Arthur Gordon Pym,

The, 158159
Newton, Isaac, and Newtons
laws of motion, 1, 39, 40, 43,
70, 240, 254
nonelectrolyte solutions, 7577,
78, 82, 101, 109
nonmetals, 123125
nonpolar molecules, 96, 9798,
104, 108
nuclear fusion, 201, 203, 205, 215,
216217, 219
O
orientation polarization, 71, 72
osmotic pressure, 8890, 108
oxide glasses, properties of,
175176, 178179
P
Parker, Eugene, 221
partial miscibility, 8586
271
Pauli exclusion principle, 137

Pauling, Linus, 193
Penrose, Roger, 191, 194
Penrose pattern, 191192
phase diagrams, 58, 6063
phase rule, 35, 6
phasons, 195
photoionization, 198, 203
photosphere, 220, 221
pinch effect, 214
Pines, David, 199
plasmas
applications of, 216219
containment of, 214215
determination of variables,
208210
extraterrestrial forms of,
219220
formation of, 204206
solar-terrestrial forms of,
220227
waves in, 210214
plastic crystals, 157
Poe, Edgar Allan, 158
polar molecules, 9697, 98
polycrystalline form, explanation of, 118119
polyelectrolytes, 111
polystyrene, 180
power production and plasmas,
216217
precipitates, 130
Q
quasicrystals
discovery of, 183184
elastic properties of, 195
electric properties of, 195196

mechanical properties of, 196
microscopic images of,
184185
origin of order, 193194
quasiperiodicity of, 190
192, 195
symmetry observed in,
192193
translational periodicity and
symmetry, 185188
R
radial distribution function, 68,
6970, 172173
Raoults law, 8485, 8687, 97, 98,
100, 105, 106
regular solutions, explanation of,
95, 102105
Reinitzer, Friedrich, 161
resonant two-photon ionization, 239
Reynolds, Osborne, 45
S
scanning tunneling microscope, 244
seeding, 145146
semiconductors, 116, 119, 127,
130, 138139, 141, 150, 151,
177, 180182, 196, 226
Shechtman, Dan, 183, 184, 188,
193
short-range order, 118, 140141,
166, 172, 173
solar wind, 198, 201, 211, 212, 217,
221223, 227
272
7 Index
solids
basic units of, 116117
classes of, 115
solutions
associated and solvated,
athermal, explanation of, 95,
105106
colligative properties of,
8690, 109
composition ratios of, 7982
electrical charge distribution
of, 9698
electrolyte, 7577, 81, 108111
endothermic, 7778
equilibrium properties of,
8286, 109
exothermic, 7778
hydrogen bonding in solutions, 99100, 102, 106, 107
molecular structure in solutions, 9598
nonelectrolyte solutions,
7577, 78, 82, 101, 109
regular solutions, explanation
of, 95, 102105
transport properties of
solutions, 9093
speed, average, of gas molecules,
10, 12, 14, 34, 42, 43
speed of sound in liquids,
7071
state, equation of, 22, 2428, 29,
36, 37, 39, 41, 42, 5354
Steinhardt, Paul, 190, 192, 194
sublimation curve, 61, 6364
supersaturation, 145, 146
surface tension, 18, 67
suspension, explanation of, 73
T
thermal diffusion of gases, 3738,
51, 52
thermal transpiration, 4445
thermomolecular pressure
difference, 44
Thomson, Joseph John, 198
Tonks, Lewi, 199, 201, 214
toroidal plasmas, 216
Townsend, John Sealy Edward, 198
transport properties
of gases, 9, 2938, 5455
of solutions, 9093
triple point, 6, 27, 60, 61, 6263,
6467
twinning, 130, 193, 194
U
unary systems, 56
unit cell, 120121, 122, 123, 125,
126, 127, 128, 134, 141, 144,
145, 191, 193
V
vacancies, 129
Van Allen radiation belts, 225
van der Waals forces/interactions, 113, 124, 138, 142, 143,
144, 230, 231, 241
vaporization, 56, 64, 65, 85, 87
vapour pressure, 44, 63, 65,
8283, 84, 106, 109110, 113,
114, 247
vapour-pressure curve, 60, 62,
6364, 66
virial equation of state, 54
273
viscosity
of gases, 29, 3032, 33, 34,
4547, 48, 52
of solutions, 9091
volume fraction, 82
weak electrolytes, 7677

whistler, 213
window glass, 178179
xerography, 181
Waals, Johannes D. van der,

2122, 53, 54, 142, 228
water desalinization, 217
wave dispersion, 214
Z
zwitterion, 111
274

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Chapter 1: Matter and Its Phases

Chapter 2: Properties of Gases

Chapter 3: Kinetic Theory of Gases

Deviations from the Ideal Model

Chapter 4: Properties of Liquids

Chapter 5: Liquid Solutions and

Effects of Chemical Interactions

atter is one of the most basic subjects of physics.

The Britannica Guide to Matter

of a gas is increased and the temperature is held constant,

The Britannica Guide to Matter

The Britannica Guide to Matter

Clusters are another form of matter, made up of groups

atter is the material substance that constitutes

The Britannica Guide to Matter

shape of the container that holds them, and gases fill an

7 Matter and Its Phases

of weakly bonded atoms with no long-range periodicity,

The Phase Rule

The Britannica Guide to Matter

theoretical chemist J. Willard Gibbs, whose work changed the face of

7 Matter and Its Phases

number of variables that must be fixed in order to define a

The Britannica Guide to Matter

phases coexist at all points along this curve. Substituting

7 Matter and Its Phases

whose composition is indicated directly below on the

The Britannica Guide to Matter

and in a fixed ratio until the remaining liquid is consumed.

he remarkable feature of gases is that they appear

The Britannica Guide to Matter

collisions are in turn controlled by the forces between the

colliding with another molecule. It has been established

The Britannica Guide to Matter

It is also relatively simple to estimate the average speed

Mean Free Path and Collision Rate

in diameter and 1 metre (39 inches) in lengthcan be used.

The Britannica Guide to Matter

starting point. Gas molecules move in three dimensions,

the product of its cross-sectional area and its length. Every

Since l has been shown to be roughly 2.0 105 cm, d could

The Britannica Guide to Matter

Since it was calculated above that the average separation

Summary of Numerical Magnitudes

The general impression of gas molecules given by these

The Britannica Guide to Matter

at 0 C (32 F) and one atmosphere pressure (2.687 1019

is very long, is also subject to free-molecule effects. Such

The Britannica Guide to Matter

The Britannica Guide to Matter

Nevertheless, van der Waals started a scientific trend

Behaviour and Properties

involved. Compared to the numbers of molecules involved,

The Britannica Guide to Matter

Touching the Spring of the Air . . . . It states that the volume

The Britannica Guide to Matter

robert Boyle. Hulton Archive/Getty Images

partial pressure of species 1 and so on. The total pressure

The Britannica Guide to Matter

Institute of Standards and Technologynamely, 8.314472

of gases in Chapter 3. The following highlights only the

Chapter 1: Matter and Its Phases

Chapter 2: Properties of Gases

Chapter 3: Kinetic Theory of Gases

Deviations from the Ideal Model

Chapter 4: Properties of Liquids

Effects of Chemical Interactions