The Britannica Guide To Matter PDF
The Britannica Guide To Matter PDF
The Britannica Guide To Matter PDF
Contents
Introduction
1
2
3
3
5
9
9
10
39
39
39
43
44
45
47
50
51
11
12
14
16
18
19
22
23
29
26
31
53
53
54
56
58
60
61
60
62
64
67
67
70
73
75
75
76
77
78
79
82
86
90
89
93
93
95
96
122
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
Structure and Symmetry
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
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
xvi
Chapter 1
Matter and
Its Phases
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
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.
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
Chapter 2
Properties
of Gases
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
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
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
7 Properties of Gases
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
7 Properties of Gases
7 Properties of Gases
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
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
7 Properties of Gases
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
7 Properties of Gases
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
7 Properties of Gases
Equilibrium Properties
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
7 Properties of Gases
25
26
7 Properties of Gases
27
28
7 Properties of Gases
Transport Properties
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
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
7 Properties of Gases
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
7 Properties of Gases
7 Properties of Gases
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
41
42
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
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
46
Thermal Conductivity
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
49
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
52
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
Transport Properties
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
55
Chapter 4
Properties
of Liquids
7 Properties of Liquids
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
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7 Properties of Liquids
59
7 Properties of Liquids
7 Properties of Liquids
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.
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7 Properties of Liquids
65
7 Properties of Liquids
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.
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
68
7 Properties of Liquids
69
7 Properties of Liquids
72
Chapter 5
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.
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-).
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)
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Equilibrium Properties
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
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,
86
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.
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)
92
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
95
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
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.
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
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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
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104
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.
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107
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
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109
112
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
116
117
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.
119
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.
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
121
(A)
(B)
(C)
(D)
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
127
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
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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
Encyclopdia Britannica; rendering for this edition by Rosen
Educational Services
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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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.
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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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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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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
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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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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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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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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
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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.
Arrangements of molecules. Copyright Encyclopdia Britannica; rendering for this edition by Rosen Educational Services
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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
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Chapter 7
Amorphous Solids
and Quasicrystals
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
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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
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Atomic-Scale Structure
The absence of long-range order is the defining characteristic of the atomic arrangement in amorphous solids.
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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
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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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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.
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;
rendering for this edition by Rosen Educational Services
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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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.
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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
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
Plasma
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
202
Plasma
203
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
204
Plasma
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.
206
Plasma
Plasma
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
210
Plasma
Plasma
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
214
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.
215
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
Plasma
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
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
220
Plasma
Plasma
Plasma
Plasma
227
Chapter 9
Clusters
228
7 Clusters
229
230
7 Clusters
231
232
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.
235
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
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.
7 Clusters
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
240
7 Clusters
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;
rendering for this edition by Rosen Educational Services
241
242
7 Clusters
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
244
7 Clusters
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
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
248
7 Clusters
249
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
252
7 Clusters
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
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
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
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
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
Liquid crystals
Works on solids in general include Lawrence H. Van
Vlack, Elements of Materials Science and Engineering, 6th
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
Amorphous solids
Works on solids in general include Lawrence H. Van
Vlack, Elements of Materials Science and Engineering, 6th
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
bonding and structure; and Linus Pauling, The Nature of
the Chemical Bond and the Structure of Molecules and Crystals,
262
Bibliography
Quasicrystals
Works on solids in general include Lawrence H. Van
Vlack, Elements of Materials Science and Engineering, 6th
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
263
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
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
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
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
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
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
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
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
O
orientation polarization, 71, 72
osmotic pressure, 8890, 108
oxide glasses, properties of,
175176, 178179
P
Parker, Eugene, 221
partial miscibility, 8586
271
Q
quasicrystals
discovery of, 183184
elastic properties of, 195
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,
explanation of, 106108
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
xerography, 181
Z
zwitterion, 111
274