In the Classroom
Entropy, Disorder, and Freezing
Brian B. Laird
Department of Chemistry, University of Kansas, Lawrence, KS 66045; *laird@pilsner.chem.ukans.edu
The entropy, S, is one of the most important concepts
in the thermodynamics of chemical systems, but it is also the
most difficult one to understand and to teach. Typically, in
introductory chemistry courses, entropy is introduced as a
measure of‘ “disorder” or “randomness”. Later, this view is
often justified by an appeal to the Boltzmann view of entropy
as a measure of the number of microstates, Ω, consistent with
a given macroscopic state; that is,
S = k ln Ω (1)
where the constant of proportionality, k, is Boltzmann’s
constant. The argument is then made that increasing the
“disorder” in a system corresponds to an increase in Ω, often
with appeals to illustrative examples from the macroscopic
world such as the probability of various poker hands and the
tendency of children’s rooms to become messy.
The Boltzmann entropy can be interpreted within the
context of information theory as a measure of “lack of infor-
mation”—the greater the number microstates consistent with
a system in a given macroscopic state, the less information is
available about the precise microscopic state of that system
at a given instant. (If there is only one microscopic state, say
for a perfect crystal at T = 0, then there is no lack of infor-
mation about the precise microscopic state and the entropy
is zero.) This is, of course, a statistical mechanical view.
Within the context of thermodynamics, one can similarly
define entropy in terms of “lack of constraint” (1) (here a
constraint is any restriction, internal or external, placed on
the number or ranges of the independent macroscopic variables
that are necessary to describe the thermodynamic state of the
system). One could, of course, define disorder as “lack of
information” or “lack of constraint”, but this is (i) unnecessary,
given that more precise descriptors exist (as discussed above),
and (ii) undesirable, since the concept of disorder is so closely
associated with structural disorder that attempting to generalize
the concept can lead to significant misunderstanding in the
classroom, for both students and educators. Some of the prob-
lems associated with the use of entropy as a measure of struc-
tural disorder have been discussed earlier in these pages (2).
The problems in the use of the term disorder to describe
entropy are perhaps most acute in the study of the freezing
transition. Namely, there exist situations where, given a liquid and
a crystal of the same material subject to the same thermodynamic
conditions, the crystal phase has a higher entropy than the
(metastable) liquid. This is in direct contradiction to the usual
assumption regarding entropy and the commonly held concept
of disorder (i.e., structural or topological disorder) because
the crystal exhibits long-range order, which is absent in the
fluid phase. So if this is true, then the usual assumption of
entropy and its relation to structural disorder would not only
be irrelevant in determining entropy differences, it could even
give the wrong answer! Such situations can indeed arise at
high density when packing considerations dominate the
thermodynamics, and the violation of the conventional
wisdom about the relationship of entropy to disorder comes
1388 Journal of Chemical Education • Vol. 76 No. 10 October 1999 • JChemEd.chem.wisc.edu
about because our intuition about this relationship has been
developed primarily at low density where packing is not
important. In the next section, the issues of packing, structural
disorder, and entropy at high density are discussed.
Packing at High Density: Suitcases and Hard-Spheres
A familiar macroscopic example of a system in which the
maximum entropy state at high density is a spatially ordered
state, as opposed to a disordered one, is the suitcase-packing
problem: Imagine packing a suitcase for a trip. If the trip is a
short one, relatively few items are required and, from experi-
ence, when the total volume of items to be packed is much
less than the volume of the suitcase we know that the easiest
way to pack is to randomly toss the items in and shut the
suitcase. Putting the items to be packed in some “ordered”
arrangement requires extra work and the order would most
probably be destroyed during transport. We put this into
statistical mechanical terms by saying that there are far more
ways in which the suitcase can be packed in a “disordered”
arrangement than in an “ordered” one; that is, the disordered
state has a higher entropy than the ordered one. This low-
density case is consistent with the standard paradigm.
Now, suppose instead that the trip is a long one and
many items are required to be packed in the same suitcase.
In this case the volume of the objects to be packed is on the
order of the total volume of the suitcase. This would be a
high-density system. From experience, one knows that if the
items to be packed are randomly tossed into the suitcase it is
impossible to shut the case. Such a configuration is then in-
compatible with the volume constraints of the suitcase. On
the other hand, if the contents are packed in a neat and
ordered arrangement, the suitcase can be closed without
difficulty. We could say then that the number of ordered
“microstates” (i.e., arrangements of suitcase contents) that are
consistent with the given “macroscopic” constraints (i.e., the
fixed volume of the suitcase) is greater than the number of
corresponding disordered states; therefore, an ordered arrange-
ment in our (high-density) suitcase can be said to have a
higher entropy, in the Boltzmann sense, than a structurally
disordered one. The disorder-to-order transition as the suitcase
density is increased can be said to be purely entropy driven,
since energetic concerns do not enter into the analogy. (The
concept of purely entropy-driven transitions is not new and
has been discussed in the physics literature by Frenkel [3].)
A classic molecular model that illustrates this effect is a
system consisting of hard spheres of diameter σ. The interatomic
interaction energy, v(r), of two such particles separated by a
distance r is given by
v(r) = ∞; r<σ
(2)
v(r) = 0 ; r ≥σ
This interaction is a cartoon of real interactions between atoms
and molecules; nevertheless, it is an important model system
because it has been well established that the structure and

dynamics of simple liquids at high density are determined
almost entirely by the repulsive part of the interaction poten-
tial. (The effects of the attractive part of the interaction can
be accounted for by treating them as a small perturbation
about the reference repulsive part, which, in turn, can be well
approximated by a hard sphere of some effective diameter
[4 ].) It is also an important model in introductory and physical
chemistry courses because of its use in motivating the van
der Waals equation of state for real gases. A experimentally
realizable system for which a classical hard-sphere potential is a
nearly exact model can be constructed using monodisperse
polystyrene spheres; the phase behavior of such systems has
been studied (5).
Since the potential energy of any configuration in which
at least two atoms overlap (i.e., are separated by less than σ)
is infinite, only non-overlapping configurations will contribute
and the potential energy will be zero; therefore, the total
internal energy will be purely kinetic. The contribution of
the kinetic energy to the Helmholtz free energy (the “ideal
gas” part) is independent of the specific interaction between
the atoms (at least classically) and is a function of only the
temperature and bulk density. As a consequence, the difference
in Helmholtz free energy, ∆A = ∆U – T∆S, between a hard-
sphere crystal and a fluid at the same density and tempera-
ture must equal {T∆S. If a transition, at fixed T, from fluid
at low density to crystal at high density occurs, then at some
density ∆A must become negative—which can only occur if
∆S = Scrystal – Sfluid becomes positive; that is, at high density
the entropy of the crystal must exceed that of a fluid at equal
temperature and density for a freezing transition to exist in
such a system.
Alder and Wainwright’s demonstration of a freezing
transition for hard spheres into a face-centered cubic crystal
(6 ) was one of the most important early results to come from
computer simulation. Later, a more detailed simulation by
Hoover and Ree (7) determined the phase diagram for such
a system. Figure 1 shows the entropy of the hard-sphere fluid
0.4
[S (fluid) – S (crystal)] / k
0.2
0.0
-0.2
-0.4
0.90 0.95 1.00
Reduced Number Density
Figure 1. The entropy in units of Boltzmann’s constant of the hard-
sphere fluid relative to that of the fcc crystal as a function of re-
duced number density, ρ* = ( N/V ) σ3. Data are taken from Table
III of ref 5.
JChemEd.chem.wisc.edu • Vol. 76 No. 10 October 1999 • Journal of Chemical Education
In the Classroom
relative to that of the fcc crystal as a function of reduced num-
ber density, ρ* = (N/V )σ 3, at fixed (arbitrary) temperature.
(The data to construct this figure were taken from Table III
of ref 5.) From this figure, it is seen that, at high density, the
entropy of the hard-sphere crystal becomes greater than the
entropy of the fluid at the same density and temperature! This
does not, however, lead to a negative latent heat of fusion,
because a Maxwell construction on the Helmholtz free energy
determined by Hoover and Ree yields (reduced) coexistence
densities for the hard-sphere crystal and fluid of ρc* = 1.043
and ρ*f = 0.945, respectively. The latent heat of this transition
would still be positive, since the entropy of the crystal at ρc*
is lower than the entropy of the fluid at ρ*, f but as Figure 1
illustrates, the lower entropy of the crystal at its coexistence
density is not due to the crystal being more ordered, but
instead simply due to the coexistence density of the fluid
being lower than that of the crystal (in this case by about
15%)—in much the same way that the entropy of an ideal
gas sample at high density is less than that of the same sample
at low density.
The relevance of this model to the real world has been
demonstrated by Crawford and Daniels (8) in their experi-
ments on the high-pressure phase diagram of argon. Using a
rough approximation for the temperature dependence of the
effective hard-sphere diameter for argon, they were able to
reproduce their experimental values for the crystal and liquid
molar volumes of argon for a variety of temperatures with
surprising accuracy, given the crude approximations involved.
Thus, one can conclude that, at least for simple systems such
as argon, the freezing transition is driven, as in hard spheres,
by the observed fact that the entropy of the fluid phase is
decreasing much faster as a function of density than that of
the crystalline phase. The attractive forces between the argon
atoms have a small role in determining the temperature
dependence of the solid–liquid phase transition, but it is the
packing constraints associated with the repulsive part of the
potential that determine the existence of the transition. This
is in direct conflict with the usual mechanism of freezing
based on attractive forces that is given in most introductory
chemistry textbooks.
Such entropy-driven phase transitions are not restricted to
freezing. In 1949, Onsager (9) speculated that a collection of
microscopic hard rods would undergo an isotropic–nematic
phase transition at high density. In other words, at low
density the rods (which could be crude models for a liquid-
crystal forming molecule) would be randomly oriented in
space (isotropic phase), but at high density there would be a
preferred orientation relative to some laboratory-fixed axis
(nematic phase). Onsager’s speculation was later confirmed by
computer simulation (10). Real systems for which the hard-
rod system is a good approximation are difficult to construct;
however, there are several examples of a related idealized
system, namely, charged hard-rods (e.g., the tobacco mosaic
virus [11]). Like hard spheres, these hard rods do not interact,
so the existence of such a transition implies that at high
1.05
density the entropy of the nematic phase would be higher
than that of the isotropic one. In the spirit of our suitcase
analogy, the easiest way to arrange the matches in a full (or
nearly full) matchbox so that they all can fit inside is to
order them orientationally—there are more ways of filling
the matchbox with all the matches lined up in (more or less)
1389
In the Classroom
the same direction than with randomly oriented matches.
Again, at high density the spatially ordered phase is seen to
be the one with the higher entropy.
An Easy Demonstration
To illustrate the above concepts, as well as the phenom-
enon of freezing, in the classroom, the following demonstration
is simple and illustrative. This demonstration comes to me
from A. D. J. Haymet, but it may have earlier origins.
Materials Needed
1. 1 bag regular M&M’s or similar disc-shaped candy.
(Ball bearings also work and have the advantage that
they respond better to the shaking process, but they
are not as tasty.)
2. A flat-bottomed glass dish (preferably square) of a size
that fits on the overhead projector. It is a good idea to
use a non-contaminated dish so that the candy can be
eaten by the students later—always a popular side
benefit to the demonstration!
Procedure
Place the glass dish on the overhead projector and place
a few of the candies inside. Shake the dish gently from side
to side to simulate the effect of temperature. At this point
the view on the overhead screen will resemble a 2-D model
of a gas. Begin placing more and more candies into the dish
while continuing the shaking motion. The gas density will
begin to increase until it approaches liquid-like values (NOTE:
for a system of hard spheres or disks there is no true liquid-
to-vapor transition.) At this point the system will still appear
to be spatially disordered. However, as the density is further
increased by continuing to add more candy, there comes a
point when clusters of hexagonal crystals appear that cannot
be dissipated by shaking. These clusters will grow until the
entire candy configuration is crystalline. It is important to
note that this point is below the maximum packing density.
What one has done here is an analog simulation of the
freezing of hard disks!
Summary
In this paper I have argued that the standard assumption
of entropy and disorder is problematic from the standpoint of
1390 Journal of Chemical Education • Vol. 76 No. 10 October 1999 • JChemEd.chem.wisc.edu
giving students a molecular-level understanding of entropy.
First, as discussed in ref 2, using a subjective term like dis-
order (which most students and educators assume refers to
structural disorder) to describe a real, quantitative property
such as entropy leads to genuine confusion when comparing
two systems that are known to differ in entropy. An example
would be two ideal gas samples with identical n, T, and P but
with differing volumes, but for which an assessment of rela-
tive spatial disorder is not a well-defined operation. Second,
as illustrated by the freezing of a system of hard spheres, there
exist systems at high density, where packing considerations
dominate, in which the more ordered phase possesses a higher
entropy than a spatially disordered phase at the same density
and temperature. The greater free volume and local mobility
afforded by the more efficient packing of the ordered phase
overcomes the effect of increased positional ordering in de-
termining the entropy at high density. Such situations have
relevance in the real world, since the structure and dynamics
of a real, simple fluid are determined primarily from the
repulsive part of the interaction, which is well approximated
by a hard-sphere potential.
Acknowledgments
I gratefully acknowledge support from the National Sci-
ence Foundation under Grant CHE-950281 and from the
Petroleum Research Fund under grant PRF#30970-AC. I also
thank the referees for insightful comments and constructive
criticism.
Literature Cited
1. Reiss, H. Methods of Thermodynamics; Dover: New York, 1996.
2. Lowe, J. P. J. Chem. Educ. 1988, 65, 403–406.
3. Frenkel, D. Phys. World 1993, 6, 24–25.
4. Hansen, J. P.; McDonald, I. R. Theory of Simple Liquids, 2nd ed.;
Academic: New York, 1986.
5. Poon, W.; Pusey, P.; Lekkerkerker, H. Phys. World 1996, 9, 27–34.
6. Alder, B. J.; Wainwright, T. E. J. Chem. Phys. 1957, 27, 1208–1209
7. Hoover, W. G.; Ree, F. H. J. Chem. Phys. 1968, 49, 3609–3617.
8. Crawford, R. K.; Daniels, W. B. Phys. Rev. Lett. 1968, 21, 367–369.
9. Onsager, L. Ann. NY Acad. Sci. 1949, 51, 627–659.
10. Frenkel, D. Mol. Phys. 1987, 60, 1–20.
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