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In the Classroom

A Closer Look at Phase Diagrams for the General W


Chemistry Course
Stephen A. Gramsch
Geophysical Laboratory and Center for High Pressure Research, Carnegie Institution of Washington,
5251 Broad Branch Road, NW, Washington, DC 20015; gramsch@gl.ciw.edu

During the year-long course of general chemistry, students CO2 from near ambient pressure and temperature up to the
are introduced to a wide range of physicochemical principles, critical point, and takes place during a cursory treatment of
but there is usually insufficient time to probe some of the solids, liquids, gases, and intermolecular forces. As a result,
more interesting applications of these constructs. Mastering students initial exposure to the concept of equilibrium is
the computational aspects of topics such as stoichiometry, gained much later, mainly through acidbase and solubility
equilibrium, thermodynamics, and kinetics requires a significant product calculations and a discussion of gas-phase chemical
amount of class time as well as out-of-class preparation on reactions, while the fundamental importance of equilibrium
the part of both students and instructors, and indeed, this in science is left largely unaddressed.
time investment is crucial if students are to be successful both Several articles in this Journal have discussed possible
in the general course and in further studies in chemistry. avenues, both in the classroom and in the laboratory, for
Quite often, however, it is the qualitative aspects of the course enriching the traditional presentation of phase diagrams (2).
that make chemistry interesting to students and kindle their A discussion of phase diagrams that focuses on the broad
enthusiasm for science, because it is at these points in the range of temperatures and pressures now accessible in the
development of the subject that they can finally allow them- laboratory can also help by addressing some new and inter-
selves to relax, concentrate on the beauty of the science rather esting applications and by providing a qualitative introduction
than the details of a rather arid calculation, and begin to adopt to the role of equilibrium in determining chemical and physical
their own view of the subject matter rather than that of the behavior.
instructor. In the ongoing debate concerning the structure
of the general chemistry curriculum, it is important to give Equilibrium and the Gibbs Phase Rule
attention to general, qualitative constructs because these often
prove to be the most efficient and useful in illustrating general Historically, a discussion of the phase rule of Gibbs has been
scientific ideas and in linking together different groups of deferred until the physical chemistry course, although there
ideas into a unified framework. is no pedagogically sound reason for not at least introducing
One very important set of physical principles that is often the concept in the first-year course. In fact, the discussion of
severely underrepresented in general chemistry textbooks and the phase rule proper in Findlays classic text (3) is almost
courses, but one that has the potential to tie together a number completely non-mathematical and relies on the common-sense
of lines of inquiry, is embodied in the phase diagrams of one- notion that the greater the number of constraints placed on
component systems. In fact, one of the most active fields of a chemical system of fixed composition, the less freedom the
both basic and applied scientific research over the last half- system has to change its physical state. (For a set of hand-drawn
century has been concerned with the chemical and physical figures whose quality easily surpasses that of any computer-
properties of condensed matter at high pressures (1). Part of generated equivalents, see the 1907 German translation (4 )
the reason for the excitement in the high-pressure research of Findlays first edition.) The mathematical formulation of
community is the fact that variations in pressure can probe these ideas into the expression of the phase rule most useful
fundamental interatomic and intermolecular interactions in for the first year student,
a way that variations in temperature cannot. The PV work
F=CP+2 (1)
done on a chemical system during compression to 1 megabar
(1000 kbar = 1 Mbar = 100 GPa) is on the order of an electron requires only a working definition of components (C), phases
volt, roughly equivalent the energy of a chemical bond. There- (P), and degrees of freedom (F ). In a treatment of unary
fore, dramatic differences in chemical bonding are expected, phase diagrams, the phase rule directly relates the number of
and even routine, at elevated pressures. As the number of new degrees of freedom the system possesses at any point in the
crystalline phases generated at pressures ranging from a few PT space to the number of phases present, since there is no
kilobars to more than two megabars continues to grow, each ambiguity concerning the number of components:
new high-pressure phase tests current theories of structure
F=3P (2)
and bonding, sometimes even challenging long-held ideas
about the way in which quantum mechanics describes inter- For example, at any general (P,T ) point in the phase
atomic interactions. diagram, one not on a coexistence curve or a triple point,
The information concerning structural chemistry and only one phase is present and the system has two degrees
phase equilibria contained in the full phase diagrams of of freedom, suggesting that either P or T may be varied,
common substances is a great deal richer than the general independently or together, and equilibrium may still be
chemistry student is given to believe. Unfortunately, however, maintained along any PT path. Along a coexistence curve,
the discussion of phase diagrams in most general chemistry however, two phases are present, and the system retains only
textbooks is restricted to the PT spaces of only H2O and one degree of freedom. Therefore, if an equilibrium between

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In the Classroom

the two phases is to be maintained, any change in P or T phase boundaries is a direct result of the lack of any substantial
strictly dictates the response in the other intensive variable. interaction (apart from van der Waals forces) between mol-
At a triple point, the system has zero degrees of freedom, and ecules of CO2, even in the solid phases. Phase IV, with an as
although pressure and temperature may be raised either yet unidentified structure, is almost identical to but clearly
independently or together (as in the case of moving from a different from phase III, on the basis of vibrational spectros-
general point or coexistence curve), the system will not be copy (7); a large hysteresis in the vibrational frequencies over
able to maintain equilibrium along any such PT path. If an different closed PT paths prevents even an approximate
equilibrium is to be established away from the triple point, determination of the stability field of this structural modifi-
then the three phases must be reduced to either two (if a cation. A particularly revealing aspect of Figure 1b is the small
coexistence curve is to be followed) or one (if a general point in area taken up by the traditional PT space from Figure 1a;
a one-phase region is to be assumed). This simple description 15 GPa is easily reached in current diamond-cell experiments,
provides an excellent introduction to the concept of equilibrium, and perhaps there are other potentially even more unusual
as well as a visual link to its physical and mathematical solid phases to be formed at still higher pressures. In fact,
representations. evidence from Raman spectroscopy suggests that CO2 adopts
With a discussion of several suitable one-component the structure of quartz at approximately 40 GPa (8). Support
phase diagrams as examples, the elegance of the phase rule can
be readily appreciated and its predictive power appropriately
demonstrated. It should be noted that this type of discussion
also prompts students to forge the link between a physical
principle and its mathematical representation, a way of
thinking that is critical for progress in all scientific disciplines.
The straightforward graphical constructions of one-component
phase diagrams provide a nonthreatening way to introduce
and develop this fundamentally important skill.

Some Illustrative High-Pressure Phase Diagrams


Carbon Dioxide
The first phase diagram most textbooks provide is the
PT diagram of the molecular compound CO2 (Fig. 1a) with
the discussion generally focused on the identification of the
triple point, critical point, and coexistence curves. (It should
be noted to students that plotting pressure on a logarithmic
scale changes the concavity of the coexistence curves, so the
diagrams presented here will be different from those plotted
with linear pressure scales.) Students usually are required to
identify the phases present at various points in the PT space
and also describe how the phases change as the state of the
system moves from one point to another along isobaric or
isothermal paths. Whereas the liquidvapor and solidvapor
coexistence curves terminate at the critical point, the solid
liquid coexistence curve does not terminate in a well-defined
endpoint, but rather continues to higher pressure. The fact
that this is an entirely general feature of one-component phase
diagrams points to the interesting solidsolid and solid
liquid phase equilibria that are possible at high pressure.
Carbon dioxide itself displays two known crystalline
modifications that differ only in a subtle reorientation of the
molecular axes that is sufficient to change the low-pressure
cubic phase to an orthorhombic phase at high pressure (5).
At present, there are also two regions in which two solid forms
appear to be stable (Fig. 1b). It should be noted to students
that this feature of the phase diagram, rather than being at
variance with the phase rule, suggests that still other as yet
unidentified crystalline modifications may also be stable in
these regions (6 ), and that the phase boundaries have yet to
be clearly delineated. Whether these regions can in fact be
determined unambiguously is also an important issue. In any Figure 1. Phase diagrams for CO2, (a) at low pressure and (b) at
case, the Clapeyron equation necessitates that phase boundaries high pressure. Within the resolution of (b), both the triple point and
become vertical as they approach the pressure axis (T = 0 K). the critical point should be at 0 GPa, but they have been displaced
The experimental difficulty associated with establishing these slightly to retain the shape of the coexistence curves from (a).

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In the Classroom

for a non-centrosymmetric, quartz-like CO2 polymorph at


high pressure is provided by the fact that the frequency of
1054-nm laser light incident upon the sample is doubled as
it passes through the pressure cell.
Water
Phase behavior in the water system is perhaps far richer
than that of any other molecular compound as a result of
waters unique hydrogen bonding properties in the bulk,
although this is clearly impossible to discern from the usual
presentation of the phase diagram (Fig. 2a). In fact, the phase
diagram of H2O looks almost identical to that of CO2 in the
region of the critical point, even though the behaviors of these
two molecules at high pressure are dramatically different.
An indication of the interesting phase equilibria possible
in the H2O system at high pressure is given by the negative slope
of the solidliquid coexistence curve. This feature suggests
that, as the temperature of the system is raised slightly at
constant pressure, the applied pressure required to maintain
equilibrium between liquid and solid actually decreases, as
shown schematically in Figure 2b. Since students attempt to
understand the behavior of solids, liquids, and gases from a
kineticmolecular viewpoint, this should be quite surprising,
and indeed counterintuitive, because they are conditioned to
believe that compression of the liquid would be necessary to
reorder the molecules into a crystalline framework. In this
view, then, maintenance of solidliquid equilibrium upon
warming should require more pressure, not less. In the case
of H2O, however, the liquid is denser than the solid, and
increasing the applied pressure at any point along the coex-
istence curve results in melting of the solid rather than solidifi-
cation of the liquid. Students can now readily appreciate that
this phenomenon, responsible for the enjoyment of ice skating
(9), is directly related to the movement of the system away
from a coexistence line (away from solidliquid equilibrium)
that must have a negative slope (ice skating would be very
difficult indeed on dry ice!). Of course, as in the case of CO2,
raising the temperature of the solidliquid H2O system at
equilibrium will cause the solid to melt; it is the pressure
temperaturevolume response of the H2O system at equilibrium
that is truly unique.
Common presentations of the H2O phase diagram, like
those of CO2, do not discuss the absence of a terminal point
in the solidliquid coexistence curve. This is unfortunate,
because the most striking consequences of the hydrogen
bonding properties of water are to be found in the region of
low temperature and high pressure (10), as shown in Figure
2c. It is important to point out that, although plotting the
phase diagram with pressure on a logarithmic scale provides
a clear visualization of the variety of phases present in this
system, it implicitly suggests that it is as easy to raise pressure
by an order of magnitude at 10 GPa as it is at 0.1 GPa. It is,
in fact, very difficult to reach static pressures greater than only
a few GPa without the use of highly specialized diamond anvil
pressure cells. This logarithmic scale allows the critical point
Figure 2. Phase diagrams for the H2O system. (a) Conventional,
to lie off the temperature axis, but it is clear that the conven-
low-pressure phase diagram. (b) Schematic representation of the
tional H2O phase diagram, like that of CO2, occupies only a negatively sloped P-T coexistence curve. (c) Complete phase diagram
very small part of the available PT space. for H2O illustrating extensive polymorphism at high pressure. Ices
Hydrogen bonding gives the ice crystal a large amount of IV and XII are metastable phases and do not appear on this dia-
open space, and with this open space, a great deal of structural gram; stability fields for ices II, IX, and XI are not currently well
flexibility; at high pressure, this leads to the wide variety of defined and are shown as dashed lines.

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In the Classroom

stable to 300 K and 210 GPa, the highest pressure yet


achieved for H2O. In a discussion of intermolecular forces,
it is useful to point out that the richness of the H2O phase
diagram, as compared to the simplicity of the diagram for
CO2, is a result of the strength and flexibility of hydrogen
bonding as opposed to the weakness and nondirectional
nature of van der Waals forces.
Hydrogen
An introduction to bonding in metals usually takes
advantage of the idea that atomic ns and np orbitals on
alkali or alkaline earth metals can overlap to produce a
partially filled energy band. For many years, this concept has
been at the heart of the quest to observe metallic behavior in
hydrogen at high pressure (15), since atomic hydrogen is
isoelectronic with the alkali metals. Studies of the H2 system
at pressures exceeding 100 GPa (1 Mbar) have shown that the
phase diagram is far more complex than originally assumed
(16). In particular, the H2 diagram contains two triple points
and two critical points, as shown in the H2 phase diagram
(Fig. 3). The first triple point is a conventional one, like those
in CO2 and H2O. The second triple point, however, is the
point in PT space at which molecular solids I, II, and III
are in equilibrium. The conventional critical point in the H2
system lies at the terminus of the liquidvapor coexistence
curve, as in CO2 and H2O, and is a boundary that separates
two phases of markedly differing density. At the conventional
critical point, the difference in density between liquid and
vapor disappears, and one fluid is formed; pressure alone will
not condense this fluid because there is no phase boundary
to cross. The second critical point also lies (as it must) at the
terminus of a two-phase coexistence line, but in this case,
the curve separates two molecular solid phases of very slightly
differing density. As pressure and temperature increase along
this coexistence curve, the difference in density between these
two phases decreases, finally vanishing as one solid phase is
formed that is neither I, II, nor III. At still higher pressures,
hydrogen becomes opaque (17), perhaps indicating the onset
Figure 3. Schematic representation of the phase diagram of the H2
of metallic behavior. This phenomenon raises questions similar
system. (a) Full phase diagram. (b) Detail of the pressure region
above 1 Mbar.
to those precipitated by the formation of quartz-like CO2
and the existence of an ice phase with symmetric OH bonds,
discussed above. What changes in electronic structure and
physical properties take place when the contacts between
different phases that exist in the H2O system. In addition to molecules are the same as those between atoms of the same
the equilibrium phases that appear in the phase diagram, molecule? In both the H2O and H2 systems, the individual
metastable cubic ice Ic and tetragonal ice IV can also exist molecules lose their identities when the pressure is high
under certain experimental conditions within the stability fields enough, but in the case of H2, the material could become an
of ices Ih and V, respectively. Recently, two new metastable atomic, metallic solid like one of the alkali metals, whereas
phases have also been discovered: a new liquidus phase appears quartz-like CO2 and symmetric H2O would most likely be
in the region of ice VI (11), and ice XII, a completely new insulating, ionic solids.
structural type characterized by five- and seven-membered
rings held together by hydrogen bonding, exists within the Iron
stability field of ice V (12). The open structure of solid H2O A key feature in geophysical models of the structure of the
can also provide a host for other molecules, as illustrated by earths interior is the nature of the earths core. This problem
the stoichiometric clathrate compound H2H2O, an elegant has received a great deal of attention in recent years, owing
demonstration of the interplay of van der Waals forces and to the importance of the core with respect to the earths
hydrogen bonding in the same crystal (13). Equally surprising magnetic and thermal properties. Students generally subscribe
is the indication of the formation of an ice phase with sym- to the belief that the earths core is molten iron because they
metric OH bonds (no difference in length between the are under the impression that the temperature at the earths
covalent OH bond and the hydrogen bond) throughout the center is hot enough to melt metallic iron. While this is true,
crystal (14 ) at pressures above 60 GPa. This phase remains of course, the pressure dimension cannot be neglected.

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In the Classroom

Figure 4a shows the experimentally determined phase of the earths inner core (P 330 GPa, T 6000 K) (19,
diagram of iron (18). Although it is in some respects still 20), liquid iron transforms to the -phase, as illustrated in
incomplete, the phase diagram of iron emphasizes that, even Figure 4b. In principle, the solidliquid coexistence curve will
though the temperature rises at greater depth than that of the continue to still higher pressure, but the earths geotherm
earths molten iron outer core, the fact that the solidliquid crosses this coexistence curve, thereby defining the outer core
coexistence curve is positively sloped dictates that increasing inner core boundary.
pressure will eventually force the liquid to solidify even as An appreciation for the pressure that exists at the center
the temperature rises (Fig. 4b). At the pressure and temperature of the earth (21) may be brought about by having students
calculate the number of moles of iron in the earths core
(diameter = 1260 km, d = 12.80 g/cm3, compared to 7.87
g/cm 3 at ambient conditions), and then determine the
diameter of an ambient-pressure iron sphere that would
contain this number of moles. At high pressure, the structures
of solids become increasingly governed by the tendency
toward closest-packing of atoms, and in the earths core, the
pressure is apparently high enough to organize this fantastic
number of moles of liquid iron into a solid, crystalline phase!
There is some evidence from computational studies of iron
at high pressure and temperature that the earths core may
be in part an oriented single crystal of (hexagonal closest-
packed) -Fe (22, 23). Reference 23 makes an excellent
classroom supplement that provides an overview of the
important developments taking place in this particular area
of geophysical research.

Concluding Remarks
The use of phase diagrams and other simple physical
constructs can add an intellectually stimulating and mean-
ingful dimension to a discussion of many of the descriptive
aspects of general chemistry. By including in these discussions
the importance of pressure and its influence on structure and
properties, students can gain an appreciation for the concept
of equilibrium even before it is formally addressed through
work in acidbase chemistry, solubility products, or thermo-
dynamics. Likewise, a discussion of phase diagrams that
contains a bit more detail than is conventionally included
provides a useful point of departure during later discussions
of equilibrium topics, particularly thermodynamics. When
provided with a phase diagram, the product of fundamental
theoretical and experimental research, and a discussion of its
physical and chemical relevance, students can begin to make
the connection between the chemistry of atoms and molecules
on the one hand, and the natural world around them on the
other. This is indeed one of the most important aims of the
general chemistry course. A wide variety of similar examples
that can provide the same sort of interdisciplinary flavor
is available, and their applicability is limited only by the
imagination of the instructor.

Acknowledgments
This paper is dedicated to the memory of Professor
Jeremy K. Burdett, whose enthusiasm for the elegant and
powerful ideas of physical chemistry and belief in the ability
of first-year students to appreciate them remains an inspira-
Figure 4. (a) Phase diagram of iron to 120 GPa. (b) Phase diagram tion. I am grateful to Charlie Prewitt, Rus Hemley, and Bob
of iron at temperature and pressure approaching those of the earths Hazen for helpful discussions, and to the NSF Center for High
core. The heavy dashed line represents the P-T profile of the earths Pressure Research, the Geophysical Laboratory, and the
deep interior. Pressures at the mantlecore and inner coreouter Carnegie Institution of Washington for a postdoctoral research
core boundaries are marked with vertical dashed lines. fellowship.

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W
Supplemental Material 7. Olijynk, H.; Jephcoat, A. P. Phys. Rev. 1998, B57, 879.
8. Iota, V.; Yoo, C. S.; Cynn, H. Science 1999, 283, 1510.
Polymerization of simple molecules into extended struc- 9. The relative contributions of friction and pressure to generat-
tures with unexpected features is possible at high pressure, ing a thin film of liquid water for ice skating have been the
where intramolecular bonding and intermolecular contacts subject of some debate. Careful experiments as well as em-
can become indistinguishable. Color images of the structures pirical evidence suggest that the major contribution is provided
of water and carbon dioxide at high pressure are available in by pressure because it is more difficult for the same person to
this issue of JCE Online. In the case of water, a face-centered skate on very cold ice than on ice that is near its melting point.
cubic array of oxygen atoms forms the basis of the proposed See: Loucks, L. F. J. Chem. Educ. 1986, 63, 115. Silberman, R.
symmetric ice H2OX, a polymorph of solid H2O in which J. Chem. Educ. 1988, 65, 186.
the hydrogen bonds are the same length as the covalent OH 10. Hemley, R. J.; Chen, L. C.; Mao, H.-k. Nature 1989, 338,
bonds. For carbon dioxide, the helical arrangement of CO4 638.
tetrahedra is the dominant structural motif of quartzlike car- 11. Chou, I.-M.; Blank, J. G.; Goncharov, A. F.; Mao, H.-k.;
bon dioxide, proposed as a new high temperature, high pres- Hemley, R. J. Science 1998, 281, 809.
sure phase of CO2. 12. Lobban, C.; Finney, J. L.; Kuhs, W. F. Nature 1998, 391, 268.
13. Vos, W. L.; Finger, L. W.; Hemley, R. J.; Mao, H.-k. Phys.
Literature Cited Rev. Lett. 1993, 71, 3150.
14. Goncharov, A. F.; Struzhkin, V. V.; Somayazulu, M. S.;
1. For an introduction to the history of high-pressure research, Hemley, R. J.; Mao, H.-k. Nature 1996, 273, 218.
see: Hazen, R. M. The New Alchemists: Breaking Through the 15. Winger, E; Huntington, H. B. J. Chem. Phys. 1935, 3, 764.
Barriers of High Pressure. Times Books: New York, 1993. 16. Mao, H.-k.; Hemley, R. J. Am. Sci. 1992, 80, 234.
2. Halpern, A. M.; Lin, M. F. J. Chem. Educ. 1986, 63, 38. 17. Mao, H.-k.; Hemley, R. J., Hanfland, M. Phys. Rev. Lett. 1990,
Peckham, G. D.; McNaught, I. J. J. Chem. Educ. 1993, 70, 65, 484.
560. Kildahl, N. K. J. Chem. Educ. 1994, 71, 1052. Lieu, V. 18. Yoo, C. S.; Akella, J.; Campbell, A. J.; Mao, H.-k.; Hemley,
T. J. Chem. Educ. 1996, 73, 837. R. J. Science 1995, 270, 1473. Shen, G.; Heinz. D. L. In Ul-
3. There have been many editions and revisions of this seminal trahigh Pressure Mineralogy: Physics and Chemistry of the Earths
text since it was first published in 1903. See, for example: Deep Interior; Hemley, R. J., Ed.; Reviews in Mineralogy, Vol.
Findlay, A. The Phase Rule and its Applications, 9th ed.; rev. by 37; Mineralogical Society of America: Washington, DC, 1998;
Campbell, A. N.; Smith, N. O.; Dover: New York, 1951; Chap- p 369.
ter 2. 19. Anderson, O. L. J. Geophys. Res. 1990, B13, 2169721707.
4. Findlay, A. Einfhrung in die Phasenlehre und ihre 20. Poirer, J.-P. Introduction to the Physics of the Earths Interior;
Anwendungen (translated by G. Siebert); In Handbuch der Cambridge University Press: New York, 1991.
Angewandten Physikalichen Chemie, Band VI; Bredig, G., Ed.; 21. Mao, H.-k.; Shu, J.; Shen, G.; Hemley, R. J.; Li, B.; Singh,
Johann Ambrosius Barth: Leipzig, Germany, 1907. A. K. Nature 1998, 396, 741.
5. Aoki, K.; Yamawaki, H.; Sakashita, M; Gotoh, Y; Takemura, 22. Stixrude, L.; Cohen, R. E. Science 1995, 267, 1972.
K. Science 1994, 263, 356. 23. Broad, W. J. The Earths Core May Be a Gigantic Crystal Made
6. Lu, R.; Hofmeister, A. M. Phys. Rev. 1995, B52, 3985. of Iron; The New York Times, April 4, 1995, p C1.

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Polymerization of simple molecules into extended structures with unexpected features is possible at high pressure, where intramolecular
bonding and intermolecular contacts can become indistinguishable.

A face-centered cubic array of oxygen atoms forms the basis of The helical arrangement of CO4 tetrahedra is the dominant struc-
the proposed symmetric ice H2OX, a polymorph of solid H2O tural motif of quartzlike carbon dioxide, proposed as a new high
in which the hydrogen bonds are the same length as the covalent temperature, high pressure phase of CO2.
OH bonds.

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