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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
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.
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.
W
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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.
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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.
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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.