Research: Science and Education

Equations of State and Phase Diagrams

L. Glasser
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, P. O. Wits 2050, South Africa;
[email protected]

An equation of state (EoS) is a mathematical summary

of the (usually thermodynamic) equilibrium properties of a
material (1). At the very minimum (in the absence of external
constraints, such as fixed temperature), such an equation relates
the mechanical, thermal, and volumetric properties of a single
phase of the material; other properties might be needed to fully
describe its behavior if the material exists in a particular
environment, such as in a strong electric or magnetic field,
or localized in a surface.
Among the simplest possible EoSs is that of the ideal gas
pVm = RT

(1)

where p (pressure) represents the mechanical state of the

system, T (absolute temperature) the thermal state, and Vm
(molar volume) the volumetric state. Clearly, there are only
two independent variables (which may be arbitrarily selected
from among the three) while the remaining variable takes on
a value dependent on the values assigned to the other two,
through the EoS. EoSs may be expressed with other variables than p, T, and Vm; for example density, , may replace
Vm, but the three- (or more)-variable structure remains.
A more elaborate EoS, such as van der Waals equation

p=

RT a
V m b V m2

(2)

retains the same structure of variables, though differently

expressed. Furthermore, the van der Waals equation and most
EoSs for the fluid state generally receive a further thermodynamic interpretation. Such cubic (as well as some other)
functions display an S-shaped structure with loops between
the liquid and vapor regions. The regions are divided into
three using Maxwells construction (2) to guide the division
into gas/vapor, liquid, and phase gap, by recognizing that the
liquid and vapor are in equilibrium at a given temperature,
so that their molar Gibbs functions are equal. Maxwells
construction then requires equal areas above and below the
tie line, which connects liquid and vapor in equilibrium,
passing through the loops of the EoS function.
Thus, the full representation of a simple EoS is a threedimensional image, encompassing the three variables. Threedimensional models (36 ) and diagrams (7 ) of single-phase
systems are not uncommonly found (Fig. 1). However, in
graphical representation of multiphase systems, partly because
of the difficulty of drawing three-dimensional images (and partly
because of the lack of the required data), it is traditional to
use projections of the three dimensions onto two-dimensional
planes in preference to the full three-dimensional representation (e.g., pV diagrams [1, 2, 810] in place of pVT diagrams),
while three-dimensional descriptions (3, 11, 12) are usually
presented schematically, not to scale. (Petrucci [13] has presented a three-dimensional diagram of p, V, and composition,
but for a hypothetical binary system, at a fixed temperature.)
Equilibria between two phases are represented by a (two874

dimensional) curve within the three-dimensional diagram, and

equilibrium among three phases is represented by a straight line
situated along the constant temperaturepressure equilibrium
condition. Figure 2 shows that the triple point of a pT
projection is actually a misnomer for a tie line in full phase
diagram space; Sandler (11) terms this the triple-point line.
Thus we see that, although the common practice of
depicting only projections suffices for many purposes, it
also hides some of the features of the relations between the
EoSs of the different phases. This paper illustrates the phase
relations in a unary (single-component) system with a full
three-dimensional diagram using authentic data. Such a diagram
does not seem to have appeared before.
To provide this authentic representation of a unary system,
we chose carbon dioxide (Fig. 3), for which much (but not
all) of the required data is available in equation form. Where
the equations required could not be found, they were fitted
to experimental data or closely approximated by standard
relations, as described in the Appendix. To encompass the
wide range of values encountered, it is necessary to represent
the pressure and volume data on logarithmic axes.
The data required are equilibrium temperatures and pressures as well as data for
Sublimation curve: solid and vapor densities (or molar
volumes)
Melting curve: solid and liquid densities
Saturation curve: liquid and vapor densities
Solid state phase changes: these data are largely uncertain or
unknown (10), and so are omitted from the diagram

The Appendix lists the equations (whether fitted or theoretical)

for carbon dioxide equilibria, or the experimental data used

Figure 1. Photograph of a model of the ideal gas pVT surface,

constructed using templates kindly provided by D. B. Hilton (5).

Journal of Chemical Education Vol. 79 No. 7 July 2002 JChemEd.chem.wisc.edu

Research: Science and Education

to generate the curves. These data were extracted from Gmelin

(14) and Landolt-Brnstein (15) for transitions involving the
solid state, and from the International Thermodynamic Tables
of the Fluid State for carbon dioxide (16 ). The calculated results
were prepared on an Excel spreadsheet.
For ease of access, a recent EoS for the single-phase fluid
region is also listed in the Appendix (17), but was not utilized
in preparation of Figure 3. Much thermophysical (and other)
data for many materials, including carbon dioxide, is available
on the WebBook of the National Institute of Standards and
Technology (18).
Literature Cited

Figure 2. Orthographic (isometric) three-dimensional pVT diagram.

Adapted from ref 11: Sandler, S. I. Chemical and Engineering
Thermodynamics, 2nd ed.; Wiley, New York, 1989; p 217; copyright 1966 by Blaisdell Publishing Co. (John Wiley & Sons, Inc.).
Reprinted by permission of John Wiley & Sons, Inc.

Figure 3. An orthographic pVT diagram for carbon dioxide, with

projections onto the pT, pV, and VT planes. To accommodate the full
range of data, the logarithms of the pressure and molar volume
axes are used. The horizontal lines (constant pT ) are tie lines connecting phases in mechanical and thermal equilibrium across the
phase gaps. The critical point condition and the triple-point tie-line
are labeled. The dot at the end of the liquidvapor line in the pT
projection represents its termination at the critical point. Volumes in
the diagram (corresponding to areas in the projections) are labeled
solid, liquid, vapor and (above the critical point) gas. The space
curves depicted are A: solid sublimation, in equilibrium with vapor;
B: vapor condensation, in equilibrium with solid; C: liquid saturation,
in equilibrium with vapor; D: vapor saturation, in equilibrium with
liquid; E: solidliquid melt equilibriumon the scale of the diagram
the two separate curves nearly overlie one another. The small break
barely discernible at the junction of curves A and C arises from the
difference in molar volumes of solid and liquid at the triple point
(cf. Fig. 2).

1. Atkins, P. W. Physical Chemistry, 6th ed.; Oxford University

Press: Oxford, 1998.
2. Wisniak, J.; Golden, M. J. Chem. Educ. 1998, 75, 200.
3. Petrucci, R. H. J. Chem. Educ. 1965, 42, 323.
4. Peretti, E. A. J. Chem. Educ. 1966, 43, 253.
5. Hilton, D. B. J. Chem. Educ. 1991, 68, 496.
6. Coch Frugoni, J. A.; Zepka, M.; Rocha Figueira, R.; Coretti, M.
J. Chem. Educ. 1984, 61, 1048.
7. Remark, J. F. J. Chem. Educ. 1975, 52, 61.
8. Halpern, A. M.; Lin, M.-F. J. Chem. Educ. 1986, 63, 38.
9. Lieu, V. T. J. Chem. Educ. 1996, 73, 837.
10. Gramsch, S. A. J. Chem. Educ. 2000, 77, 718.
11. Sandler, S. I. Chemical and Engineering Thermodynamics, 2nd ed.;
Wiley: New York, 1989; p 217.
12. Logo for 14th Russian Conference on Chemical Thermodynamics, St. Petersburg, Jun 30Jul 5, 2002; http://rcct2002.
nonel.pu.ru/ (accessed Apr 2002).
13. Petrucci, R. H. J. Chem. Educ. 1970, 47, 825.
14. Gmelins Handbuch der Anorgorganischen Chemie, 8th ed.; Section C: Part 1, Carbon Dioxide; von Backzo, C., Ed.; Verlag
Chemie: Weinheim, 1970.
15. Landolt-Brnstein Zahlenwerte und Funktionen, Vol. 2, 6th ed.;
Schfer, K.; Beggerow, G., Eds.; Springer: Heidelberg, 1971;
Part 1, p 723.
16. International Thermodynamic Tables of the Fluid State3:
Carbon Dioxide; Angus, S.; Armstrong, B.; de Reuck, K. M., Eds.;
Pergamon: Oxford, 1976.
17. Mder, U. K.; Berman, R. G. Am. Mineral. 1991, 76, 1547.
18. National Institute of Standards and Technology; NIST
WebBook; http://webbook.nist.gov (accessed Mar 2002); at
present free of charge.

Appendix (from ref 16 )

Critical point:
Tc = 304.21 K; pc = 73.825 bar; Vm,c = 94.428 cm3 mol1
Triple point:
T3 = 216.58 K; p3 = 5.18 bar; Vm,3(s) = 29.09 cm3 mol1;
Vm,3(
) = 37.338 cm3 mol1; Vm,3(g) = 3133.79 cm3 mol1
Saturated vapor pressure/temperature (16 ):

p
ln p = a 0 1 T
Tc
c

1.935

+ ai
i=1

Tc
1
T

where
a0 = 11.377371, a1 = 6.8849249, a2 = 9.5924263, a3 = 13.679755,

JChemEd.chem.wisc.edu Vol. 79 No. 7 July 2002 Journal of Chemical Education

875

Research: Science and Education

a4 = 8.6056439

T/K

Saturated liquid density (16 ):

2


T 0.347+ c 1 T
i
c 1 = c 0 1 T
T
i=1

i+1 /3

where c0 = 1.9073793, c1 = 0.38225012, c2 = 0.42897885

Saturated vapor density (16 ):
2
g
T 0.347+ d 1 T
i
c 1 = d 0 1 T
T
i=1

p p3
T
p 3 + 648.13886 = 3 ln T + ln 648.13886
3
Melting: Volume Changes (refs 14, 15)
P / bar

Vm,melt /(cm3 mol1)

267.65

2,942.0

4.71

281.65

3,922.7

4.31

294.55

4,903.4

3.94

306.25

5,884.0

3.62

317.35

6,864.7

3.32

328.35

7,845.4

3.07

338.95

8,826.0

2.83

348.55

9,806.7

2.65

357.75

10,787

2.48

368.45

11,768

2.34

220

5.185
166.91

We have fitted the above data to the following quadratic polynomial (given to 10-decimal placesthis precision is not justified by
the underlying data, but is required to yield calculated values of
sufficient accuracy):

37.34

6.38

36.77

29.82

225

412.57

6.19

36.07

29.69

230

669.39

6.01

35.49

29.57

937.63

5.82

35.02

29.45

5.75

34.85

29.41

237

1,048.2

267.65

2,942.0

4.72

33.80

28.86

281.65

3,922.7

4.30

33.40

28.68

i+1 /3

Melting curve (16 ):

T/K

216.58

235

where d0 = 1.7988929, d1 = 0.71728276, d2 =1.7739244

ln

Vm,melt(quad) Vm,
/cm3 mol1 Vm,s(calcd)

P/bar

Selected Values from Table 8, Reference 16

References 14 and 15

294.55

4,903.4

3.93

33.03

28.57

306.25

5,884.0

3.62

32.71

28.50

317.35

6,864.7

3.34

32.41

28.48

328.35

7,845.4

3.07

32.16

28.48

338.95

8,826.0

2.84

31.92

28.51

348.55

9,806.7

2.64

31.74

28.56

357.75

10,787

2.46

31.57

28.64

368.45

11,768

2.27

31.43

28.75

Sublimation curve (applicable down to 90 K) (16 ):

T
p
ln p = 14.57893 1 3 14.48067 ln T +
T
T3
3
2
3
65.35685 T 1 47.14593 T 1 + 14.53922 T 1
T3
T3
T3
Sublimation Data (Using the Ideal Gas Equation)
T/K

Vm,v/(cm3 mol1)

P/bar

90

6.63 10

1.13 1012

100

2.15 107

3.87 1010

110

3.79 106

2.41 109

120

4.21 10

2.37 108

3.34 107

Vm,melt = 6.9542 105T 2 0.0686277044T + 18.1107164247

130

3.24 10

140

0.00186

6.26 106

Melting results:
We have fitted the liquid Vm,
versus T data below to the following
cubic polynomial (given to 10 decimal placesthis precision is not
justified by the underlying data, but is required to yield calculated
values of sufficient accuracy):
Vm,
= 3.0331 106T 3 + 0.0028688133T 2

150

0.00843

1.48 106

160

0.0314

424,000

170

0.0995

142,000

180

0.276

54,300

190

0.684

23,100

200

1.55

10,700

0.9200958384T + 132.4799710302
Vm,melt(quad) is the calculated value for the volume change at the
corresponding melting temperature, using the quadratic fit above.
Vm,s(calcd) (= Vm,
Vm,melt) is the corresponding calculated molar
volume of solid CO2 using the difference of the above two equations:
Vm,melt(quad) = 3.0331 106T 3 + 2.799268 103T 2

210

3.27

5,340

216.58

5.19

3,470

0.85146813560T + 114.3692546

NOTE: The van der Waals equation, using a = 3.688 bar cm6 mol2,
b = 42.67 cm3 mol1 (1), gives essentially the same values.
Fluid equation of state (17 ):

p=

RT
V B 1 + B 2T

B3

A1
TV

A2
V4

V +C

with C = B3/(B1 + B2T ) and B1 = 28.06474, B2 = 1.728712 104,

B3 = 8.365341 104, A1 = 1.094802 109, A2 = 3.374749 109
in units of cm3 mol1, K, and bar.

876

Journal of Chemical Education Vol. 79 No. 7 July 2002 JChemEd.chem.wisc.edu