A method which uses computer graphics to construct pictorial views of three-dimensional

thermodynamic phase diagrams is demonstrated. Pressure-volume-temperature diagrams

are presented for ethylene and propylene so that quantitative comparisons can be made
between the phase surfaces representing the ideal gas law, the Redlich-Kwong equation
and a highly accurate, 20~constant equation of state proposed by Bender. Pictorial views
of enthalpy-entropy-pressure diagrams for ethylene based solely on P-V- T relations and
ideal gas heat capacities are also shown along with their Mollier projections. Interesting
comparisons that confirm our understanding o f equations of state are made with H-S-P
diagrams that represent the properties o f an ideal gas in contrast to those o f a Redlich-
Kwong fluid. Reference is made to earlier papers that describe the computer graphics
algorithms in detail.

Computer generated phase diagrams for ethylene and

propylene
K.R. Jolls and G.P. Willers

Nomenclature R Gas constant, 8.314 (MPa cm a g-l mole K-1)

a Constant in the Redlich-Kwong equation for S Entropy, Jg-tK-l
ethylene, 7.8203 x 106MPa (cma/gmole)2K 1l~ T
Temperature, K
b Constant in the Redlich-Kwong equation for
ethylene, 40.118 (cm s g- 1mole- 1) Tc Critical temperature, K
Saturation temperature, K
CD Heat capacity at constant pressure, Jg-lK -~ Ts
Volume, cm 3g-1
Cv* Ideal gas heat capacity at constant volume, V
Jg-lK-I VL Saturated liquid volume, cm 3g-1
ai Coefficients in the heat capacity Equation (3) Vv Saturated vapour volume, cmSg -1
H Enthalpy, J g-1 P Density, g cm-a
AHvap Enthalpy of vaporization, jg-i Pc Critical density, gcm -a
P Pressure, MPa 0 Rotation angle
p~ Vapour pressure, MPa Tilt angle

Thermodynamic research has produced a vast data base
from which theoretical equations, empirical correlations
and graphical results may be obtained to yield information
on the physical properties of materials of engineering
importance. Although the student or professional working
in thermodynamics must ultimately have accurate numerical
data to solve problems, the functional interrelationship
among property variables is equally important, enabling one
to see trends and overall characteristics that might otherwise
be missed by sole consideration of a few discrete points.
Nowhere is this better illustrated than in the representation
of pressure-volume-temperature (P-V-T) data. Tables of
thermodynamic properties and simple graphs provide an
accurate means for obtaining the numerical information,
but the complete three-dimensional function that comprises
K.R. Jolls is at the Department of Chemical and Nuclear Engineering,
Iowa State University, Ames, Iowa 50011, USA and G.P. Willers is at
the Phillips Petroleum Company, Bartlesville, Oklahoma, USA.
Received 16 March 1978.
0011-2275/78/1806-0329 $02.00 © 1978 IPC Business Press
CRYOGENICS. JUNE 1978
the composite of all such data for a particular substance is
often unavailable. Accurate three-dimensional plots of the
more subtle thermodynamic phase surfaces such as entropy-
pressure-temperature, enthalpy-entropy-pressure, etc., are
almost nonexistent. Needless to say, complete solution phase
diagrams (which are fundamentally of higher dimension)
are also lacking.
Clearly, the reason these diagrams are so uncommon is the
enormous amount of labour involved in making them. The
construction of an accurate pictorial view of a complex
thermodynamic phase diagram requires skill in both technical
illustration and thermodynamics and is very time consuming
and hence expensive. Any change in content, orientation, or
artistic quality requires a completely new diagram, thus
multiplying the effort.
A simple solution is to use modern computer graphics. The
authors have developed a technique whereby figures repre-
sentative of a large variety of multi-dimensional thermo-
dynamic phase diagrams may be drawn by a computer-
controlled incremental plotter. The finished diagrams are
329
 /J
/J
Fig. 1 Multiple plot of the van der Waals Equation of State. (At the time o f writing the
authors did not have a version of this Fig. constructed in SI units. The unit conversions f r o m
fps to SI are as follows: 1 000 psia = 6.895 MPa, 1° R = 0.5556 K, 1 ft3(Ib mole) -1
= 2.225cm3g -1 for ethylene)
accurate, fairly cheap, and readily available in any orienta-
tion or configuration desired. Furthermore, the computing
facilities available to the authors at Iowa State University
make possible finished visual aids that possess dramatically
illustrative artistic features. Phase diagrams may be produced
in stereo pairs, with computer-controlled shading and
highlighting, and with deliberate coordinate distortions
that emphasize topographic features of thermodynamic
interest.
This paper presents several computer generated phase
diagrams based on P-V-T equations that represent the
properties of ethylene and propylene. The details of the
computer algorithms that produce these drawings are
discussed in papers by Jolts, Willers and Jensen 1 and in a
thesis by Willers. 2 Our purpose here will be simply to present
the diagrams and comment on any noteworthy thermo-
dynamic considerations.
Example of technique
The power and versatility of the technique is easily seen in
Fig. 1 which has been termed a 'multiple plot'. This is a
pictorial view of the van der Waals equation of state with
the constants evaluated from the critical properties for
ethylene. The central figure shows the familiar P-V-T surface
displayed on an artificial base to enhance the 3-D effect. The
surface itself is represented by three sets of constant property
curves (isotherms, isobars and isochores) corresponding to
the three coordinate axes. The two-phase region defined by
the saturated liquid-vapour locus has been added to the basic
330
V
van der Waals surface through application of Maxwell's equal-
area technique as described in the next section.
The projections of the surface in the three coordinate
directions are also shown on viewing planes that are
spatially oriented in such a way as to reveal the manner in
which the two-dimensional diagrams are obtained. When
viewed normally, the left, right and upper projections
become the familiar P-V, P-T and T-V diagrams found in
most thermodynamics textbooks.
The entire multiple plot in Fig. 1 was constructed in a
single computer run. The exact orientation angles, overall
ranges of the variables, spacings, and specific constant
property curves may be varied at will to change the character
of the diagram. Each 3-D picture requires the specification
of tilt and rotation angles to orient the figure for optimal
viewing. Side views (planar projections) require that these
angles be 0 ° or 90 ° depending upon the original coordinate
system. The tilt angle is counterclockwise as viewed from
the right, and the rotation angle is clockwise as viewed from
above. In addition, the drawing possesses a controllable
degree of perspective and has the option of a linear or non-
linear scale in any coordinate direction. (Note that both
pressure and volume are plotted non-linearly in Fig. 1.)
The original of the diagram is obtained as a 35-mm microfilm
negative from which an enlargement is made. Texture material
and printed labels are then added and, in the case of Fig. 1,
projection lines have been drawn for clarity. In the diagrams
that follow several other techniques developed by the
authors are used to enhance the appearance of the drawings.
CRYOGENICS. JUNE 1978
Amount these are automatic incrementation to assure smooth
curves, variable intensity plotting, suppression of perspective
in two-dimensional views, and use of dashes rather than
solid-line plotting for additional constant property curves.
Results
The pressure-volume-temperature diagram For comparison
purposes a pictorial view of the ideal gas equation covering
the range of ethylene properties is shown in Fig. 2. This
simplest of all thermodynamic equations of state comprises
one symmetrical section of a hyperbolic paraboloid. All
isotherms are hyperbolae in space, and all isobars and
isochores are straight lines, which account for our terming
this a 'ruled surface.' Although property prediction in
the high temperature, low pressure region compares
favourably with that of the more accurate diagrams which
follow, the ideal gas equation fails rapidly as the pressure
rises, and of course, it exhibits no vapour-liquid phase
separation.
Ideal gas volumes have been plotted on a molar basis in
Fig. 2 since the surface is identical for all materials.
Properties in Figs 3 to 9 are plotted on a per gram basis for
consistency with the paper by Bender a cited below.
Fig. 3 shows the P-V-T properties of ethylene as predicted
by the Redlich-Kwong equation of state.
RT a volume. The near coincidence of the 200 K isotherm and
P - (1)
v- b v ( v + b)
At the high temperature limit (400 K) and a pressure of
2 MPa (the points labelled (~ in the figures), the ideal gas
law gives a volume that is only 4.84% greater than that
predicted by the Redlich-Kwong equation. However, as
the pressure rises along the 400 K isotherm the error increases
Fig. 2 Ideal gas equation
CRYOGENICS. JUNE 1978
to a value in excess of 30% at the highest pressures shown.
Even at 1 MPa, lowering the temperature to 225 K (points
/3 in the figures) results in an ideal gas volume nearly 17%
greater than the corresponding volume from Fig. 3.
In contrast to the ideal gas, the Redlich-Kwong isotherms
show a decided change below 325 K as the critical region is
approached. We have drawn the isotherm for 283 K, which
is only a fraction of a degree higher than the reported
critical temperature of 282.65 K. The familiar vanishing of
the first and second pressure-volume derivatives for this
isotherm at the critical point is easily seen in the three-
dimensional view, as is the discontinuity in all lower
isotherms that correspond to liquid vapour phase separation.
The saturated liquid-saturated vapour boundary that
outlines the two-phase region has been added to the basic
Redlich-Kwong surface in the same manner as was done
with Fig. 1 for the van der Waals surface. Maxwell's equal-
area technique was employed in an algorithm described by
Balzhiser et al. ¢ to calculate vapour pressures and saturated
volumes based on the R-K equation for closely spaced
temperatures between 120 K and the critical point. Single-
phase constant property curves are simply terminated at
the boundary and extended into the two-phase region as
required by the phase rule. Isotherms and isobars appear
as straight lines parallel to the volume axis, and isochores
merely reflect the vapour pressure curve P(T) at each plotted
the 0.5 MPa isobar in the two-phase region was unintentional.
The actual vapour pressure predicted for 200 K is approx-
imately 0.486 MPa.
To emphasize the general applications of our graphics
technique we have purposely drawn constant property
curves that illustrate several of the cases encountered in
331
 V= 1 . 5 6 5 ~ ~

i
S
~ tg~l~l.~-..~ '
11
i

i
./ i
o /
I
~ I ~--"~ i -
i
~ ~, ~ ~ t L " ~
i

/
i
J
J

000,
V:L583J l

Fig. 3 Redlich-Kwong Equation of State for ethylene

constructing such a diagram. Whereas, moving left to right,
the isotherm for 175 K and the isobar for 0.5 MPa remain
in the two-phase region out to and beyond the high volume
limit (70 cm 3 g-l), three isotherms and several isobars
re-emerge on the vapour side to continue as single-phase
curves. Even here two cases arise, as noted by the difference
between the 2 MPa and 1.5 MPa constant pressure curves.
The former terminates on the high temperature boundary
while the latter intersects the high volume end of the
diagram. All of these cases are handled automatically by
the graphics program which gives the user great flexibility
in selecting constant property curves and overall limits for
the diagram. It should also be noted that both pressure and
volume are plotted on non-linear scales in Fig. 3. The extent
of tiffs non-linearity is a user option and may be varied to
stretch or compress sections of the drawings as desired.
With the exception of Fig. 1, property values at comers and
other points of discontinuity are labelled to assist in the
interpretation of the diagrams.
Extending our computer graphics technique to a much more
complicated equation of state, we refer to the equations for
ethylene and propylene published by Bender 3 in 1975. The
functional form is that of an extended Benedict-Webb-Rubin
equation and is given in the original paper as follows:
the specific constant property curves are identical so that
the two equations may be compared directly. Table I gives
the precise specific volumes in cm3g -1 predicted by the
three equations for the points discussed above and labelled
on the diagrams.
The critical volume predicted by the Bender equation is
significantly smaller than that shown in Fig. 3 for the
Redlich-Kwong equation. The critical temperatures and
pressures are identical because Bender's reported values
were used specifically to evaluate the R-K constants. One
may assess the reliability of the Bender equation for
ethylene by noting the author's reported values of mean
percentage deviation, Fmp, between densities calculated
from (2) and experimental data. These values are 0.37,
0.20, and 1.22 percent for the gaseous, liquid, and critical
regions, respectively. Bender defines the critical region as
T < 1.25 Tc and 0.66 Pc < P < 1.33 Pc- The reader is
referred to the original paper for the precise details of these
comparisons.
Table 1. Specific volumes of ethylene as predicted by
three equations of state

p = pT[R+BI,+Cp2+Dp3+Ep4+Fp s
Specific volume, cm3g-1
+ (G + Hp2)p 2 exp(-a2op2)] (2)
Redlich-
where the temperature functions B to H are given in terms of Ideal Kwong Bender
19 additional constants, thus yielding a twenty-constant Point 7", K P, MPa Gas Law equation equation
equation of state. Numerical values for these constants for
both ethylene and propylene are reported by Bender based on 400 2 59.27 56.53 56.65
the best available P-V-T and saturation data. Fig. 4 is a
pictorial view of Bender's equation for ethylene obtained 225 1 66.68 57.03 56.23
in exactly the same manner as was the Redlich-Kwong 7 400 14 8.468 6.369 6.396
diagram in Fig. 3. The overall range of the properties and

332 CRYOGENICS. JUNE 1978

 V=6.369(y}

Fig. 4 Bender Equation of State for ethylene

uJ
I

J
I

Fig. 5 Bender Equation of State for propvlene

Fig. 5 is the pictorial view of Bender's equation for propylene.
Isotherms have been drawn from approximately 72 K above the
triple point to a reduced temperature of 1.37. The volume
and pressure ranges are essentially identical to those used
for ethylene. One of the more interesting comparisons
between the two P-V-T diagrams is the lower critical pressure
for propylene in spite of its higher critical temperature. The
poorer accuracy of experimental data on liquid propylene
is cited as a source of error for the liquid region shown in
Fig. 5. Nevertheless, the author reports mean percentage
deviation values of 0.28, 0.30, and 0.63 percent, respectively,
for propylene in the gaseous, liquid and critical regions.

C R Y O G E N I C S . J U N E 1978 333

Fig. 6 Enthalpy-entropy-pressurediagram for ethylene based on the Redlich-Kwong Equation of State
The enthalpy-entropy-pressure diagram One of the least
common three-dimensional phase diagrams is the enthalpy-
entropy-pressure surface from which the familiar Mollier
diagram is derived as a two-dimensional projection in the
pressure direction. Combining our computer graphics
technique with several algorithms for the generation of
constant property curves in H-S-P space has enabled us to
produce the pictorial view of the H-S-P diagram for ethylene
shown in Fig. 6.
The thermodynamic basis of the diagram comprises P-V-T
information predicted by the Redlich-Kwong equation of
state, (1), and ideal gas heat capacity data predicted by a
seventh-order polynomial of the form
7
C*v = Y-, di Ti
i=0
with constants given for ethylene in the paper by Bender. 3
As with the P-l,r-T drawings, constant property curves are
given for selected values of the coordinates spaced linearly
along the axes. An additional feature in Fig. 6 is the inclusion
of a fourth set of property curves (isotherms) as dashed
lines. Adding this important variable to the H-S-P surface
significantly aids the viewer in his interpretation of the
diagram. Comer values and important intersections are
again labelled separately as in the P-V-T diagrams.
The lightly shaded saturation region is ruled by straight
isotherms and isobars that connect equilibrium vapour and
liquid states. Curves that correspond to the critical values
of the four displayed properties have been drawn and
intersect at the critical point. It is interesting to note the
program's ability to construct without interruption the
700 jg-1 constant enthalpy curve that enters and leaves the
saturation region on the same side of the critical point.
The actual assignment of reference states for enthalpy and
334
V"
entropy in the original program was as follows:
H = 0 at T= 120K andP-~ 0
S = 0 for saturated vapour at 120 K (P= 0.000865 MPa)
A constant shift factor was applied to each coordinate to
re-establish the reference point (H = S = 0 for saturated
liquid at 120 K) at the front corner of the surface. In addition
to rendering all H and S values positive throughout the
diagram, this realignment resulted in the properties shown
in Fig. 6 for saturated vapour at 120K, namely
H = 636.5Jg-1
S = 5.304Jg-lK -1
(3) Fig. 7 is the Mollier diagram for ethylene obtained by
projecting in the pressure direction that portion of Fig. 6
with entropy values between 3.0 and 6.0 jg-l K-l and
enthalpy values between 550 and 1300Jg -1. The projection
was generated by setting the rotation angle 0 at 90 ~ and the
tilt angle 4~at 0 °, as well as removing the perspective effect.
For comparison, these angles were set at 40 ° and 20 ° ,
respectively, in Fig. 6. The specific isotherms, isentropes
and curves of constant enthalpy that have been drawn
are quite similar to those shown in Fig. 6. The constant
pressure curves in Fig. 7 have been chosen to avoid clutter
in the high pressure region and to provide better coverage
of the surface at lower pressures. The projection of the
critical point is clearly marked by the intersection of the
critical values for enthalpy and entropy.
The iterative procedures used to generate points along
constant property curves in Figs 6 to 9 were, derived from
the basic thermo-dynamics and, with considerable modifica-
tion, from algorithms published by Balzhiser et al.4
designed originally to compute work effects associated with
reversible and irreversible compressions of a gas following
CRYOGENICS. JUNE 1978

120
/A
Critical point
I H =6:)9.6 I
~T =3183
. . . . . . . . . ~~
Fig. 7 M o l l i e r diagram f o r e t h y l e n e based on the R e d l i c h - K w o n g E q u a t i o n o f State
a given equation of state. P-V-T data along the saturation
curve were available from the results used to produce Fig. 3.
Enthalpy differences between equilibrium vapour and liquid
states for a Redlich-Kwong fluid were obtained from the
following equation developed by Hederer et al. s
1.5a [ Vv(VL + b ) ]
,~d-/vap = P s ( V v - VL) + b~/Ts In VL(Vv+ b)J
Equation (4) is based on the continuity of the Redlich-
Kwong isotherms across the two-phase region which
ostensibly permits prediction of the enthalpies of the
saturated phases from a knowledge of Ts, Vv and VL. The
entropy change on vaporization follows immediately
from (4) after division by Ts.
An interesting companion diagram to Fig. 6 is the H-S-P
diagram shown in Fig. 8 for an ideal gas with a heat
capacity function identical to that of ethylene. The drawing
was constructed with the same program that generated
Fig. 6, the only exception being that the Redlich-Kwong
constants a and b were set to zero which reduces (1) to
the ideal gas form as well as all other generating equations
used to produce the H-S-P coordinates. Since phase change
is not observed with an ideal gas, no attempt was made to
include a saturation region in Fig. 8. Therefore in order to
provide numerical consistency, especially in regions of
similar P-V-T behaviour, Fig. 8 was. constrained as follows:
H = 636.5Jg -1
at 120 K and 0.000865 MPa, S = 5.304 J g-X K-X
These are the identical conditions for the saturated vapour
phase at 120 K in Fig. 6 for which the Redlich-Kwong and
ideal gas specific volumes agree to within better than 0.1%.
This reference condition is designated 'R.P.' in Fig. 8 and
in its Mollier projection, Fig. 9. One of the more striking
C R Y O G E N I C S . J U N E 1978
P=0.152
T=55.
.Z y : ) T=,,;
,~~ ~ , , ~ ,a~ , a ~
Entropy,d(q-K)"1
characteristics of the ideal gas diagrams in contrast to
Figs 6 and 7 is the strictly parallel relationship between lines
of constant enthalpy and lines of constant temperature,
which simply reflects the well known fact that the enthalpy
of an ideal gas is a function of temperature alone. Both
isothermal and isobaric entropy changes for an ideal gas
(4) may also be verified from Fig. 8 to the extent that precise
numerical values can be read from the diagram.
Fig. 9 is the Mollier projection of Fig. 8 covering essentially
the same range of values as did the Redlich-Kwong H-S
diagram in Fig. 7. The region around the reference point is
again expanded, thus permitting closer scrutiny of the
diagram at low pressure. Such partial derivative properties
as Cp, (aS/aP)T, (~H/~P)T and (aT/aP)H can be readily
approximated from the Mollier diagram, the latter two, of
course, being equal to zero for an ideal gas.
Conclusion
A new technique which utilizes computer graphics to
generate pictorial views of thermodynamic phase diagrams
has been demonstrated. Pressure-volume-temperature and
enthalpy-entropy-pressure diagrams based on the ideal gas
and Redlich-Kwong equations of state for ethylene have
been presented. The phase diagrams for ethylene and
propylene predicted by a highly accurate, twenty-constant
equation of state have also been shown to demonstrate
the usefulness of the technique with mathematically
unwieldy equations. The construction of some of the more
complicated phase diagrams, including those that represent
solution properties, can now be carried out using the methods
illustrated here. Work is continuing on the technique to
extend it to a wider variety of diagrams and to make use of
some of the more advanced methods of computer graphics
to improve the portrayal of thermodynamic properties.
335
 DI81
L8

/,1283.8]
' =508.3 J

,.=,

Fig. 8 Enthalpy-entropy-pressure diagram for an ideal gas

/7/t/ /
,¢/j--/-/

2
3

_ ~ _'_'_=

Entropy, d (9" K )'l

Fig. 9 Mollier diagram for an ideal gas

This work was supported b y the Engineering Research
Institute of Iowa State University and by a grant from the
Union Carbide Corporation.
References
1 JoBs, K.R., Willers, G.P., Jensen, I.D. Transactions of the
Computers in Education Division of ASEE 8 (1976) 10
2 Willers, G.P. The construction of thermodynamic phase
diagrams through computer graphics (1978) unpublished
MS Thesis, Department of Chemical Engineering, Iowa
State University
3 Bender, E. Cryogenics 15 (1975), 11 667
4 Balzhis~, R.E., Samuels, M.R., Eliassen, J.D. Chemical
engineering thermodynamics: the study of energy, entropy
and equilibrium (1972) Prentice Hall Inc. Englewood Cliffs
NJ, 219
5 Hederer, H., Peter, S, Wenzel, H. Chemical Engineering
Journal 11, (1976) 3 183

336 C R Y O G E N I C S . J U N E 1978