Ind. Eng. Chem. Fundam., Vol. 18, No.

2, 1979 81

REVIEW

Cubic Equations of State-Which?

Joseph J. Martin
Department of Chemical Engineering, The University of Michigan, Ann Arbor, Michigart 48 109

An analysis is made of volume-cubic equations of state, starting with the most general generating equation from
which all specific forms can easily be derived. One equation is shown to be both the simplest and the best in
performance. A new quantity, the t-chart sum, is presented, which is a useful way to compare all equations of
state, whether cubic or otherwise, while at the same time permitting excellent predictions of the second virial coefficient
at the critical temperature from the critical compressibility factor. Extensive comparisons of reliable experimental
PVTdata with a number of equations of state are given for a wide range of substances from nonpolar to polar,
and these demonstrate the superiority of the simplest two-term cubic equation.

Introduction
Since the time of van der Waals, a century ago, there
has been a steady outpouring of equations of state to
represent the pressure-volume-temperature behavior of
fluids. These have ranged from simple expressions with
one or two constants to complicated forms with up to more
than 50 constants. The longer equations have been utilized
for high-precision work and one can find in the literature
many interesting and useful ones such as the Benedict-
Webb-Rubin ( 3 ) ,the Strobridge (30),the virial form of
Onnes ( 2 4 ) to the 17th power in volume, the Martin-
Stanford (21),and some recent semitheoretical formula-
tions with two or three dozen universal constants and a
handful of molecular-parameter constants characteristic
of the substance being represented. Although these long
and complex equations are desirable for the precise
representation of PVT data and calculation of simple
thermodynamic properties, they are not generally preferred
for involved thermodynamic calculations such as vapor
pressure and latent heat of vaporization, mixture behavior
and activity coefficients of mixture components, or
multicomponent vapor-liquid equilibrium ratios because
they require tedious manipulation and excessive computer
storage in lengthy iterative calculations which tax even the
most modern electronic machines.
The attractiveness, then, of the shorter equations lies
in their simplicity of calculation. The bulk of these short
equations may be shown to be cubic in volume and these
include such well-known forms as van der Waals (32),
Clausius (6),Berthelot ( 4 ) ,Onnes third degree virial ( 2 4 ) ,
Redlich-Kwong ( 2 7 ) , Wilson (33), Barner-Pigford-
Schreiner (2),Martin (201, Lee-Edmister (15),Soave (29),
Dingran-Thodos (9),Usdin-McAuliffe (31),Redlich (28),
Peng-Robinson (25),Fuller (12),and Won (34). It is these
short cubic equations that are to be examined here.
If one is searching for a suitable equation of state and
has ruled out the extended equations as being too cum-
bersome and wishes to use a simple cubic, he might think
his problems are over, but may be in a quandary when he
faces the forelisted array of available cubic equations. How
does he decide which one to use? A previous study of cubic
equations by Abbott ( I ) analyzed some of their charac-
teristics and behavior, but did not address the central
question, similar to the queen in Snow White who asked,
0019-787417911018-0081$01,0010
Mirror, mirror on the wall, whos the fairest of them all?
Thus, it behooves this study to present a set of arguments
which will prove beyond any doubt the superiority of one
form over the rest, a formidable objective considering the
vast amount of effort that has gone into this subject
previously and the necessity to run down every conceivable
alley of approach no matter how blind. In the pursuit of
this objective it is hoped to clear up some of the myths
about the behavior of cubic equations and the supposed
advantages of one favorite form over another. The
principles developed here are fundamental and applicable
to all equations of state, be they cubic or not.
It has been common practice in recent years to compare
the simpler equations of state by noting how well they
predict saturated liquid volumes and vapor pressures
through the equality of liquid and gas fugacities. This has
merit because of the way such short equations are used;
however, in this work the comparisons will be made di-
rectly to the PVT behavior in the liquid and gas states
because this is more fundamental and through exact
thermodynamic relations precludes all equilibrium com-
parisons. Also the comparisons will be for computed
pressures rather than computed volumes which is a much
more severe test in the liquid phase. It is only by making
comparisons with actual PVT data that the subtleties in
behavior of the various cubic equations can be detected.
A. General Source of all Equations of State That
Give Pressure as a Cubic Function of Volume
The analysis will be initiated by setting down the most
general form of the volume-cubic equation of state, with
pressure, P, a function of specific volume, V , and tem-
perature, T
which is somewhat different and more inclusive than one
given earlier ( I ) . Here R is the universal gas constant, a
and 6 are functions of temperature, and P and y are
constants. The latter could also be taken as temperature
functions, but usually the improvement by doing so is
marginal. By specializing the constants and by
straightforward algebraic rearrangement including simple
translation in volume, all forms of cubic equations can
0 1979 American Chemical Society
82 Ind. Eng. Chern. Fundarn., Vol. 18, No. 2, 1979

easily be obtained from eq 1. Following are a number of or

examples.
I. Let P = y = 0 to get p = - -RT a
V - b V+2bV-b2
The denominator of the last term may be factored to give
p = - -RT a
which is the virial equation (third degree) of Onnes (24). (15)
11. Rearrange eq 1 to V - b V ( V + b) + b ( V - b)

P = RT(V + p) - aV + - 6 which is the Peng-Robinson equation (25).

VIII. A form which is not in the literature but has
V(V + 0) V ( V + P)(V + y) + V(V + P)(V +y) interesting properties is obtained from eq 7 by letting t
(3) = b = (P + y)/2, c = - [ ( p - y)/2I2, and a = a, giving
or p = - -RT
- U
RT a - PRT ay + 6 V-b V + C
p=-- (4)
V + P V ( V + P ) V ( V + P ) ( V +y)
+ A specialized case of this occurs if y = -P, then
NOWlet p = -b = -7, CY - PRT = a , a y + 6 = c to give p = -RT-- a
(17)
p = - -RT a
+ C v v+c
(5)
V - b V ( V - b) V ( V - b ) ( V +b ) Examples other than the eight presented can be given,
which is the Lee-Edmister equation (15),that as a surprise but they add nothing to the techniques of rearrangement
of eq 1.
to some is just a rearranged form of P = RT/ V - a/V(V
Clearly, if all cubic equations are merely specialized cases
+ P ) + 6/V(V + P)(V - PI. of eq 1,attention should be focused here to determine the
111. Let 6 = 0 in eq 1 to yield
characteristics of the different forms. This may be done
by first solving for the constants in eq 1 by the classical
method of van der Waals (32) that the first two pres-
sure-volume derivatives vanish at the critical point
Now translate by t in volume so that
p = - -RT a
(7)
V - t (V-t+P)(V-t+y)
Next let t = P = b, y = 2t = 2P, and a = a to get or by the alternate equivalent technique of using three
equal volume roots at the critical point, as explained by
p = - -RT a Martin and Hou (16). The latter is simpler and so will be
V - b V ( V +b) employed here. If eq 1 is multiplied out in descending
which is the Redlich-Kwong equation (27). powers of volume, it may be written as
IV. If in eq 7 we let P = y = t = b, and a = a, we have
v-
PyRT a -
0 (19)
which is the van der Waals equation (32). P P
+
V. If eq 6 is translated by P t in volume instead of A t the critical point with three equal roots
just t as in eq 7
(V - VC)3= 0 (20)
RT a
P= -
(10) which may be expanded to
v-p-t ( V - P - t + P ) ( V - P - t + y)
Letting P = b, y = P, and a = a, we have
v3 - 3VCV+ 3v:v- v,3 = 0 (21)
Comparing eq 19 and 21 for each power of Vat the critical
point, where a and 6 are taken as their critical temperature
values, for v2
which is the equation developed by Martin (20). It can
also be obtained by translating the van der Waals eq 9 by
1
L.

+
VI. If in eq 7 weset t = /3 = b, y = t c and a = a, we for V'
get
p = - -RT a
(12)
V - b V(V+C)
for V"
which is the form given by Usdin and McAuliffe (31) and
by Fuller (12).
VII. Referring again to eq 7 , let t = b, P = (2 + &)b,
y = ( 2 - h ) b , and a = a to yield It is useful to put these into dimensionless forms with
PcV,/RT, = Z,, so that eq 22 becomes
p = - -RT a
v- [ V - b + (2 + & ) b ] [ V - b + (2 - &)b] (P + YIP,
= 1 - 32,
(13) R TC
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 83

eq 23 becomes variables PR = PIP,, VR = V/V,, T R = TIT,, and Z, =

(PCVclR Tc)exp
-- - 3
prp: CUP,
2 2 - p
(P + r)Pc
+

(26)
R2T: R2TC2 RTC
and eq 24 becomes

The last three equations are independent, but there are

four unknowns, a , P, y, and 6, or their dimensionless This may be translated by t by replacing V in eq 35 with
equivalents, if P,, V,, and T , are known. Thus, a unique V - t or V Rin eq 36 or 37 with VR - tP,/Z&T,. If we then
solution can be obtained only if one of the unknowns is let t = P or y so that from eq 33
specified-usually as zero. To exploit this approach eq 25 CD .
and 27 are inserted into eq 26 to get
CUP, 6P,2
- - - --
R2T,2 R3TC3
2: + 32: - 32,+ 1 (28) and

which will be examined for its various possibilities. (39)

B. Consideration of Equations for the Critical which is a well-known reduced form of the van der Waals
Isotherm equation.
Suppose our interest first is only along the critical It is instructive to note the effect of translation on a
temperature line and we want to study two-term cubic calculated or selected 2, (not the experimental Z,). We first
equations (which the majority of them are), so 6 is set equal note that
to 0 and eq 28 becomes
-PC
.- - -2: + 32: -32, +1
R2TC2
which follows from V being replaced with V - t , thus,
The value of 2, can be set as we please, so after some giving
pretrial let us take it to be 0.25. This makes
-aPc
- - -27
R2T: 64
Here the superscripts, bt and at, mean before and after
at the critical temperature, and translation. For eq 37 translated according to eq 38 it is
seen from eq 41 that
2, = 0.25 + 1/8 = 0.375 (42)
As emphasized earlier (20,221, eq 39 gives results con-
Equation 25 then becomes sistent with its development only if 1, = 0.375 for which
RTC + -rpc 1 value it gives PR = 1 at the critical point where V R= 1 at
=- TR = 1. If, however, the actual V , or Zc is used for a given
64yPc RT, 4 substance, the representation along the TR = 1 isotherm
or up to the critical density will be vastly improved even
though the prediction right at VR = 1 is slightly off. Table
I gives a comparison with the National Bureau of
4RTc + -64= o (32) Standards data (13) of the predictions for argon whose Z,
= 0.29121.
Solving gives The earlier discussions (20,21)showed that this principle
must hold for the reduced form of any equation of state;
YPC = -1
- Le., wherever Z, enters, the experimental value should be
RT, 8
(33)
employed and not the value used to get the equation or
predicted by the equation. The reason is simply that the
Inserting this into eq 31 yields reduced volume is based on the actual critical volume so
PPC = -1 the value of Z, must also be calculated with the actual
- (34) critical volume.
RT, 8
It is of interest next to look at the second virial coef-
Here, the unknowns, a , P, and y, have been solved for as ficient of translated equations. If eq 7, where 6 = 0, is
dimensionless quantities to be used in the equation of state rearranged to solve for z
in reduced or dimensionless form which is obtained by
writing eq 1, with 6 = 0, as z = 1 + - -tP CY
RT RT[1 + P / ( V - t ) ] [ V -t + y] (43)
R T V ,T , - (aP,/ R2T:) (R2T,2VC2)
_p --
pc vpcvcTc PC2VC2(V + P)(V + y)
(35) Now in general as P - 0
RT
V - - + (T) (44)
or with the definitions of the reduced experimental P
84 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979
Table I. Pressures on the Critical Isotherm for Argon Using Values of 2, = 0.375 and 0.29121 in Eq 39
VR P, NBS % dev pR o ' 2 I ' % dev
100 0.033 95 0.026 46 -22.1 0.033 9 0 -0.1
20 0.162 09 0.128 09 -21.0 0.163 03 + 0.6
5 0.540 73 0.451 43 -16.5 0.552 30 t 2.1
2.5 0.834 2 1 0.750 77 - 10.0 0.862 35 + 3.3
1.25 0.995 97 0.989 09 - 0.7 1.000 0 4 + 0.4
1.0 1.000 00 1.000 00 0 1.041 7 4 + 4.2
- -
where t is the residual volume. Inserting this into eq 43
and letting P 0 or V a 2 /
Substance 1

Differentiating with respect to pressure a t constant

temperature

This may be put into reduced form

-
Figure 1. Generalized compressibility or i chart.
It has been shown earlier (18) that this slope of a constant
TR line as PR 0 on the usual compressibility plot of 2
vs. P R is just the generalized second virial coefficient, Table 11. 5Chart Sum, E , for a Number of Substances
-
BPJRT, where B is the second virial coefficient in the substance Z C a E
+
expression, i = 1 + B / V + C / P .... If we now combine Ne 0.309 0.325 0.634
eq 41 and 47 with 2 = Z and Zcat being Z, for any equation 0.305 0.325 0.630
with or without translation 0.295 0.330 0.625
0.294 0.324 0.618
ZC-T,(dz) ffPC 0.291 0.330 0.621
as PR -+ 0 (48) 0.291 0.332 0.623
dPR TR R2T,2TR 0.290 0.333 0.623
0.289 0.341 0.630
At the critical temperature this becomes 0.288 0.339 0.621
0.288 0.333 0.621
0.28 3 0.341 0.624
0.281 0.337 0.618
0.279 0.340 0.619
where BG1is the generalized second virial coefficient at a 0.279 0.340 0.619
0.278 0.345 0.623
reduced temperature of 1. The interesting characteristic 0.278 0.336 0.614
of this quantity is that it is independent of translation 0.278 0.339 0.617
because t has been eliminated. As an example for eq 37 0.274 0.345 0.619
0.274 0.350 0.624

zc- ( g)TR=l,pR=O
= 0.25
27
+-
64
= 0.671875 (50)
0.274
0.274
0.271
0.270
0.341
0.348
0.345
0.352
0.615
0.622
0.616
0.622
Thus, for van der Waals eq 39 it follows automatically that 0.270 0.363 0.633
0.268 0.365 0.633
0.267 0.346 0.61 3
P,=o = 0.671875 (51) 0.264 0.368 0.624
0.261 0.368 0.629
This can be checked by combining eq 30, 38, 42, and 47 0.260 0.360 0.620
0.259 0.355 0.61 4
at TR = 1 0.259 0.352 0.611
0.248 0.356 0.604
1 27
= 0.375 - -
8
+-
64
= 0.671875 (52) 0.248
0.242
0.358
0.37 0
0.606
0.612
0.238 0.365 0.603
The constancy of eq 50,51, and 52 leads one to speculate 0.234 0.340 0.574
whether this quantity, which will be designated the x, average (exclusive of H,O) = 0.62
i-chart sum
- ( dz/dPR )TR = ,,p = = - BPc 1R Tc,

a high t,,and vice versa. The verification of this idea is

is the same for all actual substances. One might guess this
to be so by noting the shape of the TR = 1 line on the .Z
chart for two specific cases as shown in Figure 1. If a
substance has a small negative slope at PR = 0, it will have
shown by Table 11, where it will be seen that the i-chart
sum is remarkably constant. The only notable exception
is water, which is highly polar, but so also is ammonia
which behaves like the other substances. In fact, what
variability there is in may be due to lack of precision
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 85

in the experimental determination of 2 , and B P J R T , , or
(dZ/dPR)TR=l=o, though it is possible that better data will
show ten&g to be slightly lower for some compounds
such as alcohols and ketones. The average value of
0.62 allows one to predict with considerable confidence the
second virial coefficient at the critical temperature from
the critical compressibility factor for any substance
Returning to eq 37, it may be translated in VR by (0+
t)P,/Z$T, instead of just tP,/@T,. Taking @P,/RT, =
118 as before
27/64
pR= - TR - (55)
z,VR - t P c / R T c - 1/8 (z,VR - tP,/RT,)'
which is the reduced form of eq 11.
The development leading to eq 37 was on the as-
sumption of a value for 2, of 0.25, but the procedure could
have followed Example V of the several cubic equations
by setting p = y. This would have made eq 25 become
Now three arbitrary values of 2, (0.23, 0.25, 0.27) are
inserted into eq 65 and each equation is translated by
t P , / R T c to give a good fit at about twice the critical
= density. As shown in the pioneer paper (20) on volume
translation, a cubic equation cannot be adjusted to fit the
critical isotherm at reduced densities of both 1.5 and 2.0.
The translation selected in most cases in this paper will
give deviations that are slightly negative a t twice the
(54) critical density and of the order of 25% positive at about
1.5 times the critical density. If interest is in reduced
densities only to 1.5, the translation can be reduced and
a good fit obtained at 1.5, but large negative deviations
would occur at twice the critical density and would be far
worse if the equation were to be used at even higher
densities. Table I11 gives the comparison with NBS data
for argon for the three values of 2,. For all densities up
to the critical the deviations are well below 1% for 2, =
0.25. The results are not so good for 2, = 0.23, where
relatively large negative deviations occur, and for 2, = 0.27,
where large positive deviations occur for densities below
the critical. Above the critical the three equations give
similarly large deviations. The best equation overall is for
2, = 0.25, translated by 0.082, and can be written

and eq 27 become (6 = 0)
-P'P-,' or in its reduced form before a specific translation is made
- 2: (57)
R2T$ 27/64
PR = - TR - (67)
Combining eq 56 and 57 to eliminate P P J R T , yields Z,VR- tP,/RTc (B,VR + 1 / 8 - t P , / R T J 2

4ZC3- 2,' + 62, - 1 = 0 (58) which is the equivalent of eq 55 or 37 with translation.

The problem of large deviations for p R above 1.2 is
This may be solved by Cardan's method for the roots, 2, characteristic of all cubic equations of state, for the actual
= 114, 1, and 1. Since 2, = 1 implies ideal gas at the
data tend to follow a fourth-degree equation as discussed
critical point, only the first root is meaningful in this previously (21). The major difference between the many
application and it is identical with the assumption which different cubic equations that have been proposed is
gave eq 30, 33, and 34. whether they fit better at about two-thirds or one-half the
Because eq 55 differs from eq 39 only by translation, it critical volume. One of the major advantages of eq 67 is
follows that = 0.671875. As pointed out earlier (20),
that a small change in translation will permit fitting exactly
however, the translation characteristic makes eq 55 much where one chooses. In obtaining eq 65 from eq 25,26, and
more powerful than eq 39 because 2, is not constrained 27, it was not necessary to solve explicitly for /3 and y, but
to 0.375 and can be made more realistic. if one wishes to do this, he would find that p and y are real
If in eq 29 2, is taken to be less than 0.25, the following numbers for 2,s 0.25, but imaginary or complex numbers
results for 2, > 0.25.
2, = 0.24; aP,/R2T,2 = 0.4390; = 0.6790 (59) We can now show how some of the well-known cubic
equations fit into the general pattern. As shown in ex-
2, = 0.23; aP,/R2T: = 0.4565; = 0.6865 (60) ample 111, if we let y = 2P and t = p, we get the Red-
Since the desired value of 2 is 0.62, it is clear that to make lich-Kwong equation. Using dimensionless quantities, eq
2, < 0.25 is going in the wrong direction. For values 25 becomes
greater than 0.25, we get 3PPc
- - - 1 - 32,
2, = 0.26; aP,/R2T: = 0.4052; E= 0.6652 (61) RTC
2, = 0.27; aP,/R2TC2= 0.3890; X = 0.6590 (62) and eq 27 with 6 = 0 gives
2, = 0.3; aP,/R2Tc2 = 0.343; = 0.643 (63) -2p2pc2
- - 2:
2, = 1 / 3 ; aP,/R2T,' = 0.2963; =0.6296 (64) R2TC2
Here the trend is toward 0.62, but it must be noted that Eliminating PP,/RT, between eq 68 and 69 yields an
is indicative of the behavior only up to the critical expression for 2, (similar to eq 58)
density, so the behavior above the critical density (or 92: - 182,' + 122, - 2 =0 (70)
volumes less than the critical volume) must be studied.
Therefore, eq 36 will first be combined with eq 25, 26, 27 Again this may be solved by Cardan's method to give two
to obtain after translation roots that are complex and the third which is real and
useful
PR = TR/(Z,VR - tP,/RT,) - (-ZC3+ 32,' - 3 2 , +
l ) / [ ( Z , V R - tP,/RT,)' + (1 - 3 2 , ) ( Z C V-~ tP,/RT,) + 2, = 0.246693 (71)
Z23 (65) The translation for eq 67 is, therefore, from eq 7 1
86 Ind. Eng. Chem. Fundam., Vol. 18, No. 2 , 1979

-tP,- ---PP, - -bP,

=--
1 - 32,
- 0.08664035 (72)
RT, RT, RT, 3
and using eq 71 in eq 65 a t the critical temperature
TR 0.4274802
P - -
- Z,VR - 0.08664035 +
Z,VR(Z,VR 0.08664035)
3mC.lmt-mmwo "m I (73)
3oo*t-wmom"woomo $23
5 0 0 0 0 0 0 0 0 A i i ~ ~ eo im which is the reduced form of the Redlich-Kwong equation
1 + + + + + + + + A * + W 00
I 1
++ I Icoa,
before temperatures other than the critical are considered.
Table I11 gives the results predicted by this equation and
it will be seen that the fit is similiar to that of eq 66. This
is expected because the two equations have a similar
mathematical form as discussed before (20) and since the
Redlich-Kwong equation gives Zcat = 0.246693 +
0.08664035 = 113 according to eq 41, while the example
of eq 66 gives 2cat = 0.25 + 0.082 = 0.332, which values are
almost identical. The Redlich-Kwong, however, must be
slightly inferior because its Z-chart sum is = 0.246693
+ 0.42748 = 0.674173, which is to be compared with
0.671875 of eq 66 and the desired value of about 0.62.
Furthermore, the Redlich-Kwong will not fit other sub-
stances nearly as well as for argon whereas eq 66 can easily
be made to do so by translation. Naturally, if one wishes
to fix the translation for many substances and never allow
it to vary (thus, fixed 2cat),this can be done by using an
average value that is best for all the substances involved.
Of course, the Redlich-Kwong equation itself could be
translated to give a better fit of the experimental data than
given by eq 73 but it would be no better than eq 67 and
would be more complex in form.
From example VI1 if we let
2-d2
P = (2 + f i ) b and y = (2 - &)b or y = -

we obtain the Peng-Robinson equation. Now eq 25 be-

comes
4PPc
= 1 - 32, (74)

and eq 27 becomes

yields the cubic equation in 2,

Eliminating pPC2/R2Tc2

As with eq 70 two roots are complex and the third and

useful root is
2, = 0.229605235 (77)
This may be inserted into eq 75 to give according to
Example VI1
bP,
-tP,- - -- PPC
= 0.077796074 (78)
RT, RT,- (2 + &)RT,
Using eq 77 and 78 in eq 65 gives
P R = TR/(Z,VR - 0.077796074) -
0.457235529/[z,vR(zcvR +
0.077796074) +0.077796O74(ZcV~- 0.077796074)l (79)
which is the reduced form of the Peng-Robinson equation

for the critical isotherm. Table I11 gives the predictions
of this equation, and it is seen that these are somewhat
lower than those of the equation based on 2, = 0.23 and
translated by 0.09. If the latter had been translated by
0.0774 so that its Zcat = 0.3074 which is almost the same
as 2, = 0.229605 + 0.077796 = 0.307401 in the Peng-
Robinson, the two would predict almost the same. Looking
at the Z-chart sum for the Peng-Robinson equation, we
+
find 1 = 0.229605 0.457236 = 0.68684. Recalling again
that the desired value is 0.62, it is seen that eq 79 is
somewhat worse than eq 55 or 67 or even the Redlich-
Kwong equation.
From example VI if we let y = P + c and t = 0,we get
the Usdin-McAuliffe or Fuller equation (12). We note that
if c = 0, we obtain 2, = 0.25 from eq 56, 57, and 58, which
with the indicated translation gives the van der Waals
equation (39). If c = P, eq 68,60, and 70 give 2, = 0.246693
which with translation gives the Redlich-Kwong equation
(73). If we take y = m@,which is equivalent to c = (m -
1)P or P + y = (m + 1)P, m may be set at will. In this
procedure eq 25 becomes
-PP,
- --1 - 32, (80)
RT, m + l
and eq 27 with 6 = 0 becomes
P2PC2 2:
-- -- (81)
R2T,2 m average predictions will be no better than eq 66. If interest
Once m is set, P can be eliminated between eq 80 and 81
to give a cubic in 2, whose roots can be determined as in
eq 58 or 70. Alternatively, 2, may be set and the two
equations solved for m. This is easier because m occurs
in a quadratic rather than a cubic. As an example, take
2, = 0.245 which determines cyPc/R2T? by eq 29. Then
eq 80 and 81 give m = 2.34962058, and either eq 80 or 81
gives PPJRT, = 0.079113438. Noting that P = t , eq 65
yields
TR 0.430368875
PR =
Z,VR - 0.079113438- ZcVR(ZcV~ + 0.106773124)
(82)
The results of this are tabulated in Table 111. Had eq 67
been translated by 0.075 instead of 0.082, it would have
given almost the same results. This is because of similarity
of form and Z,st. For eq 82 it is ZFt = 0.245 + 0.079113438
= 0.324113438 and for eq 67 it would be 0.25 + 0.075 =
0.325. The two equations are of about equivalent sim-
plicity, but it is easier to fix the translation in eq 67 than
to assume 2, and calculate m, P, and cy in eq 65 to get eq
82.
From example VI11 it is seen through eq 25 that if 2,
< 113, b turns out to be a positive number and the results
are similar to those from eq 65 for 0.25 C 2, < 113. If 2,
> 113, however, the value of the 2-chart sum can be made
close to 0.62 and the predictions are fantastically good
below the critical density. This is shown in Table I11 for
2, = 0.42, which gives the equation
TR 0.195112
PR = -
ZCVR -t 0.13 (Z,VR)~ + (0.239140)2 (83)
whose 2-chart sum is = 0.42 + 0.195112 = 0.615112.
It might be expected that this would be a good equation
to use for temperatures away from the critical and densities
up to the critical. Unfortunately, it does not have the
ability to inflect properly at the critical as can be seen by
the low pressures above the critical density. This effect
is carried back to lower densities for temperatures above
Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 87
the critical if the numerator of the second term is taken
as a temperature function (Le., a ( T ) which is 0.195112 a t
T,). For temperatures below the critical and densities up
to the critical, the equation does an excellent job.
For the three-term cubic it is instructive to start with
the conditions of example 11, backtrack to I, and then
generalize. In eq 1 let P = -7, as done to get eq 5. From
eq 25 it follows that 2, = 113. Combining eq 26 and 27
then gives a relation between cy and 6
Now let cyPc/R2T,2= 113, which makes 6P:/R3T: = 1/27.
Putting this into eq 27 makes = y = 0, which gives the
simple virial eq 2 that in reduced form is
This equation can be obtained directly as in example I by
letting = y = 0. The predictions of eq 85 are given in
Table 111. A t low densities the results are good, but a t
higher densities it gives significant deviations so that the
average overall densities to twice the critical are not so
good as for the two-term eq 55 or 66. Equation 85 can be
translated to improve the predictions at high density, but
this will worsen those below the critical density and the
is only in densities less than the critical, eq 85 can be
translated by just the right amount to do a slightly better
job than any of the other cubics. This is because its 2-chart
sum, E, of 113 + 113 = 213, is less than and closer to 0.62
than any of the others.
The Lee-Edmister equation 5 permits setting b at
something other than 0 which is the unique value giving
the virial equation. An equivalent way to do this in eq 84
is to set aP,/R2T,2 at a value other than 113, since eq 5
has been shown to be a form of eq 1 with P = -7. If
cyP,/RT, is taken as 8/27, then 6PC2/R3Tc3 = 0 and
PyPc2/R2Tc2
eq 1 becomes
= 1/27 from eq 27 so that in reduced form
m n In-
This is just a reduced form of eq 17 previously considered
and it predicts high for densities below the critical and low
for densities well above the critical.
By trial it is found that the best three-term equation for
argon, with P = -y is obtained by letting aP,/R2T,2 = 0.34
which makes 6P,2/R3T2= 0.437037037 and /3-yP,2/R2T,2
= -11150. This gives
pR=---TR 0.34 0.0437037037
+
~CVR (Z,VR)~
- 1/150 Z,VR[(Z,VR)~ - 1/150]
(87)
which is the reduced form of eq 1 that is equivalent to eq
5. Table I11 gives the results for this equation and it is
seen that it is about as good, but no better than eq 66.
Varying cyP,/R2T,2 does not improve the situation. Its
third term, therefore, does not give it any advantage at the
critical temperature over two-term cubic equations. For
temperatures away from the critical, it does offer the
possibility of two temperature functions (i.e., a(?")and
G(T))compared to just one for two-term equations, but this
does not give it any better overall behavior because of the
overpowering defect of all cubic equations at reduced
densities in the range of 1.5 to 2.0.
88 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979
PI
Figure 2. Typical pressure-temperature graph.
C. Consideration for Temperatures Other Than
the Critical
As mentioned for eq 1, the volume constants, /3 and y
could be dependent upon temperature; however, here they
will be assumed to be temperature independent as is
customarily done, and also any translation in volume will
be constant, while a and 6 will be considered to be tem-
perature dependent. Since eq 66 is as good or better than
all of the other two-term cubic equations and at the same
time is the simplest in form, it will be examined first. To
make its a a function of temperature, the least complicated
expression that can be employed is TR", and it may be
introduced into eq 66 as
This is just a slight modification of what Berthelot ( 4 ) did
80 years ago when he put T in the denominator of the
second term of the van der Waals equation.
To determine the value of n, use is made of the slope
of the critical volume line on a pressure-temperature
diagram or the slope at the high end of a vapor-pressure
plot. As developed and emphasized in earlier papers
(16,19,20,21),the critical isometric is essentially, though
not exactly, straight for all substances and its slope is the
slope of the vapor-pressure curve just as it approaches the
shows that for rather high temperatures, where T R -
critical point. Figure 2 shows this characteristic and also
the critical isometric (and all the other isometrics) tends
2,
to curve down very slightly; however, this effect is minor
compared to others and is outside the range of temper-
atures encountered most often and considered in this
discussion.
Figure 3 shows the generalized vapor-pressure plot of
log PRvs. l/TR, presented several times in the literature
= dPR/dTR as T R -
(16,19,21). The parameter on each curve is the slope M
1. All that is needed to establish
which curve a substance follows, and thus what will be the
slope of the critical isometric, is the critical point and one
vapor-pressure point such as the normal boiling point. The
curves for different substances never cross each other on
this plot so that a single vapor-pressure point determines
a curve all the way to the critical point with a unique slope
at the critical point. (This is often useful for getting
intermediate vapor pressures.) In the case of argon which
is the example used in this discussion, the normal boiling
point is 87.28 K, the critical temperature is 180.86 K, and
IO 12 14 16 ,-R ' 8 20 22 24
F i g u r e 3. Generalized vapor pressures with critical-point slopes.
+I ~ -1.0
Figure 4. Behavior of the second derivative of pressure with respect
to temperature a t lower temperatures.
the critical pressure is 48.34 atm, so 1/TR = 1.7285 and
PR= 0.020687. Placing this point in Figure 3 shows that
the slope of the critical isometric is about 6.1. (Because
of the inherent lack of precision in a derivative compared
to a primitive, this should not be taken to be necessarily
better than f 5 % .) To utilize this, differentiate eq 88 to
get
One quickly notes that for all isometrics (dPR/dTR)Vas
given by eq 89 decreases with temperature if n is a positive
constant. This is in accordance with the experimental facts
for volumes greater than the critical volume, as shown in
Figure 2, but it is contrary to the facts for volumes less
than the critical volume, and of course, the critical volume
line has little appreciable curvature as mentioned above.
Also, as the volume decreases to about half the critical
volume, (dPR/dTR)Vtends to become constant again. In
another way (dzpR/dTR2)V is negative for large volumes,
zero at about the critical volume, positive for volumes less
than the critical, and negative again for volumes less than
half the critical volume. This is shown in Figure 4 where
the solid line is the experimental data.
Despite the inability of eq 88 or any similar two-term
cubic, to give the correct curvature to the isometrics by
making CY a function of temperature, it is common practice
to use such equations and fit the data as best as possible.
The dashed line in Figure 4 shows how this approximation
works. The results, although not really precise, are good
enough to make useful calculations. The principal reason
the approximation works is that the curvature of the
isometrics is small and other deviations are of much greater
significance.
To approximate the critical isometric with eq 88, one
can use eq 89 to calculate its slope at T R = 1 and T R = 1.5
and note the downward curvature. The reason for selecting
this temperature range is not only that most situations
involve temperatures below T R = 1.5, but that the critical
isometric is linear between 1 and 1.5 and only starts to
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 89
Table IV. Comparison of Six Equations of State with Data ( I 3 ) for Argon
Martin-with Yartin-wlth
... ~

pR Redlich- Soave Peng- Martin smaller Linear

Kwong Robinson translation Isometrics
Data
(A) !Bl (D) (E) g (F) ~

R Dev. R oil.. 2 Dev. R Dev. R Dev.

TC = io0 0.5 ,02001 ,02002 1.01 ,02005 + . 1 7 ,02003 +.07 .02001 -.04 ,01994 -.35 ,02008 +.32
.03395 .a3394 -.03 ,03334 -.03 ,03390 -.16 ,03394 -.03 ,03392 -.OX ,03393 -.05
150.86X -.03 ,04087 -.03
1.2 ,04088 ,04087 ,04082 -.15 ,04088 -.02 .04087 -.04 .04086 -.06
1.5 .05127 ,05125 -.03 .05126 -.01 ,05120 -.i4 ,05126 -.02 ,05126 -.02 ,51251 -.03
FC = 20 0.7 ,10704 ,10716 +.11 ,10756 +.49 ,10703 .OO .lo699 -.05 ,10594 -1.0 ,10795 +.88
i .16209 . 1 6 1 8 7 -.14 , 1 6 1 8 7 -.14 ,16089 -.74 ,16189 -.12 ,16150 -.35 ,16171 -.23
48.34atm ,19781
1.2 ,19808 -.14 .19784 -.12 ,19562 -.74 ,19789 -.lo ,19770 -.19 ,19753 -.28
1.5 ,25159 ,25130 -.11 ,25155 -.02 .25002
-.62 ,25142 -.07 ,25136 -.09 ,25126 - . 1 3
!0 0.8 ,22813 ,22841 t.12 ,22910 t.13 ,22690
-.54 ,22806 -.03 ,22528 -1.3 ,22984 + . 7 5
13.41
C
.30565 ,30497 t . 2 2 ,30497 - . 2 2 ,30160
-1.3 ,30503 -.20 ,30366 -.65 ,30439 - . 4 1
1.2 ,38079 ,38002 -.20 ,38014 -.17 , 3 7 5 7 7 ->.3 ,38031 -.13 .37968 -.29 ,37893 - . 4 8
ymole, 1.5 ,49183 ,49092 -.19 ,49193 7 . 0 2 ,48623 -1.1 ,49136 -.lo ,49122 -.12 ,49078 -.21
3 .87 ,43008 .43128 +.28 ,43251 - . 5 7 ,42590 - . 9 7 ,43048 +.a9 ,42345 -1.5 ,43375 +.85
R = 1 ,54073 ,53993 -.15 , 5 3 9 9 3 - . 1 3
,53023 -1.9 .59004 -.l3 .33588 -.90 ,53809 - . 4 9
,082jjjjlatrr1.2 ,70432 ,70256 -.25 ,70302 -.18 ,68905 -2.2 ,70351 -.12 ,70191 -.34 ,69861 -.Xi
q r r o l e . K1.5 ,94212 ,93998 -.23 ,94390 1.19 . 9 2 4 5 2 -1.9 .94i45 -.07 ,94131 -.09 ,93940 - . 2 9
2.3 .95 .73591 ,74169 1.19 ,74278 t.93 ,72381 -.83 ,74057 +.63 ,72937 -.89 ,74311 t.98
z =
1 . 83421 ,83827 t.50 ,83837 +.50 ,82040 -1.7 .83327 -.11 ,82997 -.05 ,83439 +.02
c. 29121 1.2 1.2134 1.2130 +.2l 1.2147 +.36 1.1784 -2.1 1.2156 +.43 1.2143 -.32 1.1995 - . 9 3
1. 5 1.7430 1.7502 c.41 1.7651 1 1 . 3 1.7052 -2.2 1.7541 +.64 L.7551 +.69 1.7472 i . 2 4
1 U 3 . 6 .99 .92682 ,93542 r.93 ,93576 +.96 ,92450 -.25 ,93480 +.86 ,92738 1.06 .93436 +.8l
1 *.9632 ,96826 +.53 ,96826 +.53 ,95463 - . a 9 ,96797 +.50 ,96137 -.19 ,96494 +.18
1.2 I.5861 1.6040 +1.1 1.6077 tl.., 1.3508 -2.2 1.6080 tl.9 1.6107 -1.6 1.5766 - . 5 3
1.5 2.4836 2.5049 t.56 2.3366 +2.1 2.4235 -2.4 2.5097 +1.1 2.5096 -1.1 2.4942 + . 4 3
./0.8 1 . 99560 ,99931 t.38 ,99937 - . 3 d .99654 t.09 ,99933 +.37 ,99804 -.25 .99880 t.32
1.2 1.9C02 1.9475 +2.5 1.9537 12.8 ;.8709 -1.5 1.9515 +2.7 1.9552 +2.9 1.8983 -.OB
1.5 3.2217 3.2802 +l.8 3 . 3 3 3 9 +3.5 3.1467 -2.3 3.2813 C1.9 3.2568 +i.4 3.2484 + . d 3
d 3 . 9 1 . 99946 1.0000 t.05 1.0000 - . 3 5 ,99988 + . a 4 1.0300 +.Os .99999 +.05 1.0000 +.05
1.2 2.034- 2.1248 t 3 . 4 2.1325 +3.8 2.0291 -1.2 2.1275 +3.6 2.1267 13.3 2.0599 +.2a
1.5 3.6167 3.7314 t2.3 3.7678 - 4 . 2 3.1298 -2.4 1.6974 +2.2 3.6648 t1.3 3.6497 +.91
.99999 1.0033 t.33 1.0033 + . 3 3 1.3002 +.02 1.0029 +.29 1.0006 +.06 1.00l5 + . l 5
i.2 2.2174 2.3195 14.6 2.3288 1 5 . 0 2.1964 -.95 2.3193 +4.6 2.3072 -4.: 2.2326 +.68
1.3 4.0471 4.1604 +2.8 4.2405 -4.8 3.9381 -2.7 4.1478 12.5 4.0855 +.95 4.0791 +.79
1,l.l 1 1.0006 1.0195 +:.9 1.3195 t ? . ? L.0039 +.33 1.0174 +1.7 1.0069 7.63 1.0116 +1.1
1.2 2. 3983 2.5429 -6.0 2.5539 +6.3 2.3793 -.79 2.3371 +5.8 2.5037 +4.4 2.4254 tl.1
1. 5 4 . 5252 4.6702 - 3 . 2 4.7650 +5.3 4.3802 -3.2 4 . 6 4 4 2 +2.7 4.5314 C.14 4.3461: + . 4 6
j.;1. 2 1 1.0058 1.0598 +5.4 1.0598 -5.4 1.0182 +?.2 1 , 0 5 4 4 +4.8 1.0255 +2.0 1.0388 +:.3
1.2 2.6105 2.8076 + 7 . 5 2.8204 + a , ? 2.5863 - . 9 4 2.7923 +7.0 2.7234 +4.3 2.5473 - 1 . 4
1.5 5.0738 3.2457 7 3 . 4 5.3560 t5.6 4.8655 -4.1 5.1995 -2.5 5.0251 -.96 5,0605 - . i o
1./1.4 .99 ,96551 1.1471 t19. 1.1486 +19. 1.0069 + 4 . 3 :.1235 +16. 1.0167 +5.3 1.0789 ti2.
1 1.3635 1.2646 +18. 1.2616 +;8. 1.1084 +3.7 1.2401 -16. 1.1298 t5.7 1.1809 +11.
i. 2 3.1966 3.5202 + l o . 3.5370 +ll. 3.1063 -2.9 3.4662 +8.4 3.2625 +2.0 3.2i97 -.66
1.5 6.4759 6.6643 12.9 6.8081 + 5 . l 6 . C 0 9 3 -7.2 6.5466 +1.1 6.1489 -5.1 6 . 2 7 ~ 3-3.1
1/1.6 .96 . 79003 i.1435 -45. 1.1533 +46. ,83217 - 5 . 3 i.0773 +36. ,81123 t2.7 1.0014 +27.
1. 3426 1.7432 +30. 1.7432 -30. 1.3416 -.07 1.6655 t 2 4 . 1.3713 +2.l 1.5076 +12.
1.2 4.1993 4.6021 +lo. 4.6231 - 1 0 , 3.8411 -8.5 4.4614 76.2 3.9879 -5.0 4 . 0 3 a i -3.d
1.5 8. 5241 5.5905 +.78 8.7707 -2.9 7.4723 -12. a.3318 -2.3 7.5287 -12. 7.8343 -8.1
lVi.8 .92 .64 I 32 1.1542 +78. 1.:860 -83. ,54764 -15. ,99922 + 5 4 . ,44780 -3:. ,87751 +36.
2.1534 2.6717 -24. 1.6717 - 2 4 . 1.8117 -15. 2.4740 +15. 1.8166 -16. 2.1131 -1.7
1.2 5.9763 6.2600 +4.8 6.2855 -5.2 4.9027 -18. 5.9407 -.60 4.9733 -17. 5.2159 -13.
1.5 11.619 11.277 -2.9 11.497 -1.: 9.3949 -19. 18.752 -7.5 9.2500 -20. 9.8642 -15.
;/2 .86 ,45894 .95351 +lo8 1.0468 +128 - . @ E 0 2 -118 ,63539 +38. -.3691 -180 ,50252 +9.3
4 . 0320 4.3180 +7.1 4.3180 -7.1 2.6523 -34. 3.8622 -4.2 2.5451 -37. 3.1372 -22.
1.2 9.0682 3.8113 -2.8 8.8416 -2.5 6.4521 -29. 8.1382 -10. 6.3088 -30. 6.9039 - 2 4 .
1.5 16,318 15.117 -7.4 15.358 -5.8 11.979 -27. 14.094 - 1 4 . 11.421 -30. 12.5.7 -23.

3.42748 ? 7 ! 64Tnoj5
_ - n
?_VR -0.08664 TR05f V !?cVRf0.08564;
(D) P
R - -zcVR-O. 082 l~cV,+0.043)
c R
T
R 0.42748 [1+0.48(1-?R05) 1 TR - __ 27/(64~,~)
IBj Pa = =z C v R - 3 . 0 8 5 5 4 Z c V R ( Z c V R + O . 08664) ( E ) PR =
ZcVR-0.067
0.457236 [1+0.375(1-TRoj l 2 0 . 5 -0.178125TR
(c) a - FC V R ~ Z c V R + 0 . 0 7 7 8 ) + 0 . 0 7 7 8 ( T c v R - o o 7 7 8 ) IF) TR -

-
V -0.0778
2 2 = 5-___- R =
c R i:c V R - 0 . 0 7 5 (;cvR+0.0j)2
droop a little as TR 2. In the case of eq 88 for argon should be a good equation for argon. This is shown to be
whose 2, = 0.29121 one quickly finds that for n = 0.55 at true in Table IV where eq 90 is presented as eq (D) and
VR = 1, eq 89 gives compared with the NBS data on argon. (In making these
comparisons one can emphasize either the absolute de-
() dTR v
= 6.857 when TR = 1
viations or percentage deviations depending on the ulti-
mate use of the equation of state. Here a little more weight
is given to the percentage deviation.)
which is high, and The selection of the amount of translation depends in
part upon the critical compressibility factor and the two

() dTR v
= 5.888 when T R = 1.5
are simply related in a linear fashion. To fit data a t about
twice the critical density, but have fairly high positive
deviations (20-2570) a t about two-thirds the critical
volume, along the critical isotherm, use
which is low. The slope at an average temperature of TR
= 1.25 is 6.25 which compares favorably with the 6.1 from tP,/RT, = 0.8572, - 0.1674 (91)
the reduced vapor-pressure charts, so
To fit data well around two-thirds the critical volume, but
TR 27 / 64TR055 have high negative deviations a t twice the critical and
p R = - - (90)
ZCVR - 0.082 ( i c V +~ 0.043)2 higher densities, use
90 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979
tP,/RT, = 0.7522, - 0.152 (92)
These equations give for argon the values of 0.082 and
0.067, respectively. Clearly anything in between is ac-
ceptable depending upon where the fit is to be maximized
above the critical density.
A variation of (D) is the temperature function. In (E)
it has been made linear with the slope of the critical
isometric taken as 6.155, and the translation made a little
less than (D) and (E). The performance is exactly what
would be expected. Below the critical density it predicts
too high at the lowest temperatures because it does not
allow the isometrics to curve down as they really do. In
the region of the critical density it is superb because it does
not force downward curvature on isometrics that are es-
sentially straight, as does eq (D). At the higher densities
the effect of curvature of the isometrics is completely
dominated by the large deviations in the critical isotherm
a t reduced densities around 1.5 to 2.0, and its smaller
translation makes it better at 1.5 and worse at 2.0. On an
overall basis (E) performs as well as any other equation,
so one must conclude that in the two-term cubic linear
isometrics are as good as isometrics that always curve
down.
A number of years ago there were claims that the
Redlich-Kwong equation was the best of the two-pa-
rameter equations of state so it has been selected for
comparison as eq (A) in Table IV. For densities up to 1/4
the critical it is not as good as (D). For densities around
the critical the two are similar. At 2/3 the critical volume
(A) is not as good as (D), but at twice the critical density
it is a little better though a slight change in translation
would make (D) just as good. Overall the two equations
are about a standoff for argon, but other substances will
reveal appreciable differences. Also the Redlich-Kwong
can never be quite as good as eq (D) or (E) or eq 55 because
its 2-chart sum is = 0.33333 + 0.42748 - 0.08664 =
0.67417, which is slightly greater than that of (D).
There have been several attempts to improve the
Redlich-Kwong equation either by changing the tem-
perature function or by changing the volume-function
constants. Soave chose the former procedure, replacing
the simple l/'Td.5 with [l + m(1 - TRo.5)]2. He made m a
function of the acentric factor (26) which is just an em-
pirical parameter somewhat equivalent to the fundamental
quantity, M , but which does not constitute a basic fluid
characteristic as does M which is the slope of the critical
volume line on P-T coordinates. Soave's eq (B) is shown
in Table IV and the results indicate no improvement over
the Redlich-Kwong as the two predict almost the same
since they are identical at the critical temperature and
since it is for substances with lower experimental 2, that
a variable temperature function, such as Soave's or l/TRn,
is needed in place of 1/TRo,5.
The Peng-Robinson eq ( C ) has been shown to be a
specific case of the all-inclusive eq 1 presented in this
study, but it represented a new development because it
was not based on previous well-known equations. It uses
the same temperature function as Soave, [l+ ~ ( 1TR',~)]',
- function of Soave, or the linear temperature function (20)
with K a function of the acentric factor. Its principal
difference from the Soave equation is that it predicts the
critical compressibility factor to be 0.3074 instead of 1/3.
This is not beneficial for argon, but it does help for
substances whose z, is around 0.26 to 0.27. Table IV shows
that below the critical density it is inferior to (A), (B), or
(D) because its .%chart sum, 2 = 0.3074 + 0.4572 - 0.0778
= 0.6868, is higher than for (A), (B), or (D). The main
reason for the large negative deviations in this range is that
the generalized second virial coefficient at the critical
'Pable V.
-
substance ZC M a
Ar 0.291 6.1 0.332
c,H4 0.281 6.5 0.337
C4F8 0.278 7.8 0.336
i-C 0.270 7.2 0.352
CHF, 0.259 7.4 0.352
3
" 0.242 7.4 0.37 0
-(dZ/dP&R=l, p R = o = -BG,.
temperature for (C)is -0.379 whereas the true value for
argon is -0.332. At 213 the critical volume the Peng-
Robinson is better than (D) while at twice the critical
density, it is not so good.
The conclusion from the data on argon is that no one
equation stands clearly above the others, even though no
other equation is better than (D), and (D) is as simple as
any other in form. In order to test the versatility of any
of the equations, it is necessary to look at other substances
carefully chosen over a range of parameters that determine
-
the PVT behavior. These have been shown to be z,,M ,
and (dz/dPR),,=,, as PR 0. Substances have been se-
lected that have dependable wide-range PVT data
available and are listed in Table V.
The last two substances in Table V are polar, but that
does not affect the principles involved unless there is a high
degree of chemical association of vapor-phase molecules.
It would have been more desirable to have selected a
nonpolar substance with a low z,, such as octane or nonane,
but the experimental PVT data for these are so extremely
limited that no reliable comparisons can be made.
For ethylene the temperature function to be used in eq
67 is TR0.@while the translation is 0.074 and the resulting
eq (D) up to the critical density is clearly superior to the
Redlich-Kwong, the Soave, the Peng-Robinson, and the
Chueh-Prausnitz (5). (See Table VI.) As expected, the
latter equation is better than the Redlich-Kwong, Soave,
and Peng-Robinson below the critical because the con-
stants of the Redlich-Kwong were arbitrarily adjusted to
get a better fit for saturated vapor volumes which, of
course, are densities below the critical. Even in this range,
however, the Chueh-Prausnitz is inferior to eq (D), partly
because it has the same temperature function as the
Redlich-Kwong. Above the critical density its deviations
are so very large it must be dismissed as a serious con-
tender for the throne of cubic equations. At reduced
densities of about 1.5 the Peng-Robinson is better than
(D), but this is simply because the translation for (D) has
been selected by eq 91 so that it will do a better job near
twice the critical and higher densities. As with argon, the
translation could have been set by eq 92 and the fit at pR
= 1.5 would have been equal to that of the Peng-Robinson,
while still being far better than the Peng-Robinson below
the critical density. Equation (F)has been introduced here
to show how another simple temperature function, ek(l-Td,
behaves. It gives about the same fit as the temperature
power function, TRn. The more complex temperature
could just as easily have been chosen and the results would
have been as indicated for argon. The overall conclusion
for ethylene is that eq (D) is both the best and the simplest.
Table VI1 gives the comparisons for perfluorocyclo-
butane. Up to a reduced density of 0.8 eq (D)is better
than all the others, particularly if reliance is placed on the
higher precision data. From the critical density to about
1.8 times the critical the Peng-Robinson is very slightly
better. In general, the comparisons are about the same
as for argon.
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 91

Table VI. Comparison of Six Equations of State with Data ( I 0 ) for Ethylene
C2H4 Martin -with
Exponential
ETHYLENE Red 1 ich- Peng- Chueh- Temperature
Kwonc Soave Robinson Martin Prausnitz Function
(A) (a) (Ci (3) (El (Fi
P , bar % % % 3 %
data P Dev. P Dev. P Dev. P Dev. P Dev. P Dev.

Tc = 0.8 -25 13.903 13.966 t.46 13.932 +.21 13.779 -.E9 13.894 -.06 13.939 +.26 13.943 t.29
282.35K 10 16.582 16.569 -.08 16,570 -.07 16.374 -1.3 16.530 -.31 16.544 -.23 16.530 -.32
75 21.401 21.321 -.37 21.413 t.06 21.150 -1.2 2 1 . 3 1 7 -.39 21.301 -.47 21.302 -.46
Pc = 150 26.843 26.718 -.47 26.931 +.33 26.605 -.E9 26.732 -.42 26.703 -.52 26.764 -.30
5 0 . 4 1 9 7 bar 1.5 -25 22.054 22.367 t1.4 22.251 t.89 21.905 -.67 22.155 t.46 22.278 +l.O 22.319 t1.2
10 27.684 27.688 t.01 27.692 +.03 27.187 -1.8 27.581 -.37 27.610 -.27 27.578 -.38
-C = 7.635 75 37.502 37.289 +.57 37.604 s.27 36.845 -1.8 37.280 -.55 37.227 -.73 37.236 -.71
150 48.434 48.074 -.74 48.804 t.77 47.804 -1.3 48.122 -.64 48.028 -.E4 48.222 -.44
gmo 1e / d r n 3
3.5 0 40.984 41.561 t1.4 41.380 +.97 40.732 -.62 41.237 t.62 41.226 1.59 41.397 +1.0
R = ,0831433 75 73.323 72.800 -.71 74.393 +1.5 71.902 -1.9 72.919 -.55 72.568 -1.0 72.649 -.92
150 103.49 102.44 -1.1 106.10 t2.5 102.09 -1.4 102.55 -.91 102.27 -1.2 103.06 -.42
bar.dn3/qrnole.F 50.415 t.53 49.895 -.51 50.261 t.22 49.885 -.53 50.238 +.18
5.0 10 50.149 50.383 +.47
75 93.932 93.761 -.18 96.849 +3.1 92.929 -1.1 93.964 t.03 93.447 -.52 93.447 -.52
Z = 0.281304
140.95 -.74 148.11 t4.3 140.87 -.EO 140.85 t.81 140.83 -.E3 141.81 -.14
150 142.00
6.5 10 51.193 51.227 t.07 51.278 t.17 51.182 -.02 51.233 t.06 50.648 -1.1 51.196 +.01
75 112.77 114.17 t1.2 119.14 +5.7 113.06 +.25 114.05 tl.l 113.92 tl.0 113.23 t.41
150 182.30 182.20 -.os 193.71 +6.3 181.74 -.31 180.91 -.76 182.28 -.01 182.43 +.07
7.5 10 51.317 51.665 C.68 51.731 +.E1 51.396 +.15 51.531 t.42 51.138 -.35 51.484 +.33
75 126.05 129.56 t2.8 135.97 t7.9 127.48 tl.l 128.62 +2.0 129.49 t2.7 127.57 +1.2
150 212.47 213.50 t.49 228.36 +7.5 211.78 -.32 210.39 -.98 213.90 +.68 212.33 -.06
8.0 10 51.359 452.32 +1.9 52.393 t2.0 51.619 +.50 51.955 t 1 . 2 51.864 +.98 51.902 tl.l
75 133.33 138.32 +3.7 145.50 t9.1 135.33 >1.5 136.66 +2.5 138.39 t3.8 135.49 +1.6
150 229.16 230.90 t.76 247.54 t8.0 228.03 -.49 226.38 -1.2 231.52 +1.0 228.55 -.27
10.0 10 52.579 62.134 tL8. 62.243 +18. 55.890 t6.3 5 8 . 5 6 9 +11. 62.430 t19. 58.493 +11.
15 171.87 185.36 +7.8 195.93 +14. 174.12 tl.3 1 7 7 . 1 7 +3.1 186.60 18.6 175.48 +2.1
150 313.57 317.75 t1.3 342.25 +9.2 304.84 -2.8 302.44 -3.6 320.00 t2.1 305.57 -2.6
11.0 10 56.102 74.495 +33. 74.623 +33. 61.859 +lo. 66.848 t 1 9 . 75.578 t35. 66.759 +19.
75 201.12 219.75 t9.3 232.19 +15. 200.10 -.50 204.69 t 1 . 8 222.09 +11. 202.72 1.90
150 372.14 375.84 t.99 404.67 +8.7 352.89 -5.2 350.24 -5.9 379.53 t2.0 353.89 -4.9
12.0 10 65.202 94.845 +45. 94.994 +46. 72.048 +11. 80.180 t23. 97.140 +49. 80.073 t 2 3 .
75 241.97 264.99 t9.5 279.39 +15. 232.50 -3.9 239.03 -1.2 268.94 +11. 236.77 -2.2
125 379.14 388.18 t2.4 415.12 +11. 351.51 -7.3 352.27 -7.1 393.35 t3.8 353.66 -6.7
13.0 0 52.597 94.145 +79. 92.277 t75. 58.779 112. 70.308 +34. 97.904 +86. 71.824 t 3 7 .
50 216.39 250.24 t16. 259.96 +20. 203.03 -6.2 214.16 -1.0 255.72 t18. 211.18 -2.4
100 382.13 397.48 +4.0 421.00 t10. 342.48 -10. 347.76 -9.0 404.61 +5.9 346.83 -9.2
14.0 0 81.075 135.47 +67. 133.36 +64. 78.304 -3.4 94.601 t17. 141.81 t75. 96.297 t19.
75 380.91 404.02 +6.1 422.62 t11. 325.02 -15. 335.82 -12. 413.78 +8.6 332.97 -13.
15.0 0 133.57 196.73 t47. 194.37 t46. 107.83 -19. 129.22 -3.3 206.91 t55. 131.10 -1.9
50 375.49 408.32 +8.7 420.61 +12. 298.2: -21. 315.27 -16. 421.61 t12. 311.58 -17.
15.5 -25 39.002 116.65 +199 108.58 t 1 7 8 22.456 -42. 45.066 t16. 127.57 t227 55.152 +41.
0 172..31 237.15 t38. 234.66 +36. 127.39 -26. 151.26 -12. 249.94 +45. 1 5 3 . 2 3 -11.
30 331.68 375.97 +13. 382.25 +15. 250.60 -24. 272.26 -18. 390.95 t18. 2 6 9 . 1 8 -19.

Tu 0.42748 T"
~~ -
ZcVR- 0.08664 TR0'5?cVR(ZcVR+ 0 . 0 8 6 6 4 )

0 . 4 2 7 4 6 1 1 + 0.615(1 - T q 0 ' 5 ) 1 2
TR
ZcVR- il.08664 Z
C
v R ( ZC v R t 0-.98664)

TR - 1'
0 . 4 5 7 2 3 6 [1+0.504(1-TR0'5)
f V -0.0778 ZCVR(i V tO.0778) +0.0778(5cVR-0.0778)
C R C R

Table VI11 gives the comparisons for isopentane. Up been shown that = f , - B G is
~ practically constant a t
to the critical temperature eq (D) is clearly the best. Above 0.62. Using a single empirical parameter, such as the
the critical temperature the Peng-Robinson and eq (D) acentric factor, in a correlating equation of state cannot
give about the same average deviation, both of which are possibly do as well as (D) unless there is a consistent
better than the Redlich-Kwong, the Soave, and the relation between M and 2, or BG1,which there is not for
Chueh-Prausnitz. At the higher densities the Peng- the six substances chosen. The Soave and Peng-Robinson
Robinson and eq (D) are similar. The conclusion is that equations, for example, are constrained to fixed values of
eq (D) is the simplest and best for an overall fit for iso- 2, (1/3 and 0.3074, respectively) with the temperature
pentane. function allowed to vary with a single parameter, but no
Table IX gives the comparisons for trifluoromethane. allowance is made for different values of e,. Equation (D)
At all densities eq (D) is superior to the other equations does not have this pitfall as it is not locked into a fixed
while retaining the simplest form. 2, for all substances. Since in (D) 2, = 0.25 tP,/RT,, +
Table X gives the results for ammonia. Again for all 2, varies from 0.25 + 0.082 = 0.332 for argon down to 0.25
densities eq (D) is superior to all the others. + 0.04 = 0.29 for ammonia. At the same time the tem-
Considering the performance for the wide range of perature function, TRn,is varying simultaneously with M
substances the inescapable conclusion is that eq (D), or and 2, as shown by eq 89 where M and the translation,
eq 67 with the temperature function, TRn,(or A + BTR) tP,lRT,, enter into the slope of the critical isometric.
is not only the simplest but the best of the two-term cubics. Thus, accounting for differences in e,, having the smallest
The three-term virial does have a slightly lower value of value of E, better performance, and inherent simplicity
E, but it is one term more complicated. Certainly, there are the compelling features that make (D) superior to all
is no reason to go to other more complex two-term cubics, others.
such as the Peng-Robinson, for they do not do as well as Clearly, other temperature functions besides TRn can be
(D). used in eq 67 and they will perform as described for argon
One of the reasons for the superiority of (D) is found and ethylene, these being the linear and exponential
in Table V, which lists the PVT behavior parameters, e,, functions. The temperature function of Soave could easily
M , and B G ~one
, of which is not independent because it has be used but nothing is gained by its more complex form.
92 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979

Table VII. Comparison of Four Equations of State with Data ( I 7 ) for Perfluorocyclobutane

TC =
17.R3 18.363 + 3 . 2 18.240 -2.5 16.195 i2.2 18.140 11.9
1.37518 191.78
i.37758 545.24 20.11 23.473 i l . 8 20.383 11.4 2C.331 11.1 20.323 -1.1
699.27R i.38062 617.24 23.39 23.250 1.69 23.191 +.44 23.220
23.297 1.90 +.56
Pc =
1.38351 682.92 25.73 25.852 1 . 4 7 25.843 1.44 25.778 r.19 25.824 -. 37
.66C78: 527.69 36.92 38.421 l 4 . l 38.312 13.3 37.827 -2.5 37.726 -2.2
,682863 618.14 45.05 4 5 . 7 8 1 11.6 4 5 . 5 9 2 11.2 45.367 *.lo 4 5 . 4 7 5 *.94
403.6gsi. ,684335 688.25 51.11 51.426 +. 62 5 1 . 4 0 2 1.57 51.150 1.98 51.330 1 . 4 3
,465549 572.63 58.40 59.676 +2.2 59.040 i1.l 58.632 1.43 5s.65a 1 . 4 4
Fc = 641.52 69.20 6 8 . 1 6 7 -1.5 67.882 - 1 . 9 67.406 -2.6 67.683 -2.2
7i1.18 77.20 76.689 -.66 76.747 -.58 76.215 -1.3 75.638 - . 77
38. 71b/ft3. 785.07 86.50 86.278 -.49 85.493 -1.2 6 5 . 5 3 2 -1.2
8 5 . 6 7 7 -.95
862.42 96.70 95,040 -1.7 95.779 - . 9 5 95.145 -1.6 95.532 -1.2
MW = ,411692 571.32 65.37 55.569 i . 3 0 65.066 -.46 65.079 - . 4 4
66.389 11.6
710.19 87.95 85.829 -2.4 85.896 - 2 . 3 85.232 -3.1 85.722 -2.5
200.044. 761.52 97.47 96.231 - 1 . 3 95.469 -2.1 96.000 -1.5
95.709 -1.8
851.83 107.70 105,40 - 2 . 1 -06.28 -1.3 105.59 -2.1 1 0 5 . 9 9 -1.6
R = 10.131F 12.3
' ,406226 559.62 62.62 64.575 *3.1 64.077 64.010 12.2
& .407?67 616.10 71.92
65.497 + 4 . 6
73.700 12.5 73.174 - 1 . 7 72.601 1.95 72.859 + 1 . 3
1bnole.R ,438148 689.15 82.73 83.565 il.0 63.50: -.93 82.84d i . 1 4 63.312 r . 70
,218651 596. 02 113.79 119.26 i 4 . 8 i16.96 +2.8 115.50 + I .5 115.73 11.2
zc = ,218911 636.28 127.3 130.96 -2.9 129.63 +1.8 127.97 -.52 128.82 1.96
,219291 689.96 143.09 145.12 -1.4 144.92 r1.3 143.04 -.c4 144.36 1.88
C.27801 ,126033 634.03 187.75 195.67 i4.2 191.47 +2.0 188.15 r.22 189.40 t.88
,125177 670.19 208.37 214.47 12.9 212.63 t2.O 208.76 1.18 211.12 i 1 . 3
,126257 689.60 219.33 224.46 12.3 223.43 11.8 219.73 1.17 222.49 il. 4
,126582 651.44 199.5 204.23 i2.4 201.19 +,E5 197.62 -.94 199.45 -.03
768.55 266.7 264.42 -.a6 268.64 1.73 263.43 -1.2 267.08 + . I 4
849.84 312.0 305.30 -2.2 314.18 +.70 308.01 -1.3 3 1 1 . 4 4 -.la
*.la6771 699.08 257.91 258.31 i . 1 5 258.29 1.15 253.07 -1.9 256.65 - . 4 9
761.69 302.15 297.43 -1. 6 302.73 1.19 296.27 -2.0 300.78 -.45
851.69 362.81 352.67 -2.8 365.14 t.64 357.10 -1.6 361.36 -.lo
941.69 421.53 406.97 -3.5 426.05 11.1 416.65 -1.2 419.47 - . 4 8
1031.7 479.11 460.56 -3.9 485,66 il.4 4 7 5. 819 -.a4 475.77 -.70
*.08C078 699.06 308.29 309.46 1 . 3 8 309.44 - , 37 302.71 -1.8 307.20 -.35
761.69 372.55 364.96 -2.0 374.17 1.44 365.04 -2.0 371.21 1 . 3 6
851.69 459.77 442.99 -3.7 464.65 11.1 452.46 -1.6 458.29 -.32
941.69 543.76 519.40 -4.5 552.53 11.6 537.67 -i.l 541.10 -.49
iG31.7 625.9 594.55 -5.0 638.16 12.0 620.99 -.a0 620.80 -.82
,066534 685.89 313.40 320.22 i2.2 316.25 1.91 310.13 -1.0 113.60 1.64
761.67 419.00 410.92 -1.9 424.03 il.2 413.05 -1.4 420.23 1.29
820.86 495.50 475.78 - 4 . 0 500.69 11.1 486.55 -1.8 4 9 3 . 8 8 -.33
875.49 558. 90 534.68 -4.3 569.95 +2.0 553.14 - 1 . 0 559.25 1.06
*.053385 699.08 369.97 312.79 -.76 372.73 +,75 365.85 -1.1 370.72 1.07
761.69 480.62 465.96 -3.1 485.77 +1.1 472.78 -1.6 480.85 + . 0 5
851.69 629.04 596.11 -5.2 642.74 -2.9 621.90 -1.1 629.42 C.36
896.69 700.83 659.83 -5.9 7 1 9 . 0 7 12.6 694.68 - . a 7 700.14 -.39
986.69 041.84 785.C) - 6 . 7 867.91 13.1 837.10 -.56 836.09 -.68
,044823 694.68 376.00 382.55 11.7 380.48 11.2 375.77 -. 06 3 7 8 . 5 4 1.68
769.11 544.00 522.45 - 4 . c 553.03 11.7 537.53 -1.2 546.18 1.40
864.33 742.0 695.37 -6.3 7 6 4 . 8 6 13.1 737.16 -.65 744.07 1.28
*.040339 699.08 395.48 398.31 + . 7 1 398.20 1.69 3 9 4 . 4 0 -.27 396.76 1.32
761.69 558.11 535.81 -4.0 569.56 12.; 554.02 - . 7 3 562.46 + . 7 R
851.69 777.54 727.04 -6.5 896.46 13.7 775.80 -.22 783.08 1.71
941.69 990.26 912.34 -7.9 1033.8 14.4 989.81 - . 0 5 988.48 -.la
1031.7 1199.3 1093.0 -8.9 1252.9 +4.5 1197.1 -.la 1182.7 -1.4
*.032031 699.08 102.18 403.00 c . 2c 402.82 + . 1 7 402.45 C.07 402.76 i . 1 4
761.69 619.08 591.81 - 4 . 4 642.43 13.8 622.73 + . 5 9 631.33 i2.0
851.69 919.72 8 5 3 . 5 8 -7.2 972.69 i5.8 928.02 1.90 933.93 +1.5
941.69 1215.5 1106.5 -9.0 1288.6 16.0 1221.8 1.51 1214.0 -.12
1031.7 1508.3 1352.4 - 1 0 . 1592.2 -5.6 1505.6 -.I8 1477.6 -2.0
.030030 699.52 403.90 404.46 + . I 4 404.69 *.20 404.03 1.03 402.56 - . 3 3
738.79 555.1 535.42 -3.6 571.71 i2.9 542.98 12.2 564.35 11.6
776.94 695.4 660.06 -5.0 730.34 i 5 . 0 702.96 +I. 1 712.42 +2.5
852.59 973.4 900.85 -7.5 1035.3 16.4 983.96 il. 1 989.23 i l . 6
'.026593 716.69 479.26 475.23 -.85 495.12 +3.3 485.14 A1.2 489.79 +2.2
806.69 873.64 825.42 -5.5 943.84 18.0 894.01 i2.3 903.77 t3.5
696.69 1269.8 1161.5 - 8 . 5 1371.0 i8.0 1285.9 +1.3 1281.3 +.91 .~
986.69 1665.5 1486.8 -11. 1779.8 16.1 1662.9 - . l 5 1632.7 -2.0
'.022879 619.08 403.00 423.01 15.0 422.80 14.9 408.40 +1.3 413.13 +2.5
761.69 741.70 738.05 -.49 829.87 tl2. 775.05 14.5 789.65 16.5
851.69 1253.8 1173.3 -6.4 1389.4 -11. 1281.8 i2.2 1285.1 c2.5
941.69 1773.3 1592.4 -10. 1922.9 + a . 4 1767.8 -.31 1740.6 -1.8
1031.7 2295.6 1999.0 -13. 2433.9 - 5 . 0 2236.0 -2.6 2167.5 -5.6
,022497 707.28 453.00 470.50 13.9 482.88 16.6 460.10 c1.6 4 6 8 . 0 7 C3.3
782.89 a73.30 858.08 -1.8 983.68 113. 91i.18 + 4 . 3 926.01 16.0
857.52 13-3.4 1226.5 -6.6 1156.9 rll. 1339.7 C2.0 1341.4 C2.1
*.020020 699.08 436.9; 481.45 -18. 481.08 +la. 433.14 t6.4 447.51 +lo.
761.69 835.39 873.48 1 4 . 5 989.10 t l 8 . 886.87 C6.1 909.10 C8.8
851.69 1497.C 1415.0 -5.5 1687.1 1 1 3 . L 5 1 3 . 5 +1.1 1515.8 c1.3
941.69 2171.8 1936.1 -11. 2352.3
2989.3 16.3 14.1 2114.2 -2.7 2073.1 -4.5
1331.7 2854.8 2441.6 - 1 5 , 2692.5 - 5 , l 2594.4 -9.1
,019670 698.8 c02.00 492.75 123. 491.83 i22. 437.01 t8.7 453.11 113.
752.14 781.40 837.81 1 7 . 2 939.12 i20. 835.91 17.0 659.75 110.
796.81 1111.4 1119.0 +.69 1302.7 117. 1161.2 i 4 . 5 1180.1 16.2
838.86 1430.4 1378.2 -3.7 1636.5 -14. 1460.6 +2.; i467.6 12.6
862.04 16L2.4 i519.1 - 5 . 8 1817.3 +13. 1623.4 +.68 1621.1 1 . 5 4
,017931 695.95 405.90 572.90 i l l . 565.29 -39. 460.16 1 i 3 . 487.32 t20.
763.76 987.40 1066.8 110. 1233.8 125. i050.2 16.4 1081.3 t10.
801.60 1338.4 1365.5 12.0 1590.5 +19. 1 3 7 C . l 12.4 1391.7 i 4 . 0
861.36 1895.4 1795.5 - 5 . 3 2143.2 113. 1863.3 - 1 . 7 1903.2 c.41
*.017795 699.08 434.15 608.64 - 4 0 . 608.20 +lo. 493.54 il4. 522.74 +20.
761.69 991.76 1089.5 19.9 1230.7 124. 1045.2 i5.9 1077.3 +8.6
851.69 1847.6 1753.7 -5.1 2086.2 113. 1806.8 -2.2 1805.9 -2.3
941.69 2:20.a 2393.1 -12. 2901.5 16.6 2536.7 -6.6 2475.1 -9.0
1031.7 3607.0 3013.2 -17. 3682.4 i2.1 3239.3 - 1 0 . 3100.9 - 1 4 .
+*.014356 661.07 264.68 861.44 -226 733.20 1177 346.16 i31. 4 0 3 . 8 4 +53.
699.27 798.6 1318.6 l65. 1318.6 C65. 653.96 -6.9 917.84 1 1 5 .
761.69 1671.0 2043.8 122. 2245.8 +34. 1660.3 -.E4 1701.3 cl.8
851.69 2929.3 3051.0 t4.2 3526.4 +20. 2777.7 -5.2 2736.1 -6.6
941.69 4186.9 4022.7 -3.9 4749.7 +13. 3849.3 -8.1 3688.6 -12.
**.012920 63i.29 186.21 1169.0 +528 895.51 1381 185.21 -.54 242.78 1 3 0 .
699.27 1455.6 2206.9 +52. 2206.9 +52. 1305.9 -10. 1 3 6 4 . 0 -6.3
761.69 2621.2 3125.1 119. 3364.9 C28. 2297.6 -12. 2304.1 -12.
851.69 4301.7 4453.3 r2.4 4967.7 115. 3673.4 - 1 5 . 3548.9 -18.
* Higher p r e c ~ s ~ odna t a
** Extension o f h i g h e r p r e c i s i o n data t o twice the c r i t i c a l density

(A) IC)
PR ~ R 0.42748 p=L -
0.457236 Ilr0.89!l-TR0'ji '1
TC vR -0.08664 I v
C R
-0.~778 z v ( tC v R + ~ . o ~ ~ ~ ~ ~ ~ . o ~ ~ ~ I z ~ v ~ - o . o ~ ~ ~ I
c H
181 ID)
i =
TR .
0.42746 Iltl 0 ll-TRo'5 , 1 TR 27/64TR1"
TCVR-0.O8664 TcvR(IcvR+O.
08664) px=-
Z C V R -0.071
- (TcVR+2.05412
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 93

Table VIII. Comparison of Five Equations of State with Data ( 8 ) for Isopentane
ISOPEN TANE Redlich- Peng- Chueh-
Kwong Soave Rob 1n son Martin Prausnitz
(Ai (Bl (Cl (Di (El
% 3 % % %
T, K Z P, atm P Dev. P Dev. P Dev. P Dev. P Dev.
TC = 310 ,9445 1.35 1.3673 t1.3 1.3617 t.87 1.3587 t.64 1.3478 -.16 1.3648 tl.l
460.39K ,9395 1 1.0092 t.92 1.0062 t.62 1.0046 +.46 .99878 -.12 1.0078 +.78
330 ,9149 2.47 2.5138 tl.8 2.4983 t1.2 2.4888 +.76 7.4642 -.23 2.5065 t1.5
.9671 1 1.0065 +.65 1.0043 t.43 1.0027 t.27 .99914 -.09 1.0054 t.54
p C = 33.37atm350 ,8771 4.19 4.2855 t2.3 4.2486 t1.4 4.2224 +.77 4.1757 -.34 4.2662 t1.8
.E832 4 4.0866 t2.2 4.0534 tl.3 4.0295 c.74 3.9877 -.31 4.0693 t1.7
V = .306 .9729 1 1.0047 t.47 1.0030 t.30 1.0015 t.15 .99944 -.06 1.0038 1.38
370 ,8301 6.66 6.8484 t2.8 6.7719 t1.7 6.7098 t.75 6.6342 -.39 6.8032 +2.2
cm3 /gmol .9045 4 4.0598 t1.5 4.0363 t.91 4.0136 +.34 3.9923 -.19 4.0456 +1.1
.9775 1 1.0033 t.33 1.0021 t.21 1.0006 t.06 .99959 -.04 1.0025 +.25
R = 82.05606 390 ,7726 10.08 10.416 t3.3 10.274 +1.9 10.144 t.63 10.039 -.41 10.317 +2.4
c m atm ,8286 8 8.1932 t2.4 8.1151 11.4 8.0306 t.38 7.9791 -.26 8.1375 +1.7
.9207 4 4.0419 +1.1 4.0258 1.65 4.0041 1.10 3.9960 -.lo 4.0300 +.75
grnole .K
- .9811 1 1.0024 t.24 1.0015 f.15 1.0001 t.01 .99975 -.03 1.0017 t.17
z = 410 .7014 14.64 15.196 t3.8 14.965 +2.2 14.720 +.55 14.601 -.27 14.993 t2.4
0.270297 ,7715 12 17.332 +2.8 12.202 t1.7 12.029 +.23 11.979 -.17 12.213 +1.8
,8589 8 8.1285 t1.6 8.0811 t1.0 8.0004 t.01 7.9923 -.lo 8.0833 t1.0
,9335 4 4.0208 t.72 4.0186 t.47 3.9980 -.05 3.9981 -.05 4.0187 +.47
.9840 1 1.0017 t.17 1.0011 +.11 ,99977 -.02 .99986 -.01 1.0011 +.11
430 ,6087 20.63 21.466 t4.1 21.141 +2.5 20.749 t.58 20.645 t.07 21.056 t2.1
,6290 20 20.765 +3.8 20.477 t2.4 20.093 t.47 20.019 t.09 20.396 t2.0
.7325 16 16.420 t2.4 16.281 t1.8 16.000 00 16.013 +.OB 16.228 t1.4
.E132 12. 12.209 tl.7 12.145 t1.2 11.977 +.19 12.004 +.03 12.115 +.96
.E822 8 8.0839 +1.1 8.0591 +.74 7.9823 t.22 8.0000 00 8.0464 +.58
,9437 4 4.0194 t.49 4.0139 t.35 3.9942 +.15 3.9998 00 4.0108 t.27
,9864 1 1.0011 t.ll 1.0008 t.08 .99952 -.05 ,99991 -.01 1.0006 t.06
450 ,4649 28.41 29.377 t3.4 29.066 +2.3 28.690 +.99 28.629 +.75 28.530 +.42
.4875 28 28.957 t3.4 28.680 t2.4 28.251 t.90 28.230 t.82 28.172 t.61
,6219 24 24.679 t2.8 24.548 t2.3 24.041 t.17 24.173 t.72 24.234 1.98
.7104 20 20.427 +2.1 20.356 t1.8 19.955 -.23 20.093 t.47 20.163 t.81
,7822 16 16.248 +1.6 16.210 t1.3 15.931 -.40 16.044 +.27 16.098 t.61
.a445 12 12.128 +1.1 12.109 t.91 11.949 -.43 12.017 t.14 12.051 +.43
,9006 8 8.0521 +.65 8.0447 1.56 7.9715 -.36 8.0045 t.06 8.0205 +.26
,9521 4 4.0119 t.30 4.0102 t.26 3.9916 -.21 4.0004 t.01 4.0045 t.ll
.9883 1 1.0007 +.07 1.0006 t.06 .99944 -.06 1.0000 00 1.0003 t.03
455 ,4204 30.71 31.448 +2.4 31.210 t1.6 31.016 t1.0 30.939 +.75 30.436 -.E9
.4547 30 30.865 t2.9 30.683 +2.3 30.295 t.98 30.329 tl.l 29.973 -.09
.5391 28 28.829 t3.0 28.712 t2.5 28.167 1.60 28.317 tl.l 28.160 t.57
.6460 24 24.580 +2.4 24.518 t2.2 23.998 -.01 24.193 t.80 24.174 +.72
,7256 20 20.369 +1.9 20.334 t1.7 19.934 -.33 20.102 +.51 20.122 +.61
,7923 16 16.217 t1.4 16.198 t1.2 15.027 -.46 16.049 t.30 16.074 t.46
,8512 12 12.112 +.93 12.102 +.e5 11.944 -.47 12.019 +.16 12.038 +.32
,9046 8 8.0456 t.57 8.0419 t.52 7.9696 -.38 8.0053 +.07 8.0152 t.19
,9539 4 4.0106 t.27 4.0097 t.24 3.9913 -.22 4.0007 +.02 4.0034 +.OS
,9887 1 1.0007 +.07 1.0006 t.06 .99945 -.06 1.0001 +.01 1.0002 +.02
470 ,6046 150 213.19 +42. 216.29 t44. 132.39 -12. 114.76 -23. 259.67 t73.
.4386 100 142.38 +42. 145.08 t45. 95.256 -4.7 88.008 -12. 169.39 t69.
,3680 80 115.98 145. 118.47 +48. 81.169 t1.5 77.113 -3.6 136.10 t70.
.2949 60 89.762 t50. 92.002 t53. 67.056 +12. 65.629 t9.4 103.19 t72.
.2585 50 75.630 t51. 77.689 155. 59.384 tl9. 59.081 tl8. 85.467 t71.
.2295 40 57.007 +43. 58.735 +47. 49.232 t23. 49.907 t25. 62.025 t55.
.5891 30 30.570 t1.9 30.759 +2.5 30.069 +.23 30.485 t1.6 29.977 -.OS
.7641 20 20.227 tl.l 20.280 +1.4 19.886 -.57 20.115 t.58 20.021 -.01
,8926 10 10.047 t.47 10.057 t.57 9.9496 -.50 10.014 +.14 10.004 t.04
,9899 1 1.0004 +.04 1.0005 t.05 ,99938 -.06 1.0001 +.01 1.0000 00
500 .7651 200 258.68 t29. 271.23 +36. 182.32 -8.8 162.98 -19. 306.04 t53.
.6106 150 199.00 +33. 210.34 +40. 148.38 -1.0 138.23 -7.8 231.02 +54.
.4532 100 134.81 +35. 144.32 144. 110.29 t10. 108.13 +8.1 151.68 +52.
.3932 80 105.90 +32. 114.21 t43. 92.286 t15. 92.722 t16. 116.38 +45.
,3671 60 68.007 t13. 73.808 +23. 66.779 t11. 68.934 +15. 70.615 tl8.
.4363 50 50.407 t.81 53.483 t7.0 51.691 +3.4 53.337 +6.7 49.862 -.28
.5771 40 40.127 t.32 41.357 t3.4 40.248 +.62 41.267 +3.2 39.416 -1.5
.7097 30 30.110 t.37 30.594 +2.0 29.840 -.53 30.437 +1.5 29.733 -.E9
.a200 20 20.042 +.21 20.210 +1.1 19.836 -.82 20.115 +.58 19.891 -.55
.9152 10 10.007 +.07 10.042 t.42 9.9416 -.58 10.015 +.15 9.9726 -.27
.9919 1 1.0000 00 1.0003 t.03 .99929 -.07 1.0000 00 .9997 -.03
600 1.0606 300 309.95 t3.3 346.50 t16. 275.19 -8.3 256.45 -15. 342.43 +14.
.9309 250 267.15 t6.9 300.71 +20. 244.77 -2.1 232.39 -7.0 291.56 +17.
.a059 200 218.57 +9.3 248.00 +24. 208.56 t4.3 202.59 +1.2 234.59 117.
,6996 150 161.46 f7.6 184.47 123. 162.59 +8.4 162.12 18.1 168.94 t13.
.6625 100 100.12 +.12 112.64 t13. 105.42 t5.4 107.74 +7.7 100.97 t.97
,6937 80 78.270 -2.2 85.995 +7.5 81.939 t2.4 84.087 t5.1 78.041 -2.5
,7539 60 58.462 -2.6 62.367 t4.0 60.103 t.17 61.634 +2.7 58.037 -3.3
.7919 50 48.828 -2.3 51.358 t2.7 49.730 -.54 50.894 +1.8 48.471 -3.1
.E327 40 39.206 -2.0 40.711 tl.8 39.619 -.95 40.425 tl.l 38.952 -2.6
.a747 30 29.538 -1.5 30.325 +1.1 29.678 -1.1 30.164 +.55 29.386 -2.1
,9170 20 19.789 -1.1 20.115 t.58 19.812 -.94 20.042 t.21 19.715 -1.4
.9588 10 9.9470 -.53 10.023 t.23 9.9433 -.57 1 0 . 0 0 5 t.05 9.9291 -.71
.9959 1 ,99948 -.05 1.0002 t.02 .99937 -.06 1.0000 00 ,99930 -.07
(A) -
I 0.42748 TR - 27/64TR1'
P =
R -zcVR-0.08664 TR0'5ZcVR(ZcVR+0.08664)
ZcVR-0.064 (?cVR+0.06112
18) T 0.42748[1+0.82(l-T:'5) '1 0.4450
TR
P R = ZcVR-0.08664 - ZcVR(ZcVR+0.08664)
TcVR-0.0906 TRO'% V (?cVRt0.0906)
c R
(CI T, 0.457236[1+0.71(1-T-0'51 l 2
m
PR = zcVR-0.0778 - zcVR(z V +0.07781t0.0778(ZcVR-0.07781
K -

C R

The differences of all temperature functions are not
significant at high densities because of the inherent defect
of all cubics for reduced densities of 1.5 to 2.0.
D. The Best Two-Term Cubic Equation of State
In summary, the best two-term cubic equation is also
the simplest and it can be written either as eq 67 with a
temperature function such as TR" in the second term or
alternatively as
94 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979

Table IX. Comparison of Four Equations of State with Data (18) for Trifluoromethane
CHF3 Redlich- Penq-
Kwong Soave Robinson Martin
TRIFLUOROMETHANE (A1 IB) IC) ID1
v p, PS1 % % % e
ft3/lb T, R data P Dev. P Dev. P Dev. P Dev.

TC = ,99819 400.1 55.61 57.253 t3.0 56.818 t2.3 56.645 +1.9 56.364 +1.4
538.33 R 466.4 61.20 67.884 t1.0 61.686 t.12 67.398 +.29 61.316 t.26
517.66 16.30 76.056 -.32 75.999 -.39 15.673 -.E2 15.155 -.71
602.60 90.25 89.532 -.EO 89.707 -.60 89.328 -1.0 89.466 -.E7
Pc = 687.91 104.17 103.01 -1.1 103.30 -.74 102.98 -1.1 103.09 -1.0
701.42 p s i .70008 412.49 79.45 87.101 t3.3 81.410 +2.5 80.948 t1.9 80.496 t1.3
463.35 92.46 93.944 t1.6 93.525 +1.2 92.915 t.56 92.904 t.48
504.59 103.13 103.48 t.34 103.29 +.16 102.68 -.44 102.19 -.33
F, = 32.78 lbift 590.22 123.92 123.16 -.62 123.44 -.39 122.71 -.97 122.98 -.76
691.63 148.08 146.29 -1.2 141.11 -.65 146.27 -1.2 146.48 -1.1
455.44 179.78 187.06 t4.1 184.15 t2.8 182.67 t1.6 181.88 t1.2
R = 10.7315 .31066 206.75 11.4 204.34 t.25 204.47 +.32
psi' ft3/ltmole. R 493.01 203.82 208.02 +2.l
546.04 236.26 237.20 +.40 237.42 +.49 234.57 -.71 235.43 -.35
MW = 70.019 614.02 276.15 214.23 -.69 276.31 t.06 212.98 -1.2 214.07 -.75
- 679.54 313.09 209.58 -1.1 313.38 +.09 309.65 -1.1 310.49 -.E3
z = .259344 .20158 419.89 270.8 281.36 +3.9 217.55 t2.5 293.34 t.94 272.63 t.68
505.55 298.0 304.56 t2.2 302.42 tl.5 291.65 -.12 298.09 1.03
536.95 330.7 332.68 +.60 332.59 t.57 321.11 -1.1 328.54 -.65
538.33 332.2 333.91 t.52 333.91 t.52 328.46 -1.1 329.81 -.lo
502.52 315.2 373.06 -.57 315.91 t.19 369.62 -1.5 311.64 -.95
642.41 430.3 425.53 -1.1 432.15 t.43 424.83 -1.3 426.75 -.E3
103.64 484.3 418.41 -1.2 488.17 t.92 480.53 -.78 481.57 -.56
.12836 510.78 409.0 422.99 +3.4 418.68 t2.4 410.63 +4.0 410.97 t.48
548.42 416.9 480.18 t.69 481.15 t1.0 471.62 -1.1 414.18 -.57
591.05 548.0 543.96 -.74 552.11 +.75 539.81 -1.5 543.32 -.E5
632.09 612.2 604.54 -1.3 618.88 tl.l 604.65 -1.2 601.90 -.70
670.58 672.5 660.73 -1.8 680.72 tl.2 664.82 -1.1 667.02 -.E1
705.91 725.5 111.85 -1.9 736.88 +1.6 119.54 -.E2 120.26 -.72
,082677 519.08 525.8 541.28 +4.1 570.31 t2.8 530.31 t.89 530.18 +.E3
539.42 589.9 600.11 +1.8 601.16 t1.9 588.32 -.27 590.46 +.09
576.68 699.2 691.28 -.21 111.05 tl.1 693.00 -.E9 697.34 -.03
613.11 802.0 190.06 -1.5 816.68 t1.8 193.81 -1.0 798.08 -.49
650.58 906.1 884.08 -2.4 923.63 +1.9 896.24 -1.1 898.50 -.E4
100.06 1036.5 1006.4 -3.0 1062.5 t2.5 1029.5 -.68 1021.0 -.92
,055465 534.86 654.3 667.11 t2.1 665.06 t1.7 651.38 t.47 651.40 t.49
552.38 742.7 145.29 +.35 755.98 t1.8 142.15 -.07 144.52 t.24
587.93 910.0 911.11 -1.1 931.63 +3.0 911.93 +.21 915.19 +.57
643.00 1162.6 1134.3 -2.4 1212.3 t4.3 1169.5 t.60 1166.6 +.34
694.8 1392.5 1349.3 -3.1 1463.9 t5.1 1406.5 t1.0 1391.6 -.06
.047352 531.68 684.3 694.08 t1.4 693.42 +1.3 588.97 +.68 688.99 +.69
563.06 834.1 833.49 -.07 858.51 +2.9 841.58 +.91 843.94 +1.2
606.44 1082.2 1066.6 -1.4 1135.1 +4.9 1098.1 +1.5 1097.2 +1.4
,033604 545.6! 764.1 772.08 t1.0 785.90 +2.9 774.88 t1.4 114.52 +1.4
574.22 1014.7 1029.5 +1.5 1096.7 +8.l 1056.5 t4.1 1050.5 t3.5
602.73 1268.9 1281.4 t.99 1401.4 t10. 1333.3 +5.1 1315.3 t3.1
628.97 1496.4 1509.4 +.E7 1671.0 t12. 1584.3 +5.9 1550.7 t3.6
657.22 1148.6 1151.0 +.14 1969.1 t13. 1850.9 t5.9 1196.3 t2.7
683.05 1913.1 1968.8 -.22 2232.1 +13. 2091.5 t6.0 2014.6 12.1
,028644 545.69 715.0 828.09 t6.9 846.43 +9.2 807.27 +4.2 801.70 t3.4
568.67 1019.0 1094.6 tl.4 1169.9 t15. 1091.3 tl.7 1080.6 +6.0
581.21 1224.4 1306.3 t6.7 1421.2 +11. 1328.4 +8.5 1298.7 t6.1
613.06 1504.1 1597.1 t6.2 1780.8 tl8. 1646.1 t9.5 1593.7 +6.0
634.82 1749.9 1838.3 +5.1 2014.0 t19. 1911.2 19.2 1834.7 +4.9
656.98 1995.4 2080.8 i4.3 2368.7 t19. 2117.5 t9.1 2074.0 +3.9
,023589 538.33 705.8 951.85 t35. 951.85 t35. 808.11 +15. 175.48 tl0.
561.00 1024.3 1317.5 t29. 1396.1 +36. 1200.9 t17. 1142.8 +12.
576.86 1254.5 1569.5 +25. 1102.8 t36. 1472.6 tl7. 1391.5 t11.
596.89 1555.7 1883.8 +21. 2085.5 +34. 1812.0 1-16. 1697.4 t9.1
624.23 1974.3 2306.0 117. 2599.8 +32. 2269.2 115. 2101.9 +6.5
,023646 536.11 693.2 1017.2 t47. 1011.2 t46. 823.18 +19. 118.43 +12.
538.33 115.7 1045.6 t46. 1045.6 +46. 853.57 +19. 806.74 +13.
558.08 1014.3 1388.2 t37. 1461.7 +44. 1220.2 +20. 1145.8 t13.
517.12 1313.6 1113.1 t30. 1857.5 +41. 1569.7 t19. 1462.9 t11.
591.56 1649.1 2058.2 t25. 2276.8 t38. 1940.4 t18. 1193.5 +8.8
617.85 1978.2 2395.5 +21. 2681.5 t36. 2304.3 +16. 2112.8 +6.8
,021531 536.54 106.6 1167.5 t65. 1160.2 t64. 894.11 t21. 822.98 +16.
538.33 736.6 1201.8 t63. 1201.8 t63. 930.59 t26. 856.62 t16.
559.85 1097.5 1610.6 t41. 1697.7 +55. 1366.0 t24. 1253.3 +14.
575.60 1314.6 1905.5 t39. 2055.9 t50. 1681.0 t22. 1535.1 t12.
593.64 1698.1 2239.3 t32. 2461.7 t45. 2038.3 t20. 1850.0 t9.0
610.16 1991.0 2541.4 +28. 2829.1 +42. 2362.3 t19. 2131.6 +7.1
,020316 523.91 680.8 1339.3 t97. 1315.0 +93. 935.49 t37. 824.51 t21.
538.33 781.1 1455.3 t86. 1455.3 +86. 1057.9 t35. 935.59 +20.
548.51 974.8 1611.8 +72. 1711.3 t16. 1286.1 +32. 1144.5 +17.
561.74 1229.1 1950.7 159. 2055.1 +61. 1581.9 t29. 1404.1 t14.
512.13 1435.8 2167.7 t51. 3218.2 +61. 1812.1 t26. 1606.5 112.
598.68 1971.5 2715.2 t38. 2982.4 +51. 2394.0 +21. 2110.0 t2.0
.016045 500.02 461.8 2855.1 t512 2612.8 +458 1098.2 t134 525.33 +12.
505.25 645.3 3056.1 +373 2831.4 t339 1287.9 t100 686.45 t6.4
514.58 965.4 3393.0 t251 3236.1 t235 1624.7 t68. 969.97 +.47
522.15 1226.6 3664.5 +199 3551.7 +19C 1896.5 t54. 1196.5 -2.5
538.33 1192.4 4239.7 t136 4239.7 +136 2413.1 +38. 1670.7 -6.8
544.27 1967.9 4449.2 t126 4488.3 +128 2683.3 +36. 1841.6 -6.4

0.42748 (C) 0.451236 1 1 + 0 . 1 5 ( 1 - T ~ 51

)
p = iR P = TR -
ZcVR-0.08664 TR05EcVR(ZcVRt0. 08664) ZcVR-O. 0778 Z V (fcVRtO.077 8)to. 017 8 ( ;cVR-O. 077 8 )
C R
(B)
TR 0.42748 ilt0.86 u - T ~ ~ )1 ID) 21/64TR
PR = -
zcVR-0.08664 ~cVRl~cVR+0.08664) zcVR-0.055 l z c V R t0.07)2

where A(TR)= 2 7 / 6 4 T ~B~ =

, tPc/RTc,the translation, average slope M of the criticcl isometric based on the
and C = 1/8 - B. The translation is set to fit best at a generalized vapor-pressure diagram. It has been shown
reduced density of 1.5 or 2.0, depending upon what be- that no other two-term cubic can be developed to be
havior is sought, and n is selected to give a reasonable superior to eq 93 because they all come from the single
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 95

Table X. Comparison of Four Equations of State with Data (23) for Ammonia
Redlich- Peng-
tlH3 Kwong soave Robinson Martin
(A) (B) (C) (D!
AMMONIA V P IkPa % % 4 -5

T,OC cm 3/gm data P Dev. P Dev. P Dev. P Dev.

T = - 45 2190 50 50.479 +.96 50.435 +.87 50.421 +.E4 50.298 t.60

C - 30 1140 101.33 102.79 t1.4 102.63 t1.2 102.58 +1.2 102.21 t.87
405.44K - 10 620.3 200 202.82 +1.4 202.36 +l.2 202.16 +1.0 201.23 +.62
20 699.6 200 201.82 +.72 201.14 +.57 200.95 t.48 200.50 t.25
P = 341.5 400 406.02 11.5 404.77 tl.2 404.02 e1.0 402.12 +.53
161.7
~~
800 827.24 t3.4 821.73 +2.7 818.64 t2.3 810.26 +1.3
11278 kPa 50 776.7 200 200.75 r.38 200.57 +.29 200.40 +.20 200.18 +.09
303.2 500 504.91 +.98 503.73 +.75 502.65 +.53 501.23 1.25
v = 145.0 1000 1021.2 +2.1 1016.1 +1.6 1011.7 +1.2 1005.6 +.56
64.77 2000 2106.8 t5.3 2081.6 +4.1 2063.8 +3.2 2033.9 t1.7
4.247 cm3/gm 60 802.1 200 200.60 t.30 200.45 t.23 200.29 t.14 200.12 t.06
395.4 400 402.46 +.62 401.85 +.46 401.18 +.30 400.50 +.12
z = 169.2 900 913.19 +1.5 909.89 +1.1 906.47 +.72 902.76 +.31
89.49 1600 1647.6 1-3.0 1635.9 +2.3 1625.0 +1.6 1612.0 +.75
.242004 49.17 2600 2755.9 +6.0 2717.7 +4.5 2688.8 t3.4 2646.9 +1.8
80 852.5 200 200.40 +.20 200.30 +.15 200.15 t.07 200.05 +.G3
R = 8 3 14.4 277.7 600 603.70 t.62 602.80 +.47 601.38 +.23 600.49 t.08
133.8 1200 1215.4 t1.3 1211.6 t.96 1205.9 +.49 1202.1 +.17
cm3. kPa/gmole. K 61.93 2200 2258.7 +2.7 2244.1 +2.0 2224.9 tl.l 2212.4 +.47
31.07 4000 4263.0 +6.6 4194.7 t4.9 4123.3 +3.3 4068.1 t1.7
100 902.6 200 200.26 C.13 200.21 t.10 200.06 +.03 200.00 GO
599.0 300 300.58 t.19 300.46 1.15 300.12 +.04 300.00 -.02
295.4 600 602.19 t.37 601.71 +.28 600.36 +.06 599.91 -.02
143.4 1200 1209.4 +.79 1207.4 +.61 1202.0 1.17 1200.1 00
67.10 2400 2441.5 +1.7 2432.3 +1.3 2411.0 +.46 2402.2 +.09
38.53 3800 3919.0 +3.1 3891.3 +2.4 3839.3 +1.0 3813.1 +.35
18.04 6200 6640.8 +7.1 6519.8 +5.2 6400.9 +3.2 6298.0 +1.6
110 927.6 200 200.20 +.lo 200.16 +.08 200.01 +.01 199.99 -.0l
615.8 300 300.47 +.16 300.39 t.13 300.06 +.02 299.99 00
259.5 700 702.47 +.35 702.03 t.29 700.26 t.04 699.83 -.02
148.1 1200 1207.1 1.59 1205.8 c.48 1200.6 +.05 1199.2 -.06
69.83 2400 2431.6 ~ 1 . 3 2425.6 tl.l 2404.1 +.21 2399.2 -.04
35.84 4200 4309.3 t2.6 4287.3 +2.1 4226.4 +.63 4204.i +.lo
14.34 7400 7874.7 +6.4 7745.1 +4.7 7601.9 t2.7 7493.; +1.3
120 952.5 200 200.16 +.08 200.14 t.07 200.00 00 199.98 -.01
632.6 300 300.36 t.12 300.32 +.11 300.00 00 299.95 -.02
267.0 700 701.89 t.27 701.67 t.24 699.94 -.01 699.68 -.05
129.8 1400 1407.7 t.55 1406.7 +.48 1399.9 -.01 1398.7 -.09
66.28 2600 2628.1 +1.1 2624.4 +2.9 2601.2 +.05 2596.6 -.13
30.21 5000 5116.7 t2.3 5099.7 t2.0 5017.9 t.36 4995.8 -.OB
10.32 9000 9470.8 t5.2 9338.0 13.8 9199.5 +2.2 9089.7 +1.3
130 977.4 200 200.11 t.06 200.10 +.05 200.00 -.01 199.96 -.02
649.4 300 300.24 t.08 300.24 t.08 299.93 -.02 299.90 -.03
274.5 700 701.29 +.18 701.25 +.18 699.58 -.06 699.43 -.G8
133.8 1400 1405.5 +.40 1405.4 1.38 1398.7 -.09 1398.1 -.14
68.72 2600 2620.2 +.78 2619.5 +.75 2596.9 -.12 2594.3 -.22
35.42 4600 4667.5 +1.5 4665.2 t1.4 4597.1 -.06 4586.4 -.30
16.9 7800 8013.3 +2.7 6003.7 +2.6 7834.0 +.44 7790.7 -.12
8.524 10400 10710. t3.0 10674. t2.6 10537. t1.3 1046.1 +.59
6.549 10800 10962. +1.5 10904. t.97 10891. +.84 10852. +.48
135 989.8 200 200.10 +.05 200.10 t.05 200.00 -.02 199.96 -.G2
657.7 300 300.23 +.DE 300.24 +.08 299.93 -.02 299.92 -.03
278.2 700 701.11 t.16 701.15 t.16 699.50 -.07 699.41 -.08
135.8 1400 1404.4 +.32 1404.6 t.33 1398.0 -.13 1397.7 -.17
69.91 2600 2617.0 +.65 2617.7 1.68 2595.5 -.17 2593.6 -.25
34.41 4800 4861.0 t1.3 4863.9 +1.3 4791.3 -.18 4782.3 -.37
16.97 8000 8180.3 +2.6 8191.6 t2.4 8015.0 t.19 7979.7 -.25
12.67 9400 9639.8 t2.6 9659.1 +2.8 9448.2 +.52 9394.9 -.05
8.590 10900 11144. +2.2 11185. +2.6 11010. c1.0 10947. t.44
6.557 11500 11619. tl.O 11686. +1.6 11610. +.95 11575. +.65
4.706 11800 12043. +2.1 12164. t3.1 11947. +1.2 11891. c.77
3.620 12000 15374. t28. 15565. 130. 13564. +13. 12610. t5.1
2.588 16000 47462. +197 47798. +199 30163. +89. 18245. t14.
2.263 26000 95493. +267 95910. t269 54482. t110 24454. -6.0
2.127 36000 137753 t283 138214 t284 74957. +lo8 28734. -20.
220 1200 200 199.94 -.03 200.01 t.01 199.90 -.05 199.91 -.04
598.1 400 399.78 -.06 400.09 +.02 399.66 -.08 399.69 -.08
297.2 800 799.02 -.12 800.29 +.04 798.58 -.18 798.70 -.16
130 1800 1795.0 -.28 1801.6 +.09 1793.1 -.38 1793.6 -.36
66.98 3400 3384.2 -.46 3408.8 +.26 3379.2 -.61 3380.3 -.5B
33.69 6400 6348.5 -.E0 6443.4 t.68 6343.5 -.E8 6343.3 -.E9
17.03 11400 11260. -1.2 11617. C1.9 11327. -.64 11300. -.E8
8.396 19000 18844. -.82 20196. +6.3 19468. t2.5 19206. +1.1
4.681 28000 29793. +6.4 33672. +20. 31406. t12. 29497. +5.4
2.801 50000 76776. t54. 86079. +72. 68443. t37. 50581. t1.2
330 1470 200 199.94 -.03 200.05 +.03 200.00 -.01 199.96 -.02
587.2 500 499.20 -.16 499.90 -.02 499.39 -.12 499.29 -.14
292.7 1000 997.05 -.30 999.84 -.02 997.83 -.22 997.41 -.26
132.1 2200 2185.9 -.64 2199.5 -.02 2190.0 -.46 2187.8 -.56
68.32 4200 4152.6 -1.1 4203.0 +.07 4169.2 -.73 4160.2 -.95
34.03 8200 8050.6 -1.8 8249.5 +.60 8126.9 -.E9 8084.2 -1.4
17.62 15000 14679. -2.1 15392. +2.6 15008. t.05 14812. -1.3
8.490 28000 27922. -.28 30754. C9.8 29464. +5.2 28305. il.1
4.553 50000 53069. +6.1 61771. t24. 56966. +14. 50548. tl.l

(A! (C)
TR 0.42748 0.457236 rlC0.75 (l-TR0") 1
PR = PR =
TR
zcVR-0.08664 TR0'5Z C V R (ZcVRt0.00664) zcVR-0.0778 Z V
c R ( Z CV R+0.0778!t0.0778(ZcVR-0.0778)
(B)
TR
0.42748 [1+0.86(1-TR0'5) 1 (D) -
IR
2 7/64 TR1'
PR = -
zCVR-.O8664 z C V R (icVR+0.08664) 'R=--
2 V -0.04
C R
(ZcVR+0.085)2

generating eq 6, and eq 93 has the smallest value of 1 to combine constants just as with van der Waals or any
which makes it the best. other equation. To show how the procedure works, eq 93
If eq 93 is applied to mixtures, it is a simple procedure can be transformed from its generalized form back to its
96 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979

specific form Table XI. Compressibility Factor for n-C,H, at 470 K

RT A R2T: / Pc
P= - --.-RT
-
1 0.9894 125.518 0.9996 -0.04
10 0.8859 11.2388 9.9694 -0.31
20 0.7453 4.72755 19.935 -0.33
30 0.5292 2.23786 30.112 0.37
40 0.2047 0.64922 46.863 17.16
For a given substance, i, this is 50 0.2440 0.61909 51.663 3.33
60 0.2840 0.60048 55.441 -7.60
RT -
A 1R2Tct2/ pci 80 0.3634 0.57628 61.566 -23.04
P= (95) 100 0.4414 0.55997 66.649 -33.35
V - BcRTc,/Pc, (V + CLRT,,/PJ2 150 0.6304 0.53316 77.186 -48.54
200 0.8128 0.51557 85.976 - 57.01
where A, = 27/64TRlniaccording to the definition of A. 250 0.9901 0.50243 93.171 -62.49
Now van der Waals procedure of combining the volume
constants, b and c, linearly, and the a by geometric mean will predict the PVT behavior of C 0 2as well or better than
gives good results, though linear cube root may be better any other two-term cubic equation. One further point
for a. Thus, the constants for a mixture of two substances, concerning the selection of 0.068 .for the translation is
1 and 2, are worth noting. To fit the critical point exactly, according
to eq 41, one would set tP,/RT, = 0.2745 - 0.25 = 0.0245.
To fit the generalized second virial coefficient exactly at
(96) T R = 1 in eq 47 one would take tP,/RT, = 27/64 - 0.345
= 0.0769. The actual selection of 0.068 leans in the di-
BmTc,/Pc, = XlBlTcl/Pcl+ ~2B2Tc2/PcZ (97)
rection of the second virial coefficient, since this gives a
and better fit below the critical density where the predictions
CmTc,/Pc, = XICITcl/Pcl + x2C27'c2/pcz (98) are less sensitive to variations in the critical compressibility
factor.
For a single molar gas constant, R, the concentrations, x l As a second example take hexafluorobenzene, C6F,. Its
and x2, are to be mole fractions, and it is to be noted that constants (11) are T, = 516.74 K, Pc = 32.304 atm, pc =
R has been divided out of both sides of eq 96,97, and 98. 0.542 g/cm3, mol wt = 186.057 2, = 0.2612, BG1= -0.368,
These will give good results in the expression and the NBT = 353.41 K. From the latter, PR and 1/TR
establish M = 8.0 on the generalized vapor-pressure chart.
Equations 91 and 92 give the range of translation from
0.0445 to 0.0565, and 0.056 will be chosen to give a better
fit near twice the critical density. If n is taken as 1.3 in
for mixtures, particularly if the magnitudes of the a, b, and TRn,dPR/dTR= 7.9 for the critical isometric at TR = 1.25,
c terms being combined do not differ greatly from sub- and this compares favorably with M = 8.0. Thus, the best
stance to substance. Equation 99 can be differentiated two-term cubic equation for hexafluorobenzene is
with respect to the moles of 1 and the moles of 2 to give
the individual component fugacities in the usual expression
fi
In - =
x ;P
The last example is normal pentane, whose constants

J*"' [ -vt!- ( +
- RT dni T,V,n,
]dVt - In -

where xi = ni/n = ni/(nl n2)and V , = nV. Equation

p v t (100)
nRT
99 is useful in equilibrium calculations.
The discussion will be concluded with three examples
that show the simplicity and power of eq 93 and the ease
of obtaining appropriate constants. Suppose a PVT
equation is desired for carbon dioxide. The input con-
stants (22)are T , = 304.19 K, P, = 72.85 atm, pc = 0.468
g/cm3, 2, = 0.2745, BG1 = -0.345, 217.59 K for a boiling
point at 5.3477 atm (there is no normal boiling point at
1 atm because this is below the triple point), and mol wt
= 44.01. From these data the PR and 1/TR at the given
boiling point establish a point on the generalized vapor-
pressure diagram which shows M = 7.15. According to eq
91 and 92 the translation, tP,/RT,, may range from 0.054
to 0.068, depending upon where the best fit at high density
is to be obtained. A value of 0.068 will be chosen to give
good results near a reduced density of 2.0 rather than 1.5.
In the temperature function TRn it is quickly found from
eq 89 that n = 0.9 gives a slope of 7.10 for the critical
isometric at TR = 1.25, which agrees well with M = 7.15.
Thus, one can say with confidence that
(7) are T , = 469.65, P, = 33.25 atm, V , = 304 cm3/g-mol,
2, = 0.2623, the NBT = 309.19 K, BG = -0.352, and mol
wt = 72.151. PR and l / T R at the boiling point give =
7.35 from the generalized vapor-pressure diagram.
Equations 91 and 92 give tPc/RT,ranging from 0.045 to
0.057, and 0.057 will be selected to favor the highest
densities. If n is taken as 1in TRn,dPR/dTR for the criticd
isometric at TR = 1.25 is 7.35, which is equal to M . Thus,
an excellent equation for n-C5H12 is
Now a recent publication (7) has reviewed the PVT data
on n-C5H12 and given a table of compressibility factors for
a temperature of 470 K which is almost the critical
temperature. Thus, a check was made to determine how
well eq 103 would predict. The results are given in Table
XI. Up to the critical density eq 103 does an excellent
job, as expected. Above the critical density at 50 atm, eq
103 should predict about 20% high instead of predicting
within 3 70. As twice the critical density is approached eq
103 should predict within 5 to 2090, as all cubic equations
with the same 2, = 0.25 + 0.057 = 0.307 tend to do. The
fact that eq 103 predicts some 60% low indicates that the
correlation is in error a t high densities. This is especially
interesting in that a cubic equation, which is an obvious
 Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 97

approximation, is able to reveal an error in a correlation Literature Cited

in the literature to give a n unexpected additional ad- (1) ' Abbott, M. M., AIChE J . , 19 (3),596 (1973).
vantage to equations of the form of eq 103. (2) Barner, H. E., Pigford, R. L., Schreiner, W. C., Proc. API, 46,244 (1966).
(3) Benedict, M., Webb, G. B., Rubin, L. C., J . Chem. Phys., 8,334 (1940).
Nomenclature (4) Berthelot, D. J., J . Phys., 8,263 (1899).
(5) Chueh, P. L., Prausnitz, J. M., Znd. Eng. Chem. Fundam., 6,492 (1967).
a = constant in equation of state; may be function of tem- (6) Clausius, R.. Ann. Phys. Chem., IX, 337 (1881).
perature (7) Das, T. R., Reed, C. O., Jr., Eubank, P. T., J . Chem. Eng. Data, 22,
3 (1977).
A = constant in equation of state; may be function of tem- (8) Das, T. R., Reed, C. O., Jr., Eubank, P. T., J . Chem. Eng. Data. 22,
perature 9 (1977).
b = constant in equation of state (9) Dingrani, J. G., Thodos, G., Can. J . Chem. Eng., 53, 317 (1975).
B = constant in equation of state; second virial coefficient (10) Douslin, D. R., Harrison, R. H., Moore, R. T., J . Chem. Thermodyn., 1,
305 (1969).
c = constant in equation of state (1 1) Douslin, D. R., Harrison, R. H., J. Chem. Thermodyn., 8,301-330 (1976).
C = constant in equation of state (12)Fuller, G. G., Ind. Eng. Chem. Fundam., 15, 254 (1976).
d = differentiation sign (13) Gosman, A. L., McCarty, R. D., Hust, J. G., NSRDS-NBS,27 (1969).
i = refers to single component (14)Hou, Y . C., Martin, J. J., AIChE J . , 5 ( I ) , 125.
m = refers to a mixture; variable in generalized equation (15) Lee, B. I., Edmister, W. C.. Ind. Eng. Chem. Fundam., 10, 32 (1971).
(16)Martin, J. J., Hou, Y. C., AIChE J . , 1, 142 (1955).
n = exponent on temperature (17) Martin, J. J., J , Chem. Eng. Data, 7, 66 (1962).
P = pressure (18) Martin, J. J., Chem. Eng. Prog. Symp. Ser., 59, No. 44, 120 (1963).
R = gas constant (19)Martin, J. J., Edwards, J. B., AIChE J . , 11 (2),331 (1965).
(20)Martin, J. J., Ind. Eng. Chem., 59 (12),34 (1967).
t = translation in volume (21)Martin, J. J., Stanford, T. G., AIChE Symp. Ser., 70, 1 (1974).
T = temperatures; absolute K or R (22) Michels, C., Michels, A., Doctoral Dissertation, University of Amsterdam,
V = volume per unit mass 1937.
2 = compressibility factor, experimental (23) Milora, S . L., Combs, S . K., Oak Ridge Natl. Lab., TM-547 (1977).
(24)Onnes, ti. K., Commun. Phys. Lab., Leiden, Holland, 71 (1901).
Z = compressibility factor, calculated or fixed (25)Peng, D. Y., Robinson, D. B., Ind. Eng. Chem. Fundam., 15,59 (1976).
(Y= constant in equation of state; may be function of tem- (26) Pitzer, K. S.,Lippman, D. Z.,Curl, R. F., Jr., Huggins, C. M., Petersen,
perature D. E., J . Am. Chem. SOC.,77, 3427,3433 (1955).
p = constant in equation of state (27)Redlich, O.,Kwong, J. N. S.,Chem. Rev., 44, 233 (1949).
(28)Redlich, O.,Ind. Eng. Chem. Fundam., 14, 257 (1975).
y = constant in equation of state (29) Soave, G., Chem. Eng. Sci., 27, 1197 (1972).
6 = constant in equation of state; may be function of tem- (30) Strobridge, T. R., NaN. Bur. Stand. Tech. Note, 129 (1962).
perature (31) Usdin, E., McAuliffe, J. C., Chem. Eng. Sci., 31 (ll),1077 (1976).
(32)van der Waals, J. D.. Doctoral Dissertation, Leiden, Holland, 1873.
BG = generalized second virial coefficient (33) Wilson, G. M., Adv. Cryog. Eng., 9, 168 (1964).
BGi = generalized second virial coefficient at reduced tem- (34) Won, K. W., 69th Annual AIChE Meeting, Chicago, Ill., Nov 1976.
perature of 1
P,,V,, T , = refgr to critical point values Received f o r review June 13, 1978
PR, VR,TR = reduced values, Le., PIP,, VI V,, T I T , Accepted December 18, 1978

ARTICLES

Interferometric Study of Forced Convection Mass Transfer Boundary

Layers in Laminar Channel Flow
F. R. McLarnon,* R. H. Muller, and C. W. Tobias
Materials and Molecular Research Division, Lawrence Berkeley Laboratory, and Depatfment of Chemical Engineering, University
of California, Berkeley, California 94720

Double beam interferometry has been used to determine the development of local mass-transfer boundary layers
under laminar flow conditions. A traveling, dual-emission laser interferometer has been employed in the study of
a model transfer process, the electrodeposition of copper from copper sulfate solution in a flow channel of rectangular
cross section. Concentration profiles in the boundary layer have been derived from experimental interferograms
which were corrected for optical aberrations. Mass balance considerations were used to select the correct
concentration contour from those associated with practically indistinguishable interference fringes. Asymptotic
solutions to the convectwe diffusion equation have been found to closely describe the transient growth and steady-state
behavior of laminar, forced convection boundary layers.

Introduction
Mass transport often limits the rate of chemical pro-
cesses. Many industrially important electrochemical re-
*Department of Chemical Engineering, University of California,
Davis, Calif. 95616.
0019-7874/79/1018-0097$01.00/0
actions fall in this category; some are also used to model
transfer processes. The limiting current technique
(Selman, 1971) is an established method for the experi-
mental analysis of problems involving ionic transport to
and from electrodes. However, this method gives no direct
information about the nature of mass-transfer processes
0 1979 American Chemical Society