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 BenedictWebb-Rubin ( 3 ) ,the Strobridge (30),the virial form of
Onnes ( 2 4 ) to the 17th power in volume, the MartinStanford (21),and some recent semitheoretical formulations 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-PigfordSchreiner (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 cumbersome 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 characteristics 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 directly to the PVT behavior in the liquid and gas states
because this is more fundamental and through exact
thermodynamic relations precludes all equilibrium comparisons. 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 temperature, 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

examples.
I. Let P = y = 0 to get

which is the virial equation (third degree) of Onnes (24).

11. Rearrange eq 1 to
P = RT(V + p) - aV +
V(V + 0) V ( V + P)(V + y)

6
V(V + P)(V +y)
(3)

or

RT
a - PRT
ay + 6
p=-(4)
V + P V ( V + P ) V ( V + P ) ( V +y)
NOWlet p = -b = -7, CY - PRT = a , a y + 6 = c to give
a
C
p = - -RT
+
(5)
V - b V ( V - b) V ( V - b ) ( V +b )
which is the Lee-Edmister equation (15),that as a surprise
to some is just a rearranged form of P = RT/ V - a/V(V
+ P ) + 6/V(V + P)(V - PI.
111. Let 6 = 0 in eq 1 to yield
+

Now translate by t in volume so that

a
p = - -RT
V - t (V-t+P)(V-t+y)

or

a
p = - -RT
V - b V+2bV-b2
The denominator of the last term may be factored to give
a
p = - -RT
(15)
V - b V ( V + b) + b ( V - b)
which is the Peng-Robinson equation (25).
VIII. A form which is not in the literature but has
interesting properties is obtained from eq 7 by letting t
= b = (P + y)/2, c = - [ ( p - y)/2I2, and a = a, giving
p = - -RT
U
V-b V + C
A specialized case of this occurs if y = -P, then
a
p = -RT
-(17)
v v+c
Examples other than the eight presented can be given,
but they add nothing to the techniques of rearrangement
of eq 1.
Clearly, if all cubic equations are merely specialized cases
of eq 1,attention should be focused here to determine the
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 pressure-volume derivatives vanish at the critical point

(7)

Next let t = P = b, y = 2t = 2P, and a = a to get

a
p = - -RT
V - b V ( V +b)
which is the Redlich-Kwong equation (27).
IV. If in eq 7 we let P = y = t = b, and a = a, we have

which is the van der Waals equation (32).

V. If eq 6 is translated by P t in volume instead of
just t as in eq 7
RT
a
P=
(10)
v-p-t
( V - P - t + P ) ( V - P - t + y)

Letting P = b, y = P, and a = a, we have

or by the alternate equivalent technique of using three

equal volume roots at the critical point, as explained by
Martin and Hou (16). The latter is simpler and so will be
employed here. If eq 1 is multiplied out in descending
powers of volume, it may be written as

vPyRT a
P
P
A t the critical point with three equal roots
(V - VC)3= 0
which may be expanded to
v3 - 3VCV+ 3v:v-

v,3 = 0

0 (19)

(20)
(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

get
a
p = - -RT
(12)
V - b V(V+C)
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
a
p = - -RT

v-

[ V - b + (2

+ & ) b ] [ V - b + (2 - &)b]

(13)

for V'

for

V"

It is useful to put these into dimensionless forms with

PcV,/RT, = Z,, so that eq 22 becomes
(P + YIP,
= 1 - 32,
R TC

Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979

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

(PCVclR Tc)exp

eq 23 becomes

-- - 3
prp:
R2T:

CUP,
(P + r)Pc
2 2 - p
R2TC2
RTC

83

(26)

and eq 24 becomes

The last three equations are independent, but there are

four unknowns, a , P, y, and 6, or their dimensionless
equivalents, if P,, V,, and T , are known. Thus, a unique
solution can be obtained only if one of the unknowns is
specified-usually as zero. To exploit this approach eq 25
and 27 are inserted into eq 26 to get

CUP,
R2T,2

- - - --

6P,2
2:
R3TC3

+ 32:

32,+ 1

(28)

This may be translated by t by replacing V in eq 35 with

V - t or V Rin eq 36 or 37 with VR - tP,/Z&T,. If we then
let t = P or y so that from eq 33
CD

and
(39)

which will be examined for its various possibilities.

B. Consideration of Equations for the Critical

Isotherm
Suppose our interest first is only along the critical
temperature line and we want to study two-term cubic
equations (which the majority of them are), so 6 is set equal
to 0 and eq 28 becomes

-PC
.-

- -2: + 32:

-32,

+1

R2TC2
The value of 2, can be set as we please, so after some
pretrial let us take it to be 0.25. This makes

-aPc
R2T:

64

t , thus,

Here the superscripts, bt and at, mean before and after

translation. For eq 37 translated according to eq 38 it is
seen from eq 41 that
2, = 0.25 + 1/8 = 0.375
(42)

Equation 25 then becomes

RTC + -rpc
=64yPc RT,

1
4

or

4RTc + -64= o

(32)

Solving gives

YPC = -1
RT,

(33)

Inserting this into eq 31 yields

PPC = -1
-

(34)

Here, the unknowns, a , P, and y, have been solved for as

dimensionless quantities to be used in the equation of state
in reduced or dimensionless form which is obtained by
writing eq 1, with 6 = 0, as

R T V ,T , - (aP,/ R2T:) (R2T,2VC2)

(35)
pc vpcvcTc PC2VC2(V
+ P)(V + y)
or with the definitions of the reduced experimental

_p --

which follows from V being replaced with V

giving

- -27

at the critical temperature, and

RT,

which is a well-known reduced form of the van der Waals

equation.
It is instructive to note the effect of translation on a
calculated or selected 2, (not the experimental Z,). We first
note that

As emphasized earlier (20,221, eq 39 gives results consistent with its development only if 1, = 0.375 for which
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
substance, the representation along the TR = 1 isotherm
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
Standards data (13) of the predictions for argon whose Z,
= 0.29121.
The earlier discussions (20,21)showed that this principle
must hold for the reduced form of any equation of state;
Le., wherever Z, enters, the experimental value should be
employed and not the value used to get the equation or
predicted by the equation. The reason is simply that the
reduced volume is based on the actual critical volume so
the value of Z, must also be calculated with the actual
critical volume.
It is of interest next to look at the second virial coefficient of translated equations. If eq 7, where 6 = 0, is
rearranged to solve for z
CY
z = 1 + - -tP
RT RT[1 + P / ( V - t ) ] [ V -t + y] (43)
Now in general as P

RT
P

V - - + (T)

(44)

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 '
100
20
5
2.5
1.25
1.0

- -

0.033 95
0.162 09
0.540 73
0.834 2 1
0.995 97
1.000 00

0.026 46
0.128 09
0.451 43
0.750 77
0.989 09
1.000 00

-22.1
-21.0
-16.5
- 10.0
- 0.7
0

where t is the residual volume. Inserting this into eq 43

and letting P 0 or V
a

% dev

-0.1
+ 0.6
t 2.1
+ 3.3
+ 0.4
+ 4.2

0.033 9 0
0.163 03
0.552 30
0.862 35
1.000 0 4
1.041 7 4

Substance 1

2 /

Differentiating with respect to pressure a t constant

temperature

This may be put into reduced form

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,
BPJRT, where B is the second virial coefficient in the
expression, i = 1 + B / V + C / P .... If we now combine
eq 41 and 47 with 2 = Z and Zcat being Z, for any equation
with or without translation

ZC-T,(dz)
dPR

ffPC
as PR
R2T,2TR

TR

-+

Figure 1. Generalized compressibility or i chart.

Table 11. 5Chart Sum, E , for a Number of Substances
substance
Z C
a
E
Ne

0.309
0.305
0.295
0.294
0.291
0.291
0.290
0.289
0.288
0.288
0.28 3
0.281
0.279
0.279
0.278
0.278
0.278
0.274
0.274
0.274
0.274
0.271
0.270
0.270
0.268
0.267
0.264
0.261
0.260
0.259
0.259
0.248
0.248
0.242
0.238
0.234

(48)

At the critical temperature this becomes

where BG1is the generalized second virial coefficient at a

reduced temperature of 1. The interesting characteristic
of this quantity is that it is independent of translation
because t has been eliminated. As an example for eq 37
zc-

= 0.25

g)TR=l,pR=O

27
+= 0.671875
64

(50)

Thus, for van der Waals eq 39 it follows automatically that

P,=o = 0.671875

(51)

This can be checked by combining eq 30, 38, 42, and 47

at TR = 1
= 0.375 -

1
8

27
+= 0.671875
64

(52)

The constancy of eq 50,51, and 52 leads one to speculate

the
whether this quantity, which will be designated
i-chart sum

x,

0.634
0.630
0.625
0.618
0.621
0.623
0.623
0.630
0.621
0.621
0.624
0.618
0.619
0.619
0.623
0.614
0.617
0.619
0.624
0.615
0.622
0.616
0.622
0.633
0.633
0.61 3
0.624
0.629
0.620
0.61 4
0.611
0.604
0.606
0.612
0.603
0.574

average (exclusive of H,O) = 0.62

- ( dz/dPR )TR =

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

0.325
0.325
0.330
0.324
0.330
0.332
0.333
0.341
0.339
0.333
0.341
0.337
0.340
0.340
0.345
0.336
0.339
0.345
0.350
0.341
0.348
0.345
0.352
0.363
0.365
0.346
0.368
0.368
0.360
0.355
0.352
0.356
0.358
0.37 0
0.365
0.340

,,p

= = - BPc 1R Tc,

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

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

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
(54)

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
TR
(55)
pR= 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 assumption 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

85

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
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-,'
R2T$

- 2:

(57)

Combining eq 56 and 57 to eliminate P P J R T , yields

4ZC3- 2,'

+ 62, - 1 = 0

(58)

This may be solved by Cardan's method for the roots, 2,

= 114, 1, and 1. Since 2, = 1 implies ideal gas at the
critical point, only the first root is meaningful in this
application and it is identical with the assumption which
gave eq 30, 33, and 34.
Because eq 55 differs from eq 39 only by translation, it
follows that
= 0.671875. As pointed out earlier (20),
however, the translation characteristic makes eq 55 much
more powerful than eq 39 because 2, is not constrained
to 0.375 and can be made more realistic.
If in eq 29 2, is taken to be less than 0.25, the following
results
2, = 0.24; aP,/R2T,2 = 0.4390;
= 0.6790
(59)
2, = 0.23; aP,/R2T: = 0.4565;

= 0.6865

(60)

Since the desired value of 2 is 0.62, it is clear that to make

2, < 0.25 is going in the wrong direction. For values
greater than 0.25, we get
2, = 0.26; aP,/R2T: = 0.4052;
2, = 0.27; aP,/R2TC2= 0.3890;

E= 0.6652

2, = 0.3; aP,/R2Tc2 = 0.343;

2, = 1 / 3 ; aP,/R2T,' = 0.2963;

= 0.6590
= 0.643

(61)
(62)

l ) / [ ( Z , V R - tP,/RT,)'

+ (1

3PPc
- - 1 - 32,

RTC
and eq 27 with 6 = 0 gives

-2p2pc2
- - 2:
R2TC2

=0.6296 (64)

(-ZC3+ 32,' - 3 2 , +
3 2 , ) ( Z C V-~ tP,/RT,) +
Z23 (65)

which is the equivalent of eq 55 or 37 with translation.

The problem of large deviations for p R above 1.2 is
characteristic of all cubic equations of state, for the actual
data tend to follow a fourth-degree equation as discussed
previously (21). The major difference between the many
different cubic equations that have been proposed is
whether they fit better at about two-thirds or one-half the
critical volume. One of the major advantages of eq 67 is
that a small change in translation will permit fitting exactly
where one chooses. In obtaining eq 65 from eq 25,26, and
27, it was not necessary to solve explicitly for /3 and y, but
if one wishes to do this, he would find that p and y are real
numbers for 2,s 0.25, but imaginary or complex numbers
for 2, > 0.25.
We can now show how some of the well-known cubic
equations fit into the general pattern. As shown in example 111, if we let y = 2P and t = p, we get the Redlich-Kwong equation. Using dimensionless quantities, eq
25 becomes

(63)

Here the trend is toward 0.62, but it must be noted that

is indicative of the behavior only up to the critical
density, so the behavior above the critical density (or
volumes less than the critical volume) must be studied.
Therefore, eq 36 will first be combined with eq 25, 26, 27
to obtain after translation

PR = TR/(Z,VR - tP,/RT,)

or in its reduced form before a specific translation is made

27/64
TR
(67)
PR = Z,VR- tP,/RTc
(B,VR + 1 / 8 - t P , / R T J 2

Eliminating PP,/RT, between eq 68 and 69 yields an

expression for 2, (similar to eq 58)
92:

182,'

+ 122,

2 =0

(70)

Again this may be solved by Cardan's method to give two

roots that are complex and the third which is real and
useful
2, = 0.246693

The translation for eq 67 is, therefore, from eq 7 1

(71)

86

Ind. Eng. Chem. Fundam., Vol. 18, No. 2 , 1979

1 - 32,
-tP,- ---PP, - -bP,
=-RT,
RT, RT,
3

- 0.08664035

(72)

and using eq 71 in eq 65 a t the critical temperature

TR

P -

- Z,VR - 0.08664035

"m I

3mC.lmt-mmwo

$23

3oo*t-wmom"woomo

5 0 0 0 0 0 0 0 0 A i i ~ ~ eo im
1

+ + + + + + + + A * + W

++

00
Icoa,

0.4274802
Z,VR(Z,VR 0.08664035)
(73)

which is the reduced form of the Redlich-Kwong equation

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 substances 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

P = (2 + f i ) b and y

2-d2
or y = -

= (2 - &)b

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

4PPc

= 1 - 32,

(74)

and eq 27 becomes

Eliminating pPC2/R2Tc2
yields the cubic equation in 2,

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,- - --

RT,

RT,- (2

PPC

+ &)RT,

= 0.077796074

(78)

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

Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979 87

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 PengRobinson, 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 RedlichKwong 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:

--

R2T,2

--

(81)

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
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 simplicity, 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)

PR =

Z,VR

- 0.079113438-

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

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
average predictions will be no better than eq 66. If interest
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
= 1/27 from eq 27 so that in reduced form
eq 1 becomes
m

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
~CVR (Z,VR)~
- 1/150

0.0437037037
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

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 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 temperature 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
critical point. Figure 2 shows this characteristic and also
2,
shows that for rather high temperatures, where T R
the critical isometric (and all the other isometrics) tends
to curve down very slightly; however, this effect is minor
compared to others and is outside the range of temperatures 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
(16,19,21). The parameter on each curve is the slope M
= dPR/dTR as T R
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

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
Data

Redlich-

io0

0.5

FC =

20

1.2
1.5
0.7

,02001
.03395
,04088
.05127
,10704
.16209
,19808
,25159
,22813
30565
,38079
,49183
,43008
,54073
,70432
,94212
.73591
. 83421
1.2134
1.7430
.92682
*.9632
I.5861
2.4836
. 99560
1.9C02
3.2217
. 99946
2.0343.6167
.99999
2.2174
4.0471
1.0006
2. 3983
4 . 5252
1.0058
2.6105
5.0738
,96551
1.3635
3.1966
6.4759
. 79003
1. 3426
4.1993
8. 5241
.64 I 32
2.1534
5.9763
11.619

48.34atm
C

!0

1.2
1.5
0.8

1.2
1.5
.87

13.41
ymole,

R =

,082jjjjlatrr1.2

q r r o l e . K1.5
2.3
.95

c. 29121

1
1.2
1. 5
1 U 3 . 6 .99
1
1.2
1.5
./0.8 1
1.2
1.5
d 3 . 9 1
1.2
1.5
i.2
1.3
1,l.l 1
1.2

1. 5
1. 2 1
1.2
1.5
1./1.4 .99
1
i. 2
1.5
1/1.6 .96
j.;

1.2
1.5
lVi.8 .92
1.2
1.5
.86

;/2

,45894
4 . 0320

1.2
1.5

9.0682
16,318

_ -

-0.08664

?_VR

Peng-

,02002
.a3394
,04087
,05125
,10716

!Bl

Dev.

smaller
translation
(E) g

(D)

oil..

Dev.

1.01 ,02005 + . 1 7
-.03 ,03334 -.03
-.03 ,04087 -.03
-.03 .05126 -.01

+.11 ,10756 +.49

, 1 6 1 8 7 -.14
-.14 .19784 -.12
-.11 ,25155 -.02
t.12 ,22910 t.13
t . 2 2 ,30497 - . 2 2
-.20 ,38014 -.17
-.19 ,49193 7 . 0 2
+.28 ,43251 - . 5 7
-.15 , 5 3 9 9 3 - . 1 3
-.25 ,70302 -.18
-.23 ,94390 1.19
1.19 ,74278 t.93

. 1 6 1 8 7 -.14

,19781
,25130
,22841
,30497
,38002
,49092
.43128
,53993
,70256
,93998
,74169
,83827
1.2130
1.7502
,93542
,96826
1.6040
2.5049
,99931
1.9475
3.2802
1.0000
2.1248
3.7314
1.0033
2.3195
4.1604
1.0195
2.5429
4.6702
1.0598
2.8076
3.2457
1.1471
1.2646
3.5202
6.6643
i.1435
1.7432
4.6021
5.5905
1.1542
2.6717
6.2600
11.277
.95351
4.3180
3.8113
15.117

Martin

Robinson

(A)

TC =
150.86X

Soave

Kwong

,02003
,03390
,04082
,05120
,10703
,16089
,19562
.25002
,22690
,30160

+.07
-.16

.02001
,03394
,04088
,05126
.lo699
,16189
,19789
,25142
,22806
,30503
,38031
,49136
,43048
.59004
,70351
.94i45
,74057
.83327
1.2156
1.7541
,93480
,96797
1.6080
2.5097
,99933
1.9515
3.2813
1.0300
2.1275
1.6974
1.0029
2.3193
4.1478
1.0174
2.3371

-.15

-.i4
.OO
-.74
-.74

-.62
-.54
-1.3
, 3 7 5 7 7 ->.3
,48623 -1.1
,42590 - . 9 7
,53023 -1.9
,68905 -2.2
. 9 2 4 5 2 -1.9
,72381 -.83
t.50 ,83837 +.50 ,82040 -1.7
+.2l 1.2147 +.36 1.1784 -2.1
c.41 1.7651 1 1 . 3 1.7052 -2.2
r.93 ,93576 +.96 ,92450 -.25
+.53 ,96826 +.53 ,95463 - . a 9
+1.1 1.6077 tl.., 1.3508 -2.2
t.56 2.3366 +2.1 2.4235 -2.4
t.38 ,99937 - . 3 d
.99654 t.09
+2.5 1.9537 12.8 ;.8709 -1.5
+l.8 3 . 3 3 3 9 +3.5 3.1467 -2.3
t.05 1.0000 - . 3 5
,99988 + . a 4
t 3 . 4 2.1325 +3.8
2.0291 -1.2
t2.3 3.7678 - 4 . 2
3.1298 -2.4
t.33 1.0033 + . 3 3 1.3002 +.02
14.6 2.3288 1 5 . 0 2.1964 -.95
+2.8 4.2405 -4.8 3.9381 -2.7
+:.9 1.3195 t ? . ? L.0039 +.33
-6.0 2.5539 +6.3 2.3793 -.79
- 3 . 2 4.7650 +5.3 4.3802 -3.2
+5.4 1.0598 -5.4 1.0182 +?.2
+ 7 . 5 2.8204 + a , ?
2.5863 - . 9 4
7 3 . 4 5.3560 t5.6 4.8655 -4.1
t19. 1.1486 +19. 1.0069 + 4 . 3
+18. 1.2616 +;8.
1.1084 +3.7
+ l o . 3.5370 +ll. 3.1063 -2.9
12.9 6.8081 + 5 . l 6 . C 0 9 3 -7.2
-45. 1.1533 +46.
,83217 - 5 . 3
+30. 1.7432 -30. 1.3416 -.07
+lo. 4.6231 - 1 0 , 3.8411 -8.5
+.78 8.7707 -2.9 7.4723 -12.
+78. 1.:860 -83. ,54764 -15.
-24. 1.6717 - 2 4 .
1.8117 -15.
+4.8 6.2855 -5.2 4.9027 -18.
-2.9 11.497 -1.:
9.3949 -19.
+lo8 1.0468 +128 - . @ E 0 2 -118
+7.1 4.3180 -7.1 2.6523 -34.
-2.8 8.8416 -2.5 6.4521 -29.
-7.4 15.358 -5.8 11.979 -27.

,01994
,03392
.04087
,05126
,10594
,16150
,19770
,25136
,22528
,30366
.37968
,49122
,42345
.33588
,70191
,94131
,72937
,82997
1.2143
L.7551
,92738
,96137
1.6107
2.5096
,99804
1.9552
3.2568
.99999
2.1267
3.6648
1.0006
2.3072
4.0855
1.0069
2.5037
4.5314
1.0255
2.7234
5.0251
1.0167
1.1298
3.2625
6.1489
,81123
1.3713
3.9879
7.5287
,44780
1.8166
4.9733
9.2500
-.3691
2.5451
6.3088
11.421

-.04

-.03
-.02
-.02
-.05
-.12
-.lo
-.07

-.03
-.20
-.13

-.lo
+.a9
-.l3
-.12
-.07
+.63

-.11
+.43
+.64

+.86
+.50
tl.9
+1.1
+.37

+2.7
C1.9

+.Os
+3.6
+2.2

+.29
+4.6

12.5
+1.7
+5.8
4 . 6 4 4 2 +2.7
1 , 0 5 4 4 +4.8
2.7923 +7.0
5.1995 -2.5
:.1235 +16.
1.2401 -16.
3.4662 +8.4
6.5466 +1.1
i.0773 +36.
1.6655 t 2 4 .
4.4614 76.2
a.3318 -2.3
,99922 + 5 4 .
2.4740 +15.
5.9407 -.60
18.752 -7.5
,63539 +38.
3.8622 -4.2
8.1382 -10.
14.094 - 1 4 .

3.42748
TR05f V !?cVRf0.08564;

(D) P

Linear
Isometrics

(F)

Dev.

-.35
-.OX
-.04

-.02
-1.0
-.35
-.19
-.09
-1.3
-.65
-.29
-.12
-1.5
-.90
-.34
-.09
-.89

-.05
-.32

+.69
1.06
-.19
-1.6
-1.1
-.25
+2.9
+i.4
+.05
13.3

t1.3
+.06
-4.:

+.95
7.63
+4.4

C.14
+2.0
+4.3

-.96
+5.3
t5.7
+2.0
-5.1
t2.7
+2.l
-5.0
-12.
-3:.
-16.
-17.
-20.
-180
-37.
-30.
-30.

Dev.

,02008 +.32
,03393 -.05
.04086 -.06
,51251 -.03
,10795 +.88
,16171 -.23
,19753 -.28
,25126 - . 1 3
,22984 + . 7 5
,30439 - . 4 1
,37893 - . 4 8
,49078 -.21
,43375 +.85
,53809 - . 4 9
,69861 -.Xi
,93940 - . 2 9
,74311 t.98
,83439 +.02
1.1995 - . 9 3
1.7472 i . 2 4
.93436 +.8l
,96494 +.18
1.5766 - . 5 3
2.4942 + . 4 3
.99880 t.32
1.8983 -.OB
3.2484 + . d 3
1.0000 +.05
2.0599 +.2a
3.6497 +.91
1.00l5 + . l 5
2.2326 +.68
4.0791 +.79
1.0116 +1.1
2.4254 tl.1
4.3461: + . 4 6
1.0388 +:.3
2.5473 - 1 . 4
5,0605 - . i o
1.0789 ti2.
1.1809 +11.
3.2i97 -.66
6 . 2 7 ~ 3-3.1
1.0014 +27.
1.5076 +12.
4 . 0 3 a i -3.d
7.8343 -8.1
,87751 +36.
2.1131 -1.7
5.2159 -13.
9.8642 -15.
,50252 +9.3
3.1372 -22.
6.9039 - 2 4 .
12.5.7 -23.

? 7 ! 64Tnoj5
n
l~cV,+0.043)

R - -zcVR-O. 082

c R
T

R
IBj Pa = =z C v R - 3 . 0 8 5 5 4

(c)

V -0.0778
2 2 = 5-___-

c R

0.42748 [1+0.48(1-?R05)
1
Z c V R ( Z c V R + O . 08664)

dTR v

= 6.857 when TR = 1

which is high, and

()
dTR

= 5.888 when T R = 1.5

which is low. The slope at an average temperature of TR

= 1.25 is 6.25 which compares favorably with the 6.1 from
the reduced vapor-pressure charts, so
p R =

27 / 64TR055
TR
ZCVR - 0.082 ( i c V +
~ 0.043)2

(90)

TR

__ 27/(64~,~)

ZcVR-0.067

0.457236 [1+0.375(1-TRoj l 2
- 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)

droop a little as TR
2. In the case of eq 88 for argon
whose 2, = 0.29121 one quickly finds that for n = 0.55 at
VR = 1, eq 89 gives

()

( E ) PR =

TR

i:c V R - 0 . 0 7 5

0 . 5 -0.178125TR

(;cvR+0.0j)2

should be a good equation for argon. This is shown to be

true in Table IV where eq 90 is presented as eq (D) and
compared with the NBS data on argon. (In making these
comparisons one can emphasize either the absolute deviations or percentage deviations depending on the ultimate use of the equation of state. Here a little more weight
is given to the percentage deviation.)
The selection of the amount of translation depends in
part upon the critical compressibility factor and the two
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
tP,/RT, = 0.8572,

0.1674

(91)

To fit data well around two-thirds the critical volume, but

have high negative deviations a t twice the critical and
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 acceptable 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 essentially 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-parameter 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 temperature function or by changing the volume-function
constants. Soave chose the former procedure, replacing
He made m a
the simple l/'Td.5 with [l + m(1 - TRo.5)]2.
function of the acentric factor (26) which is just an empirical 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',~)]',
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
Ar

c,H4
C4F8
i-C
CHF,
3
"

-(dZ/dP&R=l,

ZC

0.291
0.281
0.278
0.270
0.259
0.242

6.1
6.5
7.8
7.2
7.4
7.4

0.332
0.337
0.336
0.352
0.352
0.37 0

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 PengRobinson 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 selected 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 constants 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 contender 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
function of Soave, or the linear temperature function (20)
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 perfluorocyclobutane. 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

ETHYLENE

Red 1 ichKwonc
(A)
P , bar

Tc =
282.35K

0.8

Pc =
1.5

5 0 . 4 1 9 7 bar

-25
10
75
150
-25

10
7.635
gmo 1e / d r n 3
-C =

3.5

R = ,0831433

bar.dn3/qrnole.F

75
150
0
75
150

10

5.0

75
150

= 0.281304

10

6.5

75

150
10

7.5
8.0
10.0

75
150
10
75
150
10
15
150

10

11.0

75

150
12.0

10
75
125

13.0
14.0

15.0

15.5

50
100
0
75
0
50
-25
0
30

Tu
0.08664

TR
C

-0.0778

Dev.
t.46

-.08
-.37
-.47
t1.4
t.01
+.57
-.74
t1.4

-.71
-1.1
+.47

-.18
-.74
t.07
t1.2

-.os

C.68
t2.8
t.49

+1.9
+3.7
t.76
tL8.
+7.8
t1.3
+33.
t9.3
t.99
+45.
t9.5
t2.4
+79.
t16.
+4.0

+67.
+6.1
t47.
+8.7

+199
t38.

+13.

13.932
16,570
21.413
26.931
22.251
27.692
37.604
48.804
41.380
74.393
106.10
50.415
96.849
148.11
51.278
119.14
193.71
51.731
135.97
228.36
52.393
145.50
247.54
62.243
195.93
342.25
74.623
232.19
404.67
94.994
279.39
415.12
92.277
259.96
421.00
133.36
422.62
194.37
420.61

Dev.
+.21
-.07
t.06
+.33
t.89

+.03
s.27
t.77

+.97
+1.5
t2.5
t.53

+3.1
t4.3
t.17

+5.7
+6.3

+.E1
t7.9

+7.5
t2.0
t9.1
t8.0

+18.
+14.
+9.2

+33.
+15.
+8.7
+46.

+15.
+11.

t75.
+20.
t10.
+64.
t11.
t46.
+12.
108.58 t 1 7 8
234.66 +36.
382.25 +15.

Martin
(3)

P
13.779
16.374
21.150
26.605
21.905
27.187
36.845
47.804
40.732
71.902
102.09
49.895
92.929
140.87
51.182
113.06
181.74
51.396
127.48
211.78
51.619
135.33
228.03
55.890
174.12
304.84
61.859
200.10
352.89
72.048
232.50

Dev.
-.E9
-1.3
-1.2
-.E9
-.67

-1.8
-1.8
-1.3
-.62
-1.9
-1.4

-.51
-1.1
-.EO
-.02
+.25

-.31
+.15
tl.l
-.32

+.50
>1.5
-.49
t6.3
tl.3
-2.8

+lo.
-.50
-5.2

+11.
-3.9

351.51 -7.3
58.779
203.03
342.48
78.304
325.02
107.83
298.2:
22.456
127.39
250.60

112.
-6.2
-10.
-3.4

-15.
-19.
-21.
-42.
-26.
-24.

Dev.

13.894 -.06

16.530 -.31
2 1 . 3 1 7 -.39
26.732
22.155
27.581
37.280
48.122
41.237
72.919
102.55
50.261
93.964
140.85
51.233
114.05
180.91
51.531
128.62
210.39

-.42
t.46
-.37

-.55
-.64
t.62

-.55

-.91
t.22
t.03
t.81
t.06
tl.l
-.76
t.42
+2.0
-.98
51.955 t 1 . 2
136.66 +2.5
226.38 -1.2
5 8 . 5 6 9 +11.
1 7 7 . 1 7 +3.1
302.44 -3.6
66.848 t 1 9 .
204.69 t 1 . 8
350.24 -5.9
80.180 t23.
239.03 -1.2
352.27 -7.1
70.308 +34.
214.16 -1.0
347.76 -9.0
94.601 t17.
335.82 -12.
129.22 -3.3
315.27 -16.
45.066 t16.
151.26 -12.
272.26 -18.

Martin
with
Exponential
Temperature
Function
(Fi

P
13.939
16.544
21.301
26.703
22.278
27.610
37.227
48.028
41.226
72.568
102.27
49.885
93.447
140.83
50.648
113.92
182.28
51.138
129.49
213.90
51.864
138.39
231.52
62.430
186.60
320.00
75.578
222.09
379.53
97.140
268.94
393.35
97.904
255.72
404.61
141.81
413.78
206.91
421.61
127.57
249.94
390.95

Dev.
+.26
-.23
-.47
-.52
+l.O
-.27
-.73
-.E4
1.59
-1.0
-1.2

-.53
-.52
-.E3

-1.1
tl.0

-.01
-.35
t2.7
+.68
+.98
t3.8
+1.0
t19.
18.6
t2.1
t35.
+11.
t2.0
+49.
+11.
t3.8

+86.
t18.

+5.9
t75.
+8.6
t55.
t12.
t227
+45.
t18.

13.943
16.530
21.302
26.764
22.319
27.578
37.236
48.222
41.397
72.649
103.06
50.238
93.447
141.81
51.196
113.23
182.43
51.484
127.57
212.33
51.902
135.49
228.55
58.493
175.48
305.57
66.759
202.72
353.89

Dev.
t.29
-.32
-.46
-.30
t1.2
-.38
-.71
-.44

+1.0
-.92
-.42
+.18
-.52

-.14

+.01
t.41
+.07
+.33
+1.2

-.06
tl.l

+1.6

-.27
+11.
+2.1
-2.6
+19.
1.90
-4.9
80.073 t 2 3 .
236.77 -2.2
353.66 -6.7
71.824 t 3 7 .
211.18 -2.4
346.83 -9.2
96.297 t19.
332.97 -13.
131.10 -1.9
311.58 -17.
55.152 +41.
1 5 3 . 2 3 -11.
2 6 9 . 1 8 -19.

T"

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

f V

13.966
16.569
21.321
26.718
22.367
27.688
37.289
48.074
41.561
72.800
102.44
50.383
93.761
140.95
51.227
114.17
182.20
51.665
129.56
213.50
452.32
138.32
230.90
62.134
185.36
317.75
74.495
219.75
375.84
94.845
264.99
388.18
94.145
250.24
397.48
135.47
404.02
196.73
408.32
116.65
237.15
375.97

Robinson
(Ci

(a)

0.42748

~~

ZcVR-

13.903
16.582
21.401
26.843
22.054
27.684
37.502
48.434
40.984
73.323
103.49
50.149
93.932
142.00
51.193
112.77
182.30
51.317
126.05
212.47
51.359
133.33
229.16
52.579
171.87
313.57
56.102
201.12
372.14
65.202
241.97
379.14
52.597
216.39
382.13
81.075
380.91
133.57
375.49
39.002
172..31
331.68

Soave

data

ChuehPrausnitz
(El

Peng-

v R ( ZC v R

t 0-.98664)

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

Table VI11 gives the comparisons for isopentane. Up

to the critical temperature eq (D) is clearly the best. Above
the critical temperature the Peng-Robinson and eq (D)
give about the same average deviation, both of which are
better than the Redlich-Kwong, the Soave, and the
Chueh-Prausnitz. At the higher densities the PengRobinson and eq (D) are similar. The conclusion is that
eq (D) is the simplest and best for an overall fit for isopentane.
Table IX gives the comparisons for trifluoromethane.
At all densities eq (D) is superior to the other equations
while retaining the simplest form.
Table X gives the results for ammonia. Again for all
densities eq (D) is superior to all the others.
Considering the performance for the wide range of
substances the inescapable conclusion is that eq (D), or
eq 67 with the temperature function, TRn,(or A + BTR)
is not only the simplest but the best of the two-term cubics.
The three-term virial does have a slightly lower value of
E, but it is one term more complicated. Certainly, there
is no reason to go to other more complex two-term cubics,
such as the Peng-Robinson, for they do not do as well as
(D).
One of the reasons for the superiority of (D) is found
in Table V, which lists the PVT behavior parameters, e,,
M , and B G ~one
, of which is not independent because it has

been shown that

= f , - B G is
~ practically constant a t
0.62. Using a single empirical parameter, such as the
acentric factor, in a correlating equation of state cannot
possibly do as well as (D) unless there is a consistent
relation between M and 2, or BG1,which there is not for
the six substances chosen. The Soave and Peng-Robinson
equations, for example, are constrained to fixed values of
2, (1/3 and 0.3074, respectively) with the temperature
function allowed to vary with a single parameter, but no
allowance is made for different values of e,. Equation (D)
does not have this pitfall as it is not locked into a fixed
2, for all substances. Since in (D) 2, = 0.25 tP,/RT,,
2, varies from 0.25 + 0.082 = 0.332 for argon down to 0.25
+ 0.04 = 0.29 for ammonia. At the same time the temperature function, TRn,is varying simultaneously with M
and 2, as shown by eq 89 where M and the translation,
tP,lRT,, enter into the slope of the critical isometric.
Thus, accounting for differences in e,, having the smallest
value of E, better performance, and inherent simplicity
are the compelling features that make (D) superior to all
others.
Clearly, other temperature functions besides TRn can be
used in eq 67 and they will perform as described for argon
and ethylene, these being the linear and exponential
functions. The temperature function of Soave could easily
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

1.37518
i.37758

699.27R

i.38062
1.38351

Pc =

.66C78:

,682863
,684335
,465549

403.6gsi.
Fc

38. 71b/ft3.
MW =

,411692

200.044.
R = 10.131F

&

1bnole.R
zc =

C.27801

'

,406226
.407?67
,438148
,218651
,218911
,219291
,126033
,125177
,126257
,126582
*.la6771

191.78
545.24
617.24
682.92
527.69
618.14
688.25
572.63
641.52
7i1.18
785.07
862.42
571.32
710.19
761.52
851.83
559.62
616.10
689.15
596. 02
636.28
689.96
634.03
670.19
689.60
651.44
768.55
849.84
699.08
761.69
851.69
941.69
1031.7

*.08C078

,066534

*.053385

,044823
*.040339

*.032031

699.06
761.69
851.69
941.69
iG31.7
685.89
761.67
820.86
875.49
699.08
761.69
851.69
896.69
986.69
694.68
769.11
864.33
699.08
761.69
851.69
941.69
1031.7
699.08
761.69
851.69
941.69
1031.7

.030030

'.026593

'.022879

,022497
*.020020

,019670

,017931

*.017795

+*.014356

**.012920

**
(A)
PR
~

699.52
738.79
776.94
852.59
716.69
806.69
696.69
986.69
619.08
761.69
851.69
941.69
1031.7
707.28
782.89
857.52
699.08
761.69
851.69
941.69
1331.7
698.8
752.14
796.81
838.86
862.04
695.95
763.76
801.60
861.36
699.08
761.69
851.69
941.69
1031.7
661.07
699.27
761.69
851.69
941.69
63i.29
699.27
761.69
851.69

17.R3

18.363 + 3 . 2

20.11
23.39

23.473 i l . 8
23.297 1.90
25.852 1 . 4 7
38.421 l 4 . l
4 5 . 7 8 1 11.6
51.426 +. 62
59.676 +2.2
6 8 . 1 6 7 -1.5
76.689 -.66
8 5 . 6 7 7 -.95
95,040 -1.7
66.389 11.6
85.829 -2.4
95.709 -1.8
105,40 - 2 . 1
65.497 + 4 . 6
73.700 12.5
83.565 il.0
119.26 i 4 . 8
130.96 -2.9
145.12 -1.4
195.67 i4.2
214.47 12.9
224.46 12.3
204.23 i2.4
264.42 -.a6
305.30 -2.2
258.31 i . 1 5
297.43 -1. 6
352.67 -2.8
406.97 -3.5
460.56 -3.9
309.46 1 . 3 8
364.96 -2.0
442.99 -3.7
519.40 -4.5
594.55 -5.0
320.22 i2.2
410.92 -1.9
475.78 - 4 . 0
534.68 -4.3
312.79 -.76
465.96 -3.1
596.11 -5.2
659.83 -5.9
785.C) - 6 . 7
382.55 11.7
522.45 - 4 . c
695.37 -6.3
398.31 + . 7 1
535.81 -4.0
727.04 -6.5
912.34 -7.9
1093.0 -8.9
403.00 c . 2c
591.81 - 4 . 4
8 5 3 . 5 8 -7.2
1106.5 -9.0
1352.4 - 1 0 .
404.46 + . I 4
535.42 -3.6
660.06 -5.0
900.85 -7.5
475.23 -.85
825.42 -5.5
1161.5 - 8 . 5
1486.8 -11.
423.01 15.0
738.05 -.49
1173.3 -6.4
1592.4 -10.
1999.0 -13.
470.50 13.9
858.08 -1.8
1226.5 -6.6
481.45 -18.
873.48 1 4 . 5
1415.0 -5.5
1936.1 -11.
2441.6 - 1 5 ,
492.75 123.
837.81 1 7 . 2
1119.0 +.69
1378.2 -3.7
i519.1 - 5 . 8
572.90 i l l .
1066.8 110.
1365.5 12.0
1795.5 - 5 . 3
608.64 - 4 0 .
1089.5 19.9
1753.7 -5.1
2393.1 -12.
3013.2 -17.
861.44 -226
1318.6 l65.
2043.8 122.
3051.0 t4.2
4022.7 -3.9
1169.0 +528
2206.9 +52.
3125.1 119.
4453.3 r2.4

25.73
36.92
45.05
51.11
58.40
69.20
77.20
86.50
96.70
65.37
87.95
97.47
107.70
62.62
71.92
82.73
113.79
127.3
143.09
187.75
208.37
219.33
199.5
266.7
312.0
257.91
302.15
362.81
421.53
479.11
308.29
372.55
459.77
543.76
625.9
313.40
419.00
495.50
558. 90
369.97
480.62
629.04
700.83
041.84
376.00
544.00
742.0
395.48
558.11
777.54
990.26
1199.3
102.18

619.08
919.72
1215.5
1508.3
403.90
555.1
695.4
973.4
479.26
873.64
1269.8
1665.5
403.00
741.70
1253.8
1773.3
2295.6
453.00
a73.30
13-3.4
436.9;

835.39
1497.C

2171.8
2854.8
c02.00
781.40
1111.4

1430.4
16L2.4
405.90
987.40
1338.4
1895.4
434.15
991.76
1847.6
2:20.a
3607.0
264.68
798.6
1671.0
2929.3
4186.9
186.21
1455.6
2621.2
4301.7

-2.5
11.4
1.69

16.195
2C.331
23.191
25.778
37.827
45.367
51.150
58.632
67.406
76.215
85.493
95.145
65.066
85.232
95.469
105.59
64.077
72.601
82.84d
115.50
127.97
143.04
188.15
208.76
219.73
197.62
263.43
308.01
253.07
296.27
357.10
416.65
4 7 5. 819
302.71
365.04
452.46
537.67
620.99
310.13

1.44
13.3
4 5 . 5 9 2 11.2
5 1 . 4 0 2 1.57

59.040 i1.l
67.882 - 1 . 9
76.747 -.58
55.569 i . 3 0
85.896 - 2 . 3
96.231 - 1 . 3

-06.28 -1.3
64.575 *3.1
73.174 - 1 . 7
63.50: -.93
+2.8

+1.8
r1.3

+2.0
t2.O
11.8

+,E5
1.73
+.70

1.15
1.19

365.14

t.64

426.05
485,66
309.44
374.17
464.65
552.53
638.16
316.25
424.03
500.69
569.95
372.73

11.1
il.4
- , 37
1.44
11.1

485.77

+1.1

11.6

12.0
1.91
il.2
11.1
+2.0
+,75

642.74 -2.9
7 1 9 . 0 7 12.6
867.91 13.1
380.48 11.2
553.03 11.7
7 6 4 . 8 6 13.1
398.20 1.69
569.56 12.;
896.46 13.7
1033.8 14.4
1252.9 +4.5
402.82 + . 1 7
642.43 13.8
972.69 i5.8
1288.6 16.0
1592.2 -5.6
404.69 *.20
571.71 i2.9
730.34 i 5 . 0
1035.3 16.4
495.12 +3.3
943.84 18.0
1371.0 i8.0
1779.8 16.1
422.80 14.9
829.87 tl2.
1389.4 -11.
1922.9 + a . 4
2433.9 - 5 . 0
482.88 16.6
983.68 113.
1156.9 rll.
481.08 +la.
989.10 t l 8 .
1687.1 1 1 3 .
2352.3
2989.3 16.3
14.1
491.83
939.12
1302.7
1636.5
1817.3
565.29
1233.8
1590.5
2143.2
608.20
1230.7
2086.2
2901.5
3682.4
733.20
1318.6
2245.8
3526.4
4749.7
895.51
2206.9
3364.9
4967.7

11.9
-1.1
+.56
37
-2.2
4 5 . 4 7 5 *.94
51.330 1 . 4 3

-2.5

18.140
20.323
23.220
25.824
37.726

*.lo
1.98
1.43

5s.65a 1 . 4 4

+.44
r.19

-.

-2.6
-1.3
-1.2
-1.6

67.683 -2.2
75.638 - . 77
6 5 . 5 3 2 -1.2
95.532 -1.2
-.46
65.079 - . 4 4
85.722 -2.5
-3.1
96.000 -1.5
-2.1
-2.1
1 0 5 . 9 9 -1.6
12.3
64.010 12.2
1.95
72.859 + 1 . 3
i . 1 4
63.312 r . 70
+ I .5
115.73 11.2
-.52
128.82 1.96
-.c4
144.36 1.88
189.40 t.88
r.22
211.12 i 1 . 3
1.18
1.17
222.49 il. 4
-.94
199.45 -.03
267.08 + . I 4
-1.2
-1.3
3 1 1 . 4 4 -.la
-1.9
256.65 - . 4 9
-2.0
300.78 -.45
361.36 -.lo
-1.6
419.47 - . 4 8
-1.2
-.a4
475.77 -.70
-1.8
307.20 -.35
-2.0
371.21 1 . 3 6
458.29 -.32
-1.6
-i.l
541.10 -.49
620.80 -.82
-.a0
-1.0
113.60 1.64
420.23 1.29
413.05 -1.4
486.55 -1.8
4 9 3 . 8 8 -.33
553.14 - 1 . 0
559.25 1.06
370.72 1.07
365.85 -1.1
472.78 -1.6
480.85 + . 0 5
621.90 -1.1
629.42 C.36
694.68 - . a 7
700.14 -.39
837.10 -.56
836.09 -.68
375.77 -. 06
3 7 8 . 5 4 1.68
537.53 -1.2
546.18 1.40
737.16 -.65
744.07 1.28
3 9 4 . 4 0 -.27
396.76 1.32
554.02 - . 7 3
562.46 + . 7 R
775.80 -.22
783.08 1.71
989.81 - . 0 5
988.48 -.la
1182.7 -1.4
1197.1 -.la
402.45 C.07
402.76 i . 1 4
622.73 + . 5 9
631.33 i2.0
928.02 1.90
933.93 +1.5
1214.0 -.12
1221.8 1.51
1505.6 -.I8
1477.6 -2.0
402.56 - . 3 3
404.03 1.03
542.98 12.2
564.35 11.6
702.96 +I.
1
712.42 +2.5
983.96 il. 1
989.23 i l . 6
489.79 +2.2
485.14 A1.2
894.01 i2.3
903.77 t3.5
1285.9 +1.3
1281.3 +.91
.~
1662.9 - . l 5
1632.7 -2.0
413.13 +2.5
408.40 +1.3
775.05 14.5
789.65 16.5
1285.1 c2.5
1281.8 i2.2
1740.6 -1.8
1767.8 -.31
2167.5 -5.6
2236.0 -2.6
460.10 c1.6
4 6 8 . 0 7 C3.3
91i.18 + 4 . 3
926.01 16.0
1339.7 C2.0
1341.4 C2.1
433.14 t6.4
447.51 +lo.
886.87 C6.1
909.10 C8.8
1515.8 c1.3
L 5 1 3 . 5 +1.1
2114.2 -2.7
2073.1 -4.5
2692.5 - 5 , l
2594.4 -9.1
437.01 t8.7
453.11 113.
835.91 17.0
659.75 110.
1161.2 i 4 . 5
1180.1 16.2
i467.6 12.6
1460.6 +2.;
1621.1 1 . 5 4
1623.4 +.68
487.32 t20.
460.16 1 i 3 .
i050.2 16.4
1081.3 t10.
1391.7 i 4 . 0
1 3 7 C . l 12.4
1863.3 - 1 . 7
1903.2 c.41
493.54 il4.
522.74 +20.
1077.3 +8.6
1045.2 i5.9
1806.8 -2.2
1805.9 -2.3
2536.7 -6.6
2475.1 -9.0
3100.9 - 1 4 .
3239.3 - 1 0 .
346.16 i31.
4 0 3 . 8 4 +53.
653.96 -6.9
917.84 1 1 5 .
1701.3 cl.8
1660.3 -.E4
2777.7 -5.2
2736.1 -6.6
3849.3 -8.1
3688.6 -12.
185.21 -.54
242.78 1 3 0 .
1305.9 -10.
1 3 6 4 . 0 -6.3
2297.6 -12.
2304.1 -12.
3673.4 - 1 5 .
3548.9 -18.

86.278 -.49
95.779 - . 9 5

i16.96
129.63
144.92
191.47
212.63
223.43
201.19
268.64
314.18
258.29
302.73

i2.2
11.1

i22.
i20.
117.
-14.
+13.

-39.
125.
+19.
113.
+lo.

124.
113.
16.6
i2.1
1177
C65.
+34.

+20.
+13.
1381
+52.
C28.
115.

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
IC)

0.42748

p=L
0.457236 Ilr0.89!l-TR0'ji
-

TC vR -0.08664
181

TR
i

18.240
20.383
23.250
25.843
38.312

TCVR-0.O8664

0.42746 Iltl 0 ll-TRo'5 , 1

TcvR(IcvR+O.
08664)

C R

-0.~778

'1
v ( tC v R + ~ . o ~ ~ ~ ~ ~ ~ . o ~ ~ ~ I z ~ v ~ - o . o ~ ~ ~ I

c H

ID)

27/64TR1"

TR

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

RedlichKwong

Soave

(Ai

(Bl
3

T, K
310

TC =
460.39K

330

p C = 33.37atm350

V = .306
cm3 /gmol

370

R = 82.05606
c m atm
grnole .K

390

410

0.270297

430

450

455

,9445
,9395
,9149
.9671
,8771
.E832
.9729
,8301
.9045
.9775
,7726
,8286
.9207
.9811
.7014
,7715
,8589
,9335
.9840
,6087
,6290
.7325
.E132
.E822
,9437
,9864
,4649
.4875
,6219
.7104
,7822
.a445
,9006
,9521
.9883
,4204
.4547
.5391
.6460
,7256
,7923
,8512
,9046
,9539

470

,9887
,6046
.4386
,3680

500

600

(A)
P

18)

.2949
.2585
.2295
.5891
.7641
,8926
,9899
.7651
.6106
.4532
.3932
,3671
.4363
.5771
.7097
.a200
.9152
.9919
1.0606
.9309
.a059
,6996
.6625
,6937
,7539
.7919
.E327
.a747
,9170
.9588
.9959

-zcVR-0.08664
T

P R = ZcVR-0.08664

1.35
1
2.47
1
4.19
4

1
6.66

1
10.08
8
4
1
14.64
12
8
4
1
20.63
20
16
12.
8
4

1
28.41
28
24
20
16
12
8
4
1
30.71
30

28
24
20
16

12
8
4
1
150

100
80
60
50

40
30
20
10
1
200
150
100
80
60
50
40
30
20
10
1
300
250
200
150
100
80
60
50

40
30
20
10
1

Dev.

Dev.

Dev.

Dev.

Dev.

1.3673
1.0092
2.5138
1.0065
4.2855
4.0866
1.0047
6.8484
4.0598
1.0033
10.416
8.1932
4.0419
1.0024
15.196
17.332
8.1285
4.0208
1.0017
21.466
20.765
16.420
12.209
8.0839
4.0194
1.0011
29.377
28.957
24.679
20.427
16.248
12.128
8.0521
4.0119
1.0007
31.448
30.865
28.829
24.580
20.369
16.217
12.112
8.0456
4.0106
1.0007
213.19
142.38
115.98
89.762
75.630
57.007
30.570
20.227
10.047
1.0004
258.68
199.00
134.81
105.90
68.007
50.407
40.127
30.110
20.042
10.007
1.0000
309.95
267.15
218.57
161.46
100.12
78.270
58.462
48.828
39.206
29.538
19.789
9.9470
,99948

t1.3
t.92
tl.8
+.65
t2.3
t2.2
t.47
t2.8
t1.5
t.33
t3.3
t2.4
+1.1
t.24
t3.8
+2.8
t1.6
t.72
t.17
t4.1
+3.8
t2.4
tl.7
+1.1
t.49
t.ll
t3.4
t3.4
t2.8
+2.1
+1.6
+1.1
+.65
t.30
+.07
+2.4
t2.9
t3.0
+2.4
+1.9
t1.4
+.93
t.57
t.27
+.07
+42.
+42.
145.
t50.
t51.
+43.
t1.9
tl.l
t.47
+.04
t29.
+33.
+35.
+32.
t13.
t.81
t.32
t.37
+.21
+.07
00
t3.3
t6.9
+9.3
f7.6
+.12
-2.2
-2.6
-2.3
-2.0
-1.5
-1.1
-.53
-.05

1.3617
1.0062
2.4983
1.0043
4.2486
4.0534
1.0030
6.7719
4.0363
1.0021
10.274
8.1151
4.0258
1.0015
14.965
12.202
8.0811
4.0186
1.0011
21.141
20.477
16.281
12.145
8.0591
4.0139
1.0008
29.066
28.680
24.548
20.356
16.210
12.109
8.0447
4.0102
1.0006
31.210
30.683
28.712
24.518
20.334
16.198
12.102
8.0419
4.0097
1.0006
216.29
145.08
118.47
92.002
77.689
58.735
30.759
20.280
10.057
1.0005
271.23
210.34
144.32
114.21
73.808
53.483
41.357
30.594
20.210
10.042
1.0003
346.50
300.71
248.00
184.47
112.64
85.995
62.367
51.358
40.711
30.325
20.115
10.023
1.0002

t.87
t.62
t1.2
t.43
t1.4
tl.3
t.30
t1.7
t.91
t.21
+1.9
11.4
1.65

1.3587
1.0046
2.4888
1.0027
4.2224
4.0295
1.0015
6.7098
4.0136
1.0006
10.144
8.0306
4.0041
1.0001
14.720
12.029
8.0004
3.9980
,99977
20.749
20.093
16.000
11.977
7.9823
3.9942
.99952
28.690
28.251
24.041
19.955
15.931
11.949
7.9715
3.9916
.99944
31.016
30.295
28.167
23.998
19.934
15.027
11.944
7.9696
3.9913
.99945
132.39
95.256
81.169
67.056
59.384
49.232
30.069
19.886
9.9496
,99938
182.32
148.38
110.29
92.286
66.779
51.691
40.248
29.840
19.836
9.9416
.99929
275.19
244.77
208.56
162.59
105.42
81.939
60.103
49.730
39.619
29.678
19.812
9.9433
.99937

t.64
+.46
+.76
t.27
+.77
c.74
t.15
t.75
+.34
t.06
t.63
t.38
1.10
t.01
+.55
+.23
t.01
-.05
-.02
t.58
t.47
00
+.19
t.22
+.15
-.05
+.99
t.90
t.17
-.23
-.40
-.43
-.36
-.21
-.06
t1.0
t.98
1.60
-.01
-.33
-.46
-.47
-.38
-.22
-.06
-12.
-4.7
t1.5
+12.
tl9.
t23.
+.23
-.57
-.50
-.06
-8.8
-1.0
t10.
t15.
t11.
+3.4
+.62
-.53
-.82
-.58
-.07

1.3478
.99878
7.4642
.99914
4.1757
3.9877
.99944
6.6342
3.9923
.99959
10.039
7.9791
3.9960
.99975
14.601
11.979
7.9923
3.9981
.99986
20.645
20.019
16.013
12.004
8.0000
3.9998
,99991
28.629
28.230
24.173
20.093
16.044
12.017
8.0045
4.0004
1.0000
30.939
30.329
28.317
24.193
20.102
16.049
12.019
8.0053
4.0007
1.0001
114.76
88.008
77.113
65.629
59.081
49.907
30.485
20.115
10.014
1.0001
162.98
138.23
108.13
92.722
68.934
53.337
41.267
30.437
20.115
10.015
1.0000
256.45
232.39
202.59
162.12
107.74
84.087
61.634
50.894
40.425
30.164
20.042

-.16
-.12
-.23
-.09
-.34
-.31
-.06
-.39
-.19
-.04
-.41
-.26
-.lo
-.03
-.27
-.17
-.lo
-.05
-.01
t.07
t.09
+.OB
+.03
00
00
-.01
+.75
t.82
t.72
t.47
+.27
t.14
t.06
t.01
00
+.75
tl.l
tl.l
t.80

1.3648
1.0078
2.5065
1.0054
4.2662
4.0693
1.0038
6.8032
4.0456
1.0025
10.317
8.1375
4.0300
1.0017
14.993
12.213
8.0833
4.0187
1.0011
21.056
20.396
16.228
12.115
8.0464
4.0108
1.0006
28.530
28.172
24.234
20.163
16.098
12.051
8.0205
4.0045
1.0003
30.436
29.973
28.160
24.174
20.122
16.074
12.038
8.0152
4.0034
1.0002
259.67
169.39
136.10
103.19
85.467
62.025
29.977
20.021
10.004
1.0000
306.04
231.02
151.68

tl.l
+.78
t1.5
t.54
t1.8
t1.7
1.38
+2.2
+1.1
+.25
+2.4
+1.7
+.75
t.17
t2.4
+1.8
t1.0
+.47
+.11
t2.1
t2.0
t1.4
+.96
+.58
t.27
t.06
+.42
t.61
1.98
t.81
t.61
+.43
+.26
t.ll
t.03
-.E9
-.09
t.57
+.72
+.61
t.46
+.32
t.19

0.42748[1+0.82(l-T:'5)

ChuehPrausnitz
(El

Martin
(Di

atm

0.42748
TR0'5ZcVR(ZcVR+0.08664)

P,

PengRob 1n son
(Cl

f.15

+2.2
t1.7
t1.0
t.47

+.11
+2.5
t2.4
t1.8
t1.2
+.74
t.35
t.08
+2.3
t2.4
t2.3
t1.8
t1.3
t.91
1.56
t.26
t.06
t1.6
+2.3
t2.5
t2.2
t1.7
t1.2
+.e5
t.52
t.24
t.06
t44.
t45.
+48.
t53.
155.
+47.
+2.5
+1.4
t.57
t.05
+36.
+40.
144.
t43.
+23.
t7.0
t3.4
+2.0
+1.1
t.42
t.03
t16.
+20.
+24.
123.
t13.
+7.5
t4.0
t2.7
tl.8
+1.1
t.58
t.23
t.02

-8.3

TR

'1

TR

ZcVR(ZcVR+0.08664)

TcVR-0.0906

(CI
T,
0.457236[1+0.71(1-T-0'51 l 2
m
- zcVR(z V +0.07781t0.0778(ZcVR-0.07781
K
PR = zcVR-0.0778
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

t.30
+.16
+.07
+.02
+.01
-23.
-12.
-3.6

t9.4
tl8.
t25.
t1.6
t.58
+.14
+.01
-19.
-7.8
+8.1
t16.
+15.
+6.7
+3.2
+1.5
+.58
+.15
00
-15.
-7.0
+1.2
18.1
+7.7
t5.1
+2.7
+1.8
tl.l
+.55
t.21
1 0 . 0 0 5 t.05
1.0000
00

-2.1
t4.3
+8.4
t5.4
t2.4
t.17
-.54
-.95
-1.1
-.94
-.57
-.06

ZcVR-0.064

+.51

116.38

70.615
49.862
39.416
29.733
19.891
9.9726
.9997
342.43
291.56
234.59
168.94
100.97
78.041
58.037
48.471
38.952
29.386
19.715
9.9291
,99930

+.OS
+.02
t73.
t69.
t70.
t72.
t71.
t55.
-.OS
-.01
t.04
00
t53.
+54.
+52.
+45.
tl8.
-.28
-1.5
-.E9
-.55
-.27
-.03
+14.
+17.
117.
t13.
t.97
-2.5
-3.3
-3.1
-2.6
-2.1
-1.4
-.71
-.07

27/64TR1'
(?cVR+0.06112
0.4450
TRO'% V

c R

(?cVRt0.0906)

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
TRIFLUOROMETHANE

v
TC =

p,

55.61
61.20
16.30
90.25
104.17
79.45
92.46
103.13
123.92
148.08
179.78
203.82
236.26
276.15
313.09
270.8
298.0
330.7
332.2
315.2
430.3
484.3
409.0
416.9
548.0
612.2
672.5
725.5
525.8
589.9
699.2
802.0
906.1
1036.5
654.3
742.7
910.0
1162.6
1392.5
684.3
834.1
1082.2
764.1
1014.7
1268.9
1496.4
1148.6
1913.1
715.0
1019.0
1224.4
1504.1
1749.9
1995.4
705.8
1024.3
1254.5
1555.7
1974.3
693.2
115.7
1014.3
1313.6
1649.1
1978.2
106.6

57.253
67.884
76.056
89.532
103.01
87.101
93.944
103.48
123.16
146.29
187.06
208.02
237.20
214.23
209.58
281.36
304.56
332.68
333.91
373.06
425.53
418.41
422.99
480.18
543.96
604.54

.31066
ft3/ltmole. R
MW = 70.019

.20158

.12836

,082677

,055465

.047352

563.06

,033604

,028644

,023589

606.44
545.6!
574.22
602.73
628.97
657.22
683.05
545.69
568.67
581.21
613.06
634.82
656.98
538.33
561.00
576.86

,023646

,021531

,020316

596.89
624.23
536.11
538.33
558.08
517.12
591.56
617.85
536.54
538.33
559.85
575.60
593.64
610.16
523.91
538.33

.016045

548.51
561.74
512.13
598.68
500.02
505.25
514.58
522.15
538.33
544.27

736.6

1097.5
1314.6
1698.1
1991.0
680.8
781.1
974.8
1229.1
1435.8
1971.5
461.8
645.3
965.4
1226.6
1192.4
1967.9

660.73

111.85
541.28
600.11
691.28
190.06
884.08
1006.4
667.11
145.29
911.11
1134.3
1349.3
694.08
833.49
1066.6
772.08
1029.5
1281.4
1509.4
1151.0
1968.8
828.09
1094.6
1306.3
1597.1
1838.3
2080.8
951.85
1317.5
1569.5
1883.8
2306.0
1017.2
1045.6
1388.2

1113.1
2058.2
2395.5
1167.5
1201.8
1610.6
1905.5
2239.3
2541.4
1339.3
1455.3
1611.8
1950.7
2167.7
2715.2
2855.1
3056.1
3393.0
3664.5
4239.7
4449.2

0.42748
iR
ZcVR-0.08664

(B)
PR =

IC)

400.1
466.4
517.66
602.60
687.91
412.49
463.35
504.59
590.22
691.63
455.44
493.01
546.04
614.02
679.54
419.89
505.55
536.95
538.33
502.52
642.41
103.64
510.78
548.42
591.05
632.09
670.58
705.91
519.08
539.42
576.68
613.11
650.58
100.06
534.86
552.38
587.93
643.00
694.8
531.68

psi'

IB)

,99819

R = 10.7315

(A1
PS1

.70008

= .259344

Robinson

data

= 32.78 lbift

Soave

T, R

Pc =

701.42 p s i

Kwong

ft3/lb

538.33 R

F,

Penq-

Redlich-

CHF3

TR

zcVR-0.08664

(C)
P =

TR05EcVR(ZcVRt0. 08664)
0.42748 ilt0.86 u - T ~ ~ )1
~cVRl~cVR+0.08664)

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

, tPc/RTc,the translation,
and C = 1/8 - B. The translation is set to fit best at a
reduced density of 1.5 or 2.0, depending upon what behavior is sought, and n is selected to give a reasonable

%
Dev.

t3.0
t1.0
-.32

-.EO
-1.1
t3.3
t1.6
t.34
-.62
-1.2
t4.1
+2.l
+.40
-.69
-1.1
+3.9
t2.2
+.60
t.52
-.57
-1.1
-1.2
+3.4
t.69
-.74
-1.3
-1.8
-1.9
+4.1
+1.8
-.21
-1.5
-2.4
-3.0

t2.1
+.35
-1.1
-2.4
-3.1
t1.4
-.07

-1.4
t1.0
+1.5
t.99
+.E7
+.14
-.22
t6.9
tl.4
t6.7
t6.2
+5.1
i4.3
t35.
t29.
+25.
+21.
117.
t47.
t46.
t37.
t30.
t25.
+21.
t65.
t63.
t41.
t39.
t32.
+28.
t97.
t86.
+72.
159.
t51.
t38.
t512
+373
t251
+199
t136
t126

%
Dev.

56.818
61.686
75.999
89.707
103.30
81.410
93.525
103.29
123.44
141.11
184.15
206.75
237.42
276.31
313.38
217.55
302.42
332.59
333.91
315.91
432.15
488.17
418.68
481.15
552.11
618.88
680.72
736.88
570.31
601.16
111.05
816.68
923.63
1062.5
665.06

755.98
931.63
1212.3
1463.9
693.42
858.51
1135.1
785.90
1096.7
1401.4
1671.0
1969.1
2232.1
846.43
1169.9
1421.2
1780.8
2014.0
2368.7
951.85
1396.1
1102.8
2085.5
2599.8
1011.2
1045.6
1461.7
1857.5

2276.8
2681.5
1160.2
1201.8
1697.7
2055.9
2461.7
2829.1
1315.0
1455.3
1711.3
2055.1
3218.2
2982.4
2612.8
2831.4
3236.1
3551.7
4239.7
4488.3

TR
ZcVR-O. 0778

ID)

t2.3
t.12
-.39
-.60

-.74
+2.5
+1.2
+.16
-.39
-.65
t2.8
11.4
+.49
t.06
+.09
t2.5
tl.5
t.57
t.52
t.19
t.43
t.92
t2.4
t1.0
+.75
tl.l
tl.2
+1.6
t2.8
t1.9
tl.1
t1.8
+1.9
t2.5
t1.7
t1.8
+3.0
t4.3
t5.1
+1.3
+2.9
+4.9
+2.9
+8.l
t10.
t12.
t13.
+13.

+9.2
t15.
+11.
tl8.
t19.
t19.
t35.
+36.
t36.
+34.
+32.
t46.
+46.
+44.
+41.
t38.
t36.
t64.
t63.
+55.
t50.
t45.
+42.
+93.

+86.
t16.
+61.
+61.
+51.
+458
t339
t235
+19C
+136
+128

Martin
ID1

Dev.

Dev.

56.645
67.398
15.673
89.328
102.98
80.948
92.915
102.68
122.71
146.27
182.67
204.34
234.57
212.98
309.65
293.34
291.65
321.11
328.46
369.62
424.83
480.53
410.63
471.62
539.81
604.65
664.82
119.54
530.31
588.32
693.00
193.81
896.24
1029.5
651.38
142.15
911.93
1169.5
1406.5
588.97
841.58
1098.1
774.88
1056.5
1333.3
1584.3
1850.9
2091.5
807.27
1091.3
1328.4
1646.1
1911.2
2117.5
808.11
1200.9
1472.6
1812.0
2269.2
823.18
853.57
1220.2
1569.7
1940.4
2304.3
894.11
930.59
1366.0
1681.0
2038.3
2362.3
935.49
1057.9
1286.1
1581.9
1812.1
2394.0
1098.2
1287.9
1624.7
1896.5
2413.1
2683.3

+1.9
+.29
-.E2
-1.0
-1.1
t1.9
t.56
-.44
-.97
-1.2
t1.6
t.25
-.71
-1.2
-1.1
t.94
-.12
-1.1
-1.1
-1.5
-1.3
-.78
+4.0
-1.1
-1.5
-1.2
-1.1
-.E2
t.89
-.27
-.E9
-1.0
-1.1
-.68
t.47
-.07
+.21
t.60
t1.0
+.68
+.91
+1.5
t1.4
t4.1
+5.1
+5.9
t5.9
t6.0
+4.2
tl.7
+8.5
t9.5
19.2
t9.1

56.364
61.316
15.155
89.466
103.09
80.496
92.904
102.19
122.98
146.48
181.88
204.47
235.43
214.07
310.49
272.63
298.09
328.54
329.81
311.64
426.75
481.57
410.97
414.18
543.32
601.90
667.02
120.26
530.18
590.46
697.34
798.08
898.50
1021.0
651.40
144.52
915.19
1166.6
1391.6
688.99
843.94
1097.2
114.52
1050.5
1315.3
1550.7
1196.3
2014.6
801.70
1080.6
1298.7
1593.7
1834.7
2074.0
175.48
1142.8
1391.5
1697.4
2101.9
118.43
806.74
1145.8
1462.9
1193.5
2112.8
822.98
856.62
1253.3
1535.1
1850.0
2131.6
824.51
935.59
1144.5
1404.1
1606.5
2110.0
525.33
686.45
969.97
1196.5
1670.7
1841.6

+1.4
t.26
-.71
-.E7
-1.0
t1.3
t.48
-.33
-.76
-1.1
t1.2
+.32
-.35
-.75
-.E3
t.68
1.03
-.65
-.lo
-.95
-.E3
-.56
t.48
-.57

+15.
t17.
tl7.
1-16.
115.
+19.
+19.
+20.
t19.
t18.
+16.
t21.
t26.
t24.
t22.
t20.
t19.
t37.
t35.
+32.
t29.
t26.
+21.
t134
t100
t68.
t54.
+38.
+36.

-.E5
-.70
-.E1
-.72
+.E3
+.09
-.03

-.49
-.E4
-.92
t.49
t.24
+.57
+.34
-.06
+.69
+1.2
+1.4
+1.4
t3.5
t3.1
t3.6
t2.7
12.1
t3.4
+6.0

t6.1
+6.0

+4.9
+3.9
tl0.
+12.
t11.
t9.1
+6.5
+12.
+13.
t13.
t11.
+8.8
+6.8
+16.
t16.
+14.
t12.
t9.0
+7.1
t21.
+20.
+17.
t14.
112.
t2.0
+12.
t6.4
+.47
-2.5
-6.8

-6.4

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

Z V (fcVRtO.077 8)to. 017 8 ( ;cVR-O. 077 8 )

C R

21/64TR
zcVR-0.055

l z c V R t0.07)2

average slope M of the criticcl isometric based on the

generalized vapor-pressure diagram. It has been shown
that no other two-term cubic can be developed to be
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
tlH3
AMMONIA

T,OC
T

=
C

405.44K
P

45
30
10
20

V
cm 3/gm

P IkPa
data

2190
1140
620.3
699.6
341.5
161.7
776.7
303.2
145.0
64.77
802.1
395.4
169.2
89.49
49.17
852.5
277.7
133.8
61.93
31.07
902.6
599.0
295.4
143.4
67.10
38.53
18.04
927.6
615.8
259.5
148.1
69.83
35.84
14.34
952.5
632.6
267.0
129.8
66.28
30.21
10.32
977.4
649.4
274.5
133.8
68.72
35.42
16.9
8.524
6.549
989.8
657.7
278.2
135.8
69.91
34.41
16.97
12.67
8.590
6.557
4.706
3.620
2.588
2.263
2.127
1200
598.1
297.2
130
66.98
33.69
17.03
8.396
4.681
2.801
1470
587.2
292.7
132.1
68.32
34.03
17.62
8.490
4.553

101.33
200
200
400
800
200
500
1000
2000
200
400
900
1600
2600
200
600
1200
2200
4000
200
300
600
1200
2400
3800
6200
200
300
700
1200
2400
4200
7400
200
300
700
1400
2600
5000
9000
200
300
700
1400
2600
4600
7800
10400
10800
200
300
700
1400
2600
4800
8000
9400
10900
11500
11800
12000
16000
26000
36000
200
400
800
1800
3400
6400
11400
19000
28000
50000
200
500
1000
2200
4200
8200
15000
28000
50000

~~

11278 kPa

50

v =
4.247 cm3/gm
z

60

.242004
80
R = 8 3 14.4

cm3. kPa/gmole. K
100

110

120

130

135

220

330

(A!

PR =
(B)
PR =

TR
zcVR-0.08664
TR
zCVR-.O8664

50

0.42748

RedlichKwong

soave

(A)

(B)

+.96
t1.4
+1.4
+.72
11.5
t3.4
r.38

+.98
+2.1
t5.3
t.30
+.62
+1.5
1-3.0
+6.0
+.20
t.62
t1.3
+2.7
+6.6
C.13
t.19
t.37
+.79
+1.7
+3.1
+7.1
+.lo
+.16
+.35
1.59
~ 1 . 3
t2.6
+6.4
+.08
t.12
t.27
t.55
+1.1
t2.3
t5.2
t.06
t.08

+.18
+.40
+.78
+1.5
+2.7
t3.0
+1.5
+.05
+.DE
t.16
+.32
+.65
t1.3
+2.6
t2.6
+2.2
tl.O
+2.1
t28.
+197
+267
t283
-.03
-.06
-.12
-.28
-.46
-.E0
-1.2
-.82
+6.4
t54.
-.03
-.16
-.30
-.64
-1.1
-1.8
-2.1
-.28
+6.1

PR =

(D)

TR
zcVR-0.0778

Dev.

50.435
102.63
202.36
201.14
404.77
821.73
200.57
503.73
1016.1
2081.6
200.45
401.85
909.89
1635.9
2717.7
200.30
602.80
1211.6
2244.1
4194.7
200.21
300.46
601.71
1207.4
2432.3
3891.3
6519.8
200.16
300.39
702.03
1205.8
2425.6
4287.3
7745.1
200.14
300.32
701.67
1406.7
2624.4
5099.7
9338.0
200.10
300.24
701.25
1405.4
2619.5
4665.2
6003.7
10674.
10904.
200.10
300.24
701.15
1404.6
2617.7
4863.9
8191.6
9659.1
11185.
11686.
12164.
15565.
47798.
95910.
138214
200.01
400.09
800.29
1801.6
3408.8
6443.4
11617.
20196.
33672.
86079.
200.05
499.90
999.84
2199.5
4203.0
8249.5
15392.
30754.
61771.

(C)

TR0'5Z C V R (ZcVRt0.00664)
0.42748 [1+0.86(1-TR0'5) 1

Dev.

+.87
t1.2
+l.2
+.57
tl.2
+2.7
+.29
+.75
+1.6
+4.1
t.23
+.46
+1.1
+2.3
+4.5
+.15
+.47
t.96
+2.0
t4.9
t.10
1.15
+.28
+.61
+1.3
+2.4
+5.2
+.08
t.13
t.29
c.48
tl.l
+2.1
+4.7
t.07

+.11
t.24
+.48
+2.9
t2.0
13.8
+.05
t.08
+.18
1.38
+.75
t1.4
+2.6
t2.6
t.97
t.05
+.08
t.16
t.33
1.68
+1.3
t2.4
+2.8
+2.6
+1.6
t3.1
130.
+199
t269
t284
t.01
+.02
+.04
+.09
+.26
t.68
C1.9
+6.3

+20.
+72.
+.03
-.02
-.02
-.02
+.07
+.60
+2.6
C9.8
t24.

Martin
(D!
-5

50.479
102.79
202.82
201.82
406.02
827.24
200.75
504.91
1021.2
2106.8
200.60
402.46
913.19
1647.6
2755.9
200.40
603.70
1215.4
2258.7
4263.0
200.26
300.58
602.19
1209.4
2441.5
3919.0
6640.8
200.20
300.47
702.47
1207.1
2431.6
4309.3
7874.7
200.16
300.36
701.89
1407.7
2628.1
5116.7
9470.8
200.11
300.24
701.29
1405.5
2620.2
4667.5
8013.3
10710.
10962.
200.10
300.23
701.11
1404.4
2617.0
4861.0
8180.3
9639.8
11144.
11619.
12043.
15374.
47462.
95493.
137753
199.94
399.78
799.02
1795.0
3384.2
6348.5
11260.
18844.
29793.
76776.
199.94
499.20
997.05
2185.9
4152.6
8050.6
14679.
27922.
53069.

PengRobinson
(C)

50.421
102.58
202.16
200.95
404.02
818.64
200.40
502.65
1011.7
2063.8
200.29
401.18
906.47
1625.0
2688.8
200.15
601.38
1205.9
2224.9
4123.3
200.06
300.12
600.36
1202.0
2411.0
3839.3
6400.9
200.01
300.06
700.26
1200.6
2404.1
4226.4
7601.9
200.00
300.00
699.94
1399.9
2601.2
5017.9
9199.5
200.00
299.93
699.58
1398.7
2596.9
4597.1
7834.0
10537.
10891.
200.00
299.93
699.50
1398.0
2595.5
4791.3
8015.0
9448.2
11010.
11610.
11947.
13564.
30163.
54482.
74957.
199.90
399.66
798.58
1793.1
3379.2
6343.5
11327.
19468.
31406.
68443.
200.00
499.39
997.83
2190.0
4169.2
8126.9
15008.
29464.
56966.

Dev.
+.E4
+1.2
+1.0
t.48
e1.0
t2.3
+.20
+.53
+1.2
+3.2
t.14
+.30

+.72
+1.6
t3.4
t.07
+.23
+.49
tl.l
+3.3
+.03

+.04
+.06
1.17

+.46
+1.0
+3.2
+.01
+.02
t.04
+.05
+.21
+.63
t2.7
00
00
-.01
-.01
+.05

t.36
+2.2
-.01
-.02
-.06
-.09
-.12
-.06
+.44
t1.3
+.84
-.02
-.02
-.07
-.13
-.17
-.18
t.19
+.52
c1.0
+.95
+1.2
+13.
+89.
t110
+lo8
-.05

-.08
-.18
-.38
-.61
-.E8
-.64

t2.5
t12.
t37.
-.01
-.12
-.22
-.46
-.73
-.E9
t.05
+5.2
+14.

Dev.

50.298
102.21
201.23
200.50
402.12
810.26
200.18
501.23
1005.6
2033.9
200.12
400.50
902.76
1612.0
2646.9
200.05
600.49
1202.1
2212.4
4068.1
200.00
300.00
599.91
1200.1
2402.2
3813.1
6298.0
199.99
299.99
699.83
1199.2
2399.2
4204.i
7493.;
199.98
299.95
699.68
1398.7
2596.6
4995.8
9089.7
199.96
299.90
699.43
1398.1
2594.3
4586.4
7790.7
1046.1
10852.
199.96
299.92
699.41
1397.7
2593.6
4782.3
7979.7
9394.9
10947.
11575.
11891.
12610.
18245.
24454.
28734.
199.91
399.69
798.70
1793.6
3380.3
6343.3
11300.
19206.
29497.
50581.
199.96
499.29
997.41
2187.8
4160.2
8084.2
14812.
28305.
50548.

t.60
t.87
+.62
t.25
+.53
+1.3
+.09
1.25
+.56
t1.7
t.06
+.12
+.31
+.75
+1.8
+.G3
t.08
+.17
+.47
t1.7
GO
-.02
-.02
00
+.09
+.35
+1.6
-.0l
00
-.02
-.06
-.04
+.lo
+1.3
-.01
-.02
-.05
-.09
-.13
-.OB
+1.3
-.02
-.03
-.G8
-.14
-.22
-.30
-.12
+.59
+.48
-.G2
-.03

-.08
-.17
-.25
-.37
-.25
-.05
t.44
+.65
c.77
t5.1
t14.
-6.0
-20.
-.04
-.08
-.16
-.36
-.5B
-.E9
-.E8
+1.1
+5.4
t1.2
-.02
-.14
-.26
-.56
-.95
-1.4
-1.3
il.1

tl.l

0.457236 rlC0.75 (l-TR0") 1

Z V

c R ( Z CV R+0.0778!t0.0778(ZcVR-0.0778)

2 7/64 TR1'

IR

z C V R (icVR+0.08664)

generating eq 6, and eq 93 has the smallest value of 1

which makes it the best.
If eq 93 is applied to mixtures, it is a simple procedure

'R=--

2 V -0.04
C R

(ZcVR+0.085)2

to combine constants just as with van der Waals or any

other equation. To show how the procedure works, eq 93
can be transformed from its generalized form back to its

Ind. Eng. Chem. Fundam., Vol. 18, No. 2, 1979

96

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

specific form

RT

P=

A R2T: / Pc

--.-RT
-

For a given substance, i, this is

A 1R2Tct2/ pci
RT
(95)
V - BcRTc,/Pc, (V + CLRT,,/PJ2
where A, = 27/64TRlniaccording to the definition of A.
Now van der Waals procedure of combining the volume
constants, b and c, linearly, and the a by geometric mean
gives good results, though linear cube root may be better
for a. Thus, the constants for a mixture of two substances,
1 and 2, are
P=

BmTc,/Pc, = XlBlTcl/Pcl+ ~2B2Tc2/PcZ

(96)
(97)

and

CmTc,/Pc, = XICITcl/Pcl + x2C27'c2/pcz (98)

For a single molar gas constant, R, the concentrations, x l
and x2, are to be mole fractions, and it is to be noted that
R has been divided out of both sides of eq 96,97, and 98.
These will give good results in the expression

for mixtures, particularly if the magnitudes of the a, b, and

c terms being combined do not differ greatly from substance to substance. Equation 99 can be differentiated
with respect to the moles of 1 and the moles of 2 to give
the individual component fugacities in the usual expression

1
10
20
30
40
50
60
80
100
150
200
250

0.9894
0.8859
0.7453
0.5292
0.2047
0.2440
0.2840
0.3634
0.4414
0.6304
0.8128
0.9901

125.518
11.2388
4.72755
2.23786
0.64922
0.61909
0.60048
0.57628
0.55997
0.53316
0.51557
0.50243

0.9996
9.9694
19.935
30.112
46.863
51.663
55.441
61.566
66.649
77.186
85.976
93.171

-0.04
-0.31
-0.33
0.37
17.16
3.33
-7.60
-23.04
-33.35
-48.54
- 57.01
-62.49

will predict the PVT behavior of C 0 2as well or better than

any other two-term cubic equation. One further point
concerning the selection of 0.068 .for the translation is
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
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 direction of the second virial coefficient, since this gives a
better fit below the critical density where the predictions
are less sensitive to variations in the critical compressibility
factor.
As a second example take hexafluorobenzene, C6F,. Its
constants (11) are T, = 516.74 K, Pc = 32.304 atm, pc =
0.542 g/cm3, mol wt = 186.057 2, = 0.2612, BG1= -0.368,
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
TRn,dPR/dTR= 7.9 for the critical isometric at TR = 1.25,
and this compares favorably with M = 8.0. Thus, the best
two-term cubic equation for hexafluorobenzene is

fi

In - =
x ;P
J*"'

[ -vt!- ( +
-

RT

dni

T,V,n,

]dVt - In p v t (100)
nRT

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

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 constants (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 vaporpressure 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

The last example is normal pentane, whose constants

(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.

approximation, is able to reveal an error in a correlation

in the literature to give a n unexpected additional advantage to equations of the form of eq 103.
Nomenclature
a = constant in equation of state; may be function of temperature
A = constant in equation of state; may be function of temperature
b = constant in equation of state
B = constant in equation of state; second virial coefficient
c = constant in equation of state
C = constant in equation of state
d = differentiation sign
i = refers to single component
m = refers to a mixture; variable in generalized equation
n = exponent on temperature
P = pressure
R = gas constant
t = translation in volume
T = temperatures; absolute K or R
V = volume per unit mass
2 = compressibility factor, experimental
Z = compressibility factor, calculated or fixed
= constant in equation of state; may be function of temperature
p = constant in equation of state
y = constant in equation of state
6 = constant in equation of state; may be function of temperature
BG = generalized second virial coefficient
BGi = generalized second virial coefficient at reduced temperature of 1
P,,V,, T , = refgr to critical point values
PR, VR,TR = reduced values, Le., PIP,, VI V,, T I T ,

Chem. Fundam., Vol. 18, No. 2,

1979

97

Literature Cited
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(4) Berthelot, D. J., J . Phys., 8,263 (1899).
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(6) Clausius, R.. Ann. Phys. Chem., IX, 337 (1881).
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3 (1977).
(8) Das, T. R., Reed, C. O., Jr., Eubank, P. T., J . Chem. Eng. Data. 22,
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1937.
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D. E., J . Am. Chem. SOC.,77, 3427,3433 (1955).
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(Y

Received f o r review June 13, 1978

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 processes. 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 experimental 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