Ind. Eng. Chem. Process Des. Dev.

1988,25, 531-536 531

performed at the highest temperature (242 “C) with low
excess of oxygen in run 2 and high excess in run 6. The
oscillations are very complicated and almost aperiodic in
run 2. In run 6 at the high oxygen excess, the frequency
is very high and the oscillations are almost periodic. High
excess of oxygen, together with low temperature (runs 3
and 4), will obviously favor the suppression of the emission
of sulfur trioxide.
It has been known for the past 10 years (Scheintuch and
Schmitz, 1977) that the oxidation of carbon monoxide can
oscillate under isothermal conditions and under conditions
where the surface reactions do not interact with physical
transport steps. Various explanations of this behavior have
been proposed and tested by mathematical simulations
(Scheintuch and Schmitz, 1977; Olsson, 1984).
Of special interest for the present investigation are the
observations made by Mukesh et al. (1983),who found that
carbon monoxide began to oscillate under isothermal
conditions when 1-butene was added to the feed. Unlike
the present study, their reactor was a CSTR and the
content of 1-butene was as high as 1%, i.e., half the content
of carbon monoxide. In our study, the content of carbon
monoxide was about 1% and the content of sulfur dioxide
only 0.002%. Moreover, the temperature was rather low
(150 OC) in their experiments, resulting in relaxation os-
cillations with low frequency. Cutlip and Kenney (1978)
considered that 1-butene competed with carbon monoxide
for the same active sites and thus delayed the ignition of
the rapid oxidation of carbon monoxide. During the ig-
nition, carbon monoxide is removed both from the gas
phase and from the catalyst surface. Consequently, 1-
butene will be further adsorbed followed by some oxida-
tion, and this increased adsorption eventually extinguishes
the oxidation of carbon monoxide. Carbon monoxide be-
gins again to adsorb and accumulates on the surface until
the next ignition starts.
A similar explanation may be valid for the initiating
effect of sulfur dioxide on the oscillatory carbon monoxide
oxidation. Since the oscillations are very rapid, it is
possible that only the most active sites take part in the
oxidation of sulfur dioxide. These sites are rapidly deac-
tivated by adsorbed sulfur trioxide which quenches the
carbon monoxide oxidation. The content of carbon mon-
oxide thus increases rapidly and reduces the adsorbed
sulfur trioxide to sulfur dioxide which, on rapid desorbing,
gives a fresh active surface. Subsequently, the carbon
monoxide oxidation ignites and sulfur dioxide is oxidized
to sulfur trioxide, until the active sites are deactivated by
adsorbed sulfur trioxide again.
The proposed explanation given here is partly based on
a study by Yao et al. (1981). They found that the de-
creased oxidation rate of carbon monoxide on platinum
in the presence of sulfur dioxide was attributed to the
effect of surface sulfates formed by sulfur dioxide ad-
sorption and oxidation, on the chemisorption capacity for
carbon monoxide. As shown from infrared adsorption
studies, the surface sulfates inhibited the associative
chemisorption of carbon monoxide, which resulted in a
lower activity for carbon monoxide oxidation.
The effect of the supporting material on the oscillations
was discussed by Mukesh et al. (1983). We found that the
supporting material had little influence on the oscillatory
behavior of the reaction system. The same type of oscil-
lations as in the present study was found when the oxi-
dation was performed in an unsupported platinum catalyst
tube used in a previous study (Olsson and Schoon, 1985).
Acknowledgment
The financial support of the Swedish Board for Tech-
nical Development is gratefully acknowledged.
Registry No. SO3, 7446-11-9; SO2, 7446-09-5; CO, 630-08-0;
02, 7782-44-7.
L i t e r a t u r e Cited
Cutlip, M. 0.; Kenney, C. N. ACS. Symp. Ser. 1978, No. 65, 475.
HiavZek, V.; van Rompay, P. Chem. Eng. Sci. 1981, 36, 1587.
Mukesh, D.; Kenney, C. N.; Morton, W. Chem. Eng. Sci. 1983, 38, 69.
Nayfeh, A. H.; Mook, D. T. “Nonlinear Oscillations”; Wiley: New York, 1979.
Oisson, P.; SchMn, N.-H. Chem. Eng. Scl. 1985, 4 0 , 1123.
Oisson, P. Doctoral Thesis, Chaimers University of Technology, Gothenburg,
1984.
Pierson, W. R. Chemtech 1978, 6, 333.
Scheintuch, M.; Schmitz, R. A. Catal. Rev. Sci. Eng. 1977, 15, 107.
Yao, H. C.; Stepien, H. K.; Gandhi, H. S . J. Cafal. 1981, 6 7 , 231.
Received for review July 27, 1984
Revised manuscript received August 19, 1985
Accepted August 27, 1985

A Cubic Equation of State for Polar and Apolar Fluids

Hosseln Toghlanl and Dablr S. Vlswanath’
Department of Chemical Engineering, University of Missouri-Columbia, Columbia, Missouri 652 1 1

A generalized cubic equation of state is presented which utilizes the associating parameter, x,of Halm and Stiel.
The substancedependent critical compressibility factor, re,
as well as the adimensional factor, a(T J , was obtained
by minimizing the deviatlon in calculated liquid volume, while maintaining the fugacity equivalence of the two phases
in equilibrium. These parameters were generalized as functions of Pitzer’s acentric factor, w , and the associating
parameter, x. Thus, for pure substances, calculations require knowledge of only the critical temperature and
pressure, w , and x. This incorporation extends the applicability of the equation to highly polar substances, such
as ammonia, water, acetic acid, and methanol. This equation may also be used for aromatics including naphthalene
and isoquinoline and for high molecular weight paraffins such as hexadecane and eicosane. Ninety-six substances
of different chemical nature were tested and gave average absolute percentage deviations in vapor pressure of
1.38%, 2.14%, and 2.08%, respectively, for the proposed, Soave, and Peng-Robinson equations. The deviations
in liquid volume are 3.9%, 17.61 % , and 7.71 % , respectively, for the three equations.

Equations of state have proven to be useful tools in tively small amount of input data. Although the com-
industrial applications, allowing prediction of equilibrium plexity of any equation of state no longer presents a com-
phenomena and sizing of process equipment from a rela- putational problem, the majority of authors proposing
0196-4305/86/1125-0531$01.50/0 0 1986 American Chemical Society
532 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
equations of state have attempted to retain the simplicity
found in the van der Waals’ cubic equation while trying
to improve its accuracy through modifications. In spite
of its simplicity, the van der Waals’ equation is tremen-
dously successful in representing thermodynamic prop-
erties qualitatively.
Most of the semiempirical equations of state set forth
in recent years have retained the van der Waals’ thermal
pressure term. The differences lie in the expression of the
attractive pressure term. One of the earliest attempts to
modify this attractive term was by Redlich and Kwong
(1949). Several authors have modified this term, assuming
a temperature dependence for a and replacing the de-
nominator by a quadratic polynomial in volume. Two
important modifications which have enjoyed widespread
acceptance are the Soave (1972) and the Peng-Robinson
(1976) equations of state.
Both the Soave and Peng-Robinson equations have been
widely tested to determine their predictive capabilities in
the liquid region and for vapor-liquid equilibria (VLE) for
a large number of systems. Both perform reasonably well
in VLE calculations, but the Soave equation typically
overestimates liquid volumes, whereas the Peng-Robinson
equation does better in the prediction of liquid densities
for normal fluids. However, the use of these equations for
systems containing heavy hydrocarbons and polar fluids
leads to discrepanciesbetween calculated and experimental
liquid densities. The major drawback in both the Soave
and Peng-Robinson equations is that the critical com-
pressibility takes on values of 0.333 and 0.307, regardless
of the substance.
In an effort to overcome this fixed critical compressi-
bility factor, Abbott (1973) anticipated that for many ap-
plications, the fixed value should be replaced by a sub-
stance-dependent adjustable parameter, CC. Typically, this
calculated critical compressibility factor is larger than the
experimental critical compressibility factor. Many authors
such as Harmens and Knapp (1980), Schmidt and Wenzel
(19801, and Patel and Teja (1982) have incorporated this
adjustable factor in their models, which resulted in im-
proved predictive capabilities for both vapor pressure and
liquid volume. All the above equations can be generated
from the most general cubic equation given by Martin
(1979) and also can be obtained from the equation of
Schmidt and Wenzel(l980) with an appropriate choice of
the parameters.
In this work, we have used the general cubic equation
of Schmidt and Wenzel (1980) along with the constraint
U + W = 1. However, instead of setting W = -3w, we set
it equal to -c, where c is one of the equation parameters.
We will also incorporate the polar factor of Halm and Stiel
(1967) in our modification so that polar and associating
substances can be treated. These choices result in the
predicted critical compressibility factor being substance-
dependent.
Proposed Cubic Equation
The functional form of the proposed cubic equation of
state is
RT aa(Tr)
G(P,u,T,a)= -P + -- = 0 (1)
-b u2 + bv + cbu - cb2
The three pure component parameters a, b, and c are
determined based on the observation of the pressure-
volume behavior at the critical point, where a(T,) is equal
to unity. Three constraints are imposed on eq 1 at the
gas-liquid critical point. The standard requirement of the
disappearance of the first two pressure-volume derivatives
a t the critical point comprises the first two of these three
constraints. The third constraint arises from incorporation
of Abbott’s hypothesis (1973) and defies the apparent or
calculated critical compressibility. The constraints im-
posed are
(3)
p ,,,calcd
(4)
The third constraint results in a P-V-T surface which has
a calculated critical compressibility factor different from
the experimental critical compressibilityfactor. This leads
to better quantitative prediction of properties in regions
removed from the critical point while sacrificing predictive
capabilities in the region very near the critical point. This
does not lead to the impasse that it would appear to, be-
cause methods of treating the critical region and its no-
nanalytic behavior are under investigation such as that
described by Fox (1983), which may well provide a pow-
erful tool in the future.
The parameters obtained from applying these three
constraints to the equation of state after algebraic ma-
nipulation are
(5)
1 - 3lc
cc = - (7)
Lvc
where
nb(w,x) = vctc (8)
fia(u,x) = (1- t c ( 1 - vc)I3 (9)
The value of qc may be determined analytically or nu-
merically by using the equation
17; + v2(2/lc - 3) + 3vc - 1 = 0 (10)
once the value of lcis set. If the value of c is set to 3w in
eq 7, the above results are identical with those of Schmidt
and Wenzel (1980). The critical properties used in ap-
plying the constraints at the critical point were taken from
Reid et al. (1977).
Now the problem arises of selecting the optimal value
of the calculated critical compressibility factor, lc. The
optimal value of Cc was determined by following the path
taken previously by Patel and Teja (1982) and Adachi et
al. (1983). The following steps are taken to evaluate the
optimum value.
1. A value of l, in the neighborhood of the experimental
critical compressibility factor is assumed.
2. The critical parameters are evaluated by using eq
5-10.
3. For each data point along the saturation dome, a
value of a( T,) is determined by using the fugacity equiv-
alence of the two phases in equilibrium.
f=t“ (11)
Utilizing the proposed equation of state in the relation
 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986 533

A
1 n [ i ] = ~ " [ ~ - & ] d u + Z - l - l n Z (12)

the fugacity coefficient takes the form PROPANOL A

1.2 -
PENTANOL \ A A

where B = bP/RT, H = ((b + cb)' + 4 ~ b ' ) ~FI ~=, P(b +

cb - H)/(2RT), and G = P(b + cb + H)/(2RT).
A
4. The average absolute deviation in the liquid volume

14
is calculated. A
5. The assumed value of Cc is incremented by 0.001, and
steps 2-4 are repeated until a minimum in the average A
absolute deviation in the liquid volume is found. The value .
E 1.0
of lCwhich provided this minimum is used in subsequent t-
calculations. L

The temperature dependence of a ( T ) is established by

following an approach identical with that of Soave by
assuming that a ( T ) is composed of two parts:
a(T) = aca(Tr) (14) C I
A
Thus, like Soave's equation, the term a(Tr)must equal A
I- CACETlC
unity along the critical isotherm. This provides some V
a A
insight into the functional form of a(T,), but after many
attempts to find a suitable form for a(Tr),it was decided
to use the following two expressions given by Soave (1972) LACETONE
and Mathias and Copeman (1983), respectively.
a(Tr)= (1+ m(1 - T,1/2))2 (15)
0.6 1 A
A

a'(Tr) =
(1+ C1(l - Trl/') + C2(l - Tr1/2)2+ C3(l - Tr1/2)3)2
(16)
Mathias and Copeman (1983) found it necessary to include
higher order terms in the expansion in order to correlate
the vapor pressures of highly polar substances. We de-
termined the constants in both of these correlations for
each substance by using the Britt-Luecke (1973) gener-
alized least-squares regression algorithm.
The coefficient m in eq 15 is plotted vs. the acentric
factor in Figure 1. It is seen that the associating and
highly polar substances do not follow the same trend as
the normal fluids. This has been corrected as shown in
the next section.
Generalization of a ( T , ) and Cc
In order to better predict liquid properties, investigators
such as Zudkevitch and Joffe (1970) who modified the
original Redlich-Kwong equation, Fuller (1976) who
modified the Redlich-Kwong-Soave equation, and Heyen
(1980) who modified the Peng-Robinson equation have
made the covolume parameter as well as the attraction
parameter temperature-dependent. However, as stated by
Bazua (1983), this approach may lead to difficulties in
calculating thermodynamic properties that require deriv-
atives of the equation of state. Although this approach
has proved moderately successful in the prediction of liquid
densities for polar substances, we have taken a somewhat
different approach, similar to that of Pate1 and Teja (1982).
Their generalized equation allowed prediction of both
vapor and liquid properties of nonpolar substances. In
their work, they also studied polar substances such as
water, ammonia, and alcohols. However, these substances
could not be included in their generalization as was ex-
pected. Thus, in our approach, we include a fourth tem-
perature-independent parameter, in an attempt to include
the associating and highly polar substances in our gener-
alization of CC and m.
As a possible fourth parameter, we examined the para-
chor developed by Quayle (1953), the radius of gyration
A
0 DIPOLE MOMENT > 0 . 8
A DIPOLE MOMENT 0.8 <
0 0.2 0.4 0.6 0.8 1.0
ACENTRIC FACTOR, W
Figure 1. Characteristic constant vs. acentric factor.
given by Thompson (1966), the parameter Z,, presented
by Spencer and Adler (1978), the molar polarization of
Viswanath and Prasad (1970), the polar parameter of
Nishiumi (1980), and the polar factor of Halm and Stiel
(1967). Of these parameters, only the polar factor of Halm
and Stiel can take on both positive and negative values.
The others are limited to values equal to or greater than
zero. Thus, direct incorporation of any of these other
parameters would lead to a shift in one direction only
instead of making both positive and negative corrections.
The polar factor of Halm and Stiel was developed as an
extension of the existing three parameter corresponding
states principle of Pitzer et al. (1955) to account for de-
viations from normal fluid behavior seen in polar sub-
stances. This parameter is defined as
x = log Prl~,=0,8+ 1.7(- log PrlT,=0,7 - 1) + 1.552 (17)
or utilizing the definition of the acentric factor
x = log P r l ~ , = 0 . 6+ 1 . 7 +
~ 1.552 (18)
Expressions for various thermodynamic properties as a
function of reduced temperature, the acentric factor, and
the polar factor have been formulated by Halm and Stiel
(1967,1970,1971). One of the properties generalized was
the experimental critical compressibility factor as a
function of w and x. Their expression is
z,=
0.291 - 0 . 1 1 4 ~- 1.42%+ 0.069~'- 7 . 0 5 ~ '+ 1 . 5 1 ~ ~
(19)
534 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986

Table I. Constants for Equation 22 Table 11. Constants for Equation 23

A , = 0.441926073 A2 = 1.342 755 128 El = 0.324020789 E, = -0.056 675 895
A3 = -0.328431 972 A, = -15.020 572 758 E , = -0.001 268 996 E, = -3.259 131 762
A , = -2.226936 391 A, = 21.112706213 E5 = 1.399475 880 = 4.769 592 801
A: = 0.015 079 204 A, = 234.965 900 518 B, = 0.003 431 898 B, = 59.450 596 850

Since tabulated values of the polar factor for some sub-

stances in our study were unavailable, we undertook an
effort to obtain internally consistent values for both w and
x . Three different methods were used to obtain the
acentric factor: (1)interpolation of available experimental
data on vapor pressure, using Aitken's technique; (2) the
Wagner vapor pressure equation utilized by McGarry
(1983); and (3) the Antoine equation. The Wagner equa-
tion is
In P, =
1
-{A(1 - T,)
Tr
+ B ( l - Tr)lJ2+ C(1 - + D ( l - T,)') METHANOL

(20)
Values for the coefficients in this equation are available
for 251 substances. The coefficients used for the Antoine ACID
equation are given in Reid et al. (1977). It was seen that
the values for the acentric factor obtained from the Wagner
equation were more consistent with those given by Reid
et al. (1977)than those obtained from the Antoine equation
or from interpolation. Since the temperature range where
the Wagner equation was applicable extends below a re-
duced temperature of 0.6, we also evaluated the polar
factor. For higher molecular weight hydrocarbons where
the Wagner coefficients are not available, the values of the
acentric factor given by Reid et al. (1977) were used.
A variety of definitions for normal fluids appear in the
literature. Curl and Pitzer (1958) define a normal fluid
as one whose surface tension ratio, aovo2J3/RT,, can be
calculated to within 5% by
aovo213
- - - 2.24
RT,
X lo-' + 1.42 X lo-'~

Stipp et al. (1973) define a normal fluid to be that whose

polar factor has an absolute value not exceeding 0.005, and
0.4
P
0 0.2 0.4
DIPOLE
DIPOLE

0.8
MOMENT
MOMENT

0.8
> 0.8
0.8

they state that slightly polar substances satisfying this
definition ucan be considered to follow normal fluid be-
havior exhibited by nonpolar substances".
Examining the plot of m vs. w in Figure 1, we see that
the points for polar substances with dipole moments of less
than approximately0.8 and nonpolar substances follow the
same trend. Thus, we elect to use the polar factor for only
those substances whose dipole moment is greater than 0.8,
and for all other substances, we set the polar factor to 0.
It is interesting to note from Figure 1 in the case of
methanol, ethanol, and propanol that all have a dipole
moment near 1.7 D, but methanol lies below, ethanol lies
on, and propanol lies above the nonpolar trend. The Stiel
polar factor for these follow a similar trend that the value
of x is 0.0373 for methanol, 0.0003 for ethanol, and -0.0499
for propanol. This shows that a combination of x and w
may work better compared to either x or w alone.
On the basis of these observations, the value of m was
fitted to the following expression which is identical with
that used for Z,, eq 19, with an additional higher order
term
m=
A , + Azw + A3w2 + A4x + A5x2 + A ~ W+X A703 + A,x3
(22)
and the coefficients established by using the Britt-Luecke
algorithm (1973) are shown in Table I. In a similar
1.0
ACENTRIC FACTOR, W
Figure 2. Correlation between characteristic constant and acentric
factor.
fashion, we generalized our calculated critical compressi-
bility factor by using the same expression.
L=
Bl + B2w + B3w2+ B4x + B6x2+ Bswx + B7w3 + Bsx3
(23)
The constants for eq 23 are listed in Table 11. To
illustrate the effect of including polar-factor-dependent
terms in eq 22, a plot of m - A4x - A5x2- Aswx - A8x3vs.
w is presented in Figure 2. As is apparent, use of the polar
factor forces points for the substances with dipole moments
greater than 0.8 to approach the same curve as those with
dipole moments less than 0.8. This justifies our expressing
m in terms of w and x . We also attempted to generalize
the coefficients in the Mathias and Copeman (1983) ex-
pression, but the results were not encouraging.
Data Base
Data used in establishing the performance of the pro-
posed equation of state were taken from a variety of
sources. References for each substance appear in Table
I11 in the supplementary material. For those substances
where the liquid volume data were unavailable in the
temperature range corresponding to the available vapor
 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986 535

Table IV. Comparison of Vapor Pressures and Liquid Volumes

A.A.D. (%) in vapor A.A.D. (70)in liquid
no. of no. of pressure volume
data substances PE RKS PR PE RKS PR
monoatomic 92 3 1.26 1.77 1.84 4.97 5.34 9.33
diatomic 83 5 0.65 0.80 1.07 4.55 4.79 8.25
paraffins 613 29 1.34 1.96 2.43 3.44 17.70 6.50
olefins 217 10 0.93 2.08 1.40 2.99 13.64 4.31
diolefins 36 1 0.91 1.75 0.89 3.34 12.73 3.82
acetylenes 37 2 3.33 3.17 2.79 2.71 12.13 3.48
naphthenes 56 2 1.39 1.26 1.98 3.52 11.74 4.25
halogenated benzenes 53 2 1.38 1.41 1.55 4.74 15.06 2.06
aromatics 285 10 1.19 2.04 1.99 3.31 14.17 3.73
aldehydes and ketones 42 2 1.37 2.36 0.91 2.18 37.62 21.66
amines 38 2 0.82 1.87 1.57 5.44 7.36 7.54
hydrogen bonding 175 6 2.66 4.21 3.81 3.74 27.76 13.35
ethers 37 3 1.55 2.85 2.33 4.21 17.37 4.91
sulfur compds 87 4 1.22 1.73 1.41 5.23 12.79 4.84
nitrogen compds 75 3 1.50 2.81 1.82 8.59 43.44 26.78
halogenated hydrocarbons 73 3 1.74 1.51 0.97 2.34 21.39 8.29
acetates 71 3 0.99 4.00 3.01 5.71 33.01 17.68
fluorocarbons 56 3 1.23 1.01 2.05 3.28 9.93 4.44
oxides 64 3 1.28 1.19 1.48 5.89 20.01 7.74
grand total 2190 96 1.38 2.14 2.08 3.90 17.61 7.71

0 * - -
0
EQUATION 1
0 0
0
0
-10 0
w -10
0
3
A
0
o n o n 0 n o n o o 0
0 Y
W
2
- 20 P E N G - ROBINSON EQUATION 0 - 0
0 U
0 >
i -20 0
0 9
0
5 0
0

z
0 ’ -30
0
0
0 AA A A
0
5
> -30
W
SOAVE EOUATION ’ A b
2
CI

8 & A 2 -40
0 a
A
A 9 P 0
AMMONIA
W
-40 n P

A # -50 a
0.6 0.7 0.8 0,s 1.0
n
METHANOL
REDUCED TEMPERATURE P

Figure 3. Comparison of percent deviation in saturated liquid molar -60 n

volume vs. reduced temperature for ammonia.
pressure data, the modified Rackett equation of Spencer
and Danner (1972) was used. For this equation, both the
parameter Z,, and the critical properties given by Spencer
and Adler (1978) were used in generating liquid volume
data. However, for some substances, the parameter 2, was
not available, and in these cases, the value of Z,, given by
Hankinson and Thomson (1979) along with the critical
properties given in Reid et al. (1977) were used. Also, we
have generated vapor pressure data for some of the sub-
stances by using either the equations of Ambrose et al.
(1974,1975) or the equation of Wagner given by McGarry
(1983). In this phase of our work, we have accepted the
reliability of the data generated in this manner and have
assumed it to be accurate to within experimental error.
During our analysis, it became apparent that some ex-
perimental data points were obviously in error, and these
points were eliminated from our study.
Results
A summary of the average absolute percentage devia-
tions, A.A.D.( %), for the proposed equation (PE), the
Redlich-Kwong-Soave equation (RKS), and the Peng-
0,6 0.7 0.8 0.9 1.0
REDUCED T E MPERATURE
Figure 4. Comparison of percent deviation in saturated liquid molar
volume vs. reduced temperature for methanol.
Robinson equation (PR) in calculated vapor pressure and
liquid volume and the overall weighted average for each
class of substances is presented in Table 111, which has
been submitted as supplementary material (see paragraph
at end of paper regarding this material). Table IV sum-
marizes the results by class of compound. This compilation
indicates that incorporation of the parameter x into our
proposed equation generally results in better predictive
capabilities than either the Redlich-Kwong-Soave or
Peng-Robinson equations. For high molecular weight
hydrocarbons, much better results were obtained for the
calculated liquid volume by using the proposed equation
rather than either the Peng-Robinson or Redlich-
Kwong-Soave equation.
The deviation in liquid molar volume as a function of
reduced temperature is depicted graphically in Figure 3
536 Ind. Eng. Chem. Process Des. Dev., Vol. 25, No. 2, 1986
for the highly polar substance ammonia and in Figure 4
for methanol which exhibits hydrogen bonding. As is
apparent from these figures, the proposed equation per-
forms better than the Peng-Robinson equation and the
Redlich-Kwong-Soave equation over the whole range of
reduced temperature. The proposed equation gives very
good results up to reduced temperatures of approximately
0.80.
Conclusion
Preliminary findings for the proposed equation of state
which utilizes the associating factor of Halm and Stiel
indicate a significant improvement in the representation
of liquid volumes for the majority of substances studied
compared to the highly regarded Redlich-Kwong-Soave
and Peng-Robinson equations of state. Generalized ex-
pressions for the apparent critical compressibility factor
and the adimensional factor in the attraction term have
been presented which are suitable for all the substances
studied, both polar and nonpolar. Even though it is
possible to develop correlations for each class of com-
pounds to better predict saturated liquid volume and vapor
pressure, we think it more desirable to have a single gen-
eralized expression to facilitate use of the equation. The
performance of the equation as with any cubic equation
of state is limited to regions removed from the critical
point. However, the proposed equation could be used a t
temperatures much closer to the critical point compared
to the Redlich-Kwong-Soave and Peng-Robinson equa-
tions as is evident from Figures 3 and 4.
Preliminary results of VLE calculations for systems
containing water and alcohols are very encouraging. Work
is under way to determine suitable mixing rules for the
equation of state parameters, which involve only the pure
component parameters without introduction of an addi-
tional parameter such as the empirical binary interaction
parameter, KIJ. Preliminary work in predicting P-V-T
behavior of binary systems looks optimistic in this direc-
tion without the use of KLJ.This is further supported by
a study of potential parameters for the Lennard-Jones
potential function by DeSelms (1984). This study which
compared 83 different mixing rules led to the conclusion
that use of the harmonic mean for both of the potential
parameters gives better results. Further, the ratio of the
geometric mean to the arithmetic mean for the energy
parameter yields values in good agreement with the
quantity (1- K,) as given by Maitland et al. (1981). Work
is continuing in this area, and findings will be reported in
future publications.
Acknowledgment
This work was funded by the National Science Foun-
dation under Contract PE8117031.
Nomenclature
a, b, c = equation of state parameters, eq 1
f = fugacity
K,, = binary interaction parameter
m = characteristic constant
P = pressure
R = universal gas constant
T = absolute temperature
v = molar volume
Z = compressibility factor
Z,, = Spencer and Danner (1972) 2 factor
Greek Letters
a: = adimensional factor, eq 15
a' = adimensional factor, eq 16
{c = apparent critical compressibility factor
u = surface tension
7 = smallest positive root of eq 10
p = fugacity coefficient
x = association factor
R = dimensionless premultiplier defined by eq 8 and 9
w = acentric factor
Subscripts
a = refers to parameter a
b = refers to parameter b
c = critical property
0 = hypothetical property at 0 K
r = reduced property
Superscripts
1 = liquid phase
v = vapor phase
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Received for review December 26, 1984
Revised manuscript received August 29, 1985
Accepted September 19, 1985
Supplementary Material Available: Table I11 (com-
parison of vapor pressures and liquid volumes by compound)
(7 pages). Ordering information is given on any current
masthead page.