RIIIDPI[

[QUIUBRIA
ELSEVIER Fluid Phase Equilibria 111 (1995) 175-201

A new equation of state based on nonrandom two-fluid lattice theory

for complex mixtures
K i - P u n g Y o o ", M o o n S a m Shin a, Sung Jae Y o o a, S e o n g - S i k Y o u b, Chul S o o Lee b
a Department of Chemical Engineering, Sogang University CPO 1142, Seoul 121-742, Korea
b Department of Chemical Engineering, Korea University Seoul 136-701, Korea
Received 3 October 1994; accepted 3 April 1995

Abstract

A new simplified equation of state (EOS) was derived based on the nonrandom lattice fluid model with the
introduction of the two-fluid theory. Admittedly the new EOS was originated from the density dependent
combinatory and has features similar to the UNIQUAC model. However, it results in volumetric EOS instead of
excess Gibbs energy model. The new EOS was tested for its capacity to represent the phase equilibrium
behaviors of pure components and mixtures. The model was applied to density, equilibria of vapor-liquid and
vapor-solid phases for nonpolar/ nonpolar, nonpolar/polar, and polar/polar binary mixtures of simple and
complex molecules. The simplified EOS was successfully applied to the activities of solvents in polymer
solutions. With two parameters for pure components and one binary interaction energy parameter, results
obtained to date demonstrate that the model is quantitatively applicable to a wide range of temperatures,
pressures and densities.

Keywords: Theory; Equation of state; Lattice theory; Two-fluid model; Supercritical fluids; Activities of solvents in polymer
solutions

1. Introduction

Different formulations of solutions can be considered under the framework of the generalized
Guggenheim combinatory (Panayiotou and Vera, 1981). Historically, several pioneering theories of
solutions have originated from it. A lattice with no holes has been the basis for liquid models and
excess functions. The well known UNIQUAC equation can be regarded as one of models in this genre
(Abrams and Prausnitz, 1975). From a regular lattice description with holes an EOS-type model can
be drawn. Sanchez and Lacombe (1974); Sanchez and Lacombe (1976a),Sanchez and Lacombe
(1976b) initiated the research in this field. Since then, several models have been proposed (Kehiaian
et al., 1978; Okada and Nose, 1981a; Okada and Nose, 1981b; Panayiotou and Vera, 1982; Kumar et
al., 1987; Smirnova and Victorov, 1987). The present authors (You et al., 1993; You et al., 1994a;

0378-3812/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0378-3812(95)02773-4
176 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

You et al., 1994b; You et al., 1994c) briefly reviewed the existing lattice fluid theories stemming
from the full Guggenheim's combinatory and the quasichemical approximation (Guggenheim, 1952)
and discussed in detail the unique features of the previous works, their advantages and shortcomings.
They also proposed a new method of an explicit approximation to the Guggenheim's combinatory and
a rigorous EOS. They extensively confirmed its quantitative applicability to the calculation of
vapor-liquid, liquid-liquid with UCST, vapor-solid phase equilibria and the heat of mixing for
various mixtures containing complex and/or macromolecular species and up to high pressure.
Although the formulation of the previous rigorous EOS is self-consistent with a sound theoretical
basis, a less complicated model would be more convenient in engineering-oriented phase equilibrium
calculations. In this work we present our efforts to make the previous EOS less complicated while
preserving comparable accuracy.

2. Guggenheim combinatory and lattice partition function

We briefly discuss here the nonrandom lattice hole partition function based on the full Guggenheim
combinatory (Guggenheim, 1952). The configurational part of the nonrandom lattice partition
function in a three dimensional lattice of the coordination number z and of the unit cell size VH, may
be written as
Oc = gR gNR e x p ( - / 3 U ) (1)
where the random contribution gR and the nonrandom case gNR can be defined, respectively
Z

g" [l-IN! LN !] (21

0! 0 2
(1--INi . [ I [ ( 1 / 2 N i ] ) . l )
gNR= (FiNii,Fi[(1/gNij)q2) (3t

Nr = N 0 +
L N ir i,
c
N q = N 0 + ~ N iqi (4)
i=l i=l

and No and N i are the number of vacant sites which may be called holes and the number of molecules
of species i. r i and qi are the segment number and the surface area parameter, respectively. The
summation is over all molecular species and C denotes the number of components. Also, Nij is the
number of i - j segment contacts and the quantities with superscript zero denote the same for random
mixing. Nij is related to Ni0 by Nij Nil% in the quasichemical approximation with the introduction
=

of the nonrandomness factor /'ij which is defined by

/~i2=/-'ii ~jj exp(-/3AEij ) (5)
where /3 denotes 1 / k T and the lattice interchange energy is defined in the quasichemical formalism
as A~ij -~- Eii -'1"-~ j j - 2 ~ i j .
 K. -P. Yoo et aL / Fluid Phase Equilibria I l l (1995) 175-201 177

The potential energy U in Eq. (1) is written by

U = E(Nii- 6ii) -t- Y'~ E N i j ( - % ) (6)

i i>j
where eij is the absolute value of interaction energy between segments i and j. Athermal solution
corresponds to taking U = 0 and for this solution Fij = 1 or Ni~ = N~j. The explicit dependence of Nij
on the interaction energy parameter was obtained in the quasichemical approximation by Guggenheim
for binary mixtures without considering vacant sites or holes.

3. A semiempirical expression of helmholtz free energy

The configurational Helmholtz free energy may be obtained from Eq. (1) using the relations
flA c = - In/2 c
As recently presented in detail by the authors elsewhere (You et al., 1993; You et al., 1994a; You et
al., 1994b; You et al., 1994c), the configurational Helmholtz free energy in Eq. (7) can be expanded
in terms of eij around the reference athermal solution and expressed as
A c = A c(g) + A c(R) + A c(Na) (8)

where the athermal part, A c(A), is equivalent to a combinatorial contribution in the random array, the
random part, A c(R), is due to energy of random mixing and the nonrandom part, A <NR), corrects for
effects of nonrandom mixing.
We now propose an empiricization based on the same lattice concepts. While retaining the
athermal part, we may replace the remaining parts by the sum of ideal solution part and excess part as
A c = A c(A) + A c(Is) + A c(E) (9)

The athermal part is given by

flA c ( A I = ~ N i l n 0 i + N o l n ( 1 - 0 ) - - ~ N q l n 1+ -1 0 (10)

where
q M = ~, x i q i , rM = E xir i (11)

Pi = N i r i / N r , P = • Pi (12)
and x i is the mole fraction of species i on the hole free basis. The summation is over all molecular
species unless noted otherwise.
The remaining parts are obtained using the thermodynamic relation at constant volume and
composition

- - = Ud + constant (13)
T "l/r0
178 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

as in the derivation of UNIQUAC model(Abrams and Prausnitz, 1975). The internal energy, U, is the
sum of the ideal solution part and the excess part in the frame of nonrandom two fluid theories as
Z
-- U is = -~ Y'. N i q i O [ ° ¥ i i (14)

z
- - u E = -2 ]~ giqi(]~ -j,o'~l>-j,t='"- Oi~O)•ii) (15)

where 0ji is the local surface area fraction of component j around the segment of component i and the
superscripts (0) and (1) denote the states before mixing and after mixing, respectively.
We introduce two assumptions to simplify the evaluation of Eqs. (14) and (15). The first is that the
holes are random as Panayiotou and Vera (1982) assumed in a different context. Then the following
relation holds
0 (1) = ~ N i q i / N q (16)
We have only one molecular species in the pure state. Therefore for each pure species
0~°) = 0~°) (17)
The second assumption is
0 (i) = 0~0) = 0 (18)
which implies that the total surface area fraction occupied by molecules is the same whether
molecules are in pure states or in mixtures. This assumption becomes exact as the number of holes
tends to zero, in which case 0 = 1.
Based on these assumptions, dropping the superscripts and rewriting Eqs. (14) and (15), we have

- O I s = ZNq ~ ] N i q i ( O E i i ) (19)
2

- U E = ZNq ~ 0i E Oji[ 0 ( ~ j i - Eii)] (20)

2
where the surface area fraction of component i is given by
0 i = N i qi/Nq (21)
In writing Eq. (20) we have also defined the surface area fraction on the hole free basis

a i = Niqi/~, Njqj = 0 i / 0 (22)

and use the relation

Oij = 0ij/0 (23)

0ji is then written in the following nonrandom mixing form as discussed by Wilson (1964)

Oj_ °J
~] TkiO k (24)
 K.-P. Yoo et al. / Fluid Phase Equilibria l l l (1995) 175-201 179

where the nonrandomness factor Tji is derived as

rji = exp[ 130(eji- •ii)] (25)

eij is the absolute value of the interaction energy between a segment of species i and that of species j,
which is assumed as follows for nonspecific interactions

"ij = ( eii'jj)°5(l - '~ij) (26)

where Aij is the binary interaction parameter, eij between holes and molecular species is zero.
Now using Eq. (13) we can convert Eq. (19) and (20) into corresponding Helmholtz energy
expressions.

- A c°s) = Z/Vq
0 E Niq i ~ii (27)
2

- / 3 At(E) = Z/Vq •0i ln[Z Ojrji] (28)

2
The sum of Helmholtz free
configurational Helmholtz free
model. The main difference is
from the free energy. An EOS
energies given by Eqs. (10), (27) and (28) yields the complete
energy. The free energy expression is similar to that of the UNIQUAC
that the lattice contains holes now and an EOS can readily be derived
based model may be applicable to high pressure.

4. EOS and chemical potential for mixtures

From the configurational Helmholtz free energy given by Eq. (9) with Eqs. (10), (27) and (28),
expressions for configurational thermodynamic properties can be obtained in a straightforward
manner. Since the volume V is represented by
V = VH(No + ~ Niri) (29)
the EOS is obtained from the equation of configurational Helmholtz free energy
l °Ac) 1 t°AC/
P = - t 0 V T,No-- ~TH ~ ONo ] T,Nj

When the algebra is done we have the following EOS

P= /3---V--£H In 1 + rM --1 P - - l n ( 1 - - P ) -- 02VH (31)

where
m

6M = EOjEjj + Y',-Oj E Okrkj( -- Ejj) (32)

Okrkj
180 K. -P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

The chemical potential of component i can be obtained using the following equation

= Na -- = Na + riNaVnP (33)
['£i ONi T,V T,No
where Na is the Avogadro's number. The resulting equation is

/xi =Ai(T ) - r i l n ( 1 - p ) + l n - + r
0 [
iln 1 + -1 p
RT qi rM

2
I ri .(
1
qi 0
1+ .ii l zq[ , , 'i]0k k
eM
+
--2-
1 - ln.~2 0j~'ji -
_ (34)

where Ai (T) is the reference chemical potential which depends only on temperature.
Although not presented here other thermodynamic properties are also derivable for mixtures from
Helmholtz free energy.

5. T h e r m o d y n a m i c properties for pure systems

5.1. E O S , c h e m i c a l p o t e n t i a l a n d f u g a c i t y c o e f f i c i e n t

For pure fluids, all rs become 1 because holes are assumed to be random. Also EM becomes Ell.
Therefore EOS given by Eq. (31) and chemical potential Eq. (34) are simplified as follows:

P . /3Vn. In . 1 + .
--rl 1 .p ln(1 p) ~ 07 Vn (35)

zql J~IE11022[1 r1 2
/x-2-~=AI(T ) - r l l n ( 1 - o ) + l n - + r , l n 1+ ---1 O
RT ql rl ql 01
(36)
Based on the familiar classical thermodynamic relation, the fugacity coefficient for pure component
1 is obtained as

ln~bl=-r~ln(1-p)-(1-r~)ln I(
1+ q~-i
rl
p ~ 1 ra°
ql/9
-lnZ 1 (37)

where Z1 is the compressibility factor.

5.2. M o l e c u l a r p a r a m e t e r s

In the derivation of Eq. (10) the following general relation in lattice theories is used.
zql = zr 1 -
2r I + 2 (38)
We also define the characteristic volume 1/1" as,
VI* = N a V n r l (39)
Therefore the characteristic volume gives sufficient information for determining r 1 and qv The other
molecular parameter is 411.
 K.-P. Yoo et al. / FluidPhase Equilibria 111 (1995) 175-201 181
5.3. Second order properties

For polymers, experimental data are often reported as second order thermodynamic functions such
as the thermal expansion coefficient o¢1 and the isothermal compressibility factor ill. The expressions
for them are obtained from the EOS as

[ t~Vll iE,ll ]
5[ 0V] _ T[ (gp] ._~T[ 0VI____~*
] ~ i P V H "~- O} ----2- Z
2 r~
+m
T~l=gtOTJp pL~3~+ vl* t OT Jp I-p----+ (1-- r1~--)01 iEllrl03ql
P ] r1
t
(40)

- - --1p p + (1 --rl)01ql iEllrl03

] q Pl

where ~"11 and r~ are derivatives of ell and r 1 with respect to, respectively. They can be determined
from the temperature dependence of ell and VI*.

5.4. Critical conditions and phase transition

The critical point for the vapor-liquid phase transition is determined from the well-known
criticality conditions. The criticality conditions are derived from the EOS as

~-p T = 0 , 10---
~- .r=0 (42)

OP Ze11 1 z[ ql/rl--] ] Ziellr103

(43)
Op 2V H 1 - p 2 i q- ( q l / / r l - 1)p ql p2
02p
2
zell
2V.
1
-(1-- +p)5
z[ qlJr111)p ]2 Z alr04[1 - 2 - tql
l+(ql/r I -
- -rI1
t])p 44, q~p4

Once expressions for the criticality conditions are evaluated, the critical compressibility factor Z c is
readily calculated

riPe
Zc - (45)
Tcpc
We discussed in detail elsewhere (You et al., 1994c) on the phase behaviors of the present model in
the critical region and we omit further discussion here.
182 K. -P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

6. Determination of molecular parameters for pure systems

There are apparently four molecular parameters on the EOS for pure fluids; z, VH, VI* and e11. As
in the previous works (You et al., 1993; You et al., 1994a, You et al., 1994b; You et al., 1994c), we
set z -- 10 and VH = 9.75 cm 3 mol- ~ as first used by Panayiotou and Vera (1982). Thus, for real
fluids we need only to determine two independent molecular parameters VI* and ell from two
independent property data at a system temperature. We expect that this EOS is applicable to a wide
range of molecular species. The parameters for pure fluids are determined by means of possibly
different methods depending on the property data available.
For fluids in the subcritical region, parameters are determined using the vapor pressure and the
saturated volume by utilizing relations of vapor-liquid equilibrium pressure and chemical potential
for vapor and liquid phases for each isotherm. With substances for which necessary data are not
available, one of the methods due to Antoine, Miller, Yen-Woods, Rackett, Frost-Kalkwarf-Thodos,
and Hankinson-Brost-Thomson is used. These methods are reviewed in the book by Reid et al.
(1987). For the gases above the critical point PVT data in such sources as Matheson gas Data (1980),
Timmermans (1950) and CRC Handbook (Lide, 1991) are used.
For polymeric species whose vapor pressure is negligibly low, we can only use data or correlations
for liquid density (Shin, 1994; Panayiotou and Vera, 1982). Since we cannot determine two
parameters from a single property, we need an independent relation which may be provided by atomic
group contribution methods. For this purpose, we used methods reported by Bondi (1967) and van
Krevelen (1990).
The parameters VI* and ell determined by a regression analysis at each isotherm are fitted to the
following empirical correlations as functions of temperature for reliable and convenient use in
engineering practice.

Ell
k = Ea + EbT + Ec In T (46)

VI* = Va + VbT + Vc l n T (47)

The estimated values of the coefficients for Eqs. (46) and (47) are summarized in Table 1 for
various pure fluids. As an illustration, we randomly selected 88 nonpolar, 31 weak polar, 20 strong
polar, 3 supercritical, and 10 low vapor pressure solid substances. In Table 2, coefficients of the
energy and volume parameter correlations for 12 common polymer systems are summarized. For
these substances, the characteristic volume is listed as temperature independent values due to the lack
of appropriate experimental data. Especially, the VI* for polymer in Table 2 is specific and for one
segment. As a result it become independent with respect to the molecular weight.
To discuss the fitting errors it may be convenient to regroup the substances listed in Table 1 into
light substances which range from subcritical to supercritical region, liquid substances and solid
substances. For solids the parameters are used to calculate the hypothetical fluid properties and we
can expect some degree of intrinsic errors in those properties. For liquids, the calculated value of
saturated density is often exact up to three significant digits. For most liquids the error in vapor
pressure except in the near critical region is usually less than 3%. However, the vapor pressure is
probably not very accurate for nonvolatile solid substances.
 K..P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 183

Table 1
Coefficients o f the e n e r g y and v o l u m e p a r a m e t e r correlations
Chemicals Formula Ea Eb Ec Va Vb Vc Range(K)
N o n polar s u b s t a n c e s
Propane C3H8 87.70 - .0024 - 0.57 70.60 .0320 - 1.92 253-353
Butane C4H10 90.96 .0158 - 0.98 83.70 .0191 - 1.00 253-383
Isobutane C4H10 82.93 .0189 - 0.46 88.53 .0208 - 1.77 253-383
Pentane C5H12 100.22 .0309 - 2.74 79.21 - .0007 3.48 273-450
Isopentane C5H12 84.89 .0279 - 0.27 36.05 - .0288 12.44 253-403
Neopentane C5H12 78.54 .0358 - 0.64 126.07 .0220 - 5.80 273-413
Hexane C6H14 125.08 .0510 - 7.65 59.90 - .0230 10.65 273-473
2 Methylpentane C6H14 103.89 .0447 - 4.04 107.35 .0001 1.12 273-473
3 Methylpentane C6H14 111.40 .0480 - 5.29 98.90 - .0051 2.68 273-473
2,2 D i m e t h y l b u t a n e C6H14 84.99 .0434 - 1.14 98.36 -.0083 2.97 273-473
2,3 D i m e t h y l b u t a n e C6H14 87.50 .0401 - 0.95 102.92 - .0027 1.76 273-473
Heptane C7H16 92.66 .0381 - 0.97 120.38 - .0050 1.79 273-513
2 Methylhexane C7H16 107.89 .0500 -4.65 67.22 -.0346 12.62 273-513
3 Methylhexane C7H16 91.08 .0407 - 1.07 57.09 -.0399 14.48 273-513
2,2 D i m e t h y l p e n t a n e C7H16 83.33 .0445 - 0.54 93.60 - .0239 7.29 273-513
2,3 D i m e t h y l p e n t a n e C7H16 112.73 .0546 -5.55 122.71 -.0039 0.68 273-513
2,4 D i m e t h y l p e n t a n e C7H16 92.11 .0468 - 2.16 89.44 - .0261 8.23 273-513
3,3 D i m e t h y l p e n t a n e C7H16 99.61 .0543 -3.48 118.75 -.0090 1.73 273-513
3 Ethylpentane C7H16 122.92 .0576 - 7.35 56.31 - .0388 14.26 273-513
2,2,3 T r i m e t h y l b u t a n e C7H16 83.38 .0514 - 1.60 117.46 - .0121 2.10 273-513
Octane C8H18 147.17 .0692 -11.86 137.76 -.0076 1.56 273-513
2 Methylheptane C8H18 92.76 .0500 - 4.65 67.22 - .0346 12.62 273-513
3 Methylheptane C8H18 139.63 .0694 -10.81 132.18 -.0134 2.63 273-513
4 Methylheptane C8H18 136.76 .0680 - 10.29 56.22 - .0536 18.04 273-513
2,2 D i m e t h y l h e x a n e C8H18 113.91 .0634 -6.58 131.38 -.0184 3.07 273-513
2,3 D i m e t h y l h e x a n e C8H18 131.20 .0682 -9.36 132.08 -.0143 2.42 273-513
2,4 D i m e t h y l h e x a n e C8H18 121.86 .0657 -7.94 45.60 -.0623 20.27 273-513
2,5 D i m e t h y l h e x a n e C8H18 118.73 .0632 - 7.32 50.60 - .0589 19.40 273-513
3,4 D i m e t h y l h e x a n e C8H18 135.21 .0702 - 10.02 43.11 - .0591 20.13 273-513
2,2,3 T r i m e t h y l p e n t a n e C8H18 118.16 .0686 -7.32 48.18 -.0605 19.22 273-513
2,2,4 T r i m e t h y l p e n t a n e C8H18 94.50 .0594 -3.31 53.26 -.0630 18.94 273-513
2,3,3 T r i m e t h y l p e n t a n e C8H18 115.56 .0672 - 6.54 43.52 - .0609 19.85 273-513
2,3,4 T r i m e t h y l p e n t a n e C8H18 122.63 .0678 - 7.88 131.71 - .0155 2.27 273-513
Nonane C9H20 117.88 .0576 -5.93 145.95 -.0185 3.43 343-513
2 Methyloctane C9H20 122.42 .0645 - 7.46 143.55 - .0221 4.06 323-513
3,3 D i e t h y l p e n t a n e C9H20 107.14 .0644 -4.43 146.00 -.0184 2.11 336-513
2,2,3 T r i m e t h y l h e x a n e C9H20 122.27 .0721 - 8.06 44.23 - .0756 23.37 297-513
2,2,4 T r i m e t h y l h e x a n e C9H20 118.86 .0716 -7.81 149.06 --.0259 2.78 291-513
2,2,5 T r i m e t h y l h e x a n e C9H20 102.85 .0642 - 4.78 146.85 - .0294 3.57 319-513
2,2,3,4 T e t r a m e t h y l p e n t a n e C9H20 104.19 .0672 - 4.65 146.54 - .0251 2.56 325-513
2,3,3,4 T e t r a m e t h y l p e n t a n e C9H20 112.28 .0688 - 5.70 141.81 - .0240 3.01 322-513
Decane C10H22 118.86 .0716 - 7.81 149.06 - .0259 2.78 291-513
2,2,5 T r i m e t h y l h e p t a n e C10H22 102.85 .0642 -4,78 146.85 -.0294 3.57 319-513
2,2,3,3 T e t r a m e t h y l h e x a n e C10H22 104.19 .0672 -4.65 146.54 -.0251 2.56 325-513
2,3,5,5 T e t r a m e t h y l h e x a n e C10H22 112.28 .0688 - 5.70 141.81 - .0240 3.01 322-513
Cyclopropane C3H6 102.04 - .0230 0.07 61.60 .0421 - 2.95 253-353
Cyclopentane C5H10 101.08 .0137 0.25 37.09 - .0128 8.97 273-473
184 K.-P. Yoo et aL /Fluid Phase Equilibria 111 (1995) 175-201

Table 1 (continued)
Chemicals Formula Ea Eb Ec Va Vb Vc Range(K)
Cyclohexane C6H12 180.65 .0694 - 16.33 41.08 - .0228 11.14 273-513
Methylcyclopentane C6H12 166.13 .0662 - 14.35 37.66 -.0258 12.35 273-473
Etbylcyclopentane C7H14 96.32 .0382 - 0.44 60.22 - .0249 10.93 302-513
Methylcyclohexane C7H14 96.19 .0431 -0.79 107.27 -.0049 1.61 299-513
Ethylcyclopentane C8H16 101.05 .0447 - 1.34 112.21 - .0090 3.37 293-433
Propylcyclohexane C8H16 174.08 .0915 - 16.64 53.70 -.0600 19.04 325-513
Butene C4H8 90.66 .0093 - 0.47 84.81 .0248 - 2.30 273-383
Isobutene C4H8 91.45 .0081 - 0.55 75.73 .0197 - 0.47 273-373
2 Butene,cis C4H8 96.50 .0020 - 0.26 76.10 .0235 - 1.07 273-403
Pentene C5H10 94.77 .0233 - 1.24 57.14 - .0060 6.73 273-423
2 Pentene,cis C5H10 96.01 .0188 - 0.71 39.03 - .0171 10.24 273-433
2 Pentene,trans C5H10 95.36 .0214 - 0.89 35.22 - .0229 11.48 273-433
2 Methyl-l-Butene C5H10 133.17 .0434 -8.88 91.90 .0161 -0.66 273-423
2 Methyl-2-Butene C5H10 72.85 .0158 2.41 94.71 .0126 - 0.71 273-423
2 Methyl-2-Butene C5H10 114.49 .0222 - 4.02 87.56 .0212 - 0.26 273-423
Hexene C6H12 125.25 .0496 - 7.51 74.08 - .0103 6.68 273-473
2 Hexene,cis C6H12 160.65 .0675 - 14.26 50.94 -.0249 11.28 273-373
3 Hexene,cis C6H12 110.16 .0388 -4.09 103.35 .0044 0.67 273-368
3 Hexene,trans C6H12 98.48 .0291 - 1.53 103.65 .0019 0.84 273-368
2,3 D i m e t h y l - l - b u t e n e C6H12 164.67 .0807 - 16.35 102.89 .0040 0.59 273-368
3,3 D i m e t h y l - l - b u t e n e C6H12 149.03 .0895 - 14.92 124.88 .0014 -2.85 273-453
Heptene C7H14 156.78 .0718 - 13.95 58.93 -.0297 12.92 273-473
2,3,3 T r i m e t h y l - l - b u t e n e C7H14 159.18 .0897 - 15.82 29.17 -.0626 19.41 273-373
Octene C8H16 163.22 .0785 - 15.07 129.67 -.0019 1.79 318-398
2-Octene,trans C8H16 159.53 .0827 - 14.56 41.97 -.0549 19.85 289-425
Nonene C9H18 128.61 .0619 -7.95 152.01 -.0109 1.15 340-513
Decene C10H20 92.64 .0477 -0.83 40.51 -.0717 26.39 360-513
Cyclohexene C6H10 223.90 .0844 - 23.94 32.54 - .0201 11.57 273-473
Benzene C6H6 167.01 .0292 - 9.84 19.08 - .0153 11.90 283-473
Toluene C7H8 191.44 .0592 - 16.00 39.14 -.0164 11.22 313-523
Styrene C8H8 115.06 .0237 0.01 26.97 -.0339 15.98 303-513
Ethylbenzene C8H10 234.54 .0910 - 25.43 28.56 - .0334 16.57 273-473
o-Xylene C8H10 109.15 .0271 0.25 75.90 - .0082 6.84 337-513
m-Xylene C8H10 104.99 .0256 0.66 107.90 .0059 0.79 332-513
p-Xylene C8H10 106.98 .0291 0.04 33.82 - .0289 15.55 331-513
1,2,3 Trimetbylbenzene C9H12 166.40 .0561 - 10.84 120.15 .0043 0.73 363-513
1,2,4 Trimethylbenzene C9H12 196.95 .0726 - 17.54 37.46 - .0347 17.56 358-513
1,3,5 Trimethylbenzene C9H12 101.41 .0280 1.10 24.31 -.0412 20.41 355-513
Propylbenzene C9H12 103.34 .0367 - .04 115.11 -.0041 2.69 346-513
Cumene C9H12 100.80 .0377 0.06 31.62 - .0454 19.30 343-513
Carbontetrachloride CC14 225.60 .0838 - 24.10 91.43 .0148 - 1.27 273-473
Weak polar substances
Ketene C2H20 100.52 -.1825 -0.14 106.84 -.7578 13.54 173-253
Acetone C3H60 221.51 .0013 - 17.11 67.06 .0375 - 1.74 273-473
2 Butanone C4H80 115.14 - .0231 2.24 58.10 .0191 2.99 273-473
2 Pentanone C5H100 121.37 -.0045 0.10 84.38 .0211 0.19 273-473
3 Pentanone C5H100 120.06 .0039 -0.65 96.57 .0229 - 1.46 328-538
Methylisobutylketone C6H120 102.74 .0200 0.28 50.48 - .0188 12.15 291-513
Cyclopentanone C5H80 103.93 -.0239 6.59 84.70 .0216 - 1.18 273-513
 K.-P. Yoo et al. / F l u i d Phase Equilibria 111 (1995) 175-201 185

Table 1 (continued)
Chemicals Formula Ea Eb Ec E~ Vb Vc Range(K)
Dimethylether C2H60 121.30 -.1373 8.48 36.73 .0530 - 1.53 273-393
Methylethylether C3H80 118.52 -.0036 - 3.28 72.23 .0253 - 1.01 273-393
Diethylether C4H100 98.95 .0063 - 0.42 90.71 .0204 - 1.31 273-433
Methylbutylether C5H120 98.07 .0216 -0.57 46.62 -.0203 11.30 283-473
Methyl tert-Butylether C5H120 141.07 .0513 - 10.20 99.46 .0099 - 0.01 288-473
Diisopropylether C6H140 119.57 .0486 -7.04 111.54 -.0101 2.38 273-473
Dipropylether C6H140 154.16 .0523 - 11.74 65.29 - .0093 9.09 273-473
Ethyleneoxide C2H40 120.55 - . 1138 7.75 48.99 .0372 - 2.26 273-423
1,2 Propyleneoxide C3H60 226.44 .0100 - 19.35 62.67 .0366 - 1.64 273-453
Furan C4H40 347.69 .1072 - 46.29 69.32 .0305 - 2.16 273-363
Tetrahydrofuran C4H80 128.05 - .0076 - 0.93 83.15 .0264 - 2.73 273-473
1,4 Dioxane C4H802 384.38 .1143 - 50.46 41.80 .0034 6.60 273-473
Thiophene C4H4S 281.40 .0719 - 30.50 68.30 .0148 .32 313-513
Pyrrolidine C4H9N 316.93 .0789 - 37.37 81.32 .0175 - 1.44 318-513
Pyridine C5H5N 121.68 - .0171 3.63 19.84 - .0084 10.45 343-513
Methylacetate C3H602 292.07 .0561 - 33.22 72.72 .0321 - 1.51 273-473
Ethylacetate C4H802 270.67 .0714 -31.29 21.84 -.0136 12.68 273-473
Propylacetate C5H1002 232.23 .0717 -24.90 65.09 -.0090 7.67 273-473
Vinylacetate C4H602 265.29 .0631 - 29.52 12.68 - .0165 13.55 273-473
Methylacrylate C4H702 108.50 -.0411 4.07 17.63 -.0098 12.15 273-393
Ethylacrylate C5H802 106.51 - .0085 1.79 28.09 - .0146 13.35 273-410
Formaldehyde CH20 132.79 - .2255 11.74 49.03 .0638 - 5.38 273-373
Acetaldehyde C2H40 140.59 - . 1023 3.01 54.68 .0463 - 2.75 273-423
Furfural C6H402 677.53 .2151 - 102.39 68.13 .0224 1.03 328-513
Strong polar substances
Chloroform CHC13 124.20 - .0081 - 0.29 69.98 .0194 - 0.38 273-483
Methylamine CH5N 146.75 - .1501 4.34 79.49 .0659 - 9.74 273-403
Dimethylamine C2H7N 333.86 .0699 -43.13 53.87 .0316 -0.29 273-403
Ethylamine C2H7N 360.40 .0710 - 46.72 60.61 .0341 - 1.85 273-473
Diethylamine C4HllN 125.60 .0171 -4.71 94.51 .0179 - 1.26 288-453
Triethylamine C6H15N 53.73 .0261 6.39 112.99 .0135 0.80 323-513
Aniline C6H7N 152.00 - .0253 1.56 - 3.66 - .0198 17.12 372-513
Acrylonitrile C3H3N 307.99 .0234 - 30.64 63.78 .0459 - 2.58 273-383
Acetic acid C2H202 171.43 -.1360 7.81 60.96 .0445 -3.30 303-513
Water H20 1394.12 - .2031 - 162.56 51.50 .0320 - 7.55 273-473
Methanol CH40 916.94 .0805 - 131.58 - 16.36 .0081 9.29 288-493
Ethanol C2H60 598.84 .0453 - 79.77 61.60 .0299 - 2.45 303-383
Propanol C3H80 736.17 .1585 - 111.64 -51.16 -.0274 22.80 283-517
Isopropanol C3H80 160.64 -.1403 3.15 28.96 .0214 6.27 273-473
Butanol C4H100 255.40 - 0.0649 - 16.80 33.13 .0004 9.30 273-473
Butanol,tert C4H100 142.27 - . 1250 3.00 - 80.24 - .0680 33.06 293-378
1 Pentanol C5H120 642.99 .1902 -99.15 -57.55 -.0602 31.06 288-513
2 Methyl-l-butanol C5H120 124.94 -.0587 3.75 30.08 -.0078 12.86 308-513
2 Methyl-2-butanol C5H120 605.50 .2081 - 96.04 5.97 - .0416 18.86 298-513
Phenol C6H60 176.19 -.0441 -0.65 85.27 .0202 -0.92 373-513
Supercritical substances
Carbon dioxide CO2 745.19 .3371 - 133.48 - 56.87 - .0090 16.92 246-410
Ethane C2H6 181.79 .0842 - 22.85 - 12.99 - .0401 13.46 246-480
Ethylene C2H4 162.22 .0696 - 19.09 38.17 .0113 0.94 246-480
186 K. -P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

Table 1 (continued)
Chemicals Formula Ea Eb Ec Vd Vb Vc Range(K)
Low vapor pressure substances
Bonzoic Acid C7H602 100.77 .3787 0.19 136.31 .1057 - 11.01 273-373
Naphthalene C10H8 97.41 .0114 6.39 10.85 -.0352 20.14 283-490
Biphenyl C12H10 83.49 .0206 7.44 124.22 .0021 3.10 283-525
Acridine C13H9N - 226.79 -.1833 75.11 - 132.65 - .1561 60.16 283-473
Anthracene C14H10 18.41 .0161 20.02 40.71 - .0482 23.27 283-473
Phenathrene C14H10 210.61 .0878 - 16.60 38.65 - .0578 24.41 283-473
Myristic Acid C14H2802 307.09 .1408 - 40.17 66.62 - .0835 29.97 283-473
Palmitic Acid C16H3202 459.21 .2238 - 71.73 206.82 - .0842 17.94 283-473
Stearic Acid C18H3602 303.20 .1388 - 39.50 94.89 - .0840 38.20 283-473
Penicillin V C16H18N205S 41.12 .3746 0.77 519.83 .3269 -76.15 303-423

Table 2
Coefficients of the energy and volume parameter correlations for several polymers
Polymer Ea (K) Eb Ec ( l / I n K ) V *(cm 3 g - 1)
Polystylene(atatic) 84.318 .1117 0. .8801
Poly(vinyl acetate) 120,287 -.0035 0. .7850
Polyisobutylene 95.868 .0624 0. 1.0080
Poly(propylene oxide) 102.436 .0055 0. .9162
Poly(dimethyl siloxane) 67.001 .0730 0. .8911
Polyethylene(branched) 92.833 .0710 0. 1.0954
Polyethylene(HMW,linear) 123.201 .0055 0. 1.1077
Polyethylene(linear) 113.946 .0267 0. 1.0951
Poly(o methylstyrene) 91.897 .1022 0. .9000
Poly(methyl methacrylate) 111.454 .0659 0. .790
Poly(n buthyl methacrylate) 99.633 .0518 0. .8810
Poly(c hexyl methacrylate) 99.336 .0790 0. .8400

7. Results of calculation and discussion

7.1. P r o p e r t i e s f o r p u r e c o m p o n e n t s

F o r l i g h t s u b s t a n c e s the c o m p a r i s o n o f p _ p s a t T r e l a t i o n s w i t h e x p e r i m e n t a l d a t a in the
s u b c r i t i c a l r e g i o n a n d p - P i s o t h e r m s in the s u p e r c r i t i c a l r e g i o n p r o v i d e g o o d tests for the p r o p o s e d
E O S . F o r a w i d e r a n g e o f T a n d P , the p r e s e n t m o d e l w a s e x t e n s i v e l y tested. A s a r e s u l t w e
c o n c l u d e d that the p r e s e n t m o d e l c a n q u a n t i t a t i v e l y b e u s e d f o r the c a l c u l a t i o n o f t h e r m o d y n a m i c
p r o p e r t i e s o f p u r e s y s t e m s e x c e p t n e a r the c r i t i c a l r e g i o n . A s an i l l u s t r a t i o n , c a l c u l a t i o n r e s u l t s o f
s a t u r a t i o n d e n s i t y for h e p t a n e ( T i m m e r m a n s , 1950) are s h o w n in F i g . 1. A l s o , in F i g . 2 an i l l u s t r a t i v e
c o m p a r i s o n o f the p r e s e n t m o d e l w i t h e x p e r i m e n t a l s u p e r c r i t i c a l d a t a f o r e t h a n e ( B r a k e r a n d
M o s s m a n , 1980) is s h o w n . In the p r e s s u r e r a n g e f r o m 1 to 600 b a r the a v e r a g e e r r o r in the c a l c u l a t e d
d e n s i t i e s is l e s s t h a n 1%. F o r o t h e r s u p e r c r i t i c a l p u r e s y s t e m s the a v e r a g e e r r o r s o f c a l c u l a t e d
d e n s i t i e s w e r e w i t h i n 1%. T h e s e r e s u l t s a r e s l i g h t l y i n f e r i o r to the n o n r a n d o m h o l e l a t t i c e s o l u t i o n o f
 K.-P. ]Ioo et al. // Fluid Phase Equilibria 111 (1995) 175-201 187

1.0
Data from Timmermans(1950)
• Saturated vapor density
.8 o Saturated liquid density
- -- Present EOS

~E .6 -

~" .4

.2

0.0 ....
300 400 500 600

Temperature (K)

Fig. 1. Calculated saturated t e m p e r a t u r e - d e n s i t y diagram for pure heptane.

You et al. (1994a). The pure form of EOS presented here is identical to the random lattice hole model
(Panayiotou and Vera, 1982).
Kleintjens and Koningsveld (1983) reported better agreements in the critical region with a
three-parameter lattice-hole EOS. To date most lattice EOS's formulated with the assumption of the
mean field approximation experience inaccuracy in the vicinity of the critical point. As is shown in
Fig. 3, the critical compressibility factor values are compared for some models. As well known, Z c is
a constant value 0.375 for van der Waals, 0.333 for SRK (Soave, 1972) and 0.3074 for PR (Peng and
Robinson, 1976) EOS, respectively. While the Z c of most real fluids is below 0.300, it is dependent
on the segment number r 1 in the lattice model-based EOS with the mean field approximation whether
it is random or not (You et al., 1994a). If one wishes to improve this intrinsic limitation, reference
may be made to decorated lattice theories (Gilbert and Eckert, 1986). We, thus, cannot recommend
present model for the use in the immediate vicinity of its critical region; ( T - T c ) / T c < 0.1 and
( P - P c ) / P c < 0.1) for pure systems.

.5

.4

.3

i
E

.== .2

.1 o 500 K
- - Present EOS

0.0 I I I I I I
o lO 20 30 40 50 60 70

Pressure (MPa)

Fig. 2. calculated isothermal d e n s i t y - p r e s s u r e data for pure ethane.

188 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

.40
.- . . . . . Sanchez-Lacombe Model
: "" .... Random Model
~ ""iii Nonrandom(YYL) Model
.38
LL
~- ':. vdW EOS(0.3750)
\
.~, .36

.34
8
N .32
o PR EOS(0.3074)
.30 I I I I
100 101 102 103 104 105
Number of Segment

Fig. 3. Critical compressibility factor as a function of lattice segment number for cubic and lattice EOS.

7.2. Low pressure vapor-liquid equilibria

Since we discussed in detail elsewhere (You et al., 1993; You et al., 1994a; You et al., 1994b; You
et al., 1994c; Shin, 1994) on the methods of calculating various phase equilibria with the EOS, we
omit here the calculational aspects with the present model.
The VLE mixtures may be classified as in the DIPPR (Gess et al., 1991); nonpolar (NP)-NP,
N P - w e a k polar (WP), NP-strong polar (SP), W P - W P and W P - S P binary systems. Binary interac-
tion parameters Aij as defined by Eq. (21) and errors are summarized in Table 3 for 32 systems. For
each type of systems, the present model fits quantitatively well the VLE of binary mixtures with only
one binary adjustable parameter, Aij as can be seen in Table 3. However, due to the limited space of
this article only a few examples are illustrated in Fig. 4, where experimental data are from the
DECHEMA data compilations reported by Gmehling et al. (1980). The heptane-3 pentanone system
can be regarded as an N P - W P azeotropic system and the model fits data satisfactorily with only one
temperature independent Aij.
In Fig. 5, the comparison of the present model with data for an ethanol-water (SP-SP) system is
shown. In spite of their strong polarities, improved fit was observed compared with the random hole
model lattice EOS (Panayiotou and Vera, 1982). Similar improvements were obtained for the same
system compared with UNIQUAC model as shown in Fig. 6. While the UNIQUAC uses two
adjustable parameters, the present model requires one binary parameter when the pure EOS molecular
parameters, e~l and V~* are available. For all systems tested in this section, the absolute average
deviations were within 5% except the ethanol-benzene system as shown in Table 3.

7.3. High pressure vapor-liquid equilibria

We chose carbon dioxide, ethane, and ethylene as supercritical solvents and considered their
mixtures with alkanes, alkenes, aromatics and alcohols. The binary interaction parameters, Aij, and
error percents are summarized in Table 4 for 23 binary systems and one graphical example in Fig. 7
(CO2-acetone system). We found that the present model is quantitatively applicable to such high
pressure systems. These results are frequently better than those by other existing models (Panayiotou
and Vera, 1982; Kumar et al., 1987) and the PR-EOS (Peng and Robinson, 1976). In all
 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 189

Table 3
B i n a r y i n t e r a c t i o n p a r a m e t e r s a n d e r r o r % for l o w p r e s s u r e v a p o r - l i q u i d equilibria calculations

System Aij T(K) P (kPa) Isothermal (%) Isobaric (%)

AADP a AADY b AADT ~ AADY

(1) N o n p o l a r - N o n polar system

Benzene-c Hexane - 0.0190 343 100 0.79 2.69 0.07 1.98
Benzene-Heptane -0.0235 328-353 97-100 1.36 2.78 0.12 2.10
Benzene-Toluene -0.0028 - 100 - - 0.14 2.03
c Hexane-Toluene - 0.0110 - 100 - - 0.06 0.50
Pentane-Hexane 0.0033 298 99 1.90 0.92 0.16 1.23
Hexane-Benzene - 0.0178 343 100 1.66 3.47 0.22 5.84
Hexane-c Hexane 0.0023 343 100 2.06 3.32 0.22 3.52
Hexane-c Methylpentane - 0.0025 - 100 - - 0.34 2.62
Hexane-Toluene -0.0078 - 100 - - 0.18 5.44
c Methylpentane-Benzene -0.0192 333 100 1.27 2.13 0.08 1.16
c Methylpentane-c Hexane -0.0021 - 100 - - 0.09 0.57
c Methylpentane-Toluene - 0.0100 - 100 - - 0.16 2.98
(2) N o n p o l a r - W e a k polar system
Acetone-Benzene -0.0197 298-318 99-100 0.86 1.84 0.33 3.44
Acetone-c Hexane -0.0737 318-328 100 3.74 5.10 0.31 5.27
Acetone-Hexane -0.0731 318-328 100 2.63 5.21 0.21 5.27
Benzene-2 Butanone - 0.0097 333 100 1.46 1.82 0.25 3.01
Heptane-3 Pentanone - 0.0366 338-368 - 1.72 5.12 - -
Ethylacetate-c Hexane - 0.0437 293-328 100 1.86 3.37 0.14 2.36
2 Butanone-c Hexane -0.0532 - 100 - - 0.16 4.24
(3) N o n p o l a r - S t r o n g p o l a r s y s t e m
Diethylamine-Benzene - 0.0017 308-328 100 1.45 2.27 0.12 2.13
Diethylamine-Heptane - 0.0131 308-328 - 0.43 2.24 - -
Ethanol-Benzene - 0.0819 323-333 100 4.92 8.84 0.47 9.63
(4) W e a k p o l a r - S t r o n g p o l a r s y s t e m
Acetone-Ethylacetate - 0.0090 - 100 - - 0.08 4.78
Diethylether-Acetone - 0.0294 293-303 - 1.50 5.91 - -
Ethylacetate-3 Pentanone 0.0007 - 100 - - 0.66 5.26
(5) W e a k p o l a r - S t r o n g p o l a r s y s t e m
Acetone-Methanol -0.0483 318-218 100 0.90 2.15 0.17 1.90
Acetone-ethanol - 0.0341 305-321 - 1.63 1.01 - -
Methanol-3 pentanone - 0.0593 - 100 - - 0.34 4.36
(6) S t r o n g p o l a r - S t r o n g p o l a r s y s t e m
Diethylamine-Ethanol 0.0136 - 100 - - 0.18 3.09
Methanol-Water -0.0837 333 100 1.01 1.77 0.19 4.78
Ethanol-Water -0.1493 328-343 66-100 1.71 4.43 0.10 4.31
Ethanol-Propanol - 0.0097 333-353 - 3.48 2.41 - -

Absolute average deviation of pressure, b Absolute average deviation of vapor mole fraction, c Absolute average deviation
of temperature.

comparisons, we used a single temperature independent value of Aii for each system. The results for
systems of carbon dioxide-ethanol at 304.2 K and carbon dioxide-methanol at 290 K in Figs. 8 and 9
demonstrate that the present model is almost comparable with the P R - E O S . The model by Kumar et
190 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

140 / Data from Gmehling et a1.(1980)

o 338.15 K • 383.15 K
120 - - Present EOS( Zij = -0.0366 )

100

~
= 80

o. 60

40

20
0.0 .2 .4 .6 .8 1.0

Mole fraction of Heptane

Fig. 4. Calculated isothermal P - x - y equilibria for heptane-3-pentanone system at 338.15 and 363.15 K

100
[ Data from Gmehling et a1.(1980)
I D 328.15K • 343.15K
I - - - - Random E O S ( ~ = -0.0276)
80

~ 6O

g
~ 40

20

0 L I I I I
0.0 .2 .4 .6 .8 1.0

Mole fraction of Ethanol

Fig. 5. Calculated isothermal P - x - y equilibria for ethanol-water system at 328.15 and 343.15 K.

Data from Gmehling et a1.(1980)

380 ~- • 66.6 KPa • 101.3 KPa
I-- Present EOSQ. i = -0.1493)
I--...... UNIQUAC(a,j/R = 16.82,128.08
370

340 ' ' ' , -r-

0.0 .2 .4 .6 .8 1.0
Mole fraction of Ethanol
Fig. 6. Calculated isobaric T - x - y equilibria for ethanol-water system at 66.6 and 101.3 kPa.
 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 191

Table 4
Binary interaction parameters and error% for high pressure vapor-liquid equilibria calculations
System Aij A A D X a(%) T Range (K) Ref
CO2
-Butane .0896 5.1 273.15 -310.93 1,2
-Isobutane - .0849 13.5 273.15 1
-Pentane - .0674 19.3 277.59-311.04 3
-Isopentane - .0719 15.3 277.59-310.93 4
-Hexane - .0690 8.9 303.15-313.15 5
-Heptane - .0493 15.6 310.65 6
-Octane - .0663 9.7 313.15 7
-Butene - .0760 6.9 273.15 1
-Hexene - .0230 8.8 303.15-313.15 5
-Benzene - .0900 6.0 313.40-350.00 8
-Toluene - .0818 14.2 308.16-323.17 9
-Cyclopentane - .0765 12.3 310.86-318.17 10
-Acetone - .0137 2.1 298.15-313.15 11
-Methanol - .1403 12.4 290.00-310.00 11,12
-Ethanol - . 1180 12.9 304.20-314.50 13,14
- 2 Propanol -.0918 6.0 316.65-334.95 15
Ethane
-Pentane -.1050 5.1 277.59-310.93 16
-Hexane - .0240 9.7 298.15-338.71 16
-Octane - .0276 2.6 313.15-323.15 16
-Benzene - .0510 7.0 298.15-313.15 16
-Cyclohexane - .0340 9.5 299.82-316.48 16
-Acetone - . 1111 6.3 298.15 16
Ethylene-Heptane - .0385 1.6 299.82-316.48 16

a Absolute average deviation of liquid mole fraction. Ref: 1, Nagahama et al. (1974); 2, Olds et al. (1949); 3, Besserer and
Robinson (1973); 4, Besserer and Robinson (1975); 5, Wagner and Wichterle (1987); 6, Kalra et al. (1978); 7, King et al.
(1983); 8, Kim et al. (1986); 9, Fink and Hershey (1990); 10, Eckert and Sander (1986); 11, Katayama et al. (1975); 12,
Hong and Kobayashi (1988); 13, Takishima (1986); 14, Jennings et al. (1991); 15, Radosz (1986); 16, Knapp et al. (1982).

10
Data from Katayame et al.(1975)
• 298.15 K
• 313.15 K

I1.

2
!

0
0.0 .2 .4 .6 .8 1.0

Mole fraction of CO 2

Fig. 7. Calculated isothermal P - x - y equilibria for carbon dioxide-acetone mixture at 298.15 and 313.15 K.
192 K. -P. Yoo e t a I. / Fluid Phase Equilibria 111 (1995) 175 -201

12
Data from Takishima et a1.(1986)
• 304.2 K
10 ........ Random(;~ii=0.0534)
Kumar et a1.(;~i~=0.0893)
PR-EOS~j=0.0907)
~"
Q. 8 Present EOS(~.~j=-0.1180)

n"~ 4

0 I I I I J
0.0 .2 .4 .6 .8 1.0

Mole fraction of CO 2

Fig. 8. Calculated isothermal P - x - y equilibria for carbon d i o x i d e - e t h a n e s y s t e m at 304.2 K.

8
Data from Hong et a1.(1988)
290.0 K
7 - ....... Random(;L=,=-0.0201)
6 - - - - - Kumar et a1.(~.ii=0.0575 )
- - - -- PR-EOS(k~j=0.0568 )
~" - - P r e ~
~ 5 -

~ 4
~ 3 "~

1 !

0 I I i ! J
0.0 .2 .4 .6 .8 1.0

Mole fraction of CO 2

Fig. 9. Calculated isothermal P - x - y equilibria for carbon d i o x i d e - m e t h a n o l s y s t e m at 290.0 K.

al. (1987) was originated from the nonrandom lattice theory. The resulting expressions are more
complicated than the previous equations of the present author's and the fit is less good. Although we
do not claim the generality of our conclusions, the practical usefulness of the present work is evident
from the comparison.

7.4. Solid-vapor equilibria

In Table 5, the binary interaction parameters and errors for 15 systems are summarized. A few
illustrations using Aij values in Table 5 are shown in Figs. 10 and 11. Data for naphthalene-ethane
system at 318.15 K (Schmitt and Reid, 1986) was fitted by the present EOS with a temperature
independent binary parameter, Aii, and presented with the results by other existing models in Fig. 10.
In general, P R - E O S fits better than the present model. It is probably due to better agreements of
 K. -P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 193

Table 5
Binary interaction parameters and error% for vapor-solid equilibria calculations
System T Range (K) Aij AAD(%) Ref
Carbon dioxide
-Acridicine 308.15-318.15 -.1779 21.20 1
-Anthracene 303.15-328.15 -.1250 27.80 2
-Biphenyl 308.95 -322.65 -.1301 9.97 3
-Benzoic Acid 308.15-318.15 -.1535 14.41 1
-Naphathalene 308.15-328.15 -.1426 22.50 2,4
-Phenanthrene 308.15 -.1420 5.65 1,5
Ethane
-Acridicine 308.15-318.15 -.1643 24.36 1
-Anthracene 303.15 -323.15 -.0854 4.63 2
-Biphenyl 308.15-318.15 -.0944 11.24 1
-Benzoic Acid 308.15-318.15 -.1767 14.95 1
-Naphathalene 308.15-318.15 -.1012 11.54 1
-Phenanthrene 303.15-318.15 -.0759 19.90 1,2
Ethylene
-Benzoic Acid 318.15-328.15 -.1459 5.46 5
-Naphathalene 298.15-318.15 -.1009 20.65 4
-Phenanthrene 318.15-328.15 -.0650 10.21 5,6,7

Ref: 1, Schmitt and Reid (1986); 2, Johnston et al. (1982); 3, McHugh and Paulaitis (1980); 4, Tsekhanskays et al. (1964); 5,
Kurnik et al. (1981); 6, Johnston and Eckert (1981); 7, Masuoka and Yorizane (1982).

P R - E O S in the critical region. However, at very high pressure, the present results are quantitatively
comparable or sometimes better than the PR-EOS.
In Fig. 11, experimental data (Dobbs et al., 1986) on the effect of cosolvent penthane (3.5 mol.%)
to the supercritical solubility of phenanthrene in carbon dioxide are fitted by the present EOS. The
model is seen to correlate the ternary system quantitatively.

10-1

~. 10-2

._~ - )

10"3 - ~entEOS(,k,~:-~0.10121
• ! :"~~ -- Ra nd°m(Zi~0"0145)
F .: 1--- _K~_r~_retatt~,~0:0SS0)
10 -4 ~ PR- OSE (k,j=0.'0412)

I J I
0 10 20 30 40
Pressure (MPa)
Fig. 10. Calculated solubilities of naphthalene in ethane at 318.15 K.
194 K. -P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175 -201

10 -2
==
10 .3 __=-

g. 10-'~
Data from Dobbs et a1.(1986)
o Pure CO 2
10-5 D C0~+3.5mo1% Pentane
........ Pure present E O S
Cosolvent Present E O S
u. 10_6 Q.12= -0.0959,;~13=-0.142
0
;~23=-0.0674)
10-7 _~."
I I I
10 20 30 40 50

Pressure (MPa)

Fig. 11. Calculated solubilities of phenanthrene in pentane-carbon dioxide mixture at 318.15 K.

7.5. Activities of solvents in polymer solutions

For high molecular species such as polymers, vapor pressure is frequently not well known and is
usually negligible. Thus activities of solvents are determined from the vapor-liquid equilibria of
solvents.
/£Vpure(T,P ) = I~L(T,P,{x}) for solvents (48)
/xL= L
/'~i,pure --b RT In a i
The activity of solvent species i in polymer solutions can be calculated by the present model.
Densities of coexisting phases are calculated using Eq. (35). Then evaluating chemical potentials of
both phases, solvent activities are calculated by Eq. (49). The binary interaction parameters, )tij, and
errors for 20 solvent-polymer systems are summarized in Table 6. Except for the system of
polypropylene oxide-chloroform, the absolute average errors are within 5%.
In Fig. 12, activity data for benzene in polyisobutylene (Bawn and Patel, 1956; Eichinger and
Flory, 1968a) are fitted by the present EOS and the results compared with other models such as the
random hole model EOS (Panayiotou and Vera, 1982), the new Flory's EOS (Flory, 1970), Sanchez
and Lacombe (1976a), and Kumar et al. (1987). Most of these models use two binary parameters
while we use one binary parameter.
Except for Sanchez and Lacombe's model all other models are similar in fitting data, although the
present model appears slightly better. The results by the Sanchez and Lacombe EOS might be
improved by using temperature dependent pure parameters as we did in the present work. Similar
results are obtained for experiment of cyclohexane in polyisobutylene at 298.15 K (Bawn and Patel,
1956; Eichinger and Flory, 1968b) and for cyclohexane-polystyrene at 303.15 K (Scholte, 1970a,
Scholte, 1970b) as shown in Figs. 13 and 14, respectively.
Finally we present limited comparisons of the present EOS with other existing group contribution
methods which are used frequently in engineering practices for polymer systems. They includes the
U N I F A V - F V (Oishi and Prausnitz, 1978), HA (Holten-Anderson et al., 1987), GCLF (High and
Danner, 1990). For this purpose, experimental activities of benzene in polypropylene oxide (Chang
 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 195

Table 6
Binary interaction parameters and error% for vapor-liquid equilibria of polymer solutions
System T Range (K) Aij AAD(%) Ref
Polyisobutylene
-Benzene 283.15-353.15 - .0322 3.47 1,2
-Butane 298.15 -319.65 - .0330 1.80 2
-Cyclohexane 298.15-338.15 - .0146 1.71 1,3
- Isobutane 298.15 - 319.65 - . 0346 1.81 4
-Neopentane 298.15-319.65 - .0339 1.57 4
-Pentane 298.15-308.15 - .0245 4.42 4
Polystyrene
-Acetone 298.15-323.15 - .0467 4.88 5
-Benzene 288.15-333.15 - .0151 8.65 6
-Cyclohexane 303.15-338.15 - .0260 0.49 7,8
-Chloroform 298.15-323.15 - .0086 3.55 5
-Ethylbenzene 283.15-303.15 - .0126 0.08 9
- 2 Butanone 298.15-343.15 -.0315 2.77 10,11
-Propylacetate 298.15-343.15 - .0216 1.28 5
-Toluene 298.15-353.15 - .0011 1.15 7,8,11
Polyvinylacetate
-Acetone 303.15 - .0191 5.08 12
-Benzene 303.15 - .0136 5.72 13
-Vinylacetate 303.15 - .0081 3.34 13
Polypropylene oxide
-Benzene 318.15-347.85 - .0035 1.01 14,15
-Chlorofrom 278.68 .1069 15.58 16
- Carbontetrachloride 278.68 .0028 0.70 16

Ref: 1, Bawn and Patel (1956); 2, Eichinger and Flory (1968a); 3, Eichinger and Flory (1968b); 4, Prager et al. (1953); 5,
Bawn and Wajid (1956); 6, Noda et al. (1984); 7, Scholte (1970a); 8, Scholte (1970b); 9, Hocker and Flory (1971); 10, Flory
and Hocker (1971); 11, Bawn et al. (1950); 12, Oishi and Prausnitz (1978); 13, Nakajima et al. (1959); 14, Chang and
Bonner (1975); 15, Booth and Devoy (1971); 16, Kershaw and Malcolm (1968).

1.2

f,
ID
1.0 t
.8
.6
•
~/ ~, andEit~chinnger
al.(1956)
et a1.(1968)
~/ o Mn=40000-t3 Mn=45000
7h ----- New .Flow. EOS
~/ -- -- Sanchez:LacombeEOS
.2 l ~.-~.-Rar~ad~mtEaOS
Pre~entE0~(;%='0i0322)
0.0
0.0 .2 .4 .6 .8 1.0

Weight fraction of Benzene

Fig. 12. Calculated activities of benzene in polyisobutylene solution at 298.15 K.
196 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

1.0

Q)
e-
(U
.8
c-
O
.6

"6
.4 ~~'chinger e t_al.(1_96S)
.>_ [/ o M..=40_0.00 ~_ _ Mn=45000
f/ --- N~w FloryEOS "
< / Sanchez-Lacombe EOS
.2 - - - - - Random EOS
. . . . . . . . Kumaretal.
i Present E(~S(~.,j=-1~.0146)
0.0
0.0 .2 .4 .6 .8 1.0
Weight fraction of Cyclohexane

Fig. 13. Calculated activities of cyclohexane in polyisobutylene solution at 298.15 K.

and Bonner, 1975; Booth and Devoy, 1971) are compared with the calculated results of those group
contribution methods in Fig. 15. Since there exists a difference of polarity, the results by the group
contribution methods are not satisfactory. However, the present model is seen to be quantitative. The
reformulation of the present model to group contribution EOS is now under progress by the present
authors.

7.6. Liquid-liquid equilibria

The calculation of liquid-liquid equilibria can readily be carried out with the following phase
equilibrium criterion
~L'(T,P,{x'}) = ~ ' ( T , P , { x " } ) i= 1,...,c (50)
where superscripts L' and U' represent the coexisting liquid phases. At the upper critical solution
temperatures (UCST) of partially miscible mixture compositions of coexisting phases become

1.2

.~ Of
.8

•~
(¢
.4 [41 / •
/oata.om,oho,e 1,,0>
303.~s K (M.~-~S4000)
I ~/ / - - ' - - New FloryEOS
I! / ~ e ~ k ~ b e EOS
.2 ~ / - - - - - Random EOS
J,/ ........ Kumar et al. EOS

0.0
0.0 .2 .4 .6 .8 1.0
Weight Fraction of Cyclohexane

Fig. 14. Calculated activities of cyclohexane in polystyrene solution at 303.15 K.

 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 197

1.0

.8 // ...."
==
o / ~..'
.6
"6 t/ "'" ang at a1.(1975)
.4 ~ h l t h et a1.(1_97_1)~
<15 p
7=
o 2 ~ 3 3 . 3 _ s
347.05K • 347.85K
.K_
.2 - - -- UNIFAC-FV Model
----- HA Model
........ GCLF Model
I P~esent E~3S(~,,j=]O.O0351
O.0
00 .2 .4 .6 .8 1.0
Weight Fraction of Benzene
Fig. 15. Calculated activities of benzene in polypropylene solutions by the present EOS and several group contribution
methods.

identical. The LLE and UCST behavior are sensitive criteria to test a model and we are preparing a
separate paper on the applicability of the present model. The authors discussed elsewhere in detail the
results by the previous rigorous but less flexible EOS (You et al., 1994c).

8. Conclusion

A new EOS was proposed primarily for use in the fluid phase equilibrium calculation of complex
a n d / o r macromolecular systems as well as high pressure systems. The EOS contains two molecular
parameters for pure systems and one interaction energy parameter, Aii for binary mixtures. The new
model originates from the random hole lattice model and nonrandom interaction energy effect is
formulated following the nonrandom two liquid theory. The model is relatively simple and versatile.
The applicability of the present EOS was tested for various fluid phase equilibrium calculations of
complex systems. For pure fluids the new EOS reduces to a random hole EOS (Panayiotou and Vera,
1982) and is slightly inferior to the rigorous nonrandom EOS of present authors (You et al., 1993,
You et al., 1994a). For mixtures the calculated results were found to agree with data quantitatively.

9. List of symbols

Ac configurational Helmholtz free energy

Ac(A) athermal contribution to A c
Ac(R) random contribution to A c
Ac(NR) nonrandom contribution to A c
Ac(IS) ,ideal solution' contribution to A c
Ac(E) excess' contribution A ~
gR number or non-degenerate states for the random distribution
gNR number or non-degenerate states for the nonrandom distribution
Na Avogadro's number
198 K.-P. Yoo et al. /Fluid Phase Equilibria I I I (1995) 175-201

Ni number of molecular species i

v,* number of i - j segment contacts for the random distribution
Nij number of i - j segment contacts for the nonrandom distribution
N, number or vacant sites or holes
N, defined by N, = NO+ XNiri
%I
defined by N = NO + l$Niqi
P pressure &Pa s
4i surface area parameter
qM mole fraction average of qi
‘i segment number
TM mole fraction average of ri
R universal gas constant (J mol-’ K- ‘)
T temperature (K>
UC configurational internal energy
uIS ideal solution contribution to UC
UE ‘excess’ contribution to UC
V molat volume (cm3 mol- ‘)
vi * characteristic volume of component i (cm3 mol- ‘1
VH volume of a unit cell (cm3)
xi liquid mole fraction of component i
Yi vapor mole fraction of component i
z lattice coordination number

Greek letters
a1 thermal expansion coefficient
reciprocal temperature (l/kT)
; isothermal compressibility factor
4 configurational lattice partition function
‘ij nonrandomness correction factor for i - j segment contacts
‘ij nonrandomness factor defined by Eq. (26)
‘ij interaction energy for i - j segment contacts (J)
+i fugacity coefficient for component i
P total segment fraction
Pi segment fraction of component i
Pi chemical potential for component i
4 part of chemical potential due to internal degrees of freedom
*ij binary interaction parameter for i - j contacts
8 total surface area fraction
!i surface area fraction of component i
6 surface area fraction of component i on the hole free basis

Superscripts
L liquid phase sat
sat saturation state
 K.-P. Yoo et aL / Fluid Phase Equilibria 111 (1995) 175-201 199

S solid phase
V vapor phase
, derivative with respect to In T

Acknowledgements

The authors are grateful to the Korea Science and Engineering Foundation for financial support.
KPY expresses his appreciation to the Alexander von Humboldt-Stiflung for fellowship support
during the early stage of this work.

References
Abrams, D. and Prausnitz, J.M., 1975. Statistical thermodynamics of liquid mixtures: a new expression for the excess Gibbs
energy of partly or completely miscible systems., AIChE J., 21: 116-128.
Bawn, C.E.H. and Patel, R.D., 1956. High polymer solutions. Part 8--The vapor pressure of solutions of polyisobutene in
toluene and cyclohexane. Trans. Faraday Soc., 52: 1664-1668.
Bawn, C.E.H. and Wajid, M.A., 1956. High polymer solutions. Part 7--The vapor pressure of solutions of polystyrene
solutions in acetone, chloroform, and propyl acetate., Trans. Faraday Soc., 52: 1658-1664.
Bawn, C.E.H., Freeman, R.F.J. and Kamaliddin, A.R., 1950. High polymer solutions Part I. Vapour pressure of polystyrene
solutions. Trans. Faraday Soc., 46: 677.
Besserer, G.J. and Robinson, D.B., 1973. Equilibrium-phase properties of n-pentane-carbon dioxide system. J. Chem. Eng.
Data, 18: 416-419.
Besserer, G.J. and Robinson, D.B., 1975. Equilibrium-phase properties of isopentane-carbon dioxide system., J. Chem. Eng.
Data, 20: 93.
Bondi, A., 1967. Physical Properties of Molecular Crystals, Liquids and Glasses. Shell Dev. Company. Chapter 14.
Booth C. and Devoy, C.J., 1971. Thermodynamics of mixtures of poly(ethylene oxide) and benzene, Polymer, 12: 309.
Braker, W. and Mossman, A.L., 1980. Matheson Gas Data Book, 6th edn., Matheson Gas Products.
Chang, Y.H. and Bonner, D.C., 1975. Sorption of solutes by poly(ethyl oxide). II. Benzene at finite concentrations., J. Appl.
Polym. Sci., 19: 2457.
Dobbs, J.M., Wong, J.A. and Johnston, K.P., 1986. Nonpolar co-solvents for solubility enhancement in supercritical fluid
carbon dioxide, J. Chem. Eng. Data, 31: 303.
Eckert, C.J. and Sander, S.I., 1986. Vapor-liquid equilibria for the carbon dioxide-cyclo-pentane system at 37.7, 45.0, 60.0
°C, J. Chem. Eng. Data, 31: 26-28.
Eichinger, B.E. and Flory, P.J., 1968a. Thermodynamics of polymer solutions, Part 2--Polyisobutylene and benzene, Trans.
Faraday Soc., 64: 2053-2060.
Eichinger, B.E. and Flory, P.J., 1968b. Thermodynamics of polymer solutions, Part 3--Polyisobutylene and cyclohexane,
Trans. Faraday Soc., 64: 2061-2065.
Fink, S.D. and Hershey, H.C., 1990. Modeling the vapor-liquid equilibria of 1,1,1-trichloroethane +carbon dioxide and
toluene + carbon dioxide at 308, 323, 353 K, Ind. Eng. Chem. Res., 29, 295-306.
Flory, P.J., 1970. Thermodynamics of polymer solutions, Trans. Faraday Soc., 49: 7-29.
Flory, P.J. and Hocker H., 1971. Thermodynamics of polystyrene solutions. Part 1. Polystyrene and methyl ethyl ketone,
Trans. Faraday Soc., 67: 2258-2269.
Gess, M.A., Danner, R.P. and Magvekar, M., 1991. Thermodynamic Analysis of Vapor-liquid Equilibria: Recommended
Models and a Standard Database, Pennsylvania State University Press.
Gilbert, S.W. and Eckert, C.A., 1986. A decorated lattice-gas model of supercritical fluid solubilities and partial model
volumes., Fluid Phase Equilibria, 30: 41-47.
Gmehling, J., Onken, U. and Arlt, W., 1980. Vapor-Liquid Equilibrium Data Collection, DECHEMA (Chemistry Data
Series), Vol. 1, Part 1-Part 7.
200 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201

Guggenheim, E.A., 1952. Mixtures, Clarendon Press, Oxford, Chapters 10 and 11.
High, M.S. and Danner, R.P., 1990. Application of the group contribution lattice-fluid EOS to polymer solutions, AIChE J.,
36: 1625-1632.
Hocker, H. and Flory, P.J., 1971. Thermodynamics of polystyrene solutions. Part 2. Polystyrene and ethylbenzene, Trans.
Faraday Soc., 67: 2270-2274.
Holten-Anderson J., Rasmussen, P. and Fredenslund, A., 1987. Phase equilibria of polymer solutions by group contribution.
1. Vapor-liquid equilibria, Ind. Eng. Chem. Res., 26: 1382-1390.
Hong, J.H. and Kobayashi, R., 1988. VLE studies for the carbon dioxide-methanol system, Fluid Phase Equilibria, 41:
269-276.
Jennings, D.W., Lee, R.J. and Teja, A.S., 1991. Vapor-liquid equilibria in the carbon dioxide+ethanol and carbon
dioxide + 1-butanol systems, J. Chem. Eng. Data, 36: 303-307.
Johnston, K.P. and C.A. Eckert, C.A., 1981. An analytical Carnahan-Starling-van der Waals model for solubility of
hydrocarbon solids in supercritical fluids, AIChE J., 27: 773-779.
Johnston, K.P., Ziger, D.H. and Eckert, C.A., 1982. Solubilities of hydrocarbon solids in supercritical fluids. The augmented
van der Waals treatment, Ind. Eng. Chem. Fund., 21: 191-197.
Kalra, H., Kubota, H., Robinson, D.B. and Ng, H.-J., 1978. Equilibrium-phase properties of carbon dioxide-n heptane
system. J. Chem. Eng. Data, 23: 317-321.
Katayama, T., Ohgaki, K., Maekawa, G., Goto, M. and Nagano, T., 1975. Isothermal vapor-liquid equilibria of
acetone-carbon dioxide and methanol-carbon dioxide systems at high pressure, J. Chem. Eng. Jpn., 8: 89-92.
Kehiaian, H.V., Grolier, J.P.E. and Bebson, G.C., 1978. Thermodynamics of organic mixtures. A generalized quasichemical
theory in terms of group surface interactions, J. Chem. Phys., 75: 1031-1048.
Kershaw, R.W. and Malcolm, G.N., 1968. Thermodynamics of solutions of polypropylene oxide in chloroform and in
carbon tetrachloride, Trans. Faraday Soc., 64: 323-336.
Kim, C.H., Vimalchand, P. and D. Donohue, D., 1986. Vapor-liquid equilibria for binary mixtures of carbon dioxide with
benzene, toluene, p-xylene, Fluid Phase Equilibria, 31: 299-311.
King, M.B., Alderson, D.A., Fallah, F.H., Kassim, K.M., Sheldon, J.R. and Mahmud, R.S., 1983. Some vapour/liquid and
vapour/solid equilibrium measurements of relevance for supercritical extraction operations, and their correction, in
Supercritical Chemical Engineering at Supercritical Fluid Conditions, Ann Arbor Science, Butterworths.
Kleintjens, L.A. and Koningsveld, R., 1983. Meanfield lattice-gas description of vapor-liquid and supercriticai equilibria.
Fluid Phase Equilibria, 10: 183-201.
Knapp, H., Doering, R., Oellrich, L., Ploecker, U. and Prausnitz, J.M., 1982. Vapor-liquid equilibria for mixtures of low
boiling substances, DECHEMA (Chemistry Data Series), Vol. VI.
Kumar, S.K., Suter, U.W. and R.C. Reid, R.C., 1987. A statistical mechanics based lattice model equation of state, Ind. Eng.
Chem. Res., 26: 2532-2542.
Kurnik, R.T., Holla, S.J. and Reid, R.C., 1981. Solubility of solids in supercritical carbon dioxide and ethylene, J. Chem.
Eng. Data, 26: 47.
Lide, R.L., 1991. CRC Handbook of Chemistry and Physics, 72th edn., CRC Press.
Masuoka, H. and Yorizane, M., 1982. Solubility of solid naphthalene in gaseous ethylene at high pressures, J. Chem. Eng.
Jpn., 15: 5.
McHugh, M. and Paulaitis, M.E., 1980. Solid solubilities of naphthalene and biphenyl in supercritical carbon dioxide, J.
Chem. Eng. Data, 25: 326.
Nagahama, K., Konishi, H., Hoshino, D. and Hirata, M., 1974. Binary vapor-liquid equilibriums of carbon dioxide-light
hydrocarbons at low temperature, J. Chem. Eng. Jpn., 7: 323-328.
Nakajima, A., Yamakawa, H. and Ichiro, H., 1959. Vapor pressure of polymer solutions. I. Apparatus for measurement and
some results on poly(vinyl acetate) solutions, J. Polym. Sci., 35: 489.
Noda, I., Higo, Y., Ueno, N. and Fujimoto, T., 1984. Semidilute region for linear polymers in good solvents, Macro-
molecules, 17: 1055-1059.
Oishi, T. and Prausnitz, J.M., 1978. Estimation of solvent activities in polymer solutions using a group-contribution method,
Ind. Eng. Chem. Res., 17: 333-339.
Okada, M. and Nose, T., 1981a. Quasi-chemical treatment of the hole theory for r-mers. I. Pure liquids, Polymer J., 13:
399-406.
 K.-P. Yoo et al. / Fluid Phase Equilibria 111 (1995) 175-201 201

Okada, M. and Nose, T., 1981b. Quasi-chemical treatment of the hole theory for r-mers. II. Mixtures, Polymer J., 13:
591-598.
Olds, R.H., Reamer, H.H., Sage, B.H. and Lacey, W.N., 1949. Phase equilibria in hydrocarbon systems: the n-butane-carbon
dioxide system, Ind. Eng. Chem., 41: 475-482.
Panayiotou, C. and Vera, J.H., 1981. Local compositions and local surface area fraction: a theoretical discussion, Can. J.
Chem. Eng., 59: 501-505.
Panayiotou, C. and Vera, J.H., 1982. Statistical thermodynamics of r-met fluids and their mixtures, Polymer J., 14: 681-694.
Peng, D. and Robinson, D., 1976. A new two-constant equation of state, Ind. Eng. Chem. Fund., 15: 59-64.
Prager, S., Bagley, E. and Long, F.A., 1953. Equilibrium sorption data for polyisobutylene-hydrocarbon system, J. Am.
Chem. Soc., 75: 2742-2745.
Radosz, M., 1986. Vapor-liquid equilibrium for 2-propanol and carbon dioxide, J. Chem. Eng. Data, 31: 43.
Reid, R.C., Prausnitz, J.M. and Poling, P.E., 1987. The properties of gases and liquids, 4th edn., McGraw-Hill.
Sanchez, I.C. and Lacombe, R.H., 1974. Theory of liquid-liquid and liquid-vapor equilibria, Nature, 252: 381-383.
Sanchez, I.C. and Lacombe, R.H., 1976a. An elementary molecular theory of classical fluids. Pure fluids, J. Phys. Chem.,
80: 2352-2362.
Sanchez, I.C. and Lacombe, R.H., 1976b. Statistical thermodynamics of fluid mixtures, J. Phys. Chem., 80: 2568-2580.
Schmitt W.J. and Reid, R.C., 1986. Solubility of monofunctional organic solids in chemically diverse supercritical fluids, J.
Chem. Eng. Data, 31: 204-212.
Scholte, Th.G., 1970a. Determination of thermodynamic parameters of polymer-solvent systems from sedimentation-diffu-
sion equilibrium in the ultracentrifuge, J. Polym. Sci. Part A-2, 8: 841.
Scholte, Th.G., 1970b. Determination of thermodynamic parameters of polymer-solvent systems by light scattering,
European Polymer J., 6: 1063.
Shin, M.S., 1994. A new two-liquid lattice hole model for fluid phase equilibria of mixture with specific forces, Master
Thesis, Sogang University, Seoul, Korea.
Smirnova, N.A. and Victorov, A.I., 1987. Thermodynamic properties of pure fluids and solutions from the hole
group-contribution model, Fluid Phase Equilibria, 34: 235-263.
Soave, G., 1972. Equilibrium constants from a modified Redlich-Kwong equation of state. Chem. Eng. Sci., 27:
1197-1203.
Takishima, S., 1986. Phase equilibria for C O 2 - C z H s O H - H 2 0 system. J. Chem. Eng. Jpn., 19: 48-56.
Timmermans, J., 1950. Physico-chemical Constants of Pure Organic Compounds, Vol. 1 and Vol. 2, Elsevier.
Tsekhanskays, Y.V., Iomtev, M.B. and Mushkina, E.V., 1964. Solubility of naphthalene in ethylene and carbon dioxide
under pressure, Russian J. Phys. Chem., 38:1173
van Krevelen, D.W., 1990. Properties of polymers. Their correlation with chemical structure; their numerical estimation and
prediction from additive group contributions, Elsevier, Chapters 4-9.
Wagner, Z. and Wichterle, I., 1987. High-pressure vapor-liquid equilibrium in systems containing carbon dioxide, 1-hexene,
and n-hexane, Fluid Phase Equilibria, 33: 109-123.
Wilson, G.M., 1964. Vapor-liquid equilibrium. XI. A new expression for the excess free energy of mixing, J. Am. Chem.
Soc., 86: 127-130.
You, S.S., Yoo, K.P. and C.S. Lee, 1993. Modeling of supercritical fluid-phase equilibria using a new nonrandom
lattice-fluid theory. J. Supercritical Fluids, 6: 69-84.
You, S.S., Yoo, K.P. and C.S. Lee, 1994a. An approximate nonrandom lattice fluid theory of fluids. General derivation and
application to pure fluids, Fluid Phase Equilibria, 93: 193-213.
You, S.S., Yoo, K.P. and C.S. Lee, 1994b. An approximate nonrandom lattice fluid theory of fluids. Mixtures, Fluid Phase
Equilibria, 93: 215-232.
You, S.S., You, S.J., Yoo, K.P. and Lee, C.S., 1994c. A. multiphase behaviors and critical loci in binary mixtures using a
new equation of state based on nonrandom lattice fluid theory, J. Supercrit. Fluids, 7: 251-258.