Available online at www.sciencedirect.

com

Fluid Phase Equilibria 261 (2007) 327–336

Determination of valley and ridge of isobaric vapor–liquid equilibrium

for ternary system
Kiyofumi Kurihara ∗ , Hiroyuki Matsuda, Katsumi Tochigi, Kenji Ochi, Kazuo Kojima
Department of Materials and Applied Chemistry, Nihon University, 8-14 Kanda-Surugadai, 1-chome Chiyoda-ku, Tokyo 101-8308, Japan
Received 9 May 2007; received in revised form 9 July 2007; accepted 9 July 2007
Available online 19 July 2007

Abstract
The aim of this paper is to describe a method for the determination of the valley and ridge of isobaric vapor–liquid equilibrium (VLE) for ternary
systems which have a ternary azeotropic point at atmospheric and at lower pressure. The extended Redlich–Kister equation was employed as an
activity coefficient for calculating the isobaric VLE, because this equation can be applied to the isobaric conditions provided by the Gibbs–Duhem
equation, and to complete calculation of the ternary and binary azeotropes. It is possible by this method to determine the rigorous valley and ridge
curves thermodynamically. In order to test the reliability of the proposed method, it has been applied to determine the valley and ridge for the
system of acetone + chloroform + methanol, with a saddle point azeotrope at 101.3 kPa, and the details of the obtained curves are reported.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Extended Redlich–Kister equation; Ridge; Ternary; Valley; Vapor–liquid equilibrium data

1. Introduction

The ternary system of acetone + chloroform + methanol has a strong non-ideality of vapor–liquid equilibrium (VLE). This ternary
system exhibits ternary azeotropic points, and contains one binary maximum boiling azeotrope of acetone + chloroform and two
binary minimum boiling azeotropes of chloroform + methanol and acetone + methanol under isobaric conditions. There are three
types of ternary azeotropes: the first is a minimum boiling azeotrope, the second is a maximum boiling azeotrope, and the third is a
saddle point azeotrope. This azeotrope is a saddle point type, and the existence of the valley and ridge on its composition—bubble
point surface from the topological point of view is well-known [1–3]. According to Naka et al., the terms “valley” and “ridge” have
been defined as the curves which divide the pattern of vapor–liquid tie lines [2,3].
It is important to know the exact valley and ridge on the vapor–liquid composition diagram to separate such a mixture into desired
products by distillation, because the composition profiles of a distillation column are restricted. Naka et al. [2] have previously
proposed a method for obtaining these curves using the Wilson equation. Their method can be executed by an iterative calculation
of dew point or bubble point from the appropriate starting point, which is the neighborhood of the azeotrope or pure component.
However, they have two remaining problems. First, they have used the neighborhood of the azeotrope or pure component as the
starting point. Thus, it follows that their method is a close approximation. Second, Naka et al. have used their method to determine
the valley and ridge of acetone + chloroform + methanol [2]. This valley and ridge connects the two binary azeotropes through the
ternary azeotropic point (see below for further details). However, since the azeotropic point calculated using the Wilson equation
does not perfectly agree with those experimental data for both binary and ternary systems, the valley and ridge obtained using their
method are not able to intersect the experimental azeotropes.
This paper aims to resolve these problems with the valley and ridge, and proposes a rigorous method for their determination.
This method needs an activity coefficient equation to represent the isobaric VLE. That equation must satisfy the thermodynamic

∗ Corresponding author. Tel.: +81 3 3259 0822; fax: +81 3 3293 7572.
E-mail address: kurihara@chem.cst.nihon-u.ac.jp (K. Kurihara).

0378-3812/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2007.07.043
328 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336

Fig. 1. Vapor–liquid equilibrium tie-lines (tails of arrows represent liquid-phase mole fractions x1 , x2 and heads of arrows represent vapor-phase mole fractions y1 ,
y2 ) for acetone(1) + chloroform(2) + methanol(3) at 101.3 kPa. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of the article.)

isobaric conditions given by the generalized Gibbs–Duhem equation, and can completely reproduce the ternary and three binary
azeotropes. Therefore, the extended Redlich–Kister (ERK) equation [4,5] was employed as an activity coefficient equation in this
paper. The ERK equation fulfills all these conditions. The proposed method has been tested for obtaining the valley and ridge of
acetone + chloroform + methanol with a saddle point azeotrope at atmospheric pressure.

2. Vapor–liquid equilibria of ternary systems with the valley and ridge

Fig. 1 shows the VLE data and the ternary and three binary azeotropic points for the ternary system of ace-
tone + chloroform + methanol [6] at 101.3 kPa. The experimental vapor–liquid tie lines indicated by the black arrows in Fig. 1
show the relationships between vapor commotion (the head of the arrows) and liquid composition (the tail of the arrows) in the VLE.
The composition profile of the total reflux distillation column which was calculated using the ERK equation (explained in detail
later) is shown in Fig. 2.
Since the valley and ridge can be defined by the curves which divide the patterns of vapor–liquid tie lines, those of this system
appear from the behavior of the tie lines in Figs. 1 and 2 as follows:

(1) Valley connects the two binary minimum boiling azeotropes of acetone + methanol (328.39 K) and chloroform + methanol
(326.48 K) through the ternary azeotropic point (330.82 K).
(2) Ridge connects the binary maximum boiling azeotrope of acetone + chloroform (337.62 K), the ternary azeotropic point
(330.82 K), and pure methanol (337.70 K).

Fig. 2. Distillation lines at total reflux (tails of arrows represent liquid-phase mole fractions x1 , x2 and heads of arrows represent vapor-phase mole fractions y1 , y2 )
for acetone(1) + chloroform(2) + methanol(3) at 101.3 kPa. (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of the article.)
 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336 329

3. Correlation of VLE data

The isobaric VLE data of the ternary and its three constituent binary systems [6] have been correlated by the ERK equation
[4,5]. The number of the fitting parameters (NP) in the ERK equation can be changed according to the behavior of the experimental
activity coefficient that the target system possesses. One of the notable features of the ERK equation is this variable NP. In addition,
this equation fulfills the following three conditions which the proposed method in this paper desires:

(1) Isobaric condition given by the generalized Gibbs–Duhem equation is shown in Eq. (1):
n    E  
∂ ln γi H dT
xi =− (1)
∂x1 RT 2 dx1 P
i P

(2) Complete reproduction of the experimental ternary and binary azeotropic point.
(3) Good correlation of the VLE data of the ternary and its constituent binary systems.

3.1. ERK equation for binary system

In the ERK equation for a binary system, a binary excess Gibbs energy GE12 and a ratio ln(γ 1 /γ 2 ) of activity coefficients are given
by Eqs. (2) and (3):

GE12
= x1 x2 [B12 + C12 X12 + D12 X12
2
+ E12 X12
3
+ F12 X12
4
+ G12 X12
5
+ H12 X12
6
+ I12 X12
7
+ · · ·] (2)
RT
 
γ1
ln = a12 + b12 X21 + c12 (6x1 x2 − 1) + d12 X21 (1 − 8x1 x2 ) + e12 X21
2
(10x1 x2 − 1) + f12 X21
3
(1 − 12x1 x2 )
γ2
+g12 X21
4
(14x1 x2 − 1) + h12 X21
5
(1 − 16x1 x2 ) + · · · (3)

X12 = x1 − x2 (4)

where B12 , C12 ,. . ., I12 ,. . . and a12 , b12 ,. . ., h12 ,. . . are the binary parameters of the ERK equation. Activity coefficients can be then
calculated for components 1 and 2 using Eqs. (5) and (6) thermodynamically:
 
GE γ1
ln γ1 = 12 + x2 ln (5)
RT γ2
 
GE γ1
ln γ2 = 12 − x1 ln (6)
RT γ2

Between GE12 and ln(γ 1 /γ 2 ), thermodynamic conditions at the infinite dilution shown by Eqs. (7) and (8) must be satisfied:
 E   
G12 /RT γ1
= ln = ln(γ1 )x1 =0 = ln γ1∞ (7)
x1 x2 x1 =0 γ2 x1 =0
 E   
G12 /RT γ1
= −ln = ln(γ2 )x2 =0 = ln γ2∞ (8)
x1 x2 x2 =0 γ2 x2 =0

where γ1∞ and γ2∞ are the activity coefficients of component 1 and 2 at the infinite dilution. The following relationships among the
binary parameters and γi∞ are applied to Eqs. (2) and (3):
 E 
∞ G12 /RT
ln γ1 = = B12 − C12 + D12 − E12 + F12 − G12 + H12 − I12 + · · · (9)
x1 x2 x1 =0
 E 
∞ G12 /RT
ln γ2 = = B12 + C12 + D12 + E12 + F12 + G12 + H12 + I12 + · · · (10)
x1 x2 x2 =0
 
γ1
ln γ1∞ = ln = a12 + b12 − c12 + d12 − e12 + f12 − g12 + h12 − · · · (11)
γ2 x1 =0
330 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336
 
γ1
ln γ2∞ = −ln = −a12 + b12 + c12 + d12 + e12 + f12 + g12 + h12 + · · · (12)
γ2 x2 =0

Rearranging Eqs. (9) and (10), the expressions of parameters B12 and C12 are represented by Eqs. (13) and (14), respectively:
ln γ1∞ + ln γ2∞
B12 = − D12 − F12 − H12 − · · · (13)
2
ln γ2∞ − ln γ1∞
C12 = − E12 − G12 − I12 − · · · (14)
2
Substituting Eqs. (13) and (14) into Eq. (2) and rearranging Eq. (2), Eq. (15) is derived as the ERK equation which can satisfied Eqs.
(7) and (8):

GE12 ln(γ1∞ γ2∞ ) + X12 ln(γ2∞ /γ1∞ )
= x1 x2 + D12 (X12
2
− 1) + E12 X12 (X12 2
− 1) + F12 (X12
4
− 1)
RT 2

+G12 X12 (X12 − 1) + H12 (X12 − 1) + I12 X12 (X12 − 1)
4 6 6
(15)

It should be noted that the values of ln(γ1∞ γ2∞ ) and ln(γ2∞ /γ1∞ ) are calculated by Eqs. (11) and (12) from the parameters a12 , b12 ,
c12 , d12 , e12 , f12 , g12 , h12 determined on the basis of the experimental ln(γ 1 /γ 2 ) beforehand.
In case of a correlation of the binary VLE data for an azeotropic mixture, the following equation must be used because the ERK
equation perfects the reproduction of the experimental azeotrope (the detail of these derivations is described in Appendix A reported
in the Supporting Information):

GE12 ln(γ1∞ γ2∞ ) + X12 ln(γ2∞ /γ1∞ )
= x1 x2 + (X12
2
− 1)[J12Azeo + E12 (X12 − X12Azeo ) + F12 (X12
2
− X12Azeo
2
)
RT 2
+ G12 {X12 (X12
2
+ 1) − X12Azeo (X12Azeo
2
+ 1)} + H12 (X12
4
+ X12
2
− X12Azeo
4
− X12Azeo
2
) + I12 {X12 (X12
4
+ X12
2
+ 1)

− X12Azeo (X12Azeo
4
+ X12Azeo
2
+ 1)}] (16)

   
γ1 γ1
ln = ln + b(X12Azeo − X12 ) + c12 (6x1 x2 − 6x1Azeo x2Azeo ) + d12 [X12 (8x1 x2 − 1)
γ2 γ2 Azeo

−X12Azeo (8x1Azeo x2Azeo − 1)] + e12 [X12

2
(10x1 x2 − 1) − X12Azeo
2
(10x1Azeo x2Azeo − 1)]
+f12 [X12
3
(12x1 x2 − 1) − X12Azeo
3
(12x1Azeo x2Azeo − 1)] + g12 [X12
4
(14x1 x2 − 1) − X12Azeo
4
(14x1Azeo x2Azeo − 1)]
+h12 [X12
5
(16x1 x2 − 1) − X12Azeo
5
(16x1Azeo x2Azeo − 1)] (17)
where the subscript Azeo indicates azeotropic condition.
Furthermore, the parameter E12 in Eq. (16) must be expressed by Eq. (18) so that the ERK equation satisfies one of the binary
azeotropic condition ((∂T/∂x1 )P,Azeo = 0). Eq. (18) is derived based on the generalized Gibbs–Duhem equation (see Appendix B in
the Supporting Information):
ln(γ1 /γ2 )Azeo + X12Azeo Δ12Azeo (1/2)ln(γ2∞ /γ1∞ ) + 2X12Azeo
2 J12Azeo
E12 = − − F12 (2X12Azeo )
2x1Azeo x2Azeo (X12Azeo − 1)
2 (X12Azeo − 1)
2

−G12 (3X12Azeo
2
+ 1) − H12 (4X12Azeo
3
+ 2X12Azeo ) − I12 (5X12Azeo
4
+ 3X12Azeo
2
+ 1) (18)
Consequently, the binary parameters (F12 , G12 , H12 , I12 ,. . . and b12 , c12 ,. . ., h12 ,. . .) of the ERK equation expressed by Eqs. (16)–(18)
have been estimated from both of the binary isobaric VLE data and its azeotropic data.

3.2. ERK equation for ternary system

For the ternary system, an ERK equation is given by Eqs. (19)–(46):

GE GE GE GE
= 12 + 23 + 31 + x1 x2 x3 [B + C1 X23 + C2 X31 + C3 X12 + D1 x2 X23 + D2 x3 X23 + D3 x3 X31
RT RT RT RT
+ D4 x1 X31 + D5 x1 X12 + D6 x2 X12 + · · ·] (19)
 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336 331

Xij = xi − xj (20)
       
γ1 γ1 γ1 γ1
ln = ln + ln + ln + x3 X21 b + Xγ12c1 c1 + Xγ12c2 c2 + Xγ12c3 c3 + Xγ12d1 d1
γ2 γ2 12 γ2 23 γ2 31
+Xγ12d2 d2 + Xγ12d3 d3 + Xγ12d4 d4 + Xγ12d5 d5 + Xγ12d6 d6 + · · · (21)
 
γ1
ln = a12 (1−x3 ) + X21 b12 + [6x1 x2 −(x1 + x2 )2 ]c12 + X21 [(x1 + x2 )2 − 8x1 x2 ]d12
γ2 12
+X21
2
[10x1 x2 − (x1 +x2 )2 ]e12 + X21
3
[(x1 + x2 )2 − 12x1 x2 ]f12 + X21
4
[14x1 x2 − (x1 + x2 )2 ]g12
+X21
5
[(x1 + x2 )2 − 16x1 x2 ]h12 (22)
 
γ1
ln = x3 [−a23 − b23 − (2x2 − x3 )c23 − X23 (3x2 − x3 )d23 − X23
2
(4x2 − x3 )e23 − X23
3
(5x2 − x3 )f23
γ2 23
−X234
(6x2 − x3 )g23 − X23
5
(7x2 − x3 )h23 ] (23)
 
γ1
ln = x3 [a31 + b31 + (x3 − 2x1 )c31 + X31 (x3 − 3x1 )d31 + X31
2
(x3 − 4x1 )e31 + X31
3
(x3 − 5x1 )f31
γ2 31

+ X31
4
(x3 − 6x1 )g31 + X31
5
(x3 − 7x1 )h31 ] (24)

Xγ12c1 = X21 X23 − x1 x2 (25)

Xγ12c2 = x3 (X21 X31 − x1 x2 ) (26)
Xγ12c3 = x3 (X21 X12 + 2x1 x2 ) (27)
Xγ12d1 = x3 [X21 x2 X23 + x1 x2 (−2x2 + x3 )] (28)
Xγ12d2 = x3 (X21 x3 X23 − x1 x2 x3 ) (29)
Xγ12d3 = x3 (X21 x3 X31 − x1 x2 x3 ) (30)
Xγ12d4 = x3 [X21 x1 X31 + x1 x2 (x3 − 2x1 )] (31)

Xγ12d5 = x3 [−x1 X12

2
+ x1 x2 (3x1 − x2 )] (32)

Xγ12d6 = x3 [−x2 X12

2
+ x1 x2 (−x1 + 3x2 )] (33)
       
γ3 γ3 γ3 γ3
ln = ln + ln + ln + x2 X13 b + Xγ31c1 c1 + Xγ31c2 c2 + Xγ31c3 c3 + Xγ31d1 d1 + Xγ31d2 d2
γ1 γ1 12 γ1 23 γ1 31
+ Xγ31d3 d3 + Xγ31d4 d4 + Xγ31d5 d5 + Xγ31d6 d6 (34)
 
γ3
ln = x2 [−a12 − b12 − (2x1 − x2 )c12 − X12 (3x1 − x2 )d12 − X12
2
(4x1 − x2 )e12 − X12
3
(5x1 − x2 )f12
γ1 12
−X12
4
(6x1 − x2 )g12 − X12
5
(7x1 − x2 )h12 ] (35)
 
γ3
ln = x2 [−a23 + b23 + (x2 − 2x3 )c23 + X23 (x2 − 3x3 )d23 + X23
2
(x2 − 4x3 )e23 + X23
3
(x2 − 5x3 )f23
γ1 23
+ X23
4
(x2 − 6x3 )g23 + X23
5
(x2 − 7x3 )h23 ] (36)
 
γ3
ln = a31 (1 − x2 ) + X13 b31 + [6x3 x1 − (x3 + x1 )2 ]c31 + X13 [(x3 + x1 )2 −8x3 x1 ]d31
γ1 31

+X13
2
[10x3 x1 −(x3 + x1 )2 ]e31 + X13
3
[(x3 + x1 )2 − 12x3 x1 ]f31 + X13
4
[14x3 x1 − (x3 + x1 )2 ]g31
+X13
5
[(x3 + x1 )2 − 16x3 x1 ]h31 (37)

Xγ31c1 = x2 (X13 X23 − x1 x3 ) (38)

332 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336

Xγ31c2 = x2 (X13 X31 + 2x1 x3 ) (39)

Xγ31c3 = x2 [(x1 − x3 )(x1 − x2 ) − x1 x3 ] (40)
Xγ31d1 = x2 (X13 x2 X23 − x1 x2 x3 ) (41)
Xγ31d2 = x2 [X13 x3 X23 + x1 x3 (x2 − 2x3 )] (42)

Xγ31d3 = x2 [−x3 X31

2
+ x1 x3 (3x2 − x1 )] (43)

Xγ31d4 = x2 [−x1 X31

2
+ x1 x3 (3x1 − x3 )] (44)
Xγ31d5 = x2 [X13 x1 X12 + x1 x3 (−2x1 + x2 )] (45)
Xγ31d6 = x2 (X13 x2 X12 − x1 x2 x3 ) (46)
where B, C1 ,. . ., D6 and b, c1 ,. . ., d6 are ternary parameters for the ERK equation. Activity coefficients for components 1–3 are
thermodynamically expressed by Eqs. (47)–(49):
   
GE γ1 γ3
ln γ1 = + x2 ln − x3 ln (47)
RT γ2 γ1
 
γ1
ln γ2 = ln γ1 − ln (48)
γ2
 
γ3
ln γ3 = ln γ1 + ln (49)
γ1
If the ERK equation is employed to correlate the isobaric VLE data for the ternary system which has a ternary azeotropic point,
the ternary azeotrope can be completely calculated by means of using the relationships among the ternary parameters shown in
Appendix C depicted in the Supporting Information.

3.3. Correlated results of the binary and ternary VLE data

The experimental excess Gibbs energy GE /RT and ratio of the activity coefficients ln(γ i /γ j ) were calculated using the following
rigorous equation:
 
v L (P − P S )
ϕi Pyi = xi γi PiS ϕiS exp i i
(50)
RT

where ϕi and ϕiS are the fugacity coefficients of component i in the mixture and the pure vapor, respectively, which were calculated
using the second virial coefficients obtained by the Tsonopoulos method [7–10]. The liquid molar volumes vLi were calculated by
the modified Rackett equation [11]. The vapor pressures of the pure components PiS were calculated from the Antoine equation
constants from our earlier paper [7,12]. The parameters for the Tsonopoulos method and Antoine equation are referred to in our
earlier paper [7,12].
Table 1 lists the estimated binary and ternary parameters of the ERK equation, based on the experimental GE /RT and ln(γ i /γ j )
for the binary and ternary systems. The deviations between experimental and calculated vapor-phase compositions and bubble
temperatures of the three binary systems and the ternary system acetone + chloroform + methanol are shown in Table 2 and by the
red arrows in Fig. 1. The ERK equation gave satisfactory results for all the binary and ternary systems. Table 2 contains the deviations
at the experimental binary and ternary azeotropic points. These experimental azeotropic data were completely reproduced using the
ERK equation.
We also attempted to correlate the binary VLE data by the Wilson equation [13] and to predict the ternary VLE using the binary
Wilson parameters. The determined binary parameters are listed in Table 3 and the deviations are given in Table 2. The results for the
ERK equation were better than those for the Wilson equation for all the systems. The calculated values at the azeotropic point using
the Wilson parameters did not agree with those experimental data for both the binary and ternary systems. The Wilson equation gave
the maximum deviation of a vapor-phase composition of 0.027 mol fraction and a bubble temperature of 0.83 K.

4. Principle for determination of valley and ridge

The length of the vapor–liquid tie line on the composition triangular diagram in Fig. 1 is zero at the azeotropic point, but its slope
(∂x2 /∂x1 )P,Azeo has a finite value. By means of utilizing this slope at the ternary azeotrope, it is possible to determine the valley and
ridge by the following procedure:
 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336
Table 1
Parameters of the extended Redlich–Kister equation for the three binary systems and acetone + chloroform + methanol system
System Bij ; aij Cij ; bij Dij ; cij Eij ; dij Fij ; eij Gij ; fij Hij ; gij Iij ; hij
Acetone(1) + chlorofom(2) −0.709974; 0.039460 0.061453; −0.789737 0.110031; 0.060472 0.281917; 0.048749 −0.287108; −0.046596 −0.909384; 0.0 0.146062; 0.0 0.540432; 0.0
Chlorofom(2) + methanol(3) 1.313399; −0.006512 0.470528; 1.322959 0.181056; 0.465296 −0.295027; 0.065866 0.023243; 0.062669 0.437707; 0.128874 0.0; 0.078731 0.0; 0.0
Methanol(3) + acetone(1) 0.641041; 0.011585 0.055932; 0.643127 0.066976; −0.004651 −0.550121; −0.004461 −0.167114; 0.028145 1.448936; −0.051005 0.133450; −0.046590 −0.989427; 0.086691

System B; b C1 ; c1 C2 ; c2 D2 ; d2 D4 ; d4
Acetone(1) + chlorofom(2) + methanol(3) −0.810183; −0.574224 0.028344; 0.152886 −1.800606; −0.999503 −0.711886; −0.854029 3.389361; 0.710746

333
334 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336

Table 2
Deviations between experimental and calculated vapor-phase mole fractions yi and bubble temperatures T using the extended Redlich–Kister and Wilson
equationsa
Acetone(1) + chloroform(2) Chloroform(1) + methanol(2) Acetone(1) + methanol(2) Acetone(1) + chloroform(2) + methanol(3)

100y1 T (K) 100y1 T (K) 100y1 T (K) 100y1 100y2 T (K)

ERK equation
Average 0.1 0.03 0.2 0.05 0.05 0.02 0.2 0.5 0.17
Maximum 0.3 0.08 0.7 0.21 0.2 0.06 1.0 1.7 0.75
Azeotrope 0.0 0.00 0.0 0.00 0.0 0.00 0.0 0.0 0.00
Wilson equation
Average 0.8 0.23 0.7 0.13 0.2 0.04 0.8 0.6 0.59
Maximum 1.7 0.66 1.3 0.24 0.4 0.09 1.6 2.7 0.83
Azeotrope 1.6 0.09 0.5 0.08 1.3 0.02 1.0 1.0 0.50
N |yi,exp tl −yi,calc t |j N |T exp tl −Tcalc t |j
a yi = j N , T = j N , N = number of data points.

Table 3
Parameters of the Wilson equation for the three binary systems
Parameter Acetone(1) + chloroform(2) Chloroform(1) + methanol(2) Acetone(1) + methanol(2)

λ12 − λ11 (J mol−1 ) −550.63 −1492.36 −800.60

λ21 − λ22 (J mol−1 ) −1337.61 7509.93 2726.99

1. Assume a straight line which passes the ternary azeotrope (xi,Azeo ) and has a slope (∂x2 /∂x1 )P,Azeo .
2. Calculate the slope (∂x2 /∂x1 )P,Azeo at the ternary azeotrope (see following).
3. Calculate the point very close to (x1,Azeo , x2,Azeo , x3,Azeo ) using Eqs. (51)–(53):

x1,Start = x1,Azeo ± x1 (51)

 
∂x2
x2,Start = x2,Azeo + (±x1 ) (52)
∂x1 Azeo

x3,Start = 1 − x1,Start − x2,Start (53)

where x1 is a very small mole fraction (we allowed x1 to equal 10−5 mol fraction in this paper). This point is virtually placed
on a locus of a vapor–liquid tie line which intersects the ternary azeotropic point. This locus is just on the valley or ridge. Let this
point be a starting point, and execute an iterative calculation of the bubble point or dew point from the starting point. The valley is
given using the bubble point calculation, and the ridge is given using the dew point calculation.

5. Calculation of the slope of a vapor–liquid tie line of a ternary azeotrope

The slope (∂x2 /∂x1 )P,Azeo of an isobaric vapor–liquid tie line on a composition triangular diagram in Fig. 1 was obtained by Eq.
(54) at the ternary azeotropic point (see Appendix E presented in the Supporting Information):
 
∂x2 (∂y2 /∂x1 )P,Azeo
= (54)
∂x1 P,Azeo (∂y1 /∂x1 )P,Azeo

The terms (∂y2 /∂x1 ) and (∂y1 /∂x1 ) are provided by means of differentiating the ternary VLE expression shown by Eq. (50), by liquid
composition x1 for a binary system at constant P (see Appendix F reported in the Supporting Information). After applying the
following azeotropic condition to (∂y2 /∂x1 ) and (∂y1 /∂x1 ):
xi
Ki = =1 (55)
yi
 
∂T
=0 (56)
∂x1 P,Azeo
 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336 335

to rearrange Eq. (54) by substituting the derived equations of (∂y2 /∂x1 ) and (∂y1 /∂x1 ) into Eq. (54), the quadratic equation is derived
as follows:
     
E2 F3 G1 ∂x2 2 E 1 F3 G 2 E 2 G1 H3 ∂x2 E 1 G2 H3
− E 2 F1 + E 1 F2 − E 2 H 1 − + + E 1 H2 − =0
G3 ∂x1 Azeo G3 G3 ∂x1 Azeo G3
(57)

Since the ERK equation has been adopted as the expression of an activity coefficient in Eq. (50), eight variables Ek , Fk , Gk , and Hk
in Eq. (57) are calculated by the equations given in Appendix G provided in the Supporting Information.
Therefore, the slope (∂x2 /∂x1 )P,Azeo of the vapor–liquid tie line at the ternary azeotropic point is estimated as two roots of the
second order Eq. (57). It must be noted that the ternary parameters of the ERK equation must be applicable to the azeotropic condition
expressed by Eqs. (55) and (56). The slope (∂x2 /∂x1 )P,Azeo of the ternary system was obtained on the basis of the parameters given
in Table 1 in this paper.

6. Determination of valley and ridge

The valley and ridge of the ternary system acetone + chloroform + methanol which were determined by the method proposed in
this paper are shown with blue and green lines in Figs. 1 and 2. The following values of (∂x2 /∂x1 )P,Azeo were calculated using Eq.
(57), with the parameters of the ERK shown in Table 1:
   
∂x2 ∂x2
= −0.851298 for valley, = 1.012840 for ridge
∂x1 P,Azeo ∂x1 P,Azeo
As these figures indicate, the valley and ridge calculated using our proposed method completely intersect the experimental ternary
and binary azeotropic data, and the vapor–liquid composition surface was divided into four regions by the ridge and valley. All the
vapor–liquid tie lines shown in Figs. 1 and 2 cannot be drawn across the valley and ridge in each region that they divide. We can say
that the definition of the valley and ridge employed in this paper is correct thermodynamically.
As mentioned above, the valley and ridge of the ternary system can be determined approximately by the procedure proposed by
Naka et al., combined with the Wilson equation instead of the ERK equation. Their method is simpler than our proposed method.
However, their results do not intersect all the experimental ternary and binary azeotropic points, because the azeotropic points
calculated using the Wilson equation are not in perfect agreement with those experimental data for both the binary and ternary
systems. Consequently, their valley and ridge are affected by the deviations at the experimental azeotropic point.

7. Conclusions

A method for determining the valley and ridge in the isobaric VLE is proposed for a ternary system of ace-
tone + chloroform + methanol which exhibits a saddle point azeotrope at 101.3 kPa. This method is able to determine the valley
and ridge curves strictly using the ERK equation for fitting the isobaric VLE data. The valley and ridge must connect the two binary
azeotropes through the ternary azeotropic point. However, it is impossible by the methods previously proposed to obtain the valley
and ridge which pass the experimental ternary and binary azeotropes. Our proposed method solves this problem and can calculate
the valley and ridge which completely intersect the experimental ternary and binary azeotropic points.

List of symbols
aij , bij , cij , dij , eij , fij , gij , hij ternary parameters of the ERK equation in Eq. (3)
Aij , Bij , Cij , Dij , Eij , Fij , Gij , Hij , Iij binary parameters of the ERK equation in Eq. (2)
Ai,ANT , Bi,ANT , Ci,ANT parameters of the Antoine equation of component i
b, ck , dm (k = 1–3, m = 1–6) ternary parameters of the ERK equation in Eqs. (21) and (34)
B, Ck , Dm (k = 1–3, m = 1–6) ternary parameters of the ERK equation in Eq. (7)
Bi,ANT parameters of the Antoine equation of component i (K)
Bij,vir second virial cross-coefficient between i and j (m3 mol−1 )
Bvir , Bii,vir second virial coefficient of mixture and component i (m3 mol−1 )
Ci,ANT parameters of the Antoine equation of component i (K)
En , Fn , Gn , Hn , In (n = 1–3) function to calculate (∂x2 /∂x1 )P,Azeo using Eq. (57)
GE molar excess Gibbs energy (J mol−1 )
P pressure (Pa)
PS saturated vapor pressure of pure component (Pa)
R gas constant (=8.314) (J K−1 mol−1 )
T absolute temperature (K)
336 K. Kurihara et al. / Fluid Phase Equilibria 261 (2007) 327–336

v molar volume (m3 mol−1 )

x mole fraction in liquid phase
y mole fraction in vapor phase
Z compressibility factor
ZRA parameter of the modified Racket equation

Greek letters
γi activity coefficient of component i
ϕi fugacity coefficient of component i in vapor mixture
ϕiS fugacity coefficients of component i in pure vapor at saturated T
ω acentric factor

Subscripts
Azeo azeotropic point
C critical
r reduced value
Start starting composition for determining valley or ridge
Tso parameter for the Tsonopoulos method
1, 2, 3, i, j components 1, 2, 3, and i, j

Superscripts
E excess property
L liquid phase
S saturated state
V vapor phase

Appendix. Supplementary data

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.fluid.2007.07.043.

References

[1] R.H. Perry, D.W. Green, Perry’s Chemical Engineer’s Handbook, 7th ed., McGraw-Hill, 1997.
[2] Y. Naka, K. Kobayashi, T. Takamatsu, Kagaku Kogaku Ronbunshu 1 (1975) 186–190.
[3] Y. Naka, K. Kobayashi, H. Ochi, T. Takamatsu, J. Chem. Eng. Jpn. 1 (1983) 39–42.
[4] K.C. Chao, Ind. Eng. Chem. 51 (1959) 93–94.
[5] K. Ochi, B.C.-Y. Lu, Fluid Phase Equilib. 1 (1978) 185–200.
[6] T. Hiaki, K. Kurihara, K. Kojima, J. Chem. Eng. Data 39 (1994) 714–719.
[7] K. Kurihara, H. Hori, K. Kojima, J. Chem. Eng. Data 43 (1998) 264–268.
[8] C. Tsonopoulos, AIChE J. 20 (1974) 263–272.
[9] C. Tsonopoulos, AIChE J. 21 (1975) 827–829.
[10] C. Tsonopoulos, H. Dymond, M. Szafranski, Pure Appl. Chem. 61 (1989) 1387–1403.
[11] C.F. Spencer, S.B. Adler, J. Chem. Eng. Data 23 (1978) 82–89.
[12] K. Kurihara, Y. Takimoto, K. Ochi, K. Kojima, J. Chem. Eng. Data 45 (2000) 792–795.
[13] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127–130.