Fluid Phase Equilibria 208 (2003) 199–221
Critical curves of liquid–liquid equilibria in ternary systems Description by a regularsolution model
ˇ
Josef P. Novák, Karel Rehák ^{∗} , Petr Vonka,ˇ
Jaroslav Matouš
Department of Physical Chemistry, Prague Institute of Chemical Technology, Technická 5, CZ166 28 Prague 6, Czech Republic
Received 21 June 2002; received in revised form 4 February 2003; accepted 4 February 2003
Abstract
In this paper relations between the shapes of the liquid–liquid critical curves in ternary systems and the temperature characters of the heterogeneous regions are discussed. The regularsolution model with temperaturedependent parameters was employed to describe critical curves of liquid–liquid equilibria in ternary systems. Relations for the limiting values of the slopes of critical curves were derived. The corresponding type of the critical curve and consequently the temperature character of the liquid–liquid equilibrium can be deduced from these values. Model calculations were performed for ternary systems characterised by two binary subsystems with either an upper critical solution temperature or with a lower critical solution temperature, and the third binary subsystem which is homogeneous in the considered temperature range. In the calculations the following approach was used: the behaviour of two binary systems was ﬁxed by the temperature dependencies of their parameters and ternary critical curves of LLE were then calculated for variants differing in nonideality (deviations from the Raoult’s law) of the third homogeneous binary subsystem. It was found that the level of nonideality of the homogeneous system can inﬂuence the shape of the critical curve signiﬁcantly. © 2003 Elsevier Science B.V. All rights reserved.
Keywords: Liquid–liquid equilibria; Critical state; Mixtures; Ternary system
1. Introduction
Two essential problems are encountered on studying liquid–liquid phase equilibria in ternary systems. First, the experimental study of liquid–liquid equilibria in a wider temperature range is seldom carried out, because such measurements are usually very demanding. This fact is corroborated in the compilations [1,2] in which more than 80% of experimental data on LLE in ternary systems are given for the temperature range from 0 to 35 ^{◦} C.
^{∗} Corresponding author.
ˇ
Email address: karel.rehak@vscht.cz (K. Rehak).´
03783812/03/$ – see front matter © 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S03783812(03)000372
200
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et al. / Fluid Phase Equilibria 208 (2003) 199–221
Second, thermodynamic descriptions or predictions of the liquid–liquid equilibrium often fail both qualitatively and quantitatively. This happens due to the fact that a very precise description of component activities is required [3,4]. The aim of the present paper is the study of liquid–liquid equilibrium in ternary systems using critical curves. The critical curve is understood as a set of liquid–liquid equilibrium critical points [5]. Our dis cussion is restrained to ternary systems with one homogenous and two heterogeneous binary subsystems, the heterogeneous subsystems being characterised by an upper or a lower critical solution temperature (i.e. UCST or LCST) and by a critical composition. It is also restrained to low pressures and consequently the inﬂuence of pressure on critical point compositions is omitted. In addition, it is assumed that the bi nary systems create a ternary system with the twophase regions only. An appearance of the threephase regions (see [6,7] for examples) is not discussed in this work. To describe the thermodynamic behaviour of heterogeneous systems the regularsolution model, i.e. the simplest model for the excess Gibbs energy, is used in this study. Recently, the similar approach for binary systems was applied by Rebelo [8]. In the theory of phase equilibria the equations of state are often used as well [9–11]. Their application for description of the LLE in comparison to the VLE is more complicated and number of possible ternary diagrams classes becomes enormous [11]. The different basic types of LLE are schematically outlined in Figs. 1–4. Their parts (a) show the liquid–liquid equilibria in the systems [1 + 2] and [2 + 3]; parts (b) demonstrate isotherms in ternary LLE diagrams; and parts (c) sketch shapes of the corresponding critical curves. The shaded areas represent twophase regions in these ﬁgures. Examples of ternary systems which qualitatively follow the described behaviour are summarised in Table 1. Fig. 1 shows the case that the critical curve connecting binary critical points is monotonous. At a temperature lower than the critical temperatures of both binary subsystems, the heterogeneous region is bandshaped with no critical point. With increasing temperature, the heterogeneous region ﬁrst detaches from the axis that represents the binary subsystem characterised by lower critical temperature (the [2 + 3]
Fig. 1. The liquid–liquid equilibrium in a ternary system: (a) LLE in binary subsystems [1 + 2] and [2 + 3]; (b) LLE in a ternary system at selected temperatures; (c) the composition dependence of the critical LLE temperature in a ternary system. The curve is monotonous.
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201
Fig. 2. The liquid–liquid equilibrium in a ternary system: (a) LLE in binary subsystems [1 + 2] and [2 + 3]; (b) LLE in a ternary system at selected temperatures; (c) the composition dependence of the critical LLE temperature in a ternary system. The curve shows a minimum.
system in Fig. 1). Further temperature increase makes the heterogeneous region, which now has one critical point, shrink. Fig. 2 illustrates the LLE behaviour related to a ternary critical curve with a temperature minimum. The heterogeneous region is bandlike with no critical point at a temperature below T _{m}_{i}_{n} . The twophase region narrows with increasing temperature and splits into two separate regions at T _{m}_{i}_{n} . This behaviour is also called the cosolvency effect [25].
Fig. 3. The liquid–liquid equilibrium in a ternary system: (a) LLE in binary subsystem [2 +3] (the system [1+2] is homogeneous with high positive deviations from ideality); (b) LLE in a ternary system at selected temperatures; (c) the composition dependence of the critical LLE temperature in a ternary system. The curve shows a maximum.
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Fig. 4. The liquid–liquid equilibrium in a ternary system: (a) LLE in binary subsystems (the subsystem [1 + 2] with an UCST and the subsystem [2 + 3] with a LCST); (b) LLE in a ternary system at selected temperatures; (c) the composition dependence of the critical LLE temperature in a ternary system. The curve shows two branches.
A ternary critical curve showing a temperature maximum (T _{m}_{a}_{x} ) is presented in Fig. 3. A closed heterogeneous region with two critical points appears at temperatures above T _{U}_{C}_{,}_{2}_{3} . This region shrinks on further temperature increase and disappears at T _{m}_{a}_{x} . An example of a ternary system with one binary subsystem showing an upper and the other a lower critical temperature is shown in Fig. 4. In these cases, the ternary critical curve shows two branches. Figs. 1–4 demonstrate only few basic LLE critical curves shapes and their relations to LLE temper ature dependency in ternary systems. There are also many other combinations of the abovementioned behaviours. Several questions concerning the topic can be asked and their resolution can lead not only to a better ther modynamic description but also to a better prediction of the behaviour of heterogeneous ternary systems.
Table 1 Examples of systems with different temperature characters of the LLE
System 
Figure 
Reference 
Aniline (1) + water (2) + phenol (3) Benzylalcohol (1) + water (2) + 4hydroxy4methyl2pentanone (3) Cyclohexane (1) + methanol (2) + hexane (3) Nitromethane (1) + water (2) + 1butanol (3) 1Butanol (1) + water (2) + furfural (3) Nitromethane (1) + 1hexanol (2) + octanoic acid (3) Acetone (1) + water (2) + phenol (3) Acetic acid (1) + cyclohexene (2) + dimethylformamide (3) Au (1) + Ni (2) + Cu (3) Phenol (1) + water (2) + triethylamine (3) Phenol (1) + water (2) + tetrahydrofuran (3) 
1 
[12,13] 
1 
[14] 

2 
[15] 

2 
[16] 

2 
[17] 

2 
[18] 

3 
[19,20] 

3 
[21] 

3 
[22] 

4 
[23] 

4 
[24] 
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et al. / Fluid Phase Equilibria 208 (2003) 199–221
203
(a) 
Under which conditions is the ternary critical curve monotonous (see Fig. 1)? 
(b) 
What conditions must be fulﬁlled in case that the concentration dependence of the critical temperature shows an extreme (see Figs. 2 and 3)? 
(c) 
Are other shapes (e.g. showing both maximum and minimum) possible? 
(d) 
Does a critical curve lying between two upper critical solution temperatures differ from the one lying between two lower critical solution temperatures? 
(e) 
Is it possible that a ternary system characterised by two heterogeneous binary subsystems (one with an upper and the other with a lower critical solution temperature), where T _{L}_{C}_{,}_{2}_{3} > T _{U}_{C}_{,}_{1}_{2} would be (in contrast to the system phenol (1) + water (2) + tetrahydrofuran (3)) homogeneous within the temperature interval T ∈ (T _{U}_{C}_{,}_{1}_{2} , T _{L}_{C}_{,}_{2}_{3} )? 
From this point of view it is obvious that critical curves can serve as a valuable tool to the study of the liquid–liquid equilibria. In the present paper, the regularsolution model was used to resolve these questions.
2. Theoretical
The regularsolution model was chosen to describe the thermodynamic properties of studied systems primarily for its simplicity.
2.1. Describing binary systems
In the regularsolution model the excess molar Gibbs energy in a binary subsystem (i) + (j) is given by [3]
G ^{E}
_{R}_{T} = x _{i} x _{j} b _{i}_{j} (T )
(1)
where b _{i}_{j} (T) is a temperaturedependent parameter of the corresponding binary system. At the critical temperature b _{i}_{j} (T = T _{c}_{,}_{i}_{j} ) = 2. Considering a system characterised by an upper critical solution tem perature (UCST), b _{i}_{j} > 2 at temperatures below the critical one. The parameter b _{i}_{j} (T) can, at these
)
temperatures, be evaluated from the mutual solubility x using the formula [3,26]
i
(with regard to symmetry x _{1} = x
2
= 1 − x
1
_{b} ij _{=} ln[(1 − x )/x ] 1 − 2x
i
i
i
(2)
In this work, the following temperature dependence of the parameter b _{i}_{j} = b _{i}_{j} (T ) is considered
b _{i}_{j} = β _{i}_{j} +
^{α} ^{i}^{j}
T
(3)
where α _{i}_{j} and β _{i}_{j} are constants usually determined from a selected critical temperature of the binary system (i) + (j ) and a chosen solubility at another temperature. Variants of parameters α _{i}_{j} and β _{i}_{j} were obtained (see Table 2) and were used to carry out model calculations. The employed temperature dependence of the parameters determines the behaviour of the modelled system. Eq. (3) can be used both for systems characterised by an upper critical solution temperature
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Table 2 Variants (I–VI) of parameters α _{i}_{j} and β _{i}_{j} used to carry out model calculations
UCST 
LCST 

I 
II 
III 
IV 
V 
VI 

T _{c} (K) T (K) b _{i}_{j} (T) 
300 
350 
250 
290 
350 
300 
250 
300 
350 
350 
400 
350 

2.5 
2.5 
−0.40 
2.5858 2.5 
2.5 

β _{i}_{j} 
−0.5 
−1 
−6.4 
5.4 
6 
5.5 
α _{i}_{j} (K) x (T ) H ^{E} (x _{i} = 0.5) (J mol ^{−}^{1} )
i 
750 
1050 
2100 
−986 
−1400 
−1050 
0.1448 
0.1448 
0.1272 0.1448 
0.1448 

1558 
2182 
4364 
−2049 
−2910 
−2182 
Values of T _{c} , T and b _{i}_{j} were chosen, and β _{i}_{j} , α _{i}_{j} , x
i and H ^{E} were then calculated.
(α _{i}_{j} > 0) and for those characterised by a lower critical solution temperature (α _{i}_{j} < 0). Another con sequence of the relation is the fact that the temperature dependence of the mutual solubility of the components is monotonous. Binary systems presenting a closed region of limited miscibility can however not be modelled by Eq. (3). This equation must be extended to be able to describe those systems. Appendix A summarises some circumstances concerning these cases. The conception of the regularsolution model based on Eq. (3) differs from the theory of the strictly regular solution employed by Prigogine [27], Prigogine and Defay [28] or Meijering [29,30]. These authors did not consider the absolute term in Eq. (3), i.e. they considered β _{i}_{j} = 0. The advantage of their approach lies in the fact that only one parameter in necessary to describe a binary system. On the other hand, the description of systems characterised by a lower critical solution temperature is impossible using the strictly regularsolution model. A simple G ^{E} model used for generating all basic types of binary liquid–liquid equilibria and their pressure dependence was also developed by Rebelo [8].
3. Describing ternary systems
The regularsolution model expresses the molar excess Gibbs energy in ternary systems in the following way [3,28]:
G ^{E}
_{R}_{T} = x 1 x 2 b 12 + x 1 x 3 b 13 + x 2 x 3 b 23
(4)
Relations for activity coefﬁcients and the second to the fourth derivatives of the Gibbs energy with respect to x _{1} and x _{2} derived from this equation are summarised in [3]. It should be emphasised that in this work the Gibbs energy is considered as a function of temperature and composition only. The pressure dependence of G ^{E} is disregarded. The shape of the critical curve as a function of pressure at a constant temperature will therefore not be discussed, although it exhibits similar features under these conditions
[7,25,31,32].
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et al. / Fluid Phase Equilibria 208 (2003) 199–221
205
Eq. (4) can be also extended by a ternary term x _{1} x _{2} x _{3} C with a ternary parameter C. In this case the equation no longer describes a regular solution. For that reason the effect of this ternary parameter on the liquid–liquid equilibrium character will not be discussed in the paper. Possibilities to use Eq. (4) in describing liquid–liquid equilibria were partly discussed previously [3,28,33]. Nevertheless, cited works were restrained to ternary systems at constant temperatures described by parameters b _{1}_{2} = b _{2}_{3} = b and b _{1}_{3} . The temperature dependence of these parameters was not analysed in those papers.
4. Critical curve
The molar Gibbs energy is given by the relation
G m =
3
i=1
x i G
3
m,i ^{+} ^{R}^{T}
∗
i=1
x _{i} ln x _{i} + G ^{E}
(5)
where G _{m}_{,}_{i} is the molar Gibbs energy of the pure component in the liquid state at the temperature and pressure of the system, x _{i} the mole fraction of the ith component and G ^{E} is the excess molar Gibbs energy. Let us consider temperature and mole fractions x _{1} and x _{2} as independent variables. The critical point of a ternary system at a constant temperature is given by [3,34,35]
(6)
∗
D = G 11 G 22 − G ^{2} _{1}_{2} = 0
D ^{∗} =
∂D
∂x _{1}
G 22 −
∂D
2 G _{1}_{2} = 0
∂x
(7)
Derivatives of the determinant D are given by
∂D
∂x _{1}
= G 111 G 22 + G 11 G 122 − 2G 12 G 112 ,
∂D
∂x
2
= G 112 G 22 + G 11 G 222 − 2G 12 G 122
(8)
where G _{i}_{j} = ∂ ^{2} (G _{m} /RT)/∂x _{i} ∂x _{j} and G _{i}_{i}_{j}
of the dimensionless Gibbs energy with respect to mole fractions (Modell and Reid [35] use similar symbolisation, but in another context). The critical composition at a given temperature and pressure is determined by solving a set of two nonlinear Eqs. (6) and (7). The calculation is described elsewhere [3]. Quantities D and D ^{∗} are functions of T, x _{1} and x _{2} in ternary systems, and their differentials are expressed
as
i 2 ∂x _{j} are the second and the third derivatives
= ∂ ^{3} (G _{m} /RT)/∂x
dD =
∂D
∂x _{1}
dx _{1} +
∂D
∂x
2 dx _{2} + ^{∂}^{D} dT,
∂T
dD ^{∗} = ^{∂}^{D} ^{∗} dx _{1} + ^{∂}^{D} ^{∗}
∂x _{1}
∂x _{2}
dx _{2} + ^{∂}^{D} ^{∗} dT ∂T
(9)
Eqs. (6) and (7) are valid for the critical curve and it also holds for this curve that dD = dD ^{∗} = 0. The dependence of the critical temperature and of x _{2} on x _{1} is expressed by means of Eq. (9)
^{} ∂D
∂T
dT
1 ^{+}
dx
∂D 2 ^{} dx _{2}
∂x
dx
_{1}
= −
∂D ^{} _{,} ∂x _{1}
^{} ∂D ^{∗} ∂T
dT 1 _{+} ^{} ∂D ^{∗} ^{} dx _{2}
dx
∂x _{2}
dx
_{1}
=
− ^{∂}^{D} ^{∗} ∂x _{1}
(10)
206
i.e.
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dT (∂D ^{∗} /∂x _{1} )(∂D/∂x _{2} ) − (∂D ^{∗} /∂x _{2} )(∂D/∂x _{1} )
dx
dx
_{1}
_{2}
dx
_{1}
_{=}
_{=}
(∂D ^{∗} /∂x _{2} )(∂D/∂T ) − (∂D ^{∗} /∂T )(∂D/∂x _{2} ) ^{,}
(∂D ^{∗} /∂T )(∂D/∂x _{1} ) − (∂D ^{∗} /∂x _{1} )(∂D/∂T )
(∂D ^{∗} /∂x _{2} )(∂D/∂T ) − (∂D ^{∗} /∂T )(∂D/∂x _{2} _{)}
(11)
Detailed expressions for D and D ^{∗} , and their derivatives are given in Appendix B.
4.1. Limiting values of slopes (dT _{c} /dx _{i} )
The shape of the critical curve is affected by limiting values of slopes, lim _{x} _{1} _{→}_{0} (dT _{c} /dx _{1} ) and lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ), i.e. slopes in critical points in binary subsystems [2 + 3] and [1 + 2]. The value of the slope, lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ), is used to be interpreted as a quantity characterising the effect of the third component on the mutual solubility of the ﬁrst and the second component. Prigogine and Defay [28] state that when the solubility increases as a consequence of adding third component to the mixture this leads to a decrease in the critical temperature, while as the solubility decreases this leads to an increase of the critical temperature. So, the mutual solubility of hexane and methanol increases on adding a small amount of cyclohexane to the system. In a similar manner, a small amount of hexane increases the miscibility of the system cyclohexane + methanol (see the cosolvency effect [25]). Addition of acetone in the system water + phenol causes an increase of the critical temperature and the decrease of the mutual solubility of phenol and water. Prigogine [27], Prigogine and Defay [28] and before them Wagner [36] have studied this behaviour from a thermodynamic standpoint. In his work Prigogine [27] does not use the deﬁnition of the critical point based on Eqs. (6) and (7), but he employs equivalent functions (see [28])
(12)
Ξ _{1} = x _{1} µ _{1}_{2} µ _{1}_{3} +
x _{2} µ _{1}_{2} µ _{2}_{3} + x _{3} µ _{1}_{3} µ _{2}_{3} = 0
and
Ξ 2 = ^{∂} ∂n 2 ^{µ} ^{2} ^{2}
2
T ,p,µ _{1} ,n _{3}
= 0
(13)
where µ _{i}_{j} is the derivative of the chemical potential of the ith component with respect to the number of moles of the jth component
µ _{i}_{j} = µ _{j}_{i} = ^{∂}^{µ} ^{i} ∂n _{j}
T ,p,n _{k} _{}
=j
Using these equations, Prigogine has shown that
lim
x _{3} →0
dT _{c}
dx
_{3}
_{=} _{−} lim x _{3} →0 (∂Ξ 1 /∂x _{3} ) _{T} _{,}_{x} _{2}
lim _{x} _{3} _{→}_{0} (∂Ξ _{1} /∂T ) _{x} _{2} _{,}_{x} _{3}
(14)
(15)
Prigogine’s approach was applied to the case of the regularsolution model considered in this paper and given by Eqs. (3) and (4). The following relations were derived for µ _{1}_{2} , µ _{1}_{3} , µ _{2}_{3} (n = n _{1} + n _{2} + n _{3}
J.P. Novak´
is the total number of moles):
et al. / Fluid Phase Equilibria 208 (2003) 199–221
nµ
−1 + 2x _{2} (1 − x _{2} )b _{1}_{2} − 2x
nµ _{1}_{3} = −1 + 2x _{3} (1 − x _{3} )b _{1}_{3} − 2x
nµ _{2}_{3} = −1 + 2x _{2} (1 − x _{2} )b _{1}_{2} − 2x _{3} (1 − x _{3} )b _{1}_{3} + (1 − x _{2} − x _{3} + 2x _{2} x _{3} )(b _{2}_{3} − b _{1}_{2} − b _{1}_{3} )
2
3
2
2
b
b
_{1}_{3}
_{1}_{2}
_{1}_{2}
=
+ x _{3} (b _{1}_{2}
+ x _{2} (b _{1}_{2}
b _{1}_{2} ),
+ b _{1}_{3} − b _{2}_{3} ) + 2x _{2} x _{3} (b _{2}_{3} − b _{1}_{3} − b _{1}_{2} ),
+ b _{1}_{3}
− b _{2}_{3} ) + 2x _{2} x _{3} (b _{2}_{3}
− b _{1}_{3}
−
207
(16)
The equation expressing the limiting value of dT _{c} /dx _{3} (at x _{1} = x _{2} = 0.5, x _{3} = 0) is obtained from the corresponding relations for Ξ _{1} (Eqs. (12) and (15)) with the temperature dependence of b _{i}_{j} (T) being expressed by Eq. (3).
lim
x _{3} →0
dT _{c}
dx
_{3}
_{=}
(b _{2}_{3} + b _{1}_{2} − b _{1}_{3} )(b _{2}_{3} − b _{1}_{3} − b _{1}_{2} )
2α _{1}_{2} /T ^{2}
(17)
On cyclic substitution of indexes, an analogous relation for the limiting slope of the critical curve in the binary system [2 + 3] can be obtained
lim
x _{1} →0
dT _{c}
dx
_{1}
_{=}
(b _{1}_{3} + b _{2}_{3} − b _{1}_{2} )(b _{1}_{3} − b _{1}_{2} − b _{2}_{3} )
2α _{2}_{3} /T ^{2}
(18)
One should note an important fact: the limiting value of the composition change of the critical tem perature depends only on values of b _{1}_{2} , b _{1}_{3} and b _{2}_{3} and on the derivative db _{i}_{j} /dT = −α _{i}_{j} /T ^{2} in the corresponding binary system ([1 + 2] or [2 + 3]). Prior to the analysis of Eqs. (17) and (18), the behaviour of the considered binary systems must be further speciﬁed. Positive deviations from the Raoult’s law in binary systems [1 + 2] or [2 + 3] and a critical solution temperature in the studied temperature interval for at least one of them will be supposed. In such case b _{1}_{2} > 0, b _{2}_{3} > 0. Moreover, if the subsystems [1 + 2] and [2 + 3] separate into two liquid phases at the given temperature, then b _{1}_{2} > 2 and b _{2}_{3} > 2. The temperature dependence of b _{i}_{j} is given by Eq. (3). In case that the system shows an upper critical solution temperature α _{i}_{j} > 0. For a system presenting a lower critical solution temperature α _{i}_{j} < 0. The binary system [1 + 3] will be considered as homogeneous and showing either slightly positive or negative deviations from the Raoult’s law, i.e.
b _{1}_{3} < 2. With regard to these restrictions, the following conclusions result from Eq. (17). The sign of the denominator is given by the value of α _{1}_{2} , i.e. systems with an upper critical solution temperature will be characterised by positive values of the parameter α _{1}_{2} and systems with a lower critical solution temperature will show negative values of the parameter α _{1}_{2} . Let us ﬁrst discuss the value of the ﬁrst term in the numerator of the Eq. (17), i.e. the value of (b _{2}_{3} + b _{1}_{2} −b _{1}_{3} ). Then in the considered case, i.e. at the critical temperature of the binary system [1+2], b _{1}_{2} = 2 and also, according to the assumption of positive deviations from the Raoult’s law, b _{2}_{3} > 0. In agreement with our assumptions (i.e. b _{1}_{3} < 2), the expression (b _{2}_{3} + b _{1}_{2} − b _{1}_{3} ) is always positive. The second term (b _{2}_{3} − b _{1}_{3} − b _{1}_{2} ) in the numerator of the Eq. (17) or, as the case may be the term (b _{1}_{3} + b _{2}_{3} − b _{1}_{2} ) in Eq. (18), are more interesting. They can, under the abovedescribed conditions, be positive or negative according to the value of b _{1}_{3} . The values of b _{1}_{3} that sets these terms to zero will be
referred to as b ^{0}
13(12) ^{a}^{n}^{d} ^{b} 13(23)
^{0}
^{,} ^{i}^{.}^{e}^{.}
b
^{0}
13(12) ^{=} ^{b} 23 ^{−} ^{2}^{,}
^{b}
^{0}
_{1}_{3}_{(}_{2}_{3}_{)}
= b _{1}_{2} − 2
(19)
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et al. / Fluid Phase Equilibria 208 (2003) 199–221
At this “critical” value of b _{1}_{3} , (dT _{c} /dx _{3} ) = 0. The derivative for a deﬁnite system [1 + 2] is affected by the value of the parameter b _{1}_{3} in the following way:
b 13 < b ^{0}
13(12) ^{⇒}
b _{1}_{3} > b ^{0}
13(12) ^{⇒}
^{l}^{i}^{m}
x _{3} →0
^{l}^{i}^{m}
x _{3} →0
dT
_{c}
dx
dT
_{3}
_{c}
dx
_{3}
> 0 
(20) 
< 0 
(21) 
In the former case the critical temperature increases on addition of a third component to the system and it decreases in the latter case. The conditions given by Eq. (19) remain valid for binary systems [1 + 2] showing lower critical solution temperatures with the sole difference that the effect of the third component (i.e. the signs of Eqs. (20) and (21)) is opposite. Eq. (18) can be analysed in an analogous way. All the conclusions are summarised in Table 3.
4.2. Results of model calculations
The preceding analysis concerned slopes of the critical curve at the concentration limits, i.e. in the vicinity of binary subsystems [1+2] and [2+3]. The shape of the critical curve at a speciﬁed concentration and temperature dependence of the Gibbs energy inside the ternary system can only be determined solving Eqs. (6) and (7). The following procedure has been adopted on modelling. Temperature dependencies of b _{i}_{j} (T) (see Table 2) were selected for the systems [1 + 2] and [2 + 3]. For the model calculations of critical curves
Table 3 Relations for limiting values of critical curve slopes in critical points
(I) At the critical point of systems [1 + 2], i.e. x _{3} = 0 and b _{1}_{2} = 2
(a) Systems [1 + 2] with UCST
b
b 13 < b ^{0} b 13 > b ^{0}
^{0}
_{1}_{3}_{(}_{1}_{2}_{)}
= b _{2}_{3} − 2
13(12)
_{1}_{3}_{(}_{1}_{2}_{)}
(b) Systems [1 + 2] with LCST
b
b 13 < b ^{0} b 13 > b ^{0}
^{0}
_{1}_{3}_{(}_{1}_{2}_{)}
= b _{2}_{3} − 2
_{1}_{3}_{(}_{1}_{2}_{)}
13(12)
lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ) = ^{l}^{i}^{m} x _{3} →0 ^{(}^{d}^{T} c ^{/}^{d}^{x} 3 ^{)} ^{>}
lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ) < 0
^{0}
0
lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ) = lim _{x} _{3} _{→}_{0} (dT _{c} /dx _{3} ) <
^{l}^{i}^{m} x _{3} →0 ^{(}^{d}^{T} c ^{/}^{d}^{x} 3 ^{)} ^{>} ^{0}
0
0
(II) At the critical point of systems [2 + 3], i.e. x _{1} = 0 and b _{2}_{3} = 2
(a) Systems [2 + 3] with UCST
b
b 13 < b ^{0} b 13 > b ^{0}
^{0}
_{1}_{3}_{(}_{2}_{3}_{)}
= b _{1}_{2} − 2
13(23)
_{1}_{3}_{(}_{2}_{3}_{)}
(b) Systems [2 + 3] with LCST
b
b 13 < b ^{0}
^{0}
_{1}_{3}_{(}_{2}_{3}_{)}
= b _{1}_{2} − 2
_{1}_{3}_{(}_{2}_{3}_{)}
b 13 > b ^{0}
13(23)
lim _{x} _{1} _{→}_{0} (dT _{c} /dx _{1} ) = ^{l}^{i}^{m} x _{1} →0 ^{(}^{d}^{T} c ^{/}^{d}^{x} 1 ^{)} ^{>}
lim _{x} _{1} _{→}_{0} (dT _{c} /dx _{1} ) < 0
^{0}
0
lim _{x} _{1} _{→}_{0} (dT _{c} /dx _{1} ) =
lim _{x} _{1} _{→}_{0} (dT _{c} /dx _{1} ) < 0
0
^{l}^{i}^{m} x _{1} →0 ^{(}^{d}^{T} c ^{/}^{d}^{x} 1 ^{)} ^{>} ^{0}
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209
Fig. 5. Shapes of the modelled critical curves in a ternary system in which are both binary subsystems characterised by an UCST.
in ternary systems, different values of the parameter b _{1}_{3} describing the subsystem [1 + 3] were chosen. For a better transparency of the results, the parameter b _{1}_{3} was considered as temperatureindependent. By virtue of selected parameters b _{i}_{j} , values T (=T _{c} ) and x _{2} (=x _{2}_{c} ) have been calculated from Eqs. (6) and (7) for speciﬁed values of x _{1} (=x _{1}_{c} ∈ 0, 0.5 ). It follows from the effectuated calculations that x _{2} differs only insigniﬁcantly from 0.5 (the regular solution is considered) and hence only diagrams T = T (x _{1} ) will further be discussed.
4.3. Binary systems [1 + 2] and [2 + 3] with upper critical solution temperatures
The results of the ﬁrst series of the model calculations are shown in Fig. 5. The parameters in the binary subsystem [1 + 2] were described by a temperature dependence corresponding to variant II, variant I was employed for the subsystem [2 + 3] (see Table 2 for the variants). The acquired dependencies T = T (x _{1} ) for different values of the parameter b _{1}_{3} = β _{1}_{3} are shown in Fig. 5. The dependence of the critical temperature on the mole fraction of the ﬁrst component is almost linear
in the case that b _{1}_{3} = 0 (the function is, in effect, slightly concave) and a monotonous critical curve is obtained. On increasing positive values of b _{1}_{3} the curve acquires a convex character. The critical curve
attains a zero value of the limiting slope (at x _{1} = 0) for b _{1}_{3} = b ^{0}
13(23) ^{(}^{b} ^{0}
_{1}_{3}_{(}_{2}_{3}_{)} = 0.5 in the considered case)
and for b _{1}_{3} > b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} the curve shows a minimum deepening with increasing values of b _{1}_{3} . The concave character of the critical curve accentuates itself at negative values of b _{1}_{3} and the zero value of the slope of the critical curve for b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} = b _{1}_{2} − 2 = 1.6428 − 2 = −0.3572 is attained at x _{3} = 0 or at x _{1} = x _{2} = 0.5. As the parameter b _{1}_{3} < −0.3572 then (lim _{x} _{1} _{→}_{0} (dT /dx _{1} ) > 0), (lim _{x} _{1} _{→}_{0}_{.}_{5} (dT /dx _{1} ) < 0) and there is a weak maximum on the critical curve. The coordinates of this maximum (or minimum in the preceding case), i.e. values of x _{1} , x _{2} , T for a speciﬁed set of parameters deﬁning the Gibbs energy course, can be obtained by solving a set of equations (see Eqs. (6) and (7), and dT /dx _{1} = 0, Eq. (11)):
D
= 0,
D ^{∗} = 0,
^{∂}^{D} ^{∗} ∂x _{1}
∂D 2 ^{} _{−} ^{} ∂D ^{∗}
∂x
∂x _{2}
∂D
∂x _{1}
= 0
(22)
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Fig. 6. Shapes of the modelled critical curves in a ternary system in which are both binary subsystems characterised by a LCST.
4.4. Binary systems [1 + 2] and [2 + 3] with lower critical solution temperatures
Results of the second series of calculations are shown in Fig. 6. The considered binary systems had the same values of critical temperatures as those shown in Fig. 5. The difference is that binary systems
in Fig. 5 were characterised by upper critical solution temperatures, while the subsystems [1 + 2] and [2 + 3] considered in this paragraph show lower critical solution temperatures. Parameters corresponding to variant V in Table 2 were employed for the system [1 + 2], variant VI was used for the system [2 + 3].
It follows from the obtained results that the critical curve is monotonous at b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} = −2/3 < b _{1}_{3} <
0.5 = b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} (see Table 3). A minimum occurs on the critical curve at b _{1}_{3} < −2/3 (in the vicinity of the [2 + 3] system), and the curve shows a maximum at b _{1}_{3} > 0.5 (near to the subsystem [1 + 2]). Figs. 5 and 6 differ qualitatively in the fact that the heterogeneous region lies under the critical curve in Fig. 5, while it ﬁnds itself above the critical curve in Fig. 6. The critical curve with a maximum can be observed in the system 2butanone (1) + water (2) + nicotine (3) [37]. The curve connects the hypothetical LCST in the subsystem 2butanone (1) + water (2) and the LCST in the water (2) + nicotine (3) system.
4.5. Binary system [1 + 2] with an upper critical solution temperature, binary system [2 + 3]
with a lower critical solution temperature
A variant of a system whose binary heterogeneous subsystems [1 + 2] and [2 + 3] show different types
of critical points is given in Fig. 7. Variant I (see Table 2) was employed in the binary subsystem [1 + 2]. Lower critical solution temperature and parameters corresponding to variant V (Table 2) were considered in the system [2 + 3]. Sassen et al. studied a ternary system [7] with similar behaviour type but as function of pressure.
The lower critical solution temperature in the binary subsystem [2 + 3] shown in Fig. 7 is 50 K higher than the upper critical solution temperature in the binary subsystem [1 + 2]. The parameter
= −0.3572 and b _{1}_{3}_{S} = −1.0239
b _{1}_{3} attains the following limiting values: b _{1}_{3}_{(}_{1}_{2}_{)} (see further).
^{0}
^{0}
= −2/3, b _{1}_{3}_{(}_{2}_{3}_{)}
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211
Fig. 7. Shapes of the modelled critical curves in a ternary system in which the subsystem [1 + 2] is characterised by an UCST, and the subsystem [2 + 3] by a LCST. It holds T _{L}_{C} > T _{U}_{C} : b _{1}_{3} = 0.5, curves 1; b _{1}_{3} = −0.3572, curves 2; b _{1}_{3} = −0.5, curves 3; b _{1}_{3} = −2/3, curves 4; b _{1}_{3} = −0.9, curves 5; b _{1}_{3} = −1.0237, curves 6; b _{1}_{3} = −1.5, curves 7.
According to the value of b _{1}_{3} the following shapes of critical curves and corresponding heterogeneous regions can be acquired:
b _{1}_{3} > b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} (see curves 1 in Fig. 7): both of the branches of the critical curve are monotonous. Heterogeneous regions are adjacent to binary systems [2+3] and [1+2] at corresponding temperatures (T >T _{L}_{C}_{,}_{2}_{3} for the system [2 + 3] and T <T _{U}_{C}_{,}_{1}_{2} for the system [1 + 2]). The ternary system is homogeneous in the temperature interval T ∈ (T _{U}_{C}_{,}_{1}_{2} , T _{L}_{C}_{,}_{2}_{3} ). The ternary system ethanol (2) + water (2) + triethylamine (3) can be cited as an example if a hypothetical low value of the upper critical solution temperature is attributed for the system ethanol (1) + water (2).
b _{1}_{3} = b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} (see curves 2 in Fig. 7): the critical curve starting in the binary system [2 + 3] shows a slope equal to zero.
b ^{0}
_{1}_{3}_{(}_{2}_{3}_{)} (see curves 3 in Fig. 7): the critical curve starting in the binary system [2 + 3]
(c)
(b)
(a)
^{<} ^{b} 13 ^{<} ^{b} ^{0}
13(12)
(d)
(e)
(f)
(g)
presents a weak minimum. This leads to the consequence that the heterogeneous region adjoins the binary system [2 + 3] at temperatures T >T _{L}_{C}_{,}_{2}_{3} . The ternary system forms a closed binodal curve at temperatures T _{m}_{i}_{n} <T <T _{L}_{C}_{,}_{2}_{3} , where T _{m}_{i}_{n} is the temperature corresponding to the minimum on the critical curve.
b _{1}_{3} = b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} (see curves 4 in Fig. 7): the critical curve starting in the binary system [1 + 2] shows a slope equal to zero.
b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} > b _{1}_{3} < b _{1}_{3}_{S} (see curves 5 in Fig. 7), where b _{1}_{3}_{S} is the value of b _{1}_{3} given by relations derived in Appendix C at which the two branches of the critical curve meet. Both branches of the critical curve show extremes. Temperatures corresponding to the minimum (on the branch starting in the binary system [2 + 3]) and to the maximum (on the branch starting in the binary system [1 + 2]) will
be referred to as T _{m}_{i}_{n} and T _{m}_{a}_{x} , respectively. Ternary heterogeneous regions schematically shown in Fig. 8 correspond to values of b _{1}_{3} belonging to the considered interval. Such behaviour has, so far, not been observed in any system.
b _{1}_{3} = b _{1}_{3}_{S} : both critical curves touch asymptotically (see curves 6 in Fig. 7).
b _{1}_{3} < b _{1}_{3}_{S} (curves 7 in Fig. 7): an interconnection of both the heterogeneous regions is observed and a closed region of limited miscibility is formed.
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Fig. 8. Heterogeneous regions in a ternary system satisfying the condition b _{1}_{3}_{(}_{1}_{2}_{)}
T >T _{L}_{C}_{,}_{2}_{3} ; (B) T _{m}_{i}_{n} <T <T _{L}_{C}_{,}_{2}_{3} ; (C) T _{m}_{i}_{n} <T <T _{m}_{a}_{x} ; (D) T _{m}_{a}_{x} <T <T _{U}_{C}_{,}_{1}_{2} ; (E) T <T _{U}_{C}_{,}_{1}_{2} .
^{0}
> b _{1}_{3} > b _{1}_{3}_{S} at different temperatures T: (A)
A similar inﬂuence of the parameter b _{1}_{3} can be seen in Fig. 9. The temperature dependence of the
parameter b _{1}_{2} (T) is the same as for the subsystem in Fig. 7: variant I in Table 2 was employed; variant IV
in Table 2 was used for the subsystem [2 + 3]. It holds for the considered binary systems that b ^{0}
13(12) ^{=}
0.1133, b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} = 0.0862, b _{1}_{3}_{S} = 0.1995. With decreasing value of the parameter b _{1}_{3} the following shapes of the critical curve and of the heterogeneous region can be obtained:
b _{1}_{3} > b _{1}_{3}_{S} (curves 1 and 2 in Fig. 9): both branches of the critical curve show a monotonous course. Ternary heterogeneous regions are adjacent to corresponding binary systems.
b _{1}_{3} = b _{1}_{3}_{S} (curves 3 in Fig. 9): both branches of the critical curve meet and are asymptotic to preceding (see (a)) and following (see (b)) curves.
b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} < b _{1}_{3} < b _{1}_{3}_{S} : both of the branches of the critical curve show less accentuated extremes. The branch starting in the [1 + 2] system shows a minimum, the branch corresponding to the [2 + 3] system shows a maximum. The heterogeneous region is bandshaped at temperatures lying between the minimum and the maximum. One heterogeneous region adjacent to the corresponding binary systems occurs in the ternary system out of this temperature interval.
b _{1}_{3} = b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} (curves 4 in Fig. 9): the branch of curve 5 originating in the system [1 + 2] starts with a zero slope and then becomes monotonous.
b ^{0}
^{<} ^{b} 13 ^{<} ^{b} _{1}_{3}_{(}_{2}_{3}_{)} ^{0} : the critical curve starting in the binary system [1 + 2] is monotonous and the
curve starting in the system [2 + 3] keeps its maximum.
b _{1}_{3} = b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} : the critical curve starting in the system [2 + 3] looses its maximum.
(e)
(d)
(c)
(b)
(a)
13(12)
(f)
Fig. 9. Shapes of the modelled critical curves in a ternary system in which the subsystem [1 + 2] is characterised by an UCST, and the subsystem [2 + 3] by a LCST. It holds T _{L}_{C} < T _{U}_{C} : b _{1}_{3} = 0.5, curves 1; b _{1}_{3} = 0.3, curves 2; b _{1}_{3} = 0.1995, curves 3; b _{1}_{3} = 0.1133, curves 4; b _{1}_{3} = 0, curves 5; b _{1}_{3} = −0.25, curves 6.
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213
Fig. 10. Ternary system with an Sshaped LLE critical curve. Both binary subsystems are characterised by an UCST.
(g) b _{1}_{3} < b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} (see curves 5 and 6 in Fig. 9): both of the branches of the critical curve are monotonous. The ternary heterogeneous region is adjacent to the binary system [1 + 2] at temperatures T <T _{L}_{C}_{,}_{2}_{3} and it adjoins the binary system [2 + 3] at T >T _{U}_{C}_{,}_{1}_{2} . The heterogeneous region is bandshaped with no critical point in between these two extreme temperatures. Such behaviour can be observed in systems phenol (1) + water (2) + triethylamine (3) and diethylether (1) + water (2) + triethylamine (3) [23] (the existence of an upper critical solution temperature in the system diethylether (1) + water (2) is assumed).
4.6. Binary systems [1 + 2] and [2 + 3] with upper critical solution temperatures, ternary system with an Sshaped critical curve
Fig. 10 represents a ternary system in which the critical curve is Sshaped. This was achieved using the following temperature dependencies of parameters b _{i}_{j} (T): variant II in the binary system [1 + 2], variant I in the system [2 + 3] and variant III in the system [1 + 3] (for the individual variants see Table 2). The considered dependence b _{1}_{3} (T) satisﬁes previously mentioned conditions: b _{1}_{3}_{(}_{1}_{2}_{)} ^{0} = −0.3572 >
= 0.5 < b _{1}_{3} (T = T _{U}_{C}_{,}_{2}_{3} ) = 0.6 and, in agreement with before
b _{1}_{3} (T = T _{U}_{C}_{,}_{1}_{2} ) = −0.4 and b _{1}_{3}_{(}_{2}_{3}_{)}
mentioned ﬁndings, leads to the Sshaped course of the critical curve (see Fig. 10).
^{0}
5. Discussion
The questions asked in the introduction can be now discussed.
It follows from the calculations and from Eqs. (17) and (18) that the character of the shape of the
critical curve connecting the critical points of binary subsystems [1 + 2] and [2 + 3] does not depend on whether the systems show an upper or a lower critical solution temperature (compare Figs. 5 and 6). In both cases the major inﬂuence on the shape of the curve is depending on the third binary subsystem
[1 + 3]. If the parameter b _{1}_{3} does not exceed limits given by values of b ^{0} shows a monotonous course.
_{1}_{3}_{(}_{2}_{3}_{)} , the critical curve
13(12) ^{a}^{n}^{d} ^{b} ^{0}
A more or less accentuated minimum occurs on the critical curve at b _{1}_{3} > b ^{0}
_{1}_{3}_{(}_{1}_{2}_{)} (T UC,12 < T UC,23 ) or
at b _{1}_{3} > b _{1}_{3}_{(}_{2}_{3}_{)} ^{0} (T _{U}_{C}_{,}_{1}_{2} > T _{U}_{C}_{,}_{2}_{3} ) in case that systems [1 + 2] and [2 + 3] show an upper critical solution
214
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temperature. The critical curve can, on the other hand, show a maximum at b _{1}_{3} < b ^{0}
or at b _{1}_{3} < b ^{0}
_{1}_{3}_{(}_{1}_{2}_{)} (T UC,12 > T UC,23 )
13(23) ^{(}^{T} UC,12 ^{<} ^{T} UC,23 ^{)}^{.}
These conclusions are in agreement with the behaviour of previously mentioned systems. Upper critical
temperatures of both of the heterogeneous binary subsystems differ signiﬁcantly in the system aniline (1)
+ water (2) + phenol (3) [12,13] (T _{U}_{C}_{,}_{1}_{2} = 441 K, T _{U}_{C}_{,}_{2}_{3} = 337.05 K). The binary system aniline (1)
+ phenol (2) shows negative deviations from Raoult’s law with b _{1}_{3} ≈ −0.35 (this value was determined
using the azeotropic point), deviations being relatively small to lead to an appearance of a maximum on a critical curve. Upper critical temperatures of heterogeneous binary subsystems in the system cyclohexane (1) + methanol (2) + hexane (3) are very close to one another (T _{U}_{C}_{,}_{1}_{2} = 318.93 K, T _{U}_{C}_{,}_{2}_{3} = 306.5 K). Hence, even very small positive deviations from ideal behaviour in the binary system cyclohexane (1) + hexane (3) [15,38] are sufﬁcient to lead to a creation of a minimum on the critical curve. Hradetzky and Lempe [15] have published data which lead to an approximate value of b _{1}_{3} ≈ 0.1. The binary subsystem acetone (1) + water (2) in the system acetone (1) + water (2) + phenol (3) is homogeneous at all temperatures [19,20]. However, the system shows large positive deviations from the Raoult’s law (T = 300 K, b _{1}_{2} ≈ 1.75) and can be looked upon as lying on the brink of immiscibility. The system acetone (1) + phenol (3) shows large negative deviations (b _{1}_{3} < −1) [19,20,38] which are obviously sufﬁcient for the creation of a maximum on the critical curve. On studying ternary systems characterised by two heterogeneous binary subsystems [1 + 2] and [2 + 3] showing different types of critical solution temperatures (upper versus lower) it was found that even in
cases where it holds that T _{L}_{C}_{,}_{2}_{3} < T _{U}_{C}_{,}_{1}_{2} (see Fig. 9) it was possible that the heterogeneous regions
would not touch. The two regions merge at b _{1}_{3} = b _{1}_{3}_{S} . Then, in case that for the binary system [1 + 3]
b 13 = β 13
^{(}^{2}^{3}^{)}
It holds, for example, for the system in Fig. 7 that b _{1}_{3}_{S} = −0.3572 + (−0.6666) = −1.0238. Het erogeneous regions adjacent to corresponding binary subsystems remain separate at b _{1}_{3} > b _{1}_{3}_{S} . The regions merge at b _{1}_{3} < b _{1}_{3}_{S} and form a closed binodal curve in case that T _{L}_{C}_{,}_{1}_{2} > T _{U}_{C}_{,}_{2}_{3} . The ternary system tetrahydrofuran (1) + water (2) + phenol (3) shows such behaviour. As was already said, the system is heterogeneous even at temperatures T ∈ (T _{U}_{C}_{,}_{2}_{3} , T _{L}_{C}_{,}_{1}_{2} ). According to the regularsolution model applied in this paper, such behaviour is only possible if the system tetrahydrofuran (1) + phenol (3) showed large negative deviations from the Raoult’s law, which in this particular case corresponds to reality [24,38]. Another example can also demonstrate the acquired ﬁndings. The system acetic acid (1) + cyclohexene (2) + dimethylformamide (3) form a closed region of limited miscibility. No heterogeneous region charac terised by an upper critical solution temperature was observed in the binary subsystems [21], but a similar system acetic acid + cyclohexane shows a T _{U}_{C} ≈ 273 K. Its thermodynamic behaviour (H ^{E} > 0), makes us suppose that the upper critical temperature in the system acetic acid (1) + cyclohexene (2) would be lower than the eutectic temperature in corresponding binary subsystems. The system acetic acid (1)
+ dimethylformamide (3) however shows large negative deviations from ideal behaviour, which causes
that the heterogeneous region appears at much higher temperatures than hypothetical upper critical so
lution temperatures in both of the binary subsystems [1 + 2] and [2 + 3]. The experimentally found temperature dependence of the miscibility is in agreement with these facts: the heterogeneous region gradually diminishes on increasing temperature to disappear totally in the end [21].
= f (T ), the value of b _{1}_{3}_{S} can be determined using the relation
b 13S = b 13(12) ^{0} ^{+} ^{b} 13(23)
^{0}
6. Conclusion
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215
Making general conclusions regarding results of effectuated descriptions of the critical curve by means of the regularsolution model, the following facts may be stated.
(a) 
A critical curve connecting critical points of two binary subsystems [1+2] and [2+3], characterised by the same type of the critical solution temperature (lower or upper), is monotonous if the binary system [1 + 3] shows relatively small deviations from the ideal behaviour (limits for the regularsolution model are speciﬁed in Table 3). 
(d) 
If the systems [1 + 2] and [2 + 3] show upper critical solution temperatures, then sufﬁciently high positive deviations from ideality in the binary system [1 + 3] cause the creation of a minimum on the critical curve and the ternary heterogeneous region splits at a temperature lower than the lower of the two critical temperatures. Conversely, sufﬁciently large negative deviations from the Raoult’s law result in the creation of a maximum on the critical curve and in the formation of a closed limited miscibility region at temperatures higher than the critical temperatures of both of the heterogeneous binary subsystems. In case that systems [1 + 2] and [2 + 3] show lower critical solution temperatures, opposite effects can be observed. 
(c) 
In case that binary systems [1+2] and [2+3] show different types of the critical solution temperature, two branches of the critical curve are obtained. Each of the branches originates in the critical point of the corresponding binary system. These branches may be monotonous, but may also show minima or maxima depending on the nonideality of the binary subsystem [1 + 3]. Equations derived for the limiting slopes in critical points are valid in this case as well. A relation which, when fulﬁlled, leads to the junction of both of the heterogeneous regions adjacent at sufﬁciently high values of b _{1}_{3} to heterogeneous binary subsystems, is derived in Appendix C. 
(d) 
A closed region of limited miscibility found in some ternary systems is obviously a consequence of large positive or large negative deviations from ideality in the binary system [1 + 3], which lead to the appearance of the critical curve at temperatures outside of the temperature interval determined by critical temperatures of the two heterogeneous binary subsystems. 
(e) 
A closed limited miscibility region can also occur in case that binary systems [1 + 2] and [2 + 3] are homogeneous in the whole concentration range (see Appendix A). 
List of symbols b b
_{i}_{j}
^{0}
13(12) ^{,} ^{b} _{1}_{3}_{(}_{2}_{3}_{)}
_{1}_{3}_{S}
b
^{0}
D
D ^{∗}
(G _{1}_{1} ) _{x}_{0}
G
G
G
G
_{i}_{j}
_{i}_{j}_{k}
_{m}
^{E}
∗
G _{m}_{,}_{i}
value of the parameter b _{1}_{3} at which the two branches of the critical curve meet parameter of the regularsolution model (Eq. (1)) for the system i + j
special value of the parameters b _{1}_{3} (see Eq. (19))
determinant deﬁned by Eq. (6) determinant deﬁned by Eq. (7) the minimum value of G _{1}_{1} the second derivative of the molar Gibbs energy with respect to mole fractions x _{i} and x _{j} the third derivative of the molar Gibbs energy with respect to mole fractions x _{i} , x _{j} and x _{k} molar Gibbs energy molar excess Gibbs energy
molar Gibbs energy of the pure component i at the temperature and pressure of the system
216
n _{i}
T
T _{c}
T _{L}_{C}_{,}_{1}_{2} , T _{L}_{C}_{,}_{2}_{3}
T _{m}_{a}_{x}
T _{m}_{i}_{n}
T _{U}_{C}_{,}_{1}_{2} , T _{U}_{C}_{,}_{2}_{3}
x
x
x , x
_{1}_{c}
_{i}
i
i
Greek letters
α _{i}_{j} , β _{i}_{j} , γ _{i}_{j}
µ _{i}
µ _{i}_{j}
Ξ _{1} , Ξ _{2}
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number of moles of ith component temperature critical temperature lower critical solution temperature for binary subsystem [1 + 2] and [2 + 3], respectively critical curve maximum temperature critical curve minimum temperature upper critical solution temperature for binary subsystem [1 + 2] and [2 + 3], respectively critical mole fraction of the component 1 mole fraction of the ith component
mole fraction of the ith component in the conjugated phases
constants in the equations for the temperature dependence of the b parameter (see Eqs. (3) and (4))
chemical potential of the ith component
derivative of µ _{i} with respect to the mole number of the jth component (see Eq. (14))
functions deﬁned by Eqs. (12) and (13) [28]
Acknowledgements
The authors gratefully acknowledge ﬁnancial support form the Ministry of Education of the Czech Republic under Grant No. CB MSM 2234 00008.
Appendix A. Modelling with an extended temperature dependence of the model parameters
Binary systems presenting a closed region of limited miscibility cannot be modelled by Eq. (3). Con
sidering a nonzero and constant C
b ij = β ij +
α ^{i}^{j}
T
+ γ _{i}_{j} ln T
E
p
, the relation must be extended as follows:
(A.1)
Parameters of Eq. (A.1) can be evaluated using LCST and UCST (b _{i}_{j} = 2) and a solubility at a selected temperature. The lower critical solution temperature T _{L}_{C} = 345 K, the upper critical solution temperature T _{U}_{C} = 411 K [39] and b (T = 378 K) = 2.1 (resulting from x¯ _{1} = 0.3146) permitted in the system tetrahydrofuran + water the following relation to be obtained:
b _{i}_{j} = 183.716 − ^{9}^{8}^{5}^{6}^{.}^{1}^{8}
T
− 26.2079 ln T
(A.2)
1 2 ] shows
a positive minimum. The binary systems 3methylpyridine + water, 4methylpyridyne + water and ace tone + water belong to such systems. The excess enthalpy is negative at lower temperatures, positive at higher ones and the minimum of the second derivative of the Gibbs energy with respect to composition
Eq. (A.1) is also to be applied on systems where the temperature dependence of [∂ ^{2} (G/RT)/∂x
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217
Fig. 11. Modelled LLE critical curves in ternary systems: curve 1, methanol (1) + water (2) + tetrahydrofuran (3) (b _{1}_{2} = 0.5, b _{1}_{3} = 0.5); curve 2, ethanol (1) + water (2)+tetrahydrofuran (3) (b _{1}_{2} = 1.2, b _{1}_{3} = 0.5); curve 3, 1propanol (1) + water (2) + tetrahydrofuran (3) (b _{1}_{2} = 1.8, b _{1}_{3} = 0.3); curve 4, 1butanol (1) + water (2) + tetrahydrofuran (3) (b _{1}_{2} = −0.095+834.3/T , b _{1}_{3} = 0.2); curve 5, dimethylsulfoxide (1) + tetrahydrofuran (2) + water (3) (b _{1}_{2} = 1.2, b _{1}_{3} = −2.5); curve 6, dimethylsulfoxide (1) + tetrahydrofuran (2) + water (3) (b _{1}_{2} = 1.2, b _{1}_{3} = −3).
occurs at approximately 35 ^{◦} C ((G _{1}_{1} ) _{x}_{0} ≈ 0.61) in the system acetone + water [3]. The system ace tone + water can therefore be considered as homogeneous in the whole temperature and concentration ranges.
A.1. Binary system [1 + 2] homogeneous or with an upper critical solution temperature and binary system [2 + 3] with a closed region of limited miscibility
The binary system tetrahydrofuran (2) + water (3) forms a closed region of limited miscibility and offers another possibilities of shapes of critical curves sketched in Fig. 11. Ternary systems in which the third component is methanol, ethanol, 1propanol, 1butanol and dimethylsulfoxide are discussed. Values of parameters used in calculations characterise the behaviour of corresponding binary systems only roughly and are given in the legend to Fig. 11. Eq. (A.2) was employed for the system tetrahydrofuran (2) + water (3). It follows from the effectuated calculations that the heterogeneous region is relatively small in case of methanol, ethanol and 1propanol and that the critical curve is closedshaped (see curves 1, 2 and 3 in Fig. 11). Similar critical line was found by Kumar et al. in the system 3methylpyridine + water +heavy water [40]. The critical curve presents two branches in the system containing 1butanol (see curve 4). A less accentuated minimum is assumed to occur on the upper branch. A closed region of limited miscibility at 20 ^{◦} C occurs in the system dimethylsulfoxide (1) + tetrahydrofuran (2) + water (3) [41]. The binary system dimethylsulfoxide (1) + tetrahydrofuran (2) presents positive deviations from the Raoult’s law [38] and the parameter b _{1}_{2} = 1.2 was employed to characterise the system. On the other hand, the system dimethylsulfoxide (1) + water (3) shows large negative deviations from the Raoult’s law [38] and two values of the parameter b _{1}_{3} were employed for its description: b _{1}_{3} = −2.5 and b _{1}_{3} = −3. Calculated critical curves are represented in Fig. 11 and are referred to as curves 5 and 6. It follows from the calculations that the occurrence of a closed heterogeneous region in the ternary system dimethylsulfoxide (1) + tetrahydrofuran (2) + water (3) at 20 ^{◦} C, a temperature lower than the lower critical solution
218
J.P. Novak´
et al. / Fluid Phase Equilibria 208 (2003) 199–221
Fig. 12. Shape of the modelled critical curve in a ternary system in which all binary subsystems are homogeneous.
temperature in the system tetrahydrofuran (2) + water (3), is caused by large negative deviations from the Raoult’s law in the system dimethylsulfoxide (1) + water (3).
A.2. All binary systems homogeneous and ternary system with a closed region of limited miscibility
The extreme inﬂuence on the occurrence of the heterogeneous region can be demonstrated by a system whose critical curve is sketched in Fig. 12. In this case, the following dependence of the parameter b _{i}_{j} was employed for the binary subsystems [1 + 2] and [2 + 3]:
b _{i}_{j} = 568.144 − ^{2}^{5}^{5}^{3}^{9}^{.}^{9}
T
− 84.349 ln T
(A.3)
which was obtained using parameters b _{i}_{j} = 1.5, 1.9 and 1.6 at temperatures 275, 300 and 330 K, respec tively. The dependence shows a maximum at b _{i}_{j} = 1.9063 and T = 302.79 K. Binary systems are thus homogeneous in the whole concentration and temperature range. Nevertheless, in accordance with the previously acquired ﬁndings [28,33], if the b _{1}_{3} is sufﬁciently low a heterogeneous region appears in the ternary system. A curve for b _{1}_{3} = −3 is shown in Fig. 12.
Appendix B. Expressions for D and D ^{∗} , and their derivatives
D =
^{1}
_{−} 2b 12
_{−} 2b 13
_{−} 2b 23
x
1 x 2 x 3
x
3
x
2
x
1
− b ^{2}
12
_{D} _{∗} _{=} 3x _{1} − 1
x
2
_{+}
2
2
3
_{+} b _{1}_{2} [x _{3} − x _{2} (1 + 2x _{1} )]
x _{1} x
2
2
^{x}
2
3
_{+}
1 ^{x} 2 ^{x}
b _{2}_{3} [−x _{1} (1 − x _{1} ) + 2x _{2} x _{3} (2 − x _{1} )]
x
2
1
x
2
2
x
2
3
^{−} ^{b} 13 ^{2} ^{−} ^{b}
2
_{2}_{3} + 2b 12 b 13 + 2b 12 b 23 + 2b 13 b 23
(A.4)
b _{1}_{3} [x _{2} − x _{3} (1 + 2
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