Chemical Engineering Science 55 (2000) 2121}2129

A powerful algorithm for liquid}liquid}liquid equilibria

predictions and calculations
Roumiana P. Stateva!, Georgi St. Cholakov", Anatolii A. Galushko!,
William A. Wakeham#,*
!Institute of Chemical Engineering, Bulgarian Academy of Sciences, Soxa 1113, Bulgaria
"Department of Petroleum and Solid Fuels, University of Chemical Technology and Metallurgy, Soxa 1156, Bulgaria
#Department of Chemical Engineering and Chemical Technology, Imperial College of Science, Technology and Medicine, Prince Consort Road, London SW7
2BY, UK
Received 6 January 1999; received in revised form 27 July 1999; accepted 11 August 1999

Abstract

The paper describes a new robust and e$cient algorithm for liquid}liquid}liquid equilibria (LLLE) predictions and calculation.
The architecture of the algorithm is a two-level one, and a judicious combination of a stability analysis, carried out in the "rst stage,
with phase identi"cation routines and liquid #ash calculations, carried out in the second stage, is realised. The numerical routines
require modest computational e!orts and demonstrate excellent convergence characteristics. The thermodynamic model applied to
a system does not in#uence the robustness of the new algorithm, which can treat any model and handle any number of components
and phases. The usefulness and e$ciency of the new algorithm is exempli"ed by using two model systems, a water#oil#non-ionic
surfactant system and the system ethylene glycol#lauryl alcohol#nitromethane. ( 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Liquid}liquid}liquid-phase behaviour predictions and calculations

1. Introduction lations is presented; then, to demonstrate its capabilities,

Systems exhibiting multiple liquid phases are of a con-
siderable interest for a number of industrial processes, in
particular those involving surfactants. These systems
are applied in the production of cosmetics, drugs and
herbicides, paints, lubricants, etc. They are especially
important in the petroleum engineering industry where
surfactants are used to recover residual oil, a process
often referred to as microemulsion #ooding.
In this paper we address and concentrate on the design
of a robust and e$cient algorithm for liquid}liquid}
liquid equilibrium (LLLE) predictions and calcula-
tions in multicomponent systems, which is not a trivial
task.
The paper is organised in the following way: "rstly, the
algorithm for LLLE equilibria predictions and calcu-
* Corresponding author. Tel.: 0044-171-594-5005; fax: 0044-171-594-
8802.
E-mail address: w.wakeham@ic.ac.uk (W.A. Wakeham)
two examples are given, each one of which illustrates
some of the possible di$culties associated with the LLLE
problem.
1.1. Algorithm for multiphase-liquid equilibria predictions
and calculations
At present, there are only few studies concerning the
numerical solution of the three liquid-phase equilibria
problem, applying excess Gibbs energy models. They are
discussed in some detail by McDonald and Floudas
(1995,1997) and Garcia-Sanchez, Schwartzentruber, Am-
mar and Renon (1996). It is important to point out that
the solution of this problem is particularly di$cult for
strongly non-ideal multicomponent systems with com-
plex interactions, for which the hypersurface of the Gibbs
free energy might have a very elaborate form. Therefore,
it is very easy to "nd either a solution, corresponding
with the local rather than the global minimum of the
Gibbs free energy (i.e. a `wronga solution), or a trivial
solution during phase equilibrium calculations. Thus,
special care should be taken in the design of an algorithm

0009-2509/00/$ - see front matter ( 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 4 7 0 - 4
2122 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129

Nomenclature

G total Gibbs free energy, J c mass fraction of the amphiphile in the mixture
i number of carbon atoms in the hydrophobic of all three components
part of the amphiphile u fugacity coe$cient, component i
i
j number of ethoxy groups in the hydrophilic part U(y) function, Eq. (1)
of the amphiphile t phase split for the three-phase #ash
k (y) function of the chemical potential di!erence, Eq.
i
(1) Abbreviations
kH a number, corresponding to yH A water
N total number of components in the system B oil
P pressure, Pa C amphiphile
temperature, K LLE liquid}liquid equilibrium
yH zero of the function '(y) for the initial system LLLE liquid}liquid}liquid equilibrium
z mole fraction vector of the initial system
Superscripts
Greek letters * corresponding to a zero of the function '(y)
a phase split for the two-phase #ash
b mass fraction of the oil in the mixture of water Subscripts
and oil i number of components

for multiphase-liquid equilibria in order to ascertain that where

the correct number of phases is found.
k (y)"ln u (y)#ln y !h , i"1,2, 2, N, (1a)
The algorithm advocated in the present study imple- i i i i
ments a two-stage hierarchical procedure, originally pro- h "ln z #ln u (z), i"1,2,2, N (1b)
posed by Stateva and Tsvetkov (1994) to the solution i i i
of the liquid}liquid}vapour (LLV)-phase equilibrium and k (y) is equated to k (y). From Eq. (1) it follows
N`1 -
problem, and further extended to the case of phase directly, that when y"yH , where
equilibrium predictions and calculations in chemically k (yH)"k (yH)"2"k (yH),
reacting systems by Stateva and Wakeham (1997). In 1 2 N
most general terms, the procedure can be described as then
pertaining to the `equation-solvinga methods as opposed
to the methods which solve the problem by minimising U(yH)"0, (1c)
the Gibbs energy of the system (Han & Rangaiah, 1998). which is its minimum value.
The methods of the "rst group divide the problem solu- The zeros (yH) of U(y) correspond with points on the
tion into two distinct steps * "rst the number of phases Gibbs energy surface, where the local tangent hyperplane
at equilibrium is determined and then the governing at each yH is parallel to that at z. To each vector yH,
equations are solved. These two steps may have to be a quantity kH corresponds, such that
repeated several times. Our approach, however, possesses
some interesting distinctions from these methods and kH"kH(yH)"ln u (yH)#ln yH!h
i i i i
those will be highlighted further on. for any i"1,2,2, N, (2)
The "rst stage of the hierarchical procedure involves
a rigorous phase stability analysis performed on the where kH geometrically represents the distance in the
initial system with composition z. The stability check Gibbs energy hypersurface between the hyperplane at
applies the idea of the tangent-plane criterion (Baker, z and the hyperplane at any yH. This distance can be
Pierce & Luks, 1982; Michelsen, 1982), but uses a di!er- either positive or negative. When all calculated kH are
ent objective function (Stateva & Tsvetkov, 1994): positive, the system is stable.
Locating all zeros of U(y) is not an easy task, as
N a search over the entire composition space is required.
U(y)" + [k (y)!k (y)]2, (1)
i`1 i The search is further complicated by the existence of
i/1
 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129
a number of trivial solutions, corresponding with the
number of equilibrium phases present. The speci"c form
of U(y) (its zeros are its minima) and the fact that it is
easily di!erentiated analytically, allows the application of
a non-linear minimisation technique for locating its
stationary points. We use the BFGS method with a
line-search (Fletcher, 1987). Its implementation, as well
as the implementation of any non-linear minimisation
technique, requires a set of multiple `gooda initial
estimates.
To do that we introduce two groups of initial esti-
mates. The "rst group, or starting initial estimates, is
used to begin the search, while the second * to resume
the search with the BFGS method once a minimum is
located. The `startinga initial estimates are elements of
`chainsa, each one of which originates from a corre-
sponding pure component of the system. Applying the
algorithm, suggested originally by Stateva and Tsvetkov
(1991), the `chainsa are continuously modi"ed during the
search in order to avoid the location of a minimum,
which has already been obtained. The `startinga initial
estimates allow performing the search with the BFGS
method in parallel, from very di!erent points in the
composition space, if that is desired.
The second group, or the auxiliary initial estimates, is
applied when a zero of the function is located, and the
BFGS method needs a new estimate to restart the search.
To "nd such an estimate an uni-dimensional search is
applied, which determines the best direction locally lead-
ing to the smallest increase in the value of U(y). All details
of the organisation and implementation of the initialisa-
tion strategy employed by the stability analysis proced-
ure are given by Stateva and Tsvetkov (1991) and will not
be discussed here.
Thus, a method has been created which leads, in prac-
tice, to an `extensivea search in the multidimensional
composition space. It has proved to be extremely reliable
in locating almost all zeros of the function at a reasonable
computational cost (Stateva and Tsvetkov, 1991). We
use the term `almost alla zeros because there is no
theoretically-based guarantee that our scheme will al-
ways "nd them all. Only the global optimisation
methods give such mathematical guarantee. If, however,
a zero is missed, unlike most of the `equation solvinga
methods which will eventually fail to determine correctly
the phase identi"cation of the system, our method is
self-recovering, as will be demonstrated later. Further-
more, the stability analysis is performed only once and
upon z only, which is a distinct di!erence from the
approach that `equation solvinga methods generally
adopt.
The stability analysis on its own, however, cannot
determine unequivocally which is the stable phase con"g-
uration of a system, identi"ed as unstable at the given
temperature and pressure. To do that the algorithm
continues with the second stage, which involves a se-
2123
quence of two-phase LL and one LLL #ash calculations
to determine the correct number of the phases at equili-
brium, and the distribution of the components among the
phases.
The #ash calculations employed can either be based on
the minimisation of the Gibbs energy, or can adopt the
K-value approach. We apply the `negativea #ash routine
as discussed originally by Whitson and Michelsen (1989).
To assure a steady and non-oscillatory convergence of
the LL #ash calculations it is very important to provide
as good initial estimates as possible. This is the point
where the information from the stability analysis routine
should be used to the full.
To generate a reliable initialisation scheme we intro-
duce an arrangement of the stationary points obtained,
based on the notion of a heavy and a light liquid phase
(depending on their liquid-like or vapour-like density).
Once all zeros of U(y) are located they are automatically
divided into two groups * a group, which contains the
zero with the vapour-like density and a group with all the
rest of the zeros, arranged in an ascending order depend-
ing on their density. For the case of a possible
LLL equilibrium all zeros located are liquid. However,
among them there is a zero, with a vapour-like density,
which can be accepted as a model of the light-liquid
phase.
Then all zeros from the second group are combined
with the zero of the "rst group to produce a set of initial
estimates for the subsequent two-phase LL #ashes. Be-
cause it is impossible to tell a priori which stationary
points correspond with the global solution, the applica-
tion of this set of initial estimates guarantees a highly
diversi"ed search for the phase con"guration with the
minimum Gibbs energy. Thus, the chance of using
guesses that may in the end lead to local optima or even
to infeasible solutions is eliminated. Furthermore, these
initial estimates guarantee a steady and non-oscillatory
convergence of the two-phase #ash calculations which
practically do not exhibit a strong attraction to the
trivial solution, as will be demonstrated further on. This
simple scheme is totally automated and very easy to
implement.
The two-phase #ash calculations are performed in any
order and in parallel, if it is desired. They lead to a variety
of two-phase LL solutions and that with the lowest value
of the Gibbs energy is selected for further processing.
To determine whether the inclusion of a third phase
will lead to a further minimisation of the Gibbs energy,
one additional two-phase LL #ash calculation is re-
quired. If not, then the two-phase result is the "nal, stable
solution.
1.1.1. Summary of the algorithm
The generalised scheme of the algorithm for LLLE
predictions and calculations is summarised as follows:
1. Given z, , P.
2124 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129
2. Run a stability analysis upon z. If the initial solution is
stable, the system is a homogeneous mixture. END.
Otherwise, continue with step 3.
3. Run two-phase LL #ash calculations upon z, using as
initial estimates the stationary points obtained in step
2. Choose among the LL solutions the one with the
minimum G.
4. Test this particular solution towards a LLL split by
performing a liquid}liquid #ash on its lighter phase. If
the phase split upon convergence is outside the phys-
ically acceptable bounds, the equilibrium-phase con-
"guration is a two-phase LL. END. Otherwise, the
equilibrium-phase con"guration is LLL. Initial esti-
mates for the subsequent LLL calculations are found
by performing an additional LL #ash upon the
heavier of the two liquid phases of the above LL
solution. Continue with step 5.
5. Run a LLL #ash upon z. Use as initial estimates the
converged mole fractions of the solutions determined
in step 4. END.
Several characteristics of the above algorithm ensure
its #exibility and robustness, among which two deserve
additional brief comments. The commonly accepted
practice of equation solving methods for phase equilib-
rium predictions and calculations is to assume that if
a postulated solution is found to be unstable then a phase
must be added or deleted. However, the true equilibrium
solution may in fact be one with a di!erent distribution of
the components within the same phases (e.g. in a four-
component system there might be several three-phase
solutions found, of which only one corresponds to the
global minimum). The present algorithm overcomes this
by selecting on each step the solution with the minimum
Gibbs energy for further processing.
Furthermore, the present algorithm requires only
a single application of the stability analysis routine and,
in practice, a maximum of three two-phase #ash calcu-
lations to identify the stable-phase con"guration of the
system as either LL or LLL. To obtain the component
distribution among the phases for the latter case an
additional three-phase LLL #ash is performed upon z. In
comparison, any other `equation-solving, sequentiala
method will "rstly perform a sequence of a stability
analysis and a LL #ash calculation on the initial system,
followed by a stability check on one of the phases of the
converged LL solution. Then, if unstable, a phase is
added and a new #ash is run, etc.
1.2. Test examples
The robustness and e$ciency of the algorithm will be
illustrated on two examples. The "rst one discusses
the phase equilibrium predictions and calculations for
the system ethylene glycol#lauryl alcohol#nitrome-
thane and is taken from the literature (Sun & Seider,
1995; McDonald & Floudas, 1995,1997). We have chosen
this particular example because it provides a ground for
comparison of the performance of our algorithm with the
performance of other algorithms.
The second example presents the solution of the LLLE
problem for two water#oil#non-ionic surfactant
systems. We have chosen these systems because they
demonstrate a complex phase behaviour with peculiar
phase boundaries.
1.2.1. Ethylene glycol#lauryl alcohol#nitromethane
system
For this system, at "295 K and P"0.1 MPa, a va-
pour phase is not formed and there is a potential for three
liquid phases at equilibrium. McDonald and Floudas
(1995,1997) use the UNIQUAC and UNIFAC (binary
interaction parameters for the prediction of LL equilibria
from Magnussen et al., 1981) as the thermodynamic
models for the system. We apply the original UNIFAC
model (Fredenslund, Gmehling & Rasmussen, 1977) and
three sets of feed conditions are tested and analysed with
our algorithm:
1. z"(0.4;0.1;0.5)
2. z"(0.2;0.3;0.5)
3. z"(0.4;0.3;0.3).
For the feed condition, represented by case (1), the
stability analysis routine, performed on the "rst stage of
our algorithm, "nds three distinct zeros of U(y), two of
which have negative kH. The zero rich in lauryl alcohol is
a model of the light liquid phase. The other two zeros
form the group of the heavy liquid zeros. The zeros of the
two groups are paired and a set of initial estimates for the
subsequent LL #ash calculations is obtained. Two solu-
tions are obtained * solution A (Table 1) and solution
B (Table 2).
Solution B is with a lower Gibbs energy and is chosen
for further analysis while solution A is discarded from
further consideration. If solution B represents the phase
con"guration with the minimum Gibbs energy then both
its phases would be stable to a phase split. To test that
assumption we perform a LL #ash calculation upon the
lighter phase of solution B. The converged solution is
shown in Table 3.
Since phase B of the solution with the lowest Gibbs
2
energy among all initial phase splits is unstable (a is
Table 1
Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and
P"0.1 MPa. Feed conditions of case (1). Application of the algorithm,
step 3 Converged mole fractions of solution A
Component Feed A
1
A
2
C H O 0.4 0.4071 0.2631
2 6 2
C H O 0.1 0.0766 0.5487
12 26
CH NO 0.5 0.5163 0.1882
3 2
a"0.9504; GA "!12.24534.
LL
 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129 2125

Table 2 Table 4
Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and
P"0.1 MPa. Feed conditions of case (1). Application of the algorithm, P"0.1 MPa. Feed conditions of case (2). Application of the algorithm,
step 3 Converged mole fractions of solution B step 3 Converged mole fractions of solution 1

Component Feed B B Component Feed Liquid Liquid

1 2 1 2
C H O 0.4 0.0977 0.6122 C H O 0.2 0.106458 0.285030
2 6 2 2 6 2
C H O 0.1 0.0417 0.1409 C H O 0.3 0.035722 0.540228
12 26 12 26
CH NO 0.5 0.8606 0.2469 CH NO 0.5 0.857820 0.174742
3 2 3 2
a"0.5877; GB "!12.25863. a"0.5238, G"!12.69072.
LL

Table 5
Table 3 Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and
Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and P"0.1 MPa. Feed conditions of case (2). Application of the algorithm,
P"0.1 MPa. Feed conditions of case (1). Application of the algorithm, step 4
step 4 Converged mole fractions of the LL #ash upon phase B of
2
solution B Component Liquid F F
2 1 2
Component B H H C H O 0.285030 0.6891033 0.252575
2 1 2 2 6 2
C H O 0.540228 0.0748627 0.577606
12 26
C H O 0.6122 0.6665 0.2508 CH NO 0.174742 0.2360340 0.169819
2 6 2 3 2
C H O 0.1409 0.0763 0.5708
12 26
CH NO 0.2469 0.2572 0.1784 a"0.9235; G"!12.800515.
3 2
a"0.8693.
Table 6
Ethylene glycol, lauryl alcohol, nitromethane system at "295 K and
P"0.1 MPa. Feed conditions of case (2). Application of the algorithm,
step 4
inside the physically accepted boundaries), a two-phase
LL con"guration corresponds with a local rather than Component F H H
1 1 2
a global minimum of the Gibbs energy. The stable-phase
con"guration of the system is identi"ed as a LLLE. C H O 0.6891033 0.096779 0.690811
2 6 2
C H O 0.0748627 0.035292 0.074977
The correct phase identi"cation of the system with feed 12 26
CH NO 0.2360340 0.867929 0.234212
(1) is realised at a very early stage of the calculations and 3 2
is not computationally expensive * only three two-
phase LL #ash calculations are required and, because of
the excellent initial estimates applied, they converge in
less than three iterations. Let us for the sake of argument accept that the stability
The second feed condition, represented by case (2), analysis on the "rst stage of our algorithm fails to deter-
according to McDonald and Floudas (1995) exempli"es mine all zeros of the function. Then the available initial
the di$culties and the inherent dangers associated with estimates converge only to solution 1, which, obviously,
the correct determination of the global solution by any has a very large domain of attraction (Table 4).
local optimisation method. Further, they point out that Following the steps of the algorithm, solution 1 is
Sun and Seider (1995), who apply a homotopy-continua- tested for stability by performing a LL #ash calcula-
tion method to determine the stationary points of the tion upon its lighter phase. The result shows that
tangent plane distance function, report a local LL solu- the stable phase con"guration of the system is LLL
tion as the stable-phase con"guration for this particular (Table 5).
feed condition. To obtain the distribution of the components among
This example is interesting also because it demon- the three equilibrium phases a LLL #ash is performed
strates how the location of the feed in#uences the success upon z. To secure a steady convergence of the #ash
of the stability analysis and phase identi"cation rou- routine an excellent set of initial estimates are obtained
tines. Since the feed, represented by case (2) is located in by only one more LL #ash run on the heavier phase of
a close proximity to the L L boundary of the LLL the above solution (Table 6). The set of the initial esti-
1 3
triangle (Fig. 1), the zero rich in ethylene glycol is very mates is given in Table 7.
di$cult to locate. As a result a stability analysis routine, Applying these initial estimates, the LLL #ash con-
implementing a local optimisation method, might fail to verges in three iterations. The component distribution for
"nd it. the global solution is given in Table 8.
2126 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129

Fig. 1. Liquid}liquid}liquid equilibria of the ethylene glycol#lauryl alcohol#nitromethane system at "295 K and P"0.1 MPa. The position of
the three studied feed conditions are shown as well.

Table 7
Ethylene glycol, lauryl alcohol, nitromethane system at "295 k and
P"0.1 MPa. Feed conditions of case (2). Application of the algorithm,
step 4 The set of the initial estimates (mole fractions)

Component H H F
1 2 2
C H O 0.096779 0.690811 0.252575
2 6 2
C H O 0.035292 0.074977 0.577605
12 26
CH NO 0.867929 0.234212 0.169819
3 2

Table 8
Ethylene glycol, lauryl alcohol, nitromethane system at "295 k and
P"0.1 MPa. Feed conditions of case (2). Application of the algorithm,
step 5 Actual global LLL solution, mole fractions

Component L L L
1 2 3
Fig. 2. Regions of one, two and three-liquid phases in the ternary
C H O 0.096766 0.691110 0.252738 system H O#n-C H #C E at atmospheric pressure. H O : n-
2 6 2 2 10 22 4 1 2
C H O 0.035232 0.074737 0.578284 C H ratio is 50 : 50 wt%. A surfactant-rich aqueous phase, in equi-
12 26 10 22
CH NO 0.868002 0.234153 0.168978 librium with an excess oil phase, is denoted as 2; a surfactant-rich oil
3 2
phase, in equilibrium with an excess water phase, is denoted as 21 ; the
t "0.0466, t "0.4692, t "0.4842. LLLE is denoted as 3.
1 2 3
 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129 2127

Fig. 3. In#uence of the temperature on the LLL equilibrium of the ternary system H O#C H (CH ) H#C E at atmospheric pressure.
2 6 5 28 4 2
2128 R.P. Stateva et al. / Chemical Engineering Science 55 (2000) 2121}2129
The component distribution for feed conditions, repre-
sented by case (1) and case (3) are the same and that is
why they are not given. The corresponding phase frac-
tions, however, change accordingly, for case (1) they are:
t "0.4882, t "0.4280, t "0.0838; for case (3)
1 2 3
* t "0.3897, t"0.1511, t"0.4592.
1
1.2.2. Phase behaviour predictions and calculations for
water#oil#non-ionic surfactant systems
In order to demonstrate further the usefulness, robust-
ness and e$ciency of our algorithm we consider several
numerical tests involving water#oil#non-ionic surfac-
tant systems. These systems exhibit three liquid phases,
which exist only within a well-de"ned temperature and
pressure interval. If a vertical section through the temper-
ature * composition phase prism for a water#oil#
surfactant system is plotted at b"0.5, where
b"B/(A#B) is the mass fraction of the oil in the mix-
ture of water (A) and oil (B), a pro"le of the three-phase
body will be obtained. It resembles the shape of a `"sha
and can be used to represent graphically the in#uence of
the surfactant concentration on the phase behaviour of
the system.
We used normal alkanes and phenylalkanes
(C H )(CH ) H to model the oil components and n-
6 5 2k
alkyl polyglycol ethers H(CH ) (OCH CH ) OH-C E
2i 2 2+ i j
(i denotes the number of carbon atoms in the hydropho-
bic alkyl chain and j the number of hydrophilic ethoxy
groups) * to model non-ionic surfactants. In our study
we used the MHV2 model (Dahl & Michelsen, 1990),
which combines the Soave}Redlich}Kwong CEOS, and
an excess Gibbs energy model (modi"ed UNIFAC, Lar-
sen, Rasmussen & Fredenslund, 1987), because it has
qualitatively the correct behaviour and serves the present
purposes of validation the new algorithm we are advocat-
ing.
We exemplify the results on two model systems
* water#n-C #C E system, and water#
10 4 1
phenyloctane#C E system.
4 2
Fig. 2 shows the simulated `"sha pro"le of the three-
phase body for the water#n-C #C E system, as
10 4 1
a function of the mass fraction of the amphiphile (C) in
the mixture of all three components, which is given by
c"C/(A#B#C).
Fig. 3 presents the origin (appearance), growth, and
eventual disappearance of the LLLE for the system
water#phenyloctane#C E with increasing temper-
4 2
ature.
In all cases studied, the algorithm reports correctly and
without any numerical di$culties the appearance and/or
disappearance of a three-phase region, observed experi-
mentally for these systems (Kahlweit, Strey, Haase &
Firman, 1988a; Kahlweit, Strey, Firman, Haase, Jen
& Schomacker, 1988b; Kahlweit, Strey, Schomacker
& Haase, 1989).
2. Conclusion
The present paper advocates a novel robust algorithm
for predicting and calculating LLLE in multicompo-
nent systems. The architecture of the algorithm is a two-
level one, and the numerical routines of the second
level exploit to the full the results of the stability
analysis check, carried out on the "rst level. Further-
more, the algorithm does not su!er from some of the
well-known problems like: convergence to a trivial solu-
tion; convergence to an incorrect solution (corresponding
with a local rather than a global minimum of the Gibbs
energy); a failure to converge to a physically feasible
solution at all. The #ash routines require modest com-
putational e!orts and demonstrate excellent convergence
characteristics. Convergence of the LL and LLL #ash
calculations was usually achieved in less than four iter-
ations.
The algorithm can employ successfully any thermo-
dynamic model.
Acknowledgements
R. P. Stateva, G. St. Cholakov, and A. A. Galushko
gratefully acknowledge "nancial support from the British
Council.
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