(Reviews in Chemical Engineering) Numerical Solution of The Isothermal Isobaric Phase Equilibrium Problem

NUMERICAL SOLUTION OF THE ISOTHERMAL,
ISOBARIC PHASE EQUILIBRIUM PROBLEM
William A. Wakeham1' and Roumiana P. Stateva2
λ
University of Southampton, Highfield, Southampton, SO171BJ, UK
2
Institute of Chemical Engineering, Bulgarian Academy of Sciences,
Sofia 1113, Bulgaria
1. INTRODUCTION
Thermodynamic modelling and phase equilibria are at the heart of

chemical process design. For example, 70 to 90% of the equipment and
energy costs in modern chemical plants are related to separation and
purification processes and they are designed largely on the basis of
thermodynamic equilibrium. Furthermore, the occurrence of an azeotrope or
a liquid-liquid phase split may be the determining factor in developing a flow
sheet for a new process. Thermodynamic modelling is playing an increasing
role in such diverse areas as environmental engineering and down-stream
processing in biotechnology.
The phase behaviour of multicomponent systems is a complex topic from
at least five points of view. First, the number of thermodynamic state variables
required to describe thermodynamic equilibrium in an ^-component system
is Nc + 2, and so can be quite large in industrial practice. Secondly, the
experimental study of phase equilibrium is very time consuming and difficult
especially for multicomponent systems away from ambient conditions.
Thirdly, there exists no exact, practicable theory that relates the phase
behaviour of a dense fluid system to the properties of its molecules. Fourthly,
the description of the phase behaviour of materials based upon simple
heuristic models is prone to substantial error. Finally, even when such
simplified thermodynamic models are applied, the determination of the phase
behaviour of a multicomponent fluid system (number of phases, their identity
' Corresponding author. Telephone: +44(0)23 8059 2801;

Email: vice-chancellor@soton.ac.uk
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Vol. 20, Nos. 1-2, 2004 Numerical Solution of the Isothermal, Isobaric
Phase Equilibrium Problem
and composition at equilibrium for a specified temperature and pressure) is

far from straightforward.
Among these various aspects the expense and difficulty of the experiment
has led to its decline and its replacement by a growth in empirical modelling
using simple thermodynamic models. For this reason such models are
ubiquitous in engineering practice so that a dominant problem in design
software is the robust solution of the phase equilibrium problem for such
models.
Of course, the phase equilibrium problem has been around for many years
but it is still an object of continual interest. One reason is that the simple
numerical techniques employed for its solution, which work well in most of
the cases, can fail even for simple binary systems. More importantly, new
chemical engineering processes often involve multicomponent, non-ideal
system, which can exhibit a variety of possible phase equilibria. Furthermore,
the processes are often performed at pressures and temperatures near the
critical point or near the phase boundary, which further complicates the
solution of the phase equilibrium problem. Last, but not least, phase
equilibria calculations are executed nowadays not only as stand-alone
calculations, but also as a part of a more general simulation, synthesis or
design case, performed by a process simulator, where they are run thousands
of times. In these cases the reliability and robustness of phase equilibria
calculations is of utmost importance since their failure at any stage will
disrupt the solution process completely.
In view of the above, in recent years interest has been focused primarily
on implementing known, modified, or new powerful and sophisticated
numerical techniques and optimisation methods, developed originally for the
solution of a pure mathematical problem, to the solution of the phase
equilibrium problem. These developments have led to increasingly robust
algorithms. Work is therefore more and more concentrated on tackling
unsolved problems with ever more sophisticated techniques.
For these reasons, the present review addresses only the direct application
of numerical techniques to the solution of phase equilibrium problems
described by simple thermodynamic models. We seek to outline in a
systematic manner the main trends in phase equilibria calculations, without
the ambition to be exhaustive, since the number of publications devoted to
this topic is extremely large. Moreover, during the last few years, several
excellent papers reviewing methods and algorithms for the solution of

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W.A. Wakeham and R.P.Stateva Reviews in Chemical Engineering
particular problems in phase equilibria calculations have been published, and

there is no benefit from repetition.
The review will also highlight our own experience in developing new
methods and algorithms and their application to predicting and calculating
the phase behaviour of some well-known and widely used systems.
2. STABILITY AND PHASE EQUILIBRIUM
Thermodynamics provides the mathematical framework in which an

abstract formulation of the phase equilibrium problem is readily obtained. Its
application to phase equilibria in multicomponent systems involves
translation of the real problem into an abstract mathematical problem and
solution of the latter, followed by transformation of the mathematical
solution to physical meaningful terms. The profound insight of Gibbs, who in
1875 defined the function chemical potential, made it possible to demonstrate
that at equilibrium, the chemical potential of each component must be the
same in every phase.
In dealing with a closed material system under various constraints (e.g.
constant T and P) that does no work other than that owing to changes in the
system volume against the surroundings at constant P, the application of
Clausius inequality (Poling et al., 2001):
Δί/-ΓΔ5+/>ΔΚ<0 (1)
produces criteria of its equilibrium. These criteria subsequently lead to the

conditions of equilibrium requiring uniformity of Τ and P, and chemical
potential throughout the system.
Thus, the general result for a closed, heterogeneous system consisting of
π phases and Nc species is that at equilibrium the following must hold:
/>">= P(2) =... = /><" (3)

/,,">=„<» =... =
(4)

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Eq. (4) is the fundamental equation of phase equilibrium. The left-hand

side of Eq. (1) is the Gibbs free energy change under conditions of constant T
and P, and we may write:
AG7,,,<0 (5)
Thus, in a closed system constrained to constant temperature and

pressure, spontaneous processes result in negative Gibbs free energy changes,
and at equilibrium the Gibbs free energy has its minimum value. This is the
first condition of thermodynamic stability, satisfied by all stable equilibrium
systems.
Accordingly, if we seek to describe a fluid mixture by means of an
arbitrary model that relates its Gibbs energy to T, P and composition we must
be able to determine uniquely those thermodynamic states for which the
system is in stable equilibrium. It is to that very process that we devote the
remainder of this paper.
To elucidate the problem let us consider a single-phase mixture of
components 1 and 2 constrained to constant temperature and pressure. Initial
equilibrium is presumed, and a variation is devised whereby the system is
divided into two parts, designated A and B, and a transfer of mass is made to
occur between the separate parts. The total system is closed so:
dnf+dn?=Q (6)
dnl+dn%=0 (7)
Taylor series expansion is used to represent the property change for each
phase. The series expansion will be combined to express the total Gibbs free
energy change that must then satisfy:
SGTP>Q (8)
Omitting terms higher than second order we have:
δ GTI, = //, (dn* + dnf ) + μ2 (dn* + dn%) +

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W.A. Wakeham andR.P.Stateva Reviews in Chemical Engineering
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All intensive variables of parts A and B are equal, and the two first order
terms are zero by virtue of Eq. (6) and (7). To satisfy Eq. (8) the sum of the
second order terms in Eq. (9) must be positive. If we consider a special case
of variation in the mole numbers w,A with n* held constant, it will be
necessary to include only the first second-order term to obtain the desired
stability conditions. Thus we must have:
(10 a)
or
>0 (10 b)
These derivatives may be expressed in terms of intensive variables by

utilising the definition of mole fractions, and Eq. (lOa) then becomes:
>o (Π)
< + »2e U 14
Taking into consideration that the intensive variables of part A and part B are
identical, we can write:
(12)

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Vol. 20. Λ/05. 1-2, 2004 Numerical Solution of the Isothermal, Isobaric
Because the term in parentheses will always be positive then the stability
condition for a binary system in terms of mole fractions is:
>0 (13 a)
or equivalently
>0 (13 b)
We have considered only a binary system in order to reduce the

mathematical complexity - however the same derivations can be used to
include any number of components. The stability condition given by Eq. (13)
therefore would apply to each and every component in the mixture.
In most applications we are rarely interested in verifying whether the
system is in a state of equilibrium because this is generally known or
assumed. Of more interest are the thermodynamic statements, which
characterise the equilibrium state.
The second and third conditions for thermodynamic stability are those of
mechanical and thermal stability, which will not be derived here, but which
are given by:
<0 (14)
->0 (15)
Eq. (13) together with Eq. (14) and Eq. (15) are necessary and sufficient
conditions for the thermal, mechanical and chemical stability in regard to
infinitesimal disturbances of the system state. The boundary surface (line)
determined by the above three criteria separates the unstable from the
metastable states, and is called the spinodal. The boundary between the
metastable and stable states is determined by the equilibrium conditions (Eqs.
2, 3, 4) for the co-existing phases and is called the binodal. At the critical
point the binodal and the spinodal coincide.

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The expression for the stability criterion of a multicomponent system at

fixed 7" and P in terms of mole fractions reads:
where |j denotes determinant.

Thus, the determinant given by Eq. (16) must be positive or, in other
words, for all its principal minors the following must hold:
Nc-\Ne-l
ΣΣ\# *GldXidXj\>0 (17)
1=1 J=\
This stability criterion requires that the Gibbs energy function must be
convex, as was first shown by Gibbs.
The task of thermodynamics of phase equilibrium is to describe
quantitatively the distribution at equilibrium of every component among all
the phases present. We would like to relate the abstract chemical potential of
a substance to physically measurable quantities such as Τ, Ρ, and
composition. The chemical potential does not have an immediate equivalent
in the physical world and it is therefore necessary to express it in terms of
some auxiliary function, which may be more easily connected with
measurable quantities.
For this purpose Lewis defined a function called fugacity. The definition
of fugacity for any component in the system, whether .solid, liquid or gas,
ideal or not is given by:
(18)
The fugacity provides a convenient transformation of the fundamental

equation of phase equilibrium (Eq. 4). If Eq. (18) is written respectively for
two phases and after some simple substitutions and rearrangements yields:
f?=f> (19)
The equation gives a very useful result since it tells that the equilibrium

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condition in terms of chemical potentials can be replaced without any loss of

generality by an equation, which requires that the fugacities of any species
must be the same in all phases.
In seeking to describe the thermodynamics of fluid mixtures it is
conventional to work with quantities related to the fugacities rather than the
fugacities themselves, and there are two common schemes. In the symmetric
models scheme, fugacities are related as shown:
where <p\ and φ? are fugacity coefficients of the /-th component in the
liquid and vapour phase, respectively.
While in the asymmetric models' scheme:
where γ, and f° denote the activity coefficient and the standard state
fugacity of the /-th component in the liquid phase.
This gives us the possibility to have an expression for the Gibbs energy in
measurable quantities and not in terms of chemical potentials. Furthermore,
provided there is a thermodynamic model available, one can calculate the
Gibbs free energy for any system with any number of components.
3. THE MULTIPHASE ISOTHERMAL,

ISOBARIC FLASH PROBLEM
The general multiphase problem is the single most important calculation

in phase equilibrium and consists of finding the correct number and types of
phases and their corresponding equilibrium compositions such that the Gibbs
free energy of the system is a minimum.
A: very large number of methods and algorithms have been advocated to
solve-the phase (and chemical) equilibrium problem, and all of them are
based on solving a sequence of sub-problems. Although each has its own

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specifics, from the viewpoint of problem formulation and solution, the

methods can be grouped into two different classes: equation-solving
approaches, and Gibbsfree energy minimisation approaches.
3. 1. Equation-solving approaches:
These approaches to phase (and chemical) equilibrium calculations solve
a set of non-linear equations arising from mass balances and phase (and
chemical) equilibrium relations, which satisfy the necessary conditions of
equality of the chemical potentials of every component in each phase. The
best known are the isothermal vapour-liquid calculations, which are probably
the most common in a wide variety of chemical engineering applications. The
objective is to determine the compositions of the vapour and liquid phases.
The underlying flash equations for a two-phase vapour-liquid system
include:
(22)
(23)
If Eq. (22) and Eq. (23) are combined and the flow rates are eliminated in
terms of the vapour fraction α = FV/F, the flash condition may be written:
— -1 = 0 (24)
The phase compositions then are given by:
*,=-. πτ-7Τ (25 a)
and
y, = *Λ (25 b)
The above equations give only a necessary (equality of chemical
potentials) but not a sufficient condition for equilibrium.

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There are many ways to solve the above flash equations and one
possibility is to use classical successive substitution procedures, because they
are simple and perform well in many cases. The algorithm alternates between
calculation of the thermodynamic properties and the current estimate of the
phase distribution, and a recalculation of phase amounts and compositions,
assuming composition independent thermodynamic properties.
It has been generally presumed that the successive substitution procedures
will be well behaved and "safe", even if slow to converge in some regions
(Heidemann and Michelsen, 1995). However, the procedures can be
nonconvergent for some systems, far from any points where either of the
equilibrium phases can become unstable or approach criticality. The
nonconvergent behavior is associated with large negative deviations from the
ideal solution model and results when one or more eigenvalues of the matrix
( Qf\
E = -^-
la*, ι . are
\ J Xi=i
less than -1. The consequence will be an oscillatory
sequence of phase compositions with an error that does not decrease

(Heidemann and Michelsen, 1995).
3.1.1. Newton methods

More recently, Newton and quasi-Newton type methods and their
modifications have become particularly popular local methods for the
solution of the governing equations of a multiphase flash calculation, because
of their simplicity, robustness and better convergence characteristics than the
successive substitution methods. However, they bring with them several
problems, which we will discuss below:
The above methods work in many cases, but they can fail to produce the
correct solution even for simple binary systems. The reason can be numerical
problems: computational difficulties associated with the non-linear equation
solving methods themselves. There can also be intrinsic "physical"
problems, originating from the fact that the simultaneous equations
underlying the flash routines, as pointed out, are necessary but not sufficient
conditions for phase equilibria (the sufficient condition is minimum of the
Gibbs energy).
Before enumerating these problems in some detail we would first like to
summarise very briefly the application of the Newton method to the solution
of systems of non-linear equations, like those involved in vapour-liquid
equilibrium calculations.

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In the case of a system of non-linear equations f(x) = 0, the conditions

under which the Newton method is guaranteed to converge at second order
are known and can be found in several texts (see for example Fletcher, 1987).
These conditions are if: the equations, constituting the system f(x) are
continuously differentiable functions; and the Hessian matrix satisfies a
Lipschitz condition |u(x) - H(y)| < λ \\ - y| in the neighbourhood of a local
minimiser x*; and xw is sufficiently close to x* for some k, and H* is positive
definite, then the Newton method is well defined for all k and converges at
second order.
Obviously, the basic Newton method as it stands is not suitable for a
general-purpose algorithm since H* may not be positive definite when x* is
remote from the solution, and then the Newton method fails to converge
(either does not converge at all or its convergence is very slow). In such cases
it is a common practice to use quasi-Newton methods. They approximate
H(*H by a symmetric positive definite matrix, which is updated from iteration
to iteration, and achieve a superlinear convergence only when they are well
within the neighbourhood of the solution.
Newton and quasi-Newton types are strongly initialisation dependent.
They are likely to fail if the initial guess is poor. They do not always
converge to the solution closest to the initial guess and the iterates may
oscillate between two solutions. The accuracy of the initial guess necessary
for successful implementation of Newton and quasi-Newton type methods
varies according to the degree of non-linearity of the functions involved.
Sometimes the generation of suitable starting points can be as difficult as
obtaining the actual solution, especially if the functions are highly non-linear.
In highly non-linear systems of equations, a large or even global convergence
domain is desirable, which, however, cannot be realised by local methods.
Thus, in computing equilibrium in two-phase systems, and even more so in
multiphase (multi-reaction) systems, equation solving methods are prone to
severe computational difficulties, especially for strongly non-ideal systems.
The particular features of the Newton and quasi-Newton methods applied
to the solution of phase equilibrium problem have other difficulties, e.g.
convergence to a trivial solution, especially when symmetric models are
employed to model the fugacities of all phases (Eq. 20). Green et al. (1993)
point out that since the equation of state (EOS) and the derived properties are
non-linear and the phase equilibrium problem in which they are nested is
especially non-linear, applying Newton's method can result in fractal patterns
of response, and obtaining the trivial solution is one of its demonstrations.
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Another problem may arise when the algorithm progresses into the domain of
non-physical parameters), such as negative mole fractions.
The intrinsic difficulties of the application of Newton and quasi-Newton
methods to the solution of the phase equilibrium problem include: lack of a
priori criteria for determining the number of possible phases; non-uniqueness
and the impossibility to determine with certainty if the algorithm does not
find solution whether this is the case in reality or whether this is a result of
some numerical or software issue. The non-uniqueness is a particular
problem and is a result of the mathematical presence of local minima and
maxima in the Gibbs energy surface. This, in turn, relates to convergence to a
local rather than global minimum, and to the impossibility to distinguish
among thermodynamically stable, metastable and unstable equilibrium states.
Despite the above limitations, equation-solving methods have been
extremely popular, and many robust algorithms are available for simple
vapour-liquid equilibrium calculations. Ohanomah and Thompson (1984 a-c),
Cairns and Furzer (1990), Seider, Brengel and Widagdo (1991), Seider and
Widagdo (1996) provide extensive studies of the implementation of the best
equation-solving algorithms known for the phase and chemical equilibrium
problem, and we will not review them here. We single-out as deserving
special interest and attention the "inside-out algorithms" advocated by
Boston and Britt (1978) and the thermodynamically consistent hybrid-method
of Lucia et al. (1985) and Venkataraman and Lucia (1986).
Finally, we would like to emphasise once again the extreme importance
of good initial estimates (starting points) for the equation-solving methods
and the employment of efficient procedures for their generation.
3.2. Gibbs energy minimisation approaches

As discussed in the previous section, under conditions of constant
temperature and pressure, a multicomponent and multiphase system achieves
equilibrium when its total Gibbs free energy is at the global minimum, or:
min G(n)
s.t An-b = 0 (26)
τ
0 < η <η
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W.A. Wakeham and R.P.State\>a Reviews in Chemical Engineering
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The equality An-b = 0 corresponds to the mass balances, and can take
either of the following two forms depending on whether reaction occurs in
the system:
a) Phase and chemical equilibrium (reacting systems):
α
Λ»=^ k = \,...,E (28)
b) Phase equilibrium (no reaction):
=H T /=!,...,# (29)
There are essentially two routes that can be followed to obtain or confirm
that an equilibrium solution corresponds to a global minimum of the Gibbs
free energy. The two optimisation problems associated with these approaches
are: direct minimisation of the Gibbs free energy and minimisation of the
tangent plane distance function (TPDF).
4. DIRECT MINIMISATION OF THE GIBBS FREE ENERGY
White et al. (1958) were the first to minimise the Gibbs free energy for an
ideal system. They tested two methods - a steepest descent method and a
linear-programming technique method, which later became known as the
RAND algorithm. An excellent and most extensive review of the early
contributions in this area can be found in Seider et al. (1980).
To minimise directly the Gibbs free energy a variety of optimisation
methods can be used. However, because the number and identity of phases
present at equilibrium are not known a priori the application of optimisation
methods to the solution of this particular phase equilibrium problem may
cause severe computational difficulties. Although the phase rule supplies an

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obvious upper bound on the maximum number of phases that can be present
at equilibrium, it is of limited use as it can lead to a large number of potential
phases that need be considered in the system. Thus, there has to be a strategy
to circumvent this problem and several have been proposed.
The first strategy requires fixing the number of phases (two or three
usually because this is the most common circumstance) and using nonlinear
programming to minimise the Gibbs energy function among those phases.
George et al. (1976) used an allocation function to eliminate equality
constraints and minimised an unconstrained Gibbs free energy function by
the method of Powell (1970). Ohanomah and Thompson (1984 c) proposed a
geometric programming method to transform the minimisation problem into
a Newton-Raphson procedure. Their approach proved to be successful in
establishing multiphase behavior of many polar systems with the Wilson
activity coefficient model. Other examples of this approach are the works of
Castillo and Grossmann (1981), who used a projected-variable metric method
that does not require second derivatives of the objective function with respect
to the optimisation variables (Hessian matrix), Lantagne et al. (1988), who
proposed a penalty function approach to include nonnegative inequality
constraints in the objective function. Boston and Fournier (1978) illustrated
this approach for splitting a non-ideal liquid phase into two liquid phases, and
after splitting the liquid phase use K-value algorithms to converge the
equilibrium calculations.
The second strategy adds sequentially an extra phase in the computations
and tests the stability of the resulting phase configuration (Gautaum and
Seider, 1979; Scares et al. 1982; Nghiem and Li, 1984; Wu and Bishnoi,
1986; Walraven and Rompay, 1988; Gastier et al. 1989). An example is the
work of Gautam and Seider (1979) who use Wolfe's Quadratic Programming
algorithm, and eliminate phases as the algorithm progresses. They compared
its performance to some other methods for the minimisation of the Gibbs free
energy. This approach, however, could lead either to convergence to
constrained minima if too many phases are assumed, or to convergence to
trivial or local extrema. In their review Ohanomah and Thompson (1984
a,b,c) highlight in detail the difficulties generated when a large number of
excessive phases is assumed, and this question will not be pursued further
here. It is important to underline, however, that even if the number of phases
is assumed correctly, the solution obtained may be at a local minimum.
Hence, it is necessary to address the problem of multiplicity within the
solution space, especially near phase boundaries and in the critical region.

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With their new formulation, that enables simultaneous stability and

multiphase computations at fixed temperature and pressure, Gupta et al.
(1991) tried to circumvent the above problem by introducing a reference
phase that is known to be present at equilibrium. It was shown by
optimisation theory considerations that the Lagrange multipliers (stability
variables) associated with potential additional phases are positive if these
phases are absent and 0 if they are present at equilibrium. The augmented set
of coupled non-linear algebraic equations obtained that describes both the
stability and multiphase isothermal-isobaric flash calculations for reacting
and non-reacting mixtures are solved for the phase fractions and stability
variables by Newton-Raphson iteration. This approach proved to be
successful in predicting VLLE behavior for the methane-hydrogen sulfide-
carbon dioxide system.
A problem common to all optimisation methods applied to the direct
Gibbs energy minimisation is that because any equilibrium solution to G
must satisfy equality of chemical potentials (corresponding to the first order
necessary condition of equilibrium), for non-ideal systems there may be
multiple solutions, corresponding to local extrema of the Gibbs energy
function, only one of which is at the global minimum. Thus a sufficiency
condition is required, which is provided by the tangent plane criterion.
5. MINIMISATION OF THE TANGENT PLANE DISTANCE

FUNCTION (TPDF)
The tangent plane criterion was formulated and solved theoretically

(though not computationally) more than 100 years ago by Gibbs. It is only
recently that a practical numerical realisation of the Gibbs tangent plane
stability test has been developed - derivations and figure illustrations were
given by Baker et al. (1982), and a first implementation was presented by
Michelsen (1982 a, b). These papers have revolutionised the way phase
equilibrium calculations are performed and have spawned a steady series of
papers and algorithms refining the basic ideas.
At specified temperature T, pressure P and feed mole fraction z, a
necessary and sufficient condition for a postulated solution to be an
equilibrium one is that the TPDF, denoted by F(x), should be non-negative
for all possible phases in the system. The TPDF is defined as the distance
between the Gibbs surface g(\) and the tangent plane Z,(x) associated with
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this surface at z. The optimisation formulation of the phase stability problem

can be described as follows:
i
min F(x) = g(x)-L(x) = f>, {M(x)-//,(z)}
/=!
(30)
s.t. X>,=1 (31 a)

ι=Ι
0<x, <1 (31 b)
If the tangent plane lies completely below the Gibbs surface (that means
that F(x) is nonnegative for all ranges of χ ), then the postulated solution
corresponds to a global minimum of the Gibbs free energy. If not, a phase
equilibrium configuration with lower Gibbs energy exists and must be found.
Recently, Smith et al. (1993) and Jiang et al. (1996) have provided
important new insights into stability analysis and extended the tangent-plane
criterion to apply to reacting mixtures in a reaction tangent-plane criterion.
The application of this criterion was presented in great detail by Smith et al.
(1993) and Seider and Widagdo (1996), and will not be discussed here.
The motivation for using the tangent-plane stability criterion arises from
an assumption that must be made in order to formulate the Gibbs free-energy
minimisation problem, i.e. to specify the number and identity of the phases at
equilibrium. However, for a given number and type of phase, the global
minimum of the Gibbs free energy is not a sufficient condition for the true
equilibrium. This is because a different set of phases may contain a solution
that has a lower value for the Gibbs energy. Given a candidate equilibrium
solution, the advantage of the tangent-plane criterion is that it provides an
unambiguous means of determining if the proposed solution is stable or
unstable.
Minimisation of the TPDF has been found to be more reliable and robust
than minimising the Gibbs function directly, since theoretically to guarantee
a global .minimum for G, using global optimisation, the formulation must
contain a large number of variables, making a global optimisation algorithm
computationally expensive, particularly for larger systems. For these reasons,
the minimisation of the TPDF presents many advantages.
Baker et al. (1982) formalised the concepts of thermodynamic stability
for multicomponent mixtures, the fundamental principles of which had first
been studied by Gibbs. They proved that a necessary and sufficient condition
for an equilibrium solution to correspond to a global minimum of the Gibbs

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W.A. Wakeham and R.P.Slaleva Reviews in Chemical Engineering
free energy is that the tangent plane corresponding to this solution lies on or
below the Gibbs free energy surface for all possible values of the
compositions. (See Figure 1 for a two component system). The key
characteristic is that if a tangent plane that lies completely below the Gibbs
free energy surface does exist, then the equilibrium solution, which
corresponds to the global minimum of the Gibbs free energy, is given by the
compositions at the points of tangency and ß. In other words Baker et al.
(1982) proved that a necessary and sufficient condition for a postulated
solution to be equilibrium one is that the TPDF is non-negative for all
possible phases represented in the system. However, in the general
multicomponent, multiphase problem there is no rigorous approach to
determine where the tangent plane touches the Gibbs free energy surface so
that it always lies below it.
Mole Fraction
Fig. 1: Tangents to the curve of the Gibbs free energy versus mole fraction
(constant temperature and pressure).

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In what follows firstly the formulation of the TPDF, advocated in the

pioneering work of Michelsen, will be outlined briefly, and then some of the
methods applied to minimise the TPDF will be discussed.
6. MICHELSEN'S APPROACH
The method of Michelsen (1982) utilises the tangent-plane criterion

illustrated by Baker et al. (1982). Based on this criterion, the equilibrium tie-
line between the coexisting phases must be tangent to the curve of the Gibbs
free energy versus mole fraction (Figure 1) at both α and β in order to have
equality of the chemical potential of species in the two phases.
The Gibbs free energy of a mixture of Nc components at a given
temperature and pressure with mole numbers n, is:
G =!>,/', (32)
1=1
It is assumed that the mixture is split into two phases, I and II, with mole
numbers (Ν-έ) and ε respectively, where ε is a very small amount of the
second phase.
Stability of the original mixture requires that its Gibbs free energy be at
the global minimum. Therefore, a necessary condition for stability is that:
Γ(ι)= 1=1
for all trial compositions y. Geometrically, F(y) is the vertical distance

from the tangent hyperplane to the molar Gibbs energy surface at
composition z (mole fraction vector of original mixture) to the energy surface
at composition y, as shown in Figure 2 for a binary mixture.
In an important development Michelsen (1982 a) noted that all of the
minima of the TPDF are located in the interior of the permissible region
"c
(y,>0, 2^ytr =1). Consequently, F(y) will be non-negative if it is non-
1=1
negative at all stationary points where its derivatives with respect to all of the
independent variables vanish. Differentiation with respect to the mole

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*
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ui
e
u.
H
Λ
Λ
Ο
I
Fig. 2: The vertical distance F from the tangent plane to the molar Gibbs
energy of mixing at composition z to the tangent at composition y,
for a binary mixture.
fractions gives the stationary condition as:
(34)
where Κ is independent of the component i. Thus, the original system is

stable if AT is positive or equal to zero.
Using an EOS for chemical potential like Soave-Redlich-Kwong, Eq.
(33) becomes:
(35>
1=1
The stationary condition is as follows:
l + ln<pl(y)-\nzl-\n<pl(z) = K (36)
Introducing new variables, Y, = exp(-K)yl , in order to eliminate Κ from

the computation, Eq. (36) becomes:
/ = 1,..., Nc (37)

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19
where Michelsen interprets the new variable Y, as mole number.
Stability is verified if at all stationary points K > 0 , which means that
Σ^· - ' ' a"d conversely, the phase is unstable if a stationary point is located
where ΣΥ>>1·
»=l
Before proceeding further we would like to point out that for liquid
mixtures at low to moderate pressures the stability test can be rewritten using
activity coefficients instead of the chemical potential. If the activity of any
component zy,(z) in the initial overall system is greater than unity then the
system is unstable (see for example Heidemann, 1983; Cairns and Furzer,
1990). This is because the TPDF calculated at the point, corresponding to
pure component / , is negative, if z,y,(z) >1. If this happens, then there is at
least one point in the composition space where the TPDF is negative. This
simple stability test is very fast but not absolute. The phase of composition z
is certainly unstable if the above is true for any pure component. However, it
may still be unstable even if the inequality is satisfied at all points
corresponding to pure components.
There are other alternative stability tests, which require the evaluation of
the sign definiteness of the Hessian matrix of the Gibbs free energy with
respect to Nc -1 independent mole fractions (van Dongen et al., 1983). It
should be noted that the Hessian matrices of the TPDF and the Gibbs free
energy are identical and equal to the Jacobian of the gradients of the TPDF.
Thus the Hessian matrix of the Gibbs free energy is positive definite at
stationary points corresponding to a minimum in the TPDF, and these
stationary points are stable or metastable phases. Conversely, all minima and
saddles of the TPDF lie in the region of unstable phases. Therefore, if the
Hessian matrix of the Gibbs free energy is positive definite, the mixture will
be either metastable or globally stable. It is important to underline that
Michelsen's approach does distinguish absolutely stable from metastable
regions.
Michelsen's stability method requires initial guesses, and it is
recommended to use as many initial guesses as there are components. The
pure components of the mixture act as such (Michelsen, 1982 a). However,
they prove to be insufficient in many cases of multiphase equilibria, since
solutions of Eq. (37) that are found will correspond to stationary points lying

20 Authenticated
W.A. Wakehain and R.P.Stateva Revie\vs in Chemical Engineering
on the extremities of the g surface. Furthermore, the real picture of the g

surface even for a simple mixture is not known beforehand. Thus, in many
cases of practical interest, once the set of initial estimates is exhausted, the
other solutions of Eq. (37) can be found only by "trying" completely arbitrary
initial estimates. How that should be done and at what computational cost is
not obvious. Along this line of thought the primary limitation of tangent-
plane stability analysis procedures should be emphasised - the failure to
locate a y at which the TPDF is negative does not guarantee that the phase
distribution is stable.
Some authors have suggested solving the problem by an exhaustive
check, e.g. by starting the minimisation procedures from several points - all
pure component compositions along with points generated from heuristics.
This approach can be very time consuming and still does not guarantee that
all minima of the TPDF have been found especially if these minima are close
in composition, e.g. in the vicinity of the critical point.
Other authors, like Cairns and Furzer (1990), who described a Newton-
Raphson method to obtain the stationary points of the TPDF, advocated the
initiation of a search for the stationary points using the component with the
largest activity. To select the second starting points, they used the component
with the second largest activity, etc.
The usual approach to find the global minimum of TPDF is to solve a
system of non-linear equations for the stationary points (Eq. 37), and it is
crucial that all stationary points are localised since the failure to locate
Σ^ > 1 does not guarantee that the phase distribution is stable.
/=!
However, because there is no theoretically based guarantee of reliability

owing to the non-convex and non-linear nature of the thermodynamic models
used to describe the Gibbs free energy in the TPDF, and because of the
difficulties that may arise in solving such problems by standard methods
(e.g., Michelsen, 1982 a, b), there has been significant interest in the
development of new methods with the view of guaranteeiung that all minima
of the TPDF have been found. They fall into two big classes - local and
global methods.
Newton and quasi-Newton methods pertain to the first class and we have
already briefly discussed their advantages and shortcomings. The global
optimisation methods, which can be classified either as (0 deterministic
optimisation methods or (/"/) stochastic methods, will be presented in more
detail hereunder.

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7. GLOBAL OPTIMISATION METHODS
All methods for global optimisation assume that a bounded set S c R",
containing the global optimum in its interior, is given in advance. Thus, with
χ = (Xf,...,xn) and /:S -> R, the problem will be to find:
?.= min
ΛΕ.Ι
{/(*)} (38)
Deterministic methods find the global optimum by an extensive search

over 5 or a dense countable subset of S. Clearly, in order to insure
optimality in a finite number of steps, certain restrictions have to be put on
the function: it is easy to construct objective functions for which the global
minimum can only be recognised on a subspace of arbitrary small volume. A
popular assumption in certain deterministic methods is that a Lipschilz
constant is given, i.e. a constant L = £,(/, A/) > 0 such that:
|fW-f(y)|<L|x-y| Vx,yeM (39)
where |·| denotes the Euclidean norm.

Unfortunately, this assumption is rarely verifiable in practice, and in
addition, the computational effort required by these methods is quite
formidable - it increases (in the worst case exponentially) with n, the
dimension of the problem.
Most stochastic methods start from a sample of points drawn randomly
from S. These methods offer an asymptotic guarantee: under mild
conditions on f the probability that the global optimum will be found by
stochastic method approaches 1 as the sample size increases. In addition to a
sampling or a global phase, most stochastic methods contain a local phase, in
which the sample is manipulated to yield a candidate solution value to the
optimisation problem.
In general the use of global techniques is relatively unexplored since only
deterministic global solvers have been employed. Stochastic optimisation
techniques have often been found to be as powerful and effective as
deterministic methods in many engineering applications. They require only
the objective function values and are highly likely to locate the global
minimum.

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7.1. Deterministic global optimisation methods

Recent deterministic algorithms are based on "global" methods such as
homotopy continuation methods (for example de Gance, 1993; Sun and
Seider, 1995; Jalali-Farahani and Seader, 2000, Bausa and Marquardt, 2000),
mixed integer nonlinear programming (MINLP) techniques which use
convexiflcation or convex underestimators to build upper and lower bounds
to the global minimum (for example McDonald and Floudas, 1995 a, b, c;
1997), improved branch and bound algorithm (Yushan and Zhihong, 1999),
Lipschitz algorithm (Zhu and Xu, 1999 a), interval Newton method (Hua et
al., 1996 a, b, c; 1998; 1999; Stadther et al., 1995, Tessier et al., 2000; Xu et
αϊ, 2000; Gau and Stadtherr, 2000; 2002; Gau et al., 2000).
It must be underlined that the non-convex and non-linear nature of the
thermodynamic models, which are employed to model the systems in
chemical and phase equilibrium problems, make the application of the
deterministic global optimisation techniques to minimise the TPDF very
difficult. These approaches require some sort of systematic search of the
entire composition space and can be computationally demanding. Clearly, it
is reasonable that some additional computational effort be required if
rigorous guarantees of finding a global minimum are demanded. However,
for problems with a large number of components the computational effort
associated with these approaches can become prohibitive.
7.7.7. Homotopy continuation, or incremental loading methods.

The homotopy-continuation method is a major advance in the solution of
systems of non-linear equations because it is a global method, which for
many applications has been found capable of finding multiple roots, from
which physical meaningful solutions can be selected. A comprehensive
review of the extensive literature in this area can be found in Garcia and
Zangwill (1981), Floudas (1999,2000), Jalali-Farahani and Seader (2000).
The homotopy method obtains the solution to a non-linear equation by
tracking a path from a starting point that is the solution of a much simpler
function. Both the original function and the simpler function are embedded
into a parameterised initial-value problem in ordinary differential equations,
which is solved by a predictor-corrector algorithm to obtain a solution to the
original equation.
A system of non-linear algebraic equations can be written as:

23
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Vol. 20. Nos. 1-2, 2004 Numerical Solution of the Isothermal, Isobaric
/ x =0 (40)
where / : R" -> R" is a continuously differentiable function; and χ e R" , is

the variable vector.
The basic concept behind the method is the creation of homotopy, which
is simply the deformation of a set of equations /(x) = 0 that are difficult to
solve into a set whose solution is easily found g(\) .
The homotopy equations, H(x,t) are generated by some combination of
/(x) , g(x) , and a homotopy parameter t , such that:
H(x,/) = H[/(x),g(x),f] = 0 (41)
The homotopy functions provide a smooth transition between an

approximation to the solution and the true solution, thus gradually
introducing the complex nonlinearities. Furthermore, the scalar homotopy
parameter is varied from 0 to 1 as a path is tracked from the starting point to a
solution, and when / = 0 the homotopy reduces to the simple system of
equations, g(x) , and equals the original equation /(x) when t = 1 . That is:
(42)
H(x f ,l) = g(x f ) = 0 (43)
Here x represents the vector of independent variables, x° - the initial x

and a solution to g(x)=0, and x r -the final x and a solution to /(x) = 0.
The form of the combination of /(x), g(x)and / that makes up the
homotopy varies from application to application, and each has its own
advantages and disadvantages.
Three choices for g(x) are widely used:
Newton homotopy.
(44)
Fixed-point homotopy:
(45)

24 Authenticated
W. A. Wakeham and R.P.Staleva Reviews in Chemical Engineering
Affine homotopy:
(46)
where x° is the vector of guessed values and /'(x°) is the derivative of

/(x)atx°.
Convergence to a global minimum using homotopy-continuation methods
requires that all branches of the homotopy path be followed. Because
homotopy-continuation paths of χ as a function of / often include singular
points, such as turning points, where the determinant of the Jacobian matrix
is zero, it is important to accurately trace the paths, while bypassing the
singular points. Several algorithms are available for doing this. The most
widely cited algorithms to find all solutions to the TPDF with the application
of homotopy-continuation methods are those of Sun and Seider (1995) and
Jalali-Farahani and Seader (2000).
For example, Sun and Seider (1995) apply a robust homotopy-
continuation method and work with a homotopy parameter A = l-/, which
reduces the Newton homotopy equations to:
H(x,A) = /(x)-A/(x°) (47)
where
0 at / = 0 Λ=1 (48)
H(x f ,o) = /(x f ) = 0 at t = \ A=Q (49)
and use multiple starting points in an attempt to find all stationary points of
TPDF along a single path.
The application of homotopy-continuation methods (e.g. Wayburn &
Seader, 1987; Kuno & Seader, 1988; Sun & Seider, 1995; Jalali-Farahani &
Seader, 2000) to the minimisation of the TPDF often provides much
improved reliability and the capability for locating multiple solutions.
However, these methods are still initialisation dependent, and variable
bounds and inequality constraints cannot be handled directly. More
importantly, no theoretical guarantee of identifying all solutions of the TPDF
can be given, as the formulation of TPDF always contains logarithmic terms.
Such guarantees can only be claimed for special cases like polynomial
systems of equations with no constraints.

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7.1.2. Lipscltitz algorithm

Another approach to the minimisation of the TPDF is to use Lipschtz
optimisation techniques with ε -global convergence.
The general Lipschitz algorithms with or without constrained conditions,
and their global convergence proofs were illustrated thoroughly by Horst and
Pardalos (1995). A real value function f is called a Lipschitz function on a set
Me/?" if there is a Lipschitz constant L=L(f,M) > 0 such that:
|fi»-fl;v)|< L||x-y| Vx,y e M (50)
where |·|| denotes the Euclidean norm.

The algorithm to solve the non-convex optimisation problem:
minf(x) (51)
s.txeA/ (51 a)
with M c R" non-empty and compact, is the following:

Start with an arbitrary point x° e D , and define the first underestimation
function by:
(52)
and the next iteration point by:
je1 = arg min F0(x) (53)
In step k, the underestimation function is:
(54)
and the next iteration point is:
jc l+1 = arg min /=·,(*) (55)
The stop criterion for Lipschitz optimisation is that the difference

between the original function value and the underestimation function value is

26 Authenticated
W. A. Wakehain and R. P.Stateva Reviews in Chemical Engineering
lower than the specified global tolerance ε.

In a thermodynamic application of a Lipschitz optimisation method Zhu
and Xu (1999 a) advocate an algorithm to obtain the global minimum of the
TPDF modelled by the SRK CEOS. The calculation of Lipschitz constant for
the TPDF was obtained by the upper and lower bounds of the parameters,
which were obtained by optimizing several convex or linear functions in the
feasible composition space. Thus, the phase stability problem can be solved
by Lipschitz optimization techniques with ε-global convergence. Two simple
binary mixtures at high pressures (methane+hydrogen sulphide and
methane+propane) were presented to check the global stability by a
univariate Lipschitz optimisation method, and the calculation results state
that the algorithm can be applied to obtain the global minimum of the TPDF
at elevated pressures with complete reliability. The authors point out that in
the case of systems containing three or more species, the global minimum of
the TPDF can be solved by multivariate Lipschitz optimization algorithms.
7.1.3. Interval techniques

Recent monographs, which introduce interval computations, include those
of Neumaier (1990), Kearfott (1996) and Hansen (1992). Herewith, we will
only outline very briefly the key concepts and basic ideas of the interval
methodology.
For an arbitrary function f(x), the interval extension over the interval X,
denoted F(X), is an interval enclosing all values of f(x) for χ ε X; that is, it
encloses the range of f(x) over X (interval quantities are indicated in upper
case, point quantities in lower case). It is often computed by substituting the
given interval X into the function f(x) and then evaluating the function using
' interval arithmetic. An interval extension provides upper and lower bounds
on the range of values that a function may have in a given interval. The
interval extension so determined is often wider than the actual range of
function values, but it always includes the actual range.
Let us consider the solution of a nonlinear equation system f(x) = 0,
where χ € Χ(0), and the goal is to find (or, more precisely, enclose within
very narrow intervals) all of the roots of the equation system in X(0). The
solution algorithm is applied to a sequence of intervals, beginning with the
initial interval vector (box) X(0) specified by the user. This initial interval can

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be chosen to be sufficiently large to enclose all physically feasible behavior

or to represent some constraint given in the problem. For an interval X(i) in
the sequence, the first step in the solution procedure is the function range
test.
Here, the interval extension F(X(i)) of fl[x) over the current interval X(t) is
computed and tested to determine whether it contains zero. If not, then
clearly there is no root of fi[x) = 0 in this interval, and the interval can be
discarded. If X(1) passes the function range test, then the next step is the
interval Newton test. This step requires an interval extension of the Jacobian
matrix of f(x) and involves setting up and solving the interval Newton
equation (a system of linear interval equations) for a new interval, referred to
here as the image.
Comparison of the image to the current interval being tested provides a
powerful existence and uniqueness test for roots of the equation system. In
particular, if the image is a proper subset of the current interval, then this is
mathematical proof that the current interval contains a unique solution of f(x)
= 0, which can be tightly enclosed with quadratic convergence by continued
application of the interval Newton equation. Furthermore, any root lying in
the current interval must also lie in the image. Thus, if the image and the
current interval do not intersect, this is mathematical proof that the current
interval contains no roots of fl» = 0. If the number of roots in the current
interval cannot be proven zero or one in this way, then in most cases, the
intersection of the image and the current interval is bisected, and the resulting
two intervals are added to the sequence of intervals to be tested.
There are several papers now, which advocate the application of interval
analysis techniques to the solution of a variety of phase equilibrium problem,
including locating all minima of the TPDF (Hua et al., 1996 a, 1996 b, 1996
c; 1997; 1998 a, b; 1999; Stadther et al., 1995, Tessier et al., 2000; Xu et al.,
2000; Gau and Stadtherr, 2002). Stadtherr et al. (1995) were the first to
suggest a method based on an interval Newton/generalised bisection (IN/GB)
algorithm and to apply it to small problems involving excess Gibbs energy
models, as later done also by McKinnon et al. (1996). Hua et al. (1996 a, b;
1998 b) extended this method to locate all stationary points of the TPDF
where the Gibbs energy is modelled with cubic equations of state (in
particular the Van der Waals (VDW), Peng-Robinson (PR) and Soave-
Redlich-Kwong (SRK) models with standard mixing rules) and applied it to
systems containing two and three components. Tesier et al. (2000) then
further extended the interval technique to problems involving excess Gibbs

28 Authenticated
energy models, and focussed on the NRTL and UNIQUAC models. They
examined larger problems using these two models and considered means of
enhancing further the efficiency of the technique, based on sharpening the
range of interval function evaluations.
The (IN/GB) method (Hua et al., 1996 a, b, c; 1998 b; 1999) gives an
important practical advantage since it does not require elaborate and smart
initial guesses. Furthermore, it represents a powerful and general-purpose
approach, which can be used successfully to solve a number of difficult
global optimisation and nonlinear equation solving problems, such as arise in
chemical engineering (e.g. Maier et al., 1998; 1999), in addition to the
minimisation of the TPDF. However, the (IN/GB) method cannot give
complete certainty of finding all stationary points because of rounding errors
and dependence problem of TPDF. Moreover, as discussed by Hansen et al.
(1992), Maranas and Floudas (1995) and Harding and Floudas (2000) it is not
possible for interval methods to exactly locate all finite stationary points.
Instead, it is possible to enclose all stationary points, that is, to construct tight
intervals around the stationary points. Thus, the (IN/GB) approach encloses
all stationary points of the TPDF within intervals of some tolerance ε.
Another important theoretical and computational issue that arises is that
since the (IN/GB) method ends up with intervals, it is not certain that within
an interval there exist one or multiple stationary points, that is, the
uniqueness issue. A theoretical condition for uniqueness that needs to be met
in the interval Newton methods is that the interval Jacobian matrix is a
regular Lipschitz matrix. As a result, the key issue becomes whether it is
possible to (1) state a priori whether the Jacobian matrix is regular (that is,
consider necessary and sufficient conditions for regularity), or (2) check a
posteriori whether within an interval there exists a unique solution (that is,
consider sufficient conditions for regularity).
The most significant drawback of the currently used interval methods is
the potentially high computational cost that must be paid to obtain the
mathematical and computational guarantees of certainty. New methodologies
are described for improving the efficiency of the interval approach. In
particular, a new hybrid preconditioning strategy, in which a simple pivoting
preconditioner is used in combination with the standard inverse-mid-point
method and a new scheme for selection of the real point used in formulating
the interval-Newton equation has been recently advocated by Gau and
Stadther (2002).
Brought to you by | Bibliotheek TU 29

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Vol. 20. Nos. 1-2, 2004 Numerical Solution of the Isothermal, Isobaric
These techniques can be implemented with relatively little computational

overhead, and lead to a large reduction in the number of subintervals that
must be tested during the interval-Newton procedure. Tests on a variety of
problems arising in chemical process modeling have shown that the new
methodologies lead to substantial reductions in computation time
requirements, in many cases by orders of magnitude (Gau and Stadther,
2002). For example, in a global optimisation problem to estimate parameters
in the van Laar equation for activity coefficients used to model vapor-liquid
equilibrium, Gau and Stadther (2002) using the new hybrid preconditioner,
report roughly half the CPU time required by Esposito and Floudas (1998) to
solve the same problem.
7.1.4. Mixed integer nonlinear programming (MINLP) techniques

One approach to guarantee theoretically that all solutions of the TPDF
will be identified is to reformulate the equation solving problem as an
optimisation problem (e.g. Maranas and Floudas, 1995; Harding et α/., 1997;
Harding and Floudas, 2000 a) and then to apply powerful, deterministic
global optimisation techniques such as aBB (Androulakis et al., 1995;
Adjiman and Floudas, 1996; Adjiman et al., 1998 a, b), which employ a
branch-and-bound methodology using convex underestimating functions.
This approach provides a mathematical guarantee that all solutions will be
located. However, in practice it may be necessary to perform problem
reformulations and to develop convex underestimators specific to each new
application. In an important paper, McDonald and Floudas (1994, 1995 a, b,
c) applied the Global Optimisation Algorithm (GOP) by Visweswaran and
Floudas (1990, 1993) and Floudas and Visweswaran (1990, 1993) to
guarantee ε -global convergence to the minimum of the Gibbs free energy.
They were, thus, the first to address the minimisation of the TPDF as a global
optimisation problem.
McDonald and Floudas (1994, 1995 a, b, c) showed for the first time that
for certain activity coefficient models (UNIQUAC, UNIFAC, ASOG, and
TK-Wilson), the TPDF can be reformulated to make it amenable, through the
formulation of convex underestimating functions, to be solved by powerful
GOP techniques -ε-global optimisation method and a branch and bound
algorithm, which mathematically guarantee that the global minimum of the
TPDF can be identified regardless of the starting point chosen. In a further
development McDonald and Floudas (1997) proposed the combination of the
Gibbs free energy minimisation problem with the stability criterion problem.

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They developed a special purpose programme GLOPEC and performed an

extensive computation study on difficult phase equilibrium problems. In their
most recent contribution Harding and Floudas (2000) extend the application
of global optimisation approach for the minimisation of the TPDF where the
Gibbs energy is modelled by an EOS.
The optimisation formulation for the TPD minimisation problem is given
as:
W, Ne
5>,.//,.(x,z)-5>,//,F (56)
1=1 »=l
s.t.£OS(x,z) = 0 (57 a)
=1 ( 57b >
1=1
0<*,<1 (57 c)
z>0 (57 d)
The objective function is written as a difference of two terms - the first

term represents the molar Gibbs energy surface and is a non-linear function
of compositions and compressibility. The second term represents the tangent
plane to the Gibbs energy function and is a linear function of composition.
Therefore, the formulation of the minimisation problem is a non-linear
programming problem, with non-convex terms in the objective function and
in the constraints. Owing to the presence of non-convexities, local
optimisation techniques may not converge to the global solution
(corresponding with the global minimum of the Gibbs energy) and MINLP
methods are required. The authors use convexification or convex
underestimators to build upper and lower bounds to the global minimum and
delete portions of the composition space that cannot contain a solution by
systematically tightening those bounds. Further, they argue that the
minimisation of the TPDF offers an advantage over an approach based on
enclosing all stationary points. In the minimisation approach, the solver
explicitly searches for the lowest possible value of the TPDF. Since regions
that have the lowest solution of the lower bounding problem are chosen to be
investigated first, negative TPD solutions (if they exist) are usually
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encountered in the first few iterations. An approach based on enclosing all

stationary points, since it does not focus exclusively on regions likely to
contain minimum values of the TPDF, is likely to require more iterations to
locate a negative tangent-plane distance. Moreover, as pointed out by Floudas
(1999) the fundamental difference between MINLP methods and Interval-
Newton methods is that the latter bound functions with scalars, whereas in
the former the mathematical structure of the problem is exploited, so as to
underestimate the non-convex functions by tight convex functions resulting
in much tighter bounds.
However, the high computational demand of MINLP global optimisation
methods and the requirement for a special model formulation makes them
unsuited for many simulation problems involving phase equilibria
calculations, in particular when multicomponent mixtures with more than
four components are present, since calculation time may increase rapidly
(Huae/a/., 1999).
7.2. Stochastic methods

Stochastic optimisation techniques have often been found to be as
powerful and effective as deterministic methods in many engineering
applications. Genetic algorithms (GAs) and simulated annealing (SA) have
found many applications in chemical engineering and in other fields. Both
these require only the objective function values and are highly likely to locate
the global minimum (Rangaiah, 2001).
SA is a computational procedure designed to find an optimal solution to a
combinatorial problem. It is a technique that is particularly well suited to
problems where it is not feasible to search exhaustively through every
possible combination of variables that compose the range of outcomes. An
iterative improvement scheme starts with an initial guess of the optimum
solution and attempts to generate alternative solutions that improve the value
of the objective function. Possible alternative configurations are usually
generated through a random perturbation around the most recent estimate of
the optimal configuration. This process continues until no further improved
solutions are found. In a particular phase equilibria application, Zhu and Xu
(1999 b) employed SA to locate all stationary points of TPDF. Zhu and Xu
(1999 c) and Zhu et al. (2000) extended the simulated annealing algorithm
(SAA) into high-pressure phase stability analysis on the basis of its
successful and reliable prediction of the global phase stability for liquid-

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W.A. Wakeham and R.P.Staleva Reviews in Chemical Engineering
liquid equilibrium (Zhu and Xu, 1999 b, d). However, the asymptotic
convergence of the SAA strongly depends on the suitable choice of its
"cooling schedules", otherwise it tends to get stuck in locally optimal
solutions (Zhu and Inoue, 2001). Rangaiah (2001) applied GA and SA to
phase equilibrium and stability problems, evaluated their reliability and
computational efficiency for locating the global minimum of the Gibbs free
energy and TPDF, and advocated a hybrid algorithm combining GA and SA
for difficult phase equilibrium problems. To the best of our knowledge, with
the above two exceptions, there has been no report on a detailed study on the
application of GA and SA to phase equilibrium and stability problems.
In a new development, Balogh et al. (2001, 2003) applied a stochastic
sampling and clustering method to locate the minima of a modified TPDF
(Stateva and Tsvetkov, 1991 a, b; 1994) and compared its reliability with
those of the most promising global optimisation methods. Their optimisation
algorithm GLOBAL is a modification of the method originally introduced by
Boender et al. (1982) with two local search procedures for finding a local
minimiser - either a quasi-Newton procedure with the Davidon-Fletcher-
Powell (DFP) update formula (Gill et al., 1981) or a random walk direct
search method UNIRANDI (Järvi, 1973). Both are derivative-free, i.e. they
do not use the partial derivatives of the objective functions (although in the
case of the DFP method an assumption of differentiability is made).
The optimisation algorithm GLOBAL can be described concisely as
follows:
Step 1. Draw M points with uniform distribution in the region of interest
5 (=[0,1]" ' ) , and add them to the current sample C. Construct the
transformed sample D by taking the percent of the points in C with the
lowest function values.
Step 2. Apply the clustering procedure to D. If all points of D can be
assigned to a cluster, go to Step 4.
Step 3. Apply the local search procedure to the points in D not yet clustered.
Repeat Step 3 until every point has been assigned to a cluster. If a new
local minimiser has been found, go to Step 1.
Step 4. Determine the smallest local minimum values found, and stop.
Balogh et al. (2001, 2003) chose the single linkage clustering procedure,
whose purpose is to recognise a priori those sample points starting from
which the local search might result in an already found local minimiser.

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Clusters are grown around either local minimisers or points of the local
search procedure from which an already known local minimum was reached.
These are known as seed points. A distance d(x,\') is defined for the
clustering between two points χ and χ in the neighbourhood of a local
minimiser x* by:
</(χ,χ·) = ((χ-χ·) Τ Η(χ·)(χ-χ·))" 2 (58)
The quasi-Newton method gives a good approximation to the Hessian

H(X') of the objective function, while in the case of UNIRANDI the
identity matrix replaces H(X') . A new point χ is added to a cluster if there is
a point χ in this cluster for which:
Γ 1 + -'
'(«•0 (59)
Here H(X*)| denotes the determinant of H(X*) , m(S) is a measure of the set
5, N' is the total number of sampled points, and 0 < α < 1 is a parameter of
the clustering procedure.
Balogh et al. (2001, 2003) demonstrated the robustness, efficiency and
effectiveness of their method on the example of two of the most widely used
systems in the literature - the methane+hydrogen sulphide system and the
nitrogen+methane+ethane system. They compared their results on the basis
of the roots found with the results of some of the best representatives of the
above discussed methods (Hua et al., 1998 a; 1999; Sun and Seider, 1995;
Harding and Floudas, 2000 a; Zhu and Xu, 1999 a).
Table I summarises the information about the local minima determined
for six feed compositions of the methane+hydrogen sulphide system at T=
190 K, and P= 40.53 bar. (The thermodynamic model applied is the SRK
CEOS). It must be noted that owing to a lack of space only the results
obtained with the application of the quasi-Newton local search method are
shown. For all candidate phases tried, the locations of the local minima are
identical to those reported in the literature.

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W. A. Wakeham and R.P.Stateva Reviews in Chemical Engineering
It must be noted that the CPU time required to find all roots for a feed
composition is given in Table I as an information rather than as a basis for
comparison with global optimisation methods. The reason behind this is that
global optimisation methods give different results than stochastic methods or
local methods. In a global optimisation approach, the global solution is found
usually at an early stage and subsequently CPU time spent is to prove that
this solution is global. In other words, the main computational cost of a
global optimisation method lies in guaranteeing that the global solution has
been found.
Furthermore, stochastic optimisation methods do not provide a theoretical
guarantee that all solutions will be found by all independent program
executions. Their reliability is measured by their success rate, and the CPU
time requirements of any stochastic method will increase in order to
guarantee a 100 % success rate.
Finally, as pointed out by Balogh et al. (2003), a particular problem
associated with the implementation of stochastic methods is the dependence
of the results obtained on the algorithmic parameters chosen. Thus, in
principle, the CPU time requirements of a stochastic method include also the
time to experiment with different parameter values until the best (most
suitable) set for a particular case study is found. That is why it is very
difficult to report the actual CPU time requirements for a stochastic method.
The section now concludes the review of some of the methods advocated
for locating the solutions of the TPDF with a brief description of a novel and
original approach introduced by Wasylkiewich et al. (1996). They used ideas
from differential geometry and the theory of differential equations for solving
global stability analysis and LL phase splitting. A remarkable feature of their,
method is the possibility to establish the number of local minima and saddle
points from a topological criterion. The authors point out that the major
difficulty in implementing the stability test is that the number of the minima
of the TPDF or the number of points satisfying Kuhn-Tacker condition is not
known a priori. They advocate an algorithm to locate all stationary points of
the TPDF (minima, maxima, and saddle points) by tracking the ridges and
valleys in the TPDF and continuing the exploration of the function domain
until the results are globally consistent with a topological relationship, which
they introduce. For a ternary mixture the topological criterion is given by
Nm + Nmia - N^ = 1 and represents the number of maxima, minima and the
saddles of the TPDF. Wasylkiewich et al. (1996) did a systematic exploration
of the function domain rather than repeated calculations starting from various

35
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37
points generated using heuristics. The authors conjectured that the ridges and
the valleys connect every stationary point of the TPDF and that they can be
completely explored using a line search no matter how many components
there are present in the system. The approach of Wasylkiewich et al. (1996)
has the advantage that the topological constraint reveals that sometimes one
or more stationary points remain to be found - a situation which often occurs
in difficult problems (Zhu and Inoue, 2001).
Finally, recently Wasylkiewich and Ung (2000) advocated a global
algorithm for stability analysis in multi-component, multiphase reactive
mixtures based on the Gibbs tangent plane stability test. They located all
stationary points of the TPDF expressed in terms of transformed coordinates.
The algorithm is independent of the specific fluid model, is self-starting and
significantly improves the robustness and reliability of multiphase reactive
equilibrium calculations. The method is implemented and tested on a variety
of problems, in which solutions for the entire phase diagram were found
without fail, and difficult cases were successfully calculated.
8. PHASE IDENTIFICATION AND PHASE

EQUILIBRIUM CALCULATIONS.
The application of different optimisation techniques to the minimisation

of the TPDF identifies the system under consideration as either stable or
unstable (metastable), but cannot determine unequivocally the number and
type of phases in equilibrium and does not deliver the exact compositions of
phases at equilibrium (Wasylkiewich et al., 1996; Stateva et al., 2000). For
example, in the case of possible complex phase equilibria (VLL, LLL, etc.) if
two minima of the TPDF are located, and the system is unstable, it does not
necessarily mean that it is two-phase - the feed can be in the three-phase
region. Alternatively, if three minima are found, the feed can still be in the
two-phase region. Such situations are especially typical for cases when the
feed lies in a very close proximity to the composition boundary between the
two- and the three-phase region. Furthermore, the located minima of the
TPDF can differ significantly from the true equilibrium points, and even their
number may not be the same as the number of the liquid phases present at
equilibrium. Thus, the number, identity and composition of the phases in
equilibrium cannot be determined on the basis of tangent plane analysis
alone.

38 Authenticated
W. A. Wakeham and R. P.Stateva Revie\vs in Chemical Engineering
The minimisation of the TPDF, however, provides good initial estimates

for the compositions of possible phases. This information is used in a variety
of ways by different strategies advocated to solve the isothermal, isobaric
multiphase flash problem. Hereunder, we classify them as either stage-wise
or non stage-wise, depending on whether a stability analysis is performed
once or several times.
In what follows we will present their methodology in a very concise
manner.
8.1. Stage-wise techniques

In an attempt to assure that a global solution of the multiphase flash
problem is found, some type of two-stage approach is often used (e.g.,
Michelsen, 1982 a, b; Sun and Seider, 1995; McKinnon et al., 1996;
McDonald and Floudas, 1997; Hua et al., 1997, Lucia et al., 2000).
The best-known and most widely used representative of this group is the
method proposed by Michelsen in 1982. He advocated a two-stage technique,
where initially, a single phase of the feed composition is assumed. If the TP
criterion shows the single phase to be unstable, a two-phase vapour-liquid
"equilibrium" is assumed. This initial guess insures that the molar Gibbs free
energy will have a lower value than that of the original single-phase system.
Then either a free-energy minimisation method or an equation solving
method can be used to determine the equilibrium compositions. In the second
stage of this approach, the tangent plane criterion is used as a global
optimality test on the local solution identified in the first stage. If unstable,
the first stage (phase split) calculation must then be repeated, perhaps
changing the number of phases assumed to be present, until a solution is
found that meets the second stage global optimality (phase stability) test. If
the tangent plane distance is minimised globally in the phase stability
analysis, this type of two-stage procedure can be shown to converge in a
finite number of steps to the equilibrium solution (e.g., McKinnon et al.,
1996).
Although Michelsen's method was applied originally only to phase
equilibria, it can also be applied to reacting systems, containing multiple
phases (Perez Cisneros et al., 1997). It is suggested first to assume a one-
phase reaction system and to calculate the equilibrium based on the extent of
the reaction. And then, considering the system at phase equilibrium, stability
can be checked by the same method as described above.

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The stage-wise technique uses the stability check repeatedly as a tool to

justify a conclusion about stability/instability of the system under
investigation and in the latter case to provide a conclusion about its phase
configuration. However, what matters is whether the compositions of the
stability function accessible from the starting estimates include good
approximations to the likely unstable compositions and to the equilibrium
compositions in the final mixture. This is the key element of the operation of
multiphase algorithms and has no general solution as of now. Furthermore,
the commonly accepted approach for phase-splitting techniques is 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 a solution with
the same number of phases but either with a different identification (VL vs.
LL) or with a different distribution of the components within those 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).
One additional potential problem of step-wise procedures lays when a
split into two phases yields a "trivial" solution; i.e. one that has been
computed previously. This may lead to "cycling". The effect of "cycling" is
very important, especially in respect of the ability of the algorithm to land on
the right collection of final phases, and we will briefly discuss this possible
shortcoming of the step-wise procedures. The initial estimates for the K -
factors or the phase compositions for the J-th solution are available from
stability analysis for the preceding J - 1 solution. Using these stationary
points as initial estimates for the subsequent two-phase flash calculation may
well lead to a "trivial" solution, i.e. a solution obtained previously, i/care is
not taken to avoid it. Repetitive computing of one and the same phase split
(on subsequent stages of the procedure) could lead to a failure of the step-
wise strategy in the sense that: /) if not recognised - an erroneous judgement
about the stable phase configuration can be accepted or if) if recognised - the
situation requires special treatment (for example a new set of initial estimates
and it is far from obvious how they would be obtained) and leads to
additional computational and even intellectual efforts.
8.2. Non stage-wise techniques

In a series of papers Stateva and Tsvetkov (1994), Stateva and Wakeham
(1997), and Stateva et al. (2000) discuss a new approach to phase (and
chemical) equilibrium calculations. It involves a rigorous phase stability

40 Authenticated
W.A. W akeham and R.P. Stateva Reviews in Chemical Engineering
analysis performed on the initial system with composition z . The stability

check employs the tangent-plane criterion (Baker et al., 1981; Michelsen,
1982 a), but uses a different objective function (Stateva and Tsvetkov, 1994):
where:
4 /=1,2,...A (60 a)
(60 b)
and kN+l (y) is equated to k\(y).

From Eq. (60) it follows directly, that when y = y*, where
then O(y*) = 0, which is its minimum value. The zeros y* of the function
<I>(y) are its minima, and from a computational point of view it is more
advantageous to search for minima with known zero minimum value. The
zeros of the objective function correspond with points on the Gibbs energy
surface, where the local tangent hyperplane at each y* is parallel to that at z.
To each y*, a quantity A* corresponds, such that:
(62)
This quantity can be either positive or negative. When all calculated k' are
positive, the system is stable.
As pointed out in the previous sections, it is a challenging task to locate
all zeros of the TPDF (O(y) in this particular case) because a search over the
entire composition space is required. The search is further complicated by the
existence of a number of trivial solutions, corresponding with the number of
equilibrium phases present. The specific form of <I>(y) (its zeros are its
minima) and the fact that it is easily differentiated analytically, allows the
application of a non-linear minimisation technique for locating its stationary
points, and Stateva and Tsvetkov used the BFGS method with a line-search
(Fletcher, 1987). The implementation of any non-linear minimisation

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technique requires a set of "good" initial estimates, and the BFGS method is
no exception. All details of the organisation and implementation of the
initialisation strategy employed by the stability analysis procedure are given
by Stateva and Tsvetkov (1991) and will not be discussed here.
Thus, a method has been created which leads, in practice, to an
"extensive" search in the multidimensional composition space. It has proved
to be extremely reliable in locating almost all zeros of <S(y) at a reasonable
computational cost (Stateva and Tsvetkov, 1991 a, b; 1994). The term
"almost all" zeros is used because there is no theoretically - based guarantee
that the scheme will always find them all. If, however, a zero is missed, the
method is self- recovering, as will be demonstrated later. This unique feature
is a characteristic that distinguishes this procedure from the equation solving
methods, which can eventually fail to determine correctly the phase
identification of the system. Furthermore, the TPDF is minimised once only,
which is a distinct difference from the approach that stage-wise methods
generally adopt. Since stability analysis on its own cannot determine
unequivocally which is the stable phase configuration of a system (identified
as unstable at the given temperature and pressure), it is suggested to run a
sequence of two-phase flash calculations to determine the correct number of
the phases at equilibrium, and the distribution of the components among the
phases.
To assure a steady and non-oscillatory convergence of the flash
calculations, with no tendency towards a strong attraction to the trivial
solution, a reliable initialisation scheme is generated. All possible y* pairs are
taken together as initial estimates since there is no way of telling which
minima of 4>(y) will lead to the global solution. Such application of initial
estimates guarantees a highly diversified search for the phase configuration
with the minimum Gibbs energy. Thus, the chance of using guesses that may
in the end lead to either local optima or solutions already determined or even
to infeasible solutions is greatly reduced. It is possible that some guesses may
lead to a phase configuration physically inconsistent with the overall
composition specified for the mixture and they are rejected. For the
remaining pairs, two-phase flash calculations (in any order) are performed by
any available technique. These calculations lead to different values of the
Gibbs energy and that with the lowest value is selected for further processing,
which determines whether the inclusion of a third phase leads to further
stability. If not, then the two-phase result is the final, stable solution. The
three phase system can be subjected to a further test of the same kind if

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42
necessary. It should be mentioned that the various two-phase flash

calculations could be performed in parallel, if it is desired.
For example, the generalised scheme of the algorithm for LLLE
predictions and calculations (Stateva et al., 2000) reads:
1. Given ζ, Γ and P.
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 flash 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 flash on its lighter phase. If the phase split upon convergence is
outside the physically acceptable bounds, the equilibrium phase
configuration is a two-phase LL. END. Otherwise, the equilibrium phase
configuration is LLL. Initial estimates for the subsequent LLL
calculations are found by performing an additional LL flash upon the
heavier of the two liquid phases of the above LL solution. Continue with
step 5.
5. Run a LLL flash upon z. Use as initial estimates the converged mole
fractions of the solutions determined in step 4. END.
The robustness and efficiency of the above algorithm was illustrated by

the example of the ethylene glycol + lauryl alcohol + nitromethane system
taken from the literature (Sun and Seider, 1995; McDonald and Floudas,
1995 c; 1997; Garcia-Sanchez et al., 1996; Tessier et al, 2000).
For this system, at T = 295 K and P = 0.1 MPa, a vapour phase is not
formed and there is the potential for three liquid phases at equilibrium. The
following three sets of feed conditions were tested and analysed:
1. z= (0.4; 0.1; 0.5) (Garcia-Sanchez et al. 1996)

2. z= (0.2; 0.3; 0.5) (McDonald and Floudas, 1995 c; Sun and Seider, 1995)
3. z= (0.4; 0.3; 0.4) (McDonald and Floudas, 1995 c; Sun and Seider, 1995;
Tessier et al, 2000)

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The second feed condition exemplifies particularly well the difficulties

and the inherent dangers associated with the correct determination of the
global solution by any local optimisation method. McDonald and Floudas
(199S c) considered this case in detail, using their own global optimisation
methods, and the work of Sun and Seider (1995), who apply a homotopy -
continuation method to determine the stationary points of the TPDF.
McDonald and Floudas (1995 c) report difficulties in identifying the three
phase solution, while the method of Sun and Seider (1995) failed to recognise
the existence of such solution because the zero of the function rich in
ethylene glycol is very difficult to locate.
Stateva et al. (2000) used Case 2 as an illustration of how the location of
the feed influences the success of the stability analysis and phase
identification routines. They argue that because the feed is located in a close
proximity to the L,L3 boundary of the LLL triangle (Figure 3), the stationary
NHromethane 0.0 0.1 0.2 0.3 0.4 0.5 o.e 0.7 o.» 0.9 1.0 Ethylene glycol
Fig. 3: Liquid-liquid-liquid equilibria of the ethylene glycol + lauryl alcohol

+ nitromethane system at T = 295 K and P = 0.1 MPa. The positions
of the three studied feed conditions are shown as well.

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W.A. Wakeham andR.P.Staleva Reviews in Chemical Engineering
point of the TPDF rich in ethylene glycol is very difficult to locate. As a

result a stability analysis routine, implementing a local optimisation method,
can often fail to find it. In view of this Case 2 was further used by Stateva et
al. (2000) to demonstrate the nature of the self- recovery of their algorithm.
They accept, for the sake of argument that the stability analysis failed to
determine all zeros of O(y). Then the available initial estimates converge
only to solution 1, which, obviously, has a very large domain of attraction
(Table 2). Following the steps of the algorithm, solution 1 is tested for
stability by performing a LL flash calculation upon its lighter phase. The
result shows that the stable phase configuration of the system is LLL (Table
3). To obtain the distribution of the components among the three equilibrium
phases a LLL flash must be performed upon z. To secure a steady
convergence of the flash routine an excellent set of initial estimates are
obtained by only one more LL flash run on the heavier phase of the above
Table 2
Ethylene glycol, lauryl alcohol, nitromethane system
at T = 295 K and P = 0.1 MPa.
Feed conditions of case (2). Application of the algorithm, step 3.
Converged mole fractions of solution 1.
Component Feed Liquid! Liquid2

C2H602 0.2 0.106458 0.285030
CI2H260 0.3 0.035722 0.540228
CH3N02 0.5 0.857820 0.174742
α = 0.5238
Table 3
at Ύ =295 Κ and Ρ = 0.1 MPa.
Component Liquid2 ζ LI
C2H602 0.285030 0.689103 0.252575
C,2H260 0.540228 0.0748627 0.577605
CH3NO2 0.1747420 0.2360340 0.169819
α = 0.9235
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solution (Table 4). The resulting set of the initial estimates is given in Table
5. Applying these initial estimates, the LLL flash converges in three
iterations. The component distribution for the global solution is given in
Table 6.
Table 4
at T= 295 K and P = 0.1 MPa.
Component ς Ϊ 4
C2H602 0.689103 0.096779 0.690811
C12H260 0.0748627 0.035292 0.074977
CH3NO2 0.2360340 0.867929 0.234212
Tables
at Γ = 295 Κ and Ρ = 0. l MPa.
The set of the initial estimates obtained (mole fractions)
Component L\ L\ LI
C2H602 0.096779 0.690811 0.252575
C12H260 0.035292 0.074977 0.577605
CH3N02 0.867929 0.234212 0.169819
Table 6
Ethylene glycol, lauryl alcohol, nitromethane system at T = 295 K and P =
0.1 MPa. Feed conditions of case (2). Application of the algorithm, step 5.
The actual global LLL solution, mole fractions
^^^»^^^^^^^^^— >*^^^^— ^^^^to·^^
Component L, L2 L3
C2H602 0.096766 0.691110 0.252738
C12H260 0.035232 0.074737 0.578284
CH3NO2 0.868002 0.234153 0.168978
= 0.0466; ψ2 = 0.4692; ψ3 = 0.4842

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9. THE AREA METHOD
Finally, we would like to give a brief description of a completely different

approach to phase equilibrium calculations, introduced originally by Eubank
et al. (1992), who advocated the concept of integrating rather than
differentiating the Gibbs energy surface. This procedure is called the Area
method and is based on maximising a single objective function in the Gibbs
energy surface.
The mathematical statement of the objective function for a binary system
at fixed 7 and P is given in terms of the Gibbs energy of mixing ψ as:
F(X",X*)= '·*/_» \ . j.(-«\\(x ~xl (63)

' ' " z f ' \
where at equilibrium
(64)
Geometrically F is the area between the straight line, connecting points

x* andjc,b, and the Gibbs energy curve. When F attains its maximum
(positive) value then x' andxj" represent the equilibrium compositions of
component 1 in phases a and b respectively. This is known as the maximum
AREA criterion. In their paper Eubank et al. (1992) showed briefly how the
AREA method could be generalised to the Nc component - two-phase case.
Elhassan et al. (1996) extended further this concept to the one component
(pure fluid) case and to the determination of dew and bubble point
temperatures and pressures in addition to the isothermal flash problem.
The AREA method provides a sufficient condition for Gibbs energy
minimisation and follows a different computational approach in two
important aspects. Firstly it does not calculate any inflection or stationary
points, but rather evaluates the Gibbs energy at some specified composition
points. Secondly it combines both phase stability analysis and phase
calculations in one step. Phase stability is implicitly embedded in the
objective function of the Area method; if positive area is detected, multiphase
equilibria for the given conditions are possible. If only negative area is found,
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then no phase split is possible, and the system is homogenous at the specified
conditions.
In a new development, Elhassan et al. (1998) extended the original AREA
method into the case of an Nc - component, two-phase system, and provided a
rigorous mathematical proof that the maximum AREA criterion gives a
necessary and sufficient condition for equilibrium in the case of a two
component, two-phase system. The proof demonstrates that with the
exception of a single point, which is the trivial solution, the only points that
maximise the objective function (satisfy the AREA criterion) are the
equilibrium points. Elhassan et al. (1998) proved also for the first time that
the maximum AREA criterion is a necessary but not a sufficient condition for
equilibrium in the case of an Nc component, two-phase system.
Recently, Elhassan et al. (2000), following some discussion in the
•literature (Barton and Hwang, 2000), using classical prepositional logic
demonstrated that for the two-component, two-phase case a stable phase split
always makes the objective function F stationary (maximum, minimum or a
saddle point). Further they argued that because only the maxima satisfy the
material stability criterion, the minima and the saddle points have to be
excluded, and thus proved that a connection between the AREA criterion and
phase stability had been established.
The AREA approach has been used successfully in different kinds of
phase equilibrium calculations (Stateva et al., 199S), especially in the critical
region (Eubank and Hall, 1995; Hanif et al. 1996 a, b; Shyu et al. 1995,
1996).
10. CONCLUDING REMARKS
The goal of the present review was to highlight the application of a wide
variety of numerical methods and optimisation techniques to the solution of
the phase equilibria problem. The methods we have reviewed inevitably have
their merits and disadvantages and our purpose has been to present them in as
non-biased a manner as we can.
In the future, it is expected that there will be a further development of
new methods and evolution of the existing ones. The reason behind this is
that there is still not an effective general method, which can be applied to
perform phase equilibrium calculations, and that will guarantee a
mathematically stable solution for any arbitrary equation of state at elevated

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pressures or activity coefficient model. This does indeed prompt the question
whether there can exist a general solution because more thermodynamic
models with higher accuracy are now appearing for all sorts of systems.
However, there is no proof that developing a general method is not possible.
We would like to point out that the need to develop a more reliable
numerical implementation of phase equilibria calculations is pressing also in
other chemical engineering applications. In the introduction we referred to
experimental data regression as an important but till recently neglected area.
One of the key problems in deriving thermodynamic models is adjusting the
model parameters to match experimental data. A failure to do that has a
profound influence on the ability of the model to predict correctly the phase
behaviour. In fact failure to converge to "difficult" experimental points often
causes some points to be ignored in regression even to the extent that the data
for some mixtures cannot be treated at all by the existing algorithms (Gau
and Stadtherr, 2000; Gau et al., 2000). Another important area, which was
not covered in the present review but also requires reliable phase equilibria
calculations, is the determination of homogeneous and heterogeneous
azeotropes (see for example Maier et al. 1998; 1999; Harding and Floudas,
2000b; Tolsma and Barton, 2000 a,b).
It is quite clear that the numerical solution of the phase equlibrium
problem presents considerable challenges and there still remains much to be
done.
Acknowledgement: The authors would like to acknowledge with gratitude

the financial support of the Royal Society.
LIST of SYMBOLS
A atom matrix (elemental abundance matrix), Eq. (26)

b element abundance vector, Eq. (26)
C current sample
rf(x,x') distance, Eq. (58), Eq. (59)
D transformed sample
/ ftigacity
/° fugaciry of component / at the reference state

Delft
Authenticated
ft» arbitrary function

F flow rate, Eq. (22)
F(x) tangent plane distance function (TPDF), Eq. (30)
F,(x) underestimation function, Eq. (53 - 55)
F(X) interval extension over the interval X
FOt"/) area between the straight line, connecting points x* andjt,b, and
the Gibbs energy curve, Eq. (63), Eq. (64)
g(x) molar Gibbs energy surface, Eq. (30)
g(x) simple system of equations, for which the solution is known, Eq.
(41-43)
G,° Gibbs free energy of formation of species i in the standard state for
phasey
Gy partial molar Gibbs free energy (chemical potential)
G(n) total Gibbs free energy of a system
H(x*) Hessian matrix of the objective function at a local minimiser x*,
Eq.(59)
H(x, /) homotopy equations, Eq. (41)
k iteration number
A* a number, corresponding to y*, Eq. (62)
A,(y) function of the chemical potential difference, Eq. (60 a)
K, distribution coefficient
L Lipschitz constant, Eq. (39)
i(x) tangent plane to the molar Gibbs free energy at z, Eq. (30)
m(S) measure of the set S, Eq. (59)
M set
n number of moles
/7,T total number of moles of component i in the system, Eq. (29)
Nc number of components (species)
N' the total number of sampled points, Eq. (59)
N total number of moles in the system
P number of phases, Eq. (27 - 29)
P pressure
R universal gas constant
S search domain
AS entropy change
/ homotopy parameter
T temperature

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W.A. Wakeham and R.P.Stateva Revie\vs in Chemical Engineering
ΔΙ/ energy change

ΔΚ volume change
χ mole fraction vector
x' local minimiser
X interval
y* zeroes of O(y)
y mole fraction vector
7, mole number, Eq. (37), component /
ζ feed mole fraction vector
Greek letters
α phase split for a two-phase flash
0<a< 1 parameter of the clustering procedure
ε specified global tolerance
φ Gibbs energy of mixing, Eq. (63)
φ, fugacity coefficient, component /
<D(y) modified TPDF, Eq. (60)
γ, activity coefficient, component /
λ homotopy parameter, Eq. (47 - 49)
μ, chemical potential, component /
π number of phases, Eq. (2 - 4)
•ψ phase split for a three-phase flash
Subscripts
L liquid
V vapour
max maximum
min minimum
sad saddle
Superscripts
L liquid
F feed
V vapour
Abbreviations
EOS equation of state
LL liquid-liquid

51
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LLL liquid-liquid-liquid
VL vapor-liquid
VLL vapor-liquid-liquid
TPDF tangent-plane distance function
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(Reviews in Chemical Engineering) Numerical Solution of The Isothermal Isobaric Phase Equilibrium Problem

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(Reviews in Chemical Engineering) Numerical Solution of The Isothermal Isobaric Phase Equilibrium Problem

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NUMERICAL SOLUTION OF THE ISOTHERMAL,

ISOBARIC PHASE EQUILIBRIUM PROBLEM

William A. Wakeham1' and Roumiana P. Stateva2

Thermodynamic modelling and phase equilibria are at the heart of

' Corresponding author. Telephone: +44(0)23 8059 2801;

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and composition at equilibrium for a specified temperature and pressure) is

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particular problems in phase equilibria calculations have been published, and

2. STABILITY AND PHASE EQUILIBRIUM

Thermodynamics provides the mathematical framework in which an

produces criteria of its equilibrium. These criteria subsequently lead to the

/>">= P(2) =... = /><" (3)

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Eq. (4) is the fundamental equation of phase equilibrium. The left-hand

Thus, in a closed system constrained to constant temperature and

Omitting terms higher than second order we have:

δ GTI, = //, (dn* + dnf ) + μ2 (dn* + dn%) +

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These derivatives may be expressed in terms of intensive variables by

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We have considered only a binary system in order to reduce the

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The expression for the stability criterion of a multicomponent system at

where |j denotes determinant.

The fugacity provides a convenient transformation of the fundamental

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condition in terms of chemical potentials can be replaced without any loss of

3. THE MULTIPHASE ISOTHERMAL,

The general multiphase problem is the single most important calculation

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specifics, from the viewpoint of problem formulation and solution, the

The phase compositions then are given by:

*,=-. πτ-7Τ (25 a)

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sequence of phase compositions with an error that does not decrease

3.1.1. Newton methods

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In the case of a system of non-linear equations f(x) = 0, the conditions

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3.2. Gibbs energy minimisation approaches

12 Brought to you by | Bibliotheek TU Delft

a) Phase and chemical equilibrium (reacting systems):

b) Phase equilibrium (no reaction):

4. DIRECT MINIMISATION OF THE GIBBS FREE ENERGY

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14 Brought to you by | Bibliotheek TU Delft

With their new formulation, that enables simultaneous stability and

5. MINIMISATION OF THE TANGENT PLANE DISTANCE

The tangent plane criterion was formulated and solved theoretically

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this surface at z. The optimisation formulation of the phase stability problem

s.t. X>,=1 (31 a)

0<x, <1 (31 b)

16 Brought to you by | Bibliotheek TU Delft

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In what follows firstly the formulation of the TPDF, advocated in the

The method of Michelsen (1982) utilises the tangent-plane criterion

for all trial compositions y. Geometrically, F(y) is the vertical distance

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fractions gives the stationary condition as:

where Κ is independent of the component i. Thus, the original system is

The stationary condition is as follows: