Chemical Engineering Research and Design 194 (2023) 163–178

Available online at www.sciencedirect.com

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Phase stability analysis and phase equilibrium

calculations in reactive and nonreactive systems
]]
]]]]]]
]]

using new hybrids of Pelican and Gorilla troops

algorithms
⁎
John O. Bamikole a, Caleb Narasigadu a,
a
Chemical Engineering Department, Faculty of Engineering and the Built Environment, University of
Johannesburg, Doornfontein 2028, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Phase stability and equilibrium calculations are very significant in the process industries,
Received 17 December 2022 ranging from process simulation, equipment design, operation and design. These pro­
Received in revised form 13 March blems involve several systems of complex and nonlinear equations, which are mathe­
2023 matically challenging. An alternative solution is formulating the problems into a global
Accepted 19 April 2023 optimisation problem. A robust and reliable optimisation technique is required to solve
Available online 21 April 2023 these global optimisation problems. In this study, two recently developed stochastic
global optimisation algorithms, POA and GTO were applied to phase stability and equili­
Keywords: brium problems. The need to enhance their performance necessitated the development of
Phase stability two modified algorithms, PGOA1 and PGOA2, which are the hybridisation of POA and GTO.
Equilibrium All the algorithms’ abilities were explored for solving computationally challenging and
Stochastic optimisation multidimensional phase stability and equilibrium problems, and their performances were
Pelican algorithm compared. The implementation of POA and GTO was good in solving most problems,
Gorilla though GTO slightly outperformed POA. The hybridisation of both to develop PGOA1 and
Hybrid PGOA2 was worthwhile as both outperformed the POA and GTO. PGOA2 is more robust
and reliable in solving phase stability and equilibrium, and its performance superseded
the performances of the other algorithms.
© 2023 The Authors. Published by Elsevier Ltd on behalf of Institution of Chemical
Engineers.

condition at which phases coexist in a system with no major

1. Introduction
change in the composition of all the phases in the system.
Phase stability and equilibrium problems can be solved
Phase stability and equilibrium are two interrelated funda­
through a system of nonlinear equations. These equations
mental concepts that play a significant role in the design,
are often generated from the mass balance, equilibrium laws,
simulation, operation and optimisation of separation units in
reactions, and correlation equations for physical properties
the process industries. In most cases, phase stability analysis
such as the Antoine equation, activity coefficient models,
is a precursor to phase equilibrium. Phase stability of any
equations of state and others. The analytical solution of all
chemical system is the ability of the system to remain in a
these problems is quite challenging. A viable option is to
single phase at a given condition of temperature, pressure
solve them numerically by formulating the problems into an
and composition. While phase equilibrium has to do with the
optimisation problem and minimising the objective func­
tions (Khalil et al., 2016). The objective function of phase
⁎
stability is the tangent plane distance function (TPDF), while
Corresponding author.
that of phase equilibrium is the Gibbs free energy.
E-mail address: cnarasigadu@uj.ac.za (C. Narasigadu).
https://doi.org/10.1016/j.cherd.2023.04.042
0263-8762/© 2023 The Authors. Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.
164 Chemical Engineering Research and Design 194 (2023) 163–178

tendency to converge to the global minimum (Khalil

Nomenclature
et al., 2016).
c number of components Stochastic algorithms have been applied to phase stability
CS cuckoo search and equilibrium problems, and include; genetic algorithms
D Dimension and simulated annealing (Rangaiah, 2001), particle swarm
EoS Equation of state optimisation (Bonilla-Petriciolet and Segovia-hernández,
g reduced Gibbs free energy 2010), differential evolution and unified bare-bones particle
G Gibbs free energy swarm optimisation (Zhang et al., 2011), genetic algorithm
GTO Gorilla troops optimiser and differential evolution with tabu list (Bonilla-Petriciolet
HB Honey badger et al., 2011), Covariance Matrix Adaptation Evolution
HH Horse herd optimisation algorithm Strategy, Shuffled Complex Evolution and Firefly Algorithms
IDE integrated differential evolution algorithm (Fateen et al., 2012; Fateen and Bonilla-Petriciolet, 2015),
Keq equilibrium constant improved ant colony (Fernández-Vargas et al., 2013), Herd
KH Krill herd algorithm algorithm and the modified Lévy-Flight Krill Herd algorithm
LKH Lévy-flight krill herd algorithm (Moodley et al., 2015), Charged System Search Algorithms
LLE liquid liquid equilibria (Elnabawy et al., 2014), Hybrid of Monkey and Krill herd al­
LB Lower parameter bound gorithm (Khalil et al., 2015), Intelligent Firefly Algorithm,
n number of moles Cuckoo Search, Artificial Bee Algorithm and Bat Algorithm
NFE number of function evaluations (Fateen and Bonilla-Petriciolet, 2015), Gravitational Search,
NP Number of population Monkey and Krill Herd Swarm Algorithms (A. M. E. Khalil
PE phase equilibria et al., 2016), Pathfinder, Honey Badger, Red Fox and Horse
PGOA Pelican-Gorilla optimisation algorithms Herd (Bamikole and Narasigadu, 2023) and others.
POA Pelican optimisation algorithm The widespread use of stochastic algorithms to solve
PS Phase stability phase stability and equilibrium problems has shown that
rPE reactive phase equilibria different algorithms perform differently for various pro­
SC stopping criteria blems; this corroborates the no-free launch theory, which
TPDF Tangent plane distance function says that it is quite impossible for a given algorithm to suf­
UB Upper parameters bound ficiently solve all problems (Wolpert and Macready, 1997).
VLE Vapour liquid equilibria Therefore it is a worthwhile venture to check the perfor­
yi component i for the trial phase mances of newly developed algorithms, improve existing
zi mole fraction of component i in the ones and check their performances in solving phase stability
εi fraction of component i and phase equilibrium problems. This work aims to apply
μi Chemical potential of component i two new algorithms: the Pelican (Trojovský and Dehghani,
µio Chemical potentials for pure component i 2022) and Gorilla (Abdollahzadeh et al., 2021) stochastic al­
ˆi component i fugacity coefficient gorithms to phase stability and equilibrium, and compare
i pure fugacity coefficient for component i their performances and develop new hybrids of both algo­
γi component i activity coefficient rithms for enhanced performance.
π number of phases

Subscripts and superscripts

T Total
ref reference components
i component i
j Phase j
Optimisation methods are generally classified into two
classes; deterministic and stochastic algorithms. Phase sta­
bility and equilibrium issues have seen increased use of de­
terministic algorithms. McDonald and Floudas (1995) solved
stability problems for NRTL and UNIQUAC activity models
using global optimisation and the bound and branch algo­
rithms. Several stationary points for TPDF were obtained
using the Newton homotopy-continuation method (Sun and
Seider, 1995; Hua et al., 1998a,1998b; Jalali et al., 2008), In­
terval analysis ( Tessier et al., 2000), continuation method
(Wasylkiewicz et al., 2013).
Despite the popularity of the deterministic method to
phase stability and equilibrium problems, it was observed
that the higher the dimension of the problems, the higher the
computational effort exponentially (Nichita et al., 2002,
Wakeham and Stateva, 2004). Stochastic algorithms are ea­
sier to implement without assumption and have a higher
2. The description of the stochastic
optimisation algorithms
The formulation of an optimisation problem is to minimise
an objective function F(x) that is dependent on the D vari­
ables, which are known as decision variables (x1,x2,x3,…xD)
that are bounded between the minimum limit
1 2 3 D
(xmin , x min , x min …x min ) and a maximum limit
1 2 3 D
(xmax , x max , x max …x max ).
This study examined two new hybrid and metaheuristic
algorithms to tackle phase stability and equilibrium pro­
blems. The application of these algorithms to phase stability
and equilibriums are of interest because it has not been re­
ported in the literature. An overview of the algorithms is
discussed in the following section.
2.1. Pelican optimisation algorithms
The pelican optimisation algorithm (POA) is a stochastic
optimisation algorithm that was recently proposed by
Trojovský and Dehghani (2022) to mimic the hunting strategy
of the pelican. The algorithm is modelled using the pelican’s
hunting strategy in two stages; the exploration stage, in
which the pelican moves towards its prey and the exploita­
tion stage, winging on the water’s surface. The mathematical
 Chemical Engineering Research and Design 194 (2023) 163–178 165

model of the exploration phase of the pelican algorithms is L = C *l (7)

shown in Eq. (1): where l is used to enhance the leadership of the silverback,
and it has values within the range of − 1 and 1.
xit + rand *(P I . xit ), Fp < Fi
xit + 1 = H = Z *xit
xit + rand *(xit P ), else (8)
(1)

where xit + 1 is the location of ith pelican member at an itera­ Z = [ C, C ] (9)

tion time t + 1, P is the location of the prey, I is a set of
random numbers that range from 0 to 1. Fp is the value of the
objective function of the prey’s location.
At every stage of the iteration, it is necessary to check the
fitness of the newly calculated members’ positions and up­
date accordingly. This is done using Eq. (2):
xit + 1, Fit + 1 < Fit
xit + 1 =
xit else (2)
The second phase of POA involves modelling the process
in which the pelican spreads its wings on the water’s surface
to attract more fish. This process is modelled mathematically
using Eq. (3):
t
xit + 1 = xit + R. 1 *(rand 1)*xit
T (3)
Eqs. (1) and (3) are the fundamental and peculiar equa­
tions for the pelican algorithms, the first set of the popula­
tion is randomly generated within the lower and upper limit
of the decision variables. At every point, there is a need to
check new members’ fitness before updating them, and it
terminates as soon as the stopping criteria are satisfied. The
pelican algorithm has no unique parameters that must be
declared before or during the optimisation process. Details of
the pelican algorithms can be found in the work of Trojovský
and Dehghani ( 2022).
2.2. Artificial Gorilla troop optimizer
The artificial Gorilla troop optimiser (GTO) was modelled to
mimic the Gorilla troop’s social intelligence (Abdollahzadeh
et al., 2021). The Gorilla troop walk in groups, and in the
application of their pattern to solving optimisation problems,
each of the member in the group is considered as a solution,
but the best of all the solutions at a particular time is called
the silverback. The algorithm is modelled using three me­
chanisms for the exploration phase: movement to an un­
known location, transit to a well-defined location, and the
group movements of other gorillas to the known location. A
selection criteria P is imposed to determine the condition for
switching within the mechanisms. If rand < P, the first me­
chanism is activated, if rand < 0.5, it switches to the known
location, and if rand ≥ 0.5, the other gorillas move to the
known location, as seen in Eq. (4) (Abdollahzadeh et al., 2021).
(UB LB )*r1 + LB , rand < P
xit + 1 = (r2 C )*xrt L *B , rand 0.5
xit L *(L *(xit xrt ) + r3*(xit xrt ), rand < 0.5 (4)
where xit + 1 is the Gorilla individual position at t + i iterations,
r1, r2 and r3 are random parameters which range from 0 to 1.
The P value should be chosen between 0 and 1. LB and UB are
the lower and upper limits, respectively. xrt is a randomly
selected member of the gorilla troop at time t.
t process will intensify the explored space for the best solu­
C = F* 1
T (5)
At the exploitation stage, the silverback takes the lead,
and other members of the troops follow. As time goes on,
some members can decide not to follow but compete for the
headship of the colony and female gorillas with the silver­
back. These characteristics are factored in the mathematical
formulation of the exploitation stage, and this is done by
assigning a specific value to C. If C ≥ W, the silverback leads,
but if C < W, the female competition is enhanced, given that
W must be selected before the optimisation process
(Abdollahzadeh et al., 2021).
The following set of equations was modelled to factor in
the lead of the silverback and competition with other
members of the troops.
xit + 1 = L *M *(xit t
xsilverback ) + xit (10)
1
N g g
1
M= xit
N i=1 (11)
g = 2L (12)
The competition for the adult female is modelled with
Eq. (13):
t
xit + 1 = xsilverback t
(xsilverback *Q xit *Q )* *E (13)
Q = r5 1 (14)
N1, rand 0.5
E=
N2, rand < 0.5 (15)
where is a parameter that is assigned a value before the
optimisation process, and r5 is a random number that ranges
between 0 and 1.
2.3. The proposed hybrid algorithms
The evaluation of the performances of both POA and GTO on
phase stability and equilibrium problems has necessitated
the need to enhance the performance of both algorithms by
developing new algorithm, which will be a hybrid of both
algorithms. Hybridisation aims to improve the performance
of algorithms by using the comparative strength of both al­
gorithms to compensate for their weaknesses. Each algo­
rithm has its unique characteristic and property, which can
favour the exploration or exploitation phases.
The POA seems to be more effective in solving phase
problems, but findings in this research showed that it could
sometimes be trapped in the local minimum, depending on
the nature of the problem and the stopping criteria. On the
other hand, the GTO has a fast convergence rate, but the
probability of locating the global minimum of some problems
is low.
These new algorithms combine the POA’s exploration
strength with the GTO’s exploitative strength. A good ex­
plorative technique ensures that the search space is well
combed for possible solutions, while a robust exploitative
tion. The proposed algorithms ensure a dynamic balance and

F = cos(2*r4 ) + 1 (6)
166 Chemical Engineering Research and Design 194 (2023) 163–178

dimension and the constraints for phase stability and phase

equilibrium for nonreactive and reactive problems, are given
in the following sections.

3.1. Phase stability

A chemical system’s phase stability determines whether it

will separate into various phases under a specific condition.
It is often a precursor to phase equilibrium calculations. The
objective function employed for solving phase stability issues
is frequently the tangent plane distance function (TPDF). It is
the vertical distance between the tangent of the Gibbs energy
surface at the feed composition and any other location on the
Gibbs energy surface. Anywhere else on the Gibbs free energy
surface where the tangent contacts, indicate that the system
is unstable at that composition (Michelsen,1982). The pur­
pose of solving PS problems is to identify the objective
function’s global minimum values. The system is unstable if
this value is negative; otherwise, it is stable. Eq. (18) is the
TPDF formulation (Michelsen,1982; Sun and Seider, 1995;
Fig. 1 – Pseudo-Code for PGOA. Harding and Floudas, 2000).
c
TPDF = yi (µi |y µi |zi )
i (18)
stability between the extensive and intensive phases. The i

proposed algorithms integrate the explorative ability of the
POA, as given in Eq. (1), with the exploitative power of GTO,
as given in Eqs. (10) and (13), which were modified to Eqs. 16
and 17 , and were used in place of Eqs. (10) and (13) for better
performance. The pseudo-code and flowchart are shown in
Figs. 1 and 2, respectively.
Two sets of hybrid algorithms were developed and stu­
died; the first is called PGOA1, while the second is called
PGOA2. In both modifications, the explorative phase adapts
the exploration phase of POA, which is given in Eq. (1). The
exploitative phase is a modification of that of GTO.
In PGOA1, in the exploitative stage, if C ≥ W, the silverback
leads, but if C < W, the female competition is enhanced, and
this is done using Eq. (16).
xit + 1
where c is the number of components in the system, z and y
are the feed mole fractions and the mole fractions at the split
point, µi | y and µi |zi are the chemical potentials at the split
i
and feed composition, respectively.
The chemical potential is expressed in terms of the fu­
gacity coefficient and activity coefficient in Eq. (19):
xi ˆ i
µi = µio + RTln = µio + RTln(xi i )
i (19)
Where µio ,
ˆ i , i , i are the chemical potential of pure
component, fugacity coefficient, the pure fugacity coefficient,
and the activity coefficients for component i respectively.
The fugacity and activity coefficient can be evaluated via the
equation of state and activity models, respectively.
Eq. (20) is the reformulation of the TPDF given in Eq. (18).

t
xbest t
[xbest *(2*rand 1) xit *(2*rand 1)]* µi µio xi ˆ i
= ln = ln(xi i )
= RT i (20)
*g , C W
t t
xbest [xbest *(2*rand 1) xit *(2*rand 1)]* *E , else The mole fractions, x, are often the decision variables
(16) used to minimise the problem when solving the TPDF. A new
parameter can be introduced into the formulation for ex­
The objective’s fitness will determine each member’s
pressing the mole fractions of component i and a percentage
status in Eq. (16), and the update will be done, while the best
of the previous feed composition. Another variable that can
solution will be saved as the global minimum.
be utilised is the number of moles (n).
In PGOA2, a modified exploitative phase is given in Eq.
Stability problems can be solved by globally minimising
(17), and it replaces Eq. (16) of PGOA1.
Eq. (18) subject to the constraint of mole balance as shown in
xit + 1 Eq. (21).

( )*(2*rand
t c
xit + 0.2* 1 tmax
1)*xit , C W yi = 10 yi 1for i = 1, …c
= (21)
t t i= 1
xbest [xbest *(2*rand 1) xit *(2*rand 1)]* *E , else
With a new decision variable i , the problem’s constraint
(17)
formulation given in Eq. (21) can be changed to an un­
Eqs. (16) and (17) are followed by a fitness estimation and constraint formulation.
update to get the global minimum values.
niy = i zi nT (22)

3. Formulation of PS, PE and rPE problems niy

yi = c
i = 1 niy (23)
The description of the global optimisation problems, in­
cluding the objective functions, decision variables, This reformulation can be applied to more phases.
 Chemical Engineering Research and Design 194 (2023) 163–178 167

Fig. 2 – The flowchart for PGOA.

3.2. Phase Equilibrium a constraint to an unconstraint optimisation problem. i, j is

the fraction of component i in the phase j.
Phase equilibrium calculation involves knowing the compo­ ni, j
sitions in all the phases in an unstable system. A phase i, j = k=
k =j nik (26)
equilibrium problem can be formulated into an optimisation
problem by minimising the Gibbs free energy of all phases.
The reformulation by using i, j as a decision variable re­
Phase equilibrium reduced Gibbs free energy formulation duces the complexity of the optimisation problems and
is given as (Rangaiah, 2001; Srinivas and Rangaiah, computational time without violating the mass balance
2007a,2007b; Fernández-Vargas et al., 2013): constraint.
c c The number of moles ni ,j of any component i in any phase
xi ˆ i
g= nij ln(xi i ) = nij ln j can be related using Eq. (27):
j i j i i (24)
K =j 1
Eq. (24) is subjected to mass balance constraint, which is ni ,j = i .j zi nT nik
k =1 (27)
given as:
With the inclusion of Eq. (27), the direct relationship of ni ,j
ni, j = zi nF , 0 ni, j nF to the initial feed composition is established.
j= 1 (25)
For the last phase , Eq. (27) can be written as:
where π is the number of phases involved and nF is the total K= 1
number of moles for the feed. The introduction of i, j [0,1], ni , = zi nT nik
k =1 (28)
which is given in Eq. (26) can be used to convert Eq. (25) from
168 Chemical Engineering Research and Design 194 (2023) 163–178

3.3. Phase equilibrium calculations for chemically

(Bonilla-Petriciolet et al., 2006)

(Bonilla-Petriciolet et al., 2006)

(McDonald and Floudas, 1997)
(McDonald and Floudas, 1995)
reacting systems

(Harding and Floudas, 2000)

(Sun & Seider, 1995; Balogh

(Ammar and Renon, 1987)

The reactive phase equilibrium is the determination of

References

(Nichita et al., 2002)

equilibrium compositions in the presence of a reaction. The
inclusion of reaction kinetics makes the problem more
complicated than the nonreactive system. The objective

et al., 2003)
function for a reactive system with multiple components,
phases and reactions r, phase equilibrium is given by Eq. (29)
(Srinivas and Rangaiah, 2007a,2007b; Bonilla-Petriciolet et al.,
2011; Bhargava et al., 2013).

-0.032466

-0.015767

-0.003932

-0.000002

-0.002688

-1.486205

-2.05E-05
-0.29454
GT = g ln K eqN 1nref , j

Global optimum

PS
j =1 (29)

Where g is given in Eq. (24), K eq

is the equilibrium constant, N

-0.35296
-0.54779

-0.01989

-1.18365

-0.83878

-0.76977

-1.12118
is a square matrix of the stoichiometric coefficients of re­

-0.0202
PE
ference components in r reactions. nref , j is a matrix with a
single column that relates other components with the re­
ference components. The extent of reaction and reduction in

SRK EoS with classical mixing rules (Hua et al.,

SRK EoS with classical mixing rules (Hua et al.,

NRTL model (Heidemann and Mandhane, 1973)
decision variables are usually done with the introduction of
the reference components and transformed variables (Ung
and Doherty, 1995).

NRTL model(Bender and Block, 1975)

SRK EoS with classical mixing rules

SRK EoS with classical mixing rules

SRK EoS with classical mixing rules

SRK EoS with classical mixing rules

Thermodynamic models
In reactive systems, the rate of production and reaction
must be accounted for, and this is not similar to phase
equilibria without reactions in which the total mole is con­
stant. The composition of a component in a given phase is
the difference in the number of moles of the component in
the feed with that of other phases. But, in reactive systems,
the rate of consumption and reaction must be accounted for.
1998a,1998b)

1998a,1998b)
The stoichiometric coefficients can effectively be used for
accounting for the changes in composition due to reactions,
as shown in Eq. (30).
n 1
ni = zi nT vi N 1 (n nref , ) (ni , j vi N 1nref , j )
ref ,
nF = (0.401, 0.293, 0.199, 0.0707, 0.0363) at 390 K and 5583 kP

j =1

nF = (0.6436, 0.0752, 0.0474, 0.0412, 0.0297, 0.0138, 0.0303,

(30)
nF = (0.29989, 0.20006,0.50005) at 298 K and 101.325 kPa

nF = (0.7212, 0.09205,0.04455, 0.03123, 0.01273, 0.01361,

nF = (0.614, 0.10259,0.04985, 0.008989, 0.02116, 0.00722,

The value of ni the number of moles of component i in
0.01187,0.01435, 0.16998) at 314 K and 2010.288 kPa
the last phase π, is significant in formulating the optimisa­
tion problem for phase equilibrium. It is the difference be­
nF = (0.30, 0.10, 0.60) at 270 K and 7600 kPa

nF = (0.9813, 0.0187) at 190 K and 4053 kPa

tween the components in all the other phases and the feed
0.07215, 0.01248) at 353 K and 38,500 kPa
Feed Conditions

nF =(0.5, 0.5) at 298 K and 101.3250kPa

compositions. During optimisation, it can have a negative

value, which is an infeasible region of the search environ­
0.0371, 0.0415, 0.0402) at 435.35 K

ment. A penalty is included in the objective function to cor­

rect this anomaly, as shown in Eq. (31).

Fobj if ni, j > 0 for i = 1, 2…C and j = 1, 2…

f= otherwise
Table 1 – Details of studied PS and PE problems.

Fobj + Penalty
(31)
where Penalty is the penalty function given in Eq. (32)
(Srinivas and Rangaiah, 2007a,2007b).
nunf
Penalty = 10. |ni |
C1 +C2 +C3 + iC4 + C4 + iC5 + C5

i =1 (32)
n-Butyl acetate + H2O (LLE)

C1 +C2 +C3 + C4 + C5 + C6

C1 +C2 +C3 + C4 + C5 + C6

where nunf is the number of ni

Toluene + H2O + aniline

that have negative va­

lues, ni < 0 .
C2 +C3 + C4 + C5 + C6

+ C7 + C8 + C9 + C10
+ C6 + C7 −16 + C17+
System

+ C7 −16 + C17+

4. Implementation of the methods

N2 + C1 + C2

C1 + H2S

The studied algorithms were used to solve several phase

(VLE)

(VLE)

(VLE)

stability, nonreactive phase equilibrium, and reactive phase

equilibrium benchmark problems, as shown in Tables 1 and
2. In using the algorithms, the objective function of PS pro­
No

1
2
3

blems to be minimised is the TPDF given in Eq. (18); the

Table 2 – Detailed of phase equilibrium of chemically reacting systems.
No System Feed Condition Model Global Reference
minimum

1 Ethanol + acetic acid ↔ ethyl acetate + water (LLE) nF = (0.5, 0.5, 0.0, 0.0)
at 355 K and
101.325 kPa
2 Isobutene + methanol ↔ methyl tert-butyl ether with n- F = (0.30, 0.30, 0.0, 0.40)
butane as an inert component at 373.15 K and
(LLE) 101.325 kPa
Wilson model and ideal gas.
Grxs◦/R =
− 4205.05 + 10.0982 T − 0.2667
3 2-Methyl-1-butene + 2-methyl-2-butene + 2 *methanol ↔ (0.354, 0.183,
2 *tert-amyl methyl ether 0.463, 0.0) at 355 K
(reactive with liquid–liquid equilibrium) and 151.95 kPa
4 Acetic acid + n-butanol ↔ water + n-butyl acetate(LLE) = (0.3, 0.4, 0.3, 0.0)
at 298.15 K and
101.325 kPa
5 (reactive with liquid–liquid equilibrium) (0.6, 0.4, 0.0)
6 2-Methyl-1-butene + 2-methyl-2- nF = (0.1, 0.15, 0.7,
butene + 2 *methanol ↔ 2 *tert-amyl methyl ether 0.0, 0.05) at 335 K
with n-pentane as an inert component and 151.9875 kPa
(reactive with liquid–liquid equilibrium)
7 A1 + A2 ↔ A3(LLE) nF = (0.52, 0.48, 0.0)
NRTL model and ideal gas
Keq= 18.670951
Wilson model and ideal gas.
Keq= 15.6465
Keq= 36.6646
UNIQUAC model and ideal gas
Keq= 10.0674
Margules solution model
Keq= 0.9825
Wilson model and ideal gas
Keq= 36.6646
Margules solution model. Keq
− 2.058120 (Peng Lee et al., 1999)
− 1.434267 (McDonald and Floudas, 1997)
− 1.226367 (Ung and Doherty, 1995) (Vianna Neto and
Oliveira, 2017)
− 1.106300 (Wasylkiewicz and Ung, 2000)
(Vianna Neto and Oliveira, 2017)
− 0.144508 (Bonilla-Petriciolet et al., 2008)
(Vianna Neto and Oliveira, 2017)
− 0.872577 (Bonilla-Petriciolet et al., 2008) (Vianna Neto
and Oliveira, 2017)
− 0.653756 (Wasylkiewicz and Ung, 2000) (Bonilla-
Chemical Engineering Research and Design 194 (2023) 163–178

at 323.15 K and = 3.5 Petriciolet et al., 2011)

101.325 kPa
8 A1 + A2↔ A3 + A4 (0.048, 0.5, 0.452, NRTL model 0.311918 (Wasylkiewicz and Ung, 2000) (Bonilla-
0.0) at 360 K and Keq= 4.0 Petriciolet et al., 2011)
101.325 kPa
169
170 Chemical Engineering Research and Design 194 (2023) 163–178
decision variables are the mole fractions which are the po­
sition of members in the algorithms. The objective functions
for PE and rPE are given in Eqs. (24) and (29), respectively.
MATLAB software was used for coding, implementing,
and computing all the problems, thermodynamic models
and algorithms. The algorithms’ ability to solve all problems
was carried out using two major terminating criteria.
Implementing the first stopping criteria (SC1) terminates the
optimisation process when the maximum number of itera­
tions is reached. While in the second stopping criteria (SC2),
the program terminates, if there is no significant change in
the value of the objective function after a declared number
(SCmax) of successive iterations. The algorithms that were
considered are population-based, a fixed population (NP)
= 10D was used for all the simulations, where D is the
number of decision variables. The study considered 24 pro­
blems with different degrees of computational complexity, 8
for each set of problems, as shown in Tables 1 and 2. Each
problem was solved 100 times with a different set of random
populations, and the performance of each algorithm was
evaluated based on their success rate in obtaining the global
minimum within the two stopping criteria. The number of
objective functions evaluation (NFE) for each problem and
algorithms using SC2 was also considered. A run is suc­
cessful if the tolerance i.e. the difference between its best
global value and the known global minimum, is less than the
set tolerance limits. PS5 and PS8 were assigned a 10−6, while
others were assigned a tolerance of 10−5. The Global success
rate (GSR) was also used to compare the performances of all
algorithms for all the problems. The GSR is shown in Eq. (33):
np
SRi
GSR =
i=1 np
Where SRi is the success rate for problem i and np is the total
number of problems.
The performance profile (PP) by Dolan and Mor (2002) was
also used in comparing the performances of all the algo­
rithms. There is a need for a performance matrix in evalu­
ating the PP, a performance matrix contains the performance
measure of interest, which could be the computation time,
NFE or objective function deviation from the global value. In
this study, the element of the performance matrix i, j was
chosen as a deviation between the mean values of the cal­
culated global minimum fij obtained in solving problem i and
solver j and the known global minimum value f j* as shown in
Eq. (34). For a total number of solver Ns and problems Np, i ϵ
Np and j ϵ Ns
i, j = fij f j*
The smallest value of i, j of all solvers for a given problem
serves as the basis for comparison with the performance of
all other solvers. As shown in Eq. (35).
The solver with the smallest value of i, j for a particular
problem was used as the basis of comparison as shown in
Eqs. (35) and (36).
i* = min( i , j ), 1 j Ns
i, j
ij = i Np, j Ns,
i*
The performance ratio ij is the ratio of i, j all solvers for
the particular problem to the best solver with i* for the
problem. The solver with the best performance will have a
value of 1. The fraction of all problems Np in which a solver j
with ij , is given as j as seen in Eq. (36).
1
j ( )= size { problem : ij }
Np (36)
j ( ) is the cumulative probability of a solver j to optimise
all the problems under consideration within the set value of
, while size is the number of problems with ij . The plot of
the j ( ) versus is known as the performance profile. The
higher the pp, the better the performance of the solver (Dolan
& More, 2002). As soon the stochastic optimisation is over,
the final values of the decision variable for the best minimum
of an iteration becomes the initial values for the local opti­
misation. Sequential quadratic program (SQP) was the local
optimiser used in this study.
HP EliteBook 840 G4 computer, Processor Intel(R) Core(TM)
i5–7300 U CPU @ 2.60 GHz, 2712 Mhz, 2 Core(s), 4 Logical
Processor(s) and 16 GB was used for all computations.
5. Results and discussion
5.1. The performance of all the algorithms on PS problems
The ability of all the stochastic algorithms with and without
a local intensifier to solve phase stability problems of dif­
ferent dimensions and complexity, as given in Table 1, was
explored using the two stopping criteria described in
Section 4.
PS1 is a phase stability problem of a dimension of 2, and it
has low computational resolution (Fonseca-Pérez et al.,
2021), the result without a local optimiser shows that at the
10th iteration, the SR of POA, PGOA2, GTO and PGOA1 are 22
%, 74 %, 84 % and 100 %, respectively. From 50 iterations and
above, all the stochastic algorithms attained an SR of 100.
(33)
The average SR of all the algorithms for SC1 is 84.4, 94.8, 96.8
and 100 for POA, PGOA2, GTO and PGOA1, and PGOA1 has the
best average SR. The effects of stopping criteria SC2, using
SCmax of 10, 20 and 50, were explored and shown in Table 3.
At SCmax = 10, all the algorithms except PGOA1 have an SR of
100 %. GTO has the smallest average value of NFE, 46, while
GPOA2, POA, and PGOA1 have average NFE of 54, 58 and 65,
respectively. Including a local optimiser improved the SR to
100 % for all cases in SC1 and SC2. These results show that all
the algorithms are reliable in the accurate prediction of the
point of instability and composition of the components of
PS1 system.
PS2 has a medium computational complexity (Fonseca-
Pérez et al., 2021), as the number of iterations increases, the
SR of all the algorithms increases. At 50 iterations, GTO and
(34) PGOA1 have an SR of 98 %, while POA and PGOA2 have an SR
of 100 %. For SC2, all the algorithms have an average SR of
100 % except for PGOA1, with an average SR of 96 %, and SR
value of 90 % at SCmax = 10. The presence of an intensifier
equates the SR of all the algorithms for all cases in SC1 and
SC2. The accuracy of the algorithms in locating the global
minimum of PS2 problems is an indicator that the predicted
compositions at the point of instability are correct.
(35) PS3 is a low computational resolution problem (Fonseca-
Pérez et al., 2021), using SC2 for stochastic algorithms
without a local optimiser shows that PGOA1 has the highest
(36)
SR of 93 % at the 10th iteration. POA, GTO, PGOA2 and PGOA1
have average SR of 85.4 %, 96.8 %, 96.8 % and 98.6 %, re­
spectively. In SC2, PGOA1 has an average SR of 96.7 %, which
is the lowest of all the algorithms, while the other algorithms
have an average value of 100 %. Including local optimisation
has little effect on SC2 but is more effective in SC1.
 Chemical Engineering Research and Design 194 (2023) 163–178 171

Table 3 – SR and NFE for PS Problems with SC2.

D Scmax POA GTO PGOA1 PGOA2

SR NFE SR NFE SR NFE SR NFE

10 100 3588 100 2810 95 3358 100 3392

PS1 2 25 100 5751 100 4240 100 6815 100 5174
50 100 8172 100 6794 100 9219 100 7741
10 87 5815 98 3586 70 5143 94 5452
PS2 3 25 99 8794 100 5129 100 10,323 100 7415
50 100 11,490 99 7622 100 12,944 100 10,217
10 100 4969 100 2955 90 5642 100 4308
PS3 3 25 100 6957 100 4441 100 8686 100 6023
50 100 9386 100 6994 100 11,021 100 8473
10 97 2908 98 2246 99 2767 98 2885
PS4 2 25 100 5568 100 3724 100 4515 100 4963
50 100 8605 100 6232 100 7093 100 7364
10 24 6105 100 5921 65 11,544 75 8823
PS5 5 25 81 17,718 98 7268 100 21,431 96 14,822
50 95 32,114 100 10,151 100 22,258 95 18,223
10 7 4314 92 12,289 0 970,050 62 9234
PS6 8 25 22 13,793 100 16,674 0 200,000 99 22,210
50 40 38,537 100 19,136 0 200,000 100 26,568
10 100 1200 100 1200 100 1200 100 1200
PS7 9 25 100 2700 100 2700 100 2700 100 2700
50 100 5200 100 5200 100 5200 100 5200
10 1 8320 72 42,177 17 63,821 19 18,243
PS8 10 25 4 18,293 85 59,032 30 152,670 90 104,442
50 8 44,084 74 64,097 39 143,398 99 116,093

Problem PS4 has similar computational complexity to PS1,
in solving PS4 with the algorithms, using SC1 without a local
optimiser shows average values of 98.4 %, 99.8 %, 99.8 % and
100 % for POA, GTO, PGOA2 and PGOA1, respectively. For SC2
in Table 3, all the algorithms have an average SR of 99 %. The
intensification by local optimisation improved the SR of all
the algorithms.
Problem PS5 has a medium computational resolution
(Fonseca-Pérez et al., 2021), at the 10th iteration, all the al­
gorithms failed to solve the problem, but as the SC1 in­
creased, there was an improvement in the SR of POA, while
the SR of GTO, PGOA1 and PGOA2 were fairly constant. The
same trend was experienced in the implementation of SC2,
as seen in Table 3, as SCmax increased. In both SC1 and SC2,
POA has the lowest SR.
PS6 is computationally demanding with high resolution
(Fonseca-Pérez et al., 2021), using SC1, the average SR of
PGOA1, POA, GTO and PGOA2 are 7.4 %, 62.4 %, 69 % and 77 %,
respectively. The result of implementing SC2 in Table 3
shows that GTO has the highest SR of 97. 3 % followed by 87
% of PGOA2, while POA and PGOA1 performed poorly. In­
cluding a local optimiser improved the performances of POA,
GTO and PGOA2, and it did not affect the performance of
PGOA1. This shows that the inclusion of local optimisation
may not be necessary for PGOA1. To correctly predict the
point of instability and the composition of various compo­
nents in this system, GTO and PGOA2 can be used with an
average NFE of 200 iterations.
PS7 has a high computational resolution, and despite its
high computational demand, all algorithms have fast con­
vergence with high success rates for all the considered
stopping criteria. This shows that all the algorithms can ac­
curately predict the split point for this system, and the need
for a local optimiser is not necessary.
PS8 is computationally challenging and belongs to the
group with the high computational resolution, as recently
classified by Fonseca-Pérez et al. ( 2021). The implementation
of the first stopping criteria showed that at the 10th iteration,
all algorithms failed to locate the global minimum, while at
the 50th iteration, PGOA1 had the highest SR of 14 %. As the
iteration increases, the SR of POA, GTO, and POA2 increases
while that of POA1 decreases. The average SR in SC1 for
PGOA2, GTO, POA and PGOA1 are 50 %, 39 %, 30.5 % and 30 %,
respectively. In implementing SC2, as shown in Table 3, the
SR of POA was very poor in all the cases, while GTO had a
relatively constant SR of 74 %, 85 % and 74 % for SCmax of 10,
25 and 50, respectively. The SR of PGOA1 was too low, with an
average of 28.6 %. At SCmax = 10, the SR of PGOA2 was 19 %,
but it became 99 % at SCmax = 50. With local optimisation, the
SR of the algorithms were significantly changed, though the
SR of PGOA1 trailed the others. There was a sharp contrast in
the SR of POA for SC1 and SC2 for PS8, the SR of the former
was far better than that of the latter; this anomaly affects the
overall GSR of POA for all the PS problems in SC2.
Considering the GSR of all PS problems in SC1 without the
local optimiser, as seen in Fig. 3a, the GSR increases as the
iterations increase. At the 10th iteration, PGOA1 had a GSR of
51.8 %, which was the highest among all the algorithms. The
trend changed at 50 iterations; the GSR of PGOA2 and GTO
were higher than that of PGOA1. At the 100th iteration, the
GSR of all the algorithms was better than that of PGAO1. This
trend was maintained till the 1000th iteration, with PGOA2
having the highest GSR of 98.3 %. Fig. 3, plot b shows that
with the intensification by a local optimiser, the reliability of
all the algorithms increases irrespective of the number of
iterations. The GSR of all the algorithms was greatly en­
hanced and looked alike except for PGOA1, which trailed the
others.
The result of the implementation of SC2 are shown in
Table 3; as SC2 increases, the GSR and overall NFE increase.
At SCmax= 50, the GSR of PGAO1, POA, GTO and PGOA2 are 80
172 Chemical Engineering Research and Design 194 (2023) 163–178

In PS problems, different algorithms performed differ­

ently for various problems with varying criteria of termina­
tion. The GSR of all the algorithms in SC2 was slightly better
with fewer NFE, except for POA, which was affected by the SR
of PS8 in SC2. The implication of the wrong global solution
for PS stability problems will lead to wrong phase split and
wrong compositions at the point of instability. PGOA2 has the
best performance and reliability for PS problems.

5.2. The performance of all the algorithms on PE problems

The studied PE problems have different degrees of compu­

Fig. 3 – The GSR versus the number of Iteration for PS
Problems with SC1 (a) Stochastic Algorithms only (b)
Stochastic and local optimisation.
%, 80.3 %, 96.6 % and 99.3 %, respectively. Intensification with
local optimiser increases the GSR slightly.
For the performance profile (PP) of all the algorithms for
all the PS problems, The PP of PGOA2 was higher and better
than others, closely followed by that of GTO, while the PP of
PGOA1 and POA are similar. PGOA1 has the fastest con­
vergence profile to the global minimum for most PS pro­
blems. This was closely followed by the convergence profile
of PGOA2, while the convergence profile of GTO was slightly
better than that of POA.
tational difficulties, which are similar to the PS problems.
The global solutions predict the composition of all the equi­
librium phases at phase split.
For PE1, the performances of the stochastic algorithms
alone show that in SC1, the SR increases as the iteration in­
creases. The rate increase of the SR with iterations was faster
in GTO, PGOA1 and PGOA2 than in POA. The average SR for
all the algorithms are 35 %, 68.2 %, 71.8 % and 76 % for POA,
GTO, PGOA2 and PGOA1, respectively. The inclusion of local
optimisation in SC1 brought a slight increase in the SR of the
algorithms, with an average SR of 52.2 %, 79.4 %, 85.6 % and
88.8 % for POA, GTO, PGOA2 and PGOA1, respectively. The
implementation of SC2 without a local optimiser was not
favourable to all the algorithms, as seen in Table 4; they all
have an average SR of 43 % except for POA, with an average
SR of 33 %. Local optimisation in SC2 brought a slight in­
crease in the SR of the algorithms.
For problem PE2, in implementing SC1, without a local
optimiser, the success rate of GTO was lower than that of
others; the average SR were 49 %, 79 %, 81.8 % and 84.6 % for
GTO, POA, PGOA1 and PGOA2, respectively. The presence of a
local optimiser for SC1 improved the performances of all the
algorithms. The result of the SC2 for all the algorithms is
shown in Table 4, the average SR of all algorithms in SC2

Table 4 – SR and NFE of all algorithms using SC2 For PE Problems.

Scmax POA GTO PGOA1 PGOA2

D SR NFE SR NFE SR NFE SR NFE

10 31 3172 32 3318 14 2614 29 3071

PE1 2 25 35 6188 48 6303 37 9702 45 7539
50 33 9412 55 9141 78 21,878 56 12,333
10 87 6534 55 3373 74 16,473 95 6959
PE2 3 25 100 12,540 56 4962 98 32,577 100 9079
50 100 16,290 49 7589 96 55,225 100 11,922
10 97 6178 98 3457 87 7174 100 6066
PE3 3 25 99 10,090 100 4996 100 11,554 100 8019
50 100 13,876 98 7536 100 14,194 100 10,823
10 100 3898 100 2932 99 4182 100 3702
PE4 2 25 100 6247 100 4280 100 8184 100 5612
50 100 9017 100 7001 100 11,295 100 8222
10 80 7499 75 6661 60 11,161 94 10,672
PE5 5 25 96 17,543 79 9542 100 25,656 100 22,690
50 100 34,556 68 13,601 100 28,856 100 33,271
10 1 4630 73 18,468 24 7346 24 11,440
PE6 8 25 1 11,753 79 22,398 96 31,500 85 73,149
50 3 33,911 81 26,691 100 36,117 98 94,556
10 0 4590 99 14,818 47 9663 38 8069
PE7 9 25 0 11,942 98 16,373 99 26,607 93 26,166
50 1 31,556 99 20,367 100 30,763 99 32,318
10 1 5702 100 31,918 32 10,024 42 11,397
PE8 10 25 2 13,820 100 46,871 100 53,203 91 72,353
50 6 35,603 100 89,478 100 61,472 100 193,195
 Chemical Engineering Research and Design 194 (2023) 163–178
without a local optimiser are 53.3 %, 89.5 %, 95.7 % and 98.3 %
for GTO, PGOA1, POA and PGOA2, respectively. GTO has the
lowest NFE, which was followed by PGOA2. The best algo­
rithm for PE2 using SC2 without a local optimiser is POA2
because it has the highest SR and low NFE. With the inclu­
sion of local optimisation, the success rate of all the algo­
rithms improved and are similar.
In solving PE3, the average SR of all algorithms using SC1
without a local optimiser are 84.2 %, 91.6 %, 95.4 % and 96.4 %
of POA, PGOA1, PGOA2 and GTO, respectively. These SRs
were high and similar, though POA is slightly lower than the
rest. Including local optimisation brought a slight improve­
ment in the SR of all the algorithms. Implementing SC2
without local optimisation, as seen in Table 4, the SR of all
the algorithms were higher than that of SC1.
The solution of problem PE4 for all cases in SC1 and SC2
shows that all the algorithms performed well with high SR,
which are pretty similar.
In problem PE5, as SC1 increases, the SR of all the algo­
rithms increases, though the SR of GTO were slightly lower
than the rest. The average SR is 63.8 %, 74.8 %, 77.8 % and 80
% for GTO, POA, PGOA1 and PGAO2, respectively. The im­
plementation of SC2 with a local optimiser brought about
average SR of 74 %, 92 %, 86.7 % and 98 % for GTO, PGOA1,
POA and PGOA2, respectively.
For problem PE6, in implementing SC1 without a local
optimiser, the SR of POA was very poor for the set of SC1 until
the 500th iteration, when it became 88 %. The SR of GTO has
a slight increase, with the highest value of 77 % at 500
iterations, while the SR of PGOA1 and PGOA2 were better
than the others. The implementation of SC2, as seen in
Table 4, was not favourable to POA; the SR were very poor
and far below the SR of SC1. The SR for all the other algo­
rithms were better than that of POA. Including a local opti­
miser improved the SR in all cases; this improvement was
more pronounced in SC2 of POA, with a wide difference in
the SR, it is most likely that the convergence rate of POA was
slow, and it was trapped in a local minimum with proximity
to the global minimum, and this led to the predictions of
compositions that are slightly different from the equilibrium
compositions of the global solutions. The performances of
the algorithms for PE7 and PE8 in all the cases are similar to
that of PE6.
The plot of the overall performance of all the algorithms
for all PE problems in case SC1 is shown in Fig. 4a, at SC1 = 10,
the GSR of GTO, PGOA1 and PGO2 are quite similar, while
that of POA was lower. At SC1 = 50, PGOA1 has the highest
GSR, and PGOA2 is closely followed; the same trend was
experienced when SC1 = 100. At SC1 = 500, the GSR of PGOA2
was slightly higher than that of PGOA1, and this trend was
maintained at the 1000th iteration. At 1000 iterations, the
GSR of POA, GTO, PGOA1, and PGO2 are 87 %, 88 %, 97.8 % and
99.5 %, respectively. Including local optimisation improved
the GSR for all the iterations, as seen in Fig. 4b. The result for
the implementation of SC2 without a local optimiser is
shown in Table 4; at SC2 = 10, GTO has the highest GSR, at
SC2 = 25, PGOA1 has the highest GSR, and PGAO2 closely
followed, while the GSR of GTO trails that of PGOA1 and
PGOA2, and POA has the worst GSR. The GSR of all algorithms
at SC2 = 50 was similar to that of SC2 = 25. The NFE of SC2 can
be seen in Table 4; at SC2 = 10, POA has the lowest NFE,
though the GSR value was also the lowest; therefore, its
performance does not supersede that of others.
173
Fig. 4 – The GSR versus the number of Iteration for PE
Problems with SC1 (a) Stochastic Algorithms only (b)
Stochastic and local optimisation.
The performance profile of PGOA2 was far better than the
rest, and it was faster and higher. The PP of POA was better
than that of GTO, while PGOA1 has the lowest performance
profile. In most problems, PGOA1 and PGOA2 convergence
profiles are similar and faster than that of POA and GTO.
These results also showed that to predict the points of
equilibrium and the compositions of all the components in
all the phases for PE systems, PGOA2 has the highest relia­
bility and performance with an average NFE of 50 and 100
iterations for SC1 stopping criterion with and without local
optimization, respectively.
5.3. The performance of all the algorithms on rPE
problems
rPE problems are computationally demanding; the studied
problem has different degrees of computational complexity.
The presence of a chemical reaction increases the com­
plexity because the reaction’s extent must be accounted for,
thereby increasing the problems’ dimensionality.
For problem rPE1, in implementing SC1 without a local
optimiser, there was an increase in all the SR of all the al­
gorithms; the average SR of POA, GTO, PGOA1 and PGOA2 are
58.4 %, 60.2 %, 78.4 % and 78.4 % respectively. The im­
plementation of SC2 shown in Table 5 was far better than
SC1, with an average SR of 92 %, 76 %, 100 % and 100 % for
POA, GTO, PGOA1 and PGOA2, respectively. Including local
optimisation improved the performance of all the algorithms
for SC1 and that of POA and GTO.
For rPE2, implementing the SC1, at the 10th iteration, all
the algorithms failed to locate the global minimum. As the
number of iterations increased, there were improvements in
the SR of all the algorithms. The average SR for all the algo­
rithms are 52.8 %, 60 %, 76.2 % and 78.4 % for GTO, POA,
PGOA1 and PGOA2, respectively. The implementation of SC2
with local optimisation was favourable to all the algorithms,
the SR were far better than those in SC1 and with fewer NFE.
174 Chemical Engineering Research and Design 194 (2023) 163–178

Table 5 – SR and Total NFE of algorithms for rPE problems.

D Scmax POA GTO PGOA1 PGOA2

SR NFE NFE SR NFE SR NFE

6D 79 24,609 72 10,283 100 23,616 100 22,849

rPE1 5 12D 97 54,570 81 13,467 100 27,430 100 27,430
24D 100 101,520 75 19,525 100 32,047 100 33,135
6D 68 21,021 62 9761 100 33,810 100 22,859
rPE2 5 12D 90 63,131 58 13,662 99 36,329 100 26,435
24D 97 112,337 59 19,108 100 43,193 100 34,047
6D 100 20,222 99 12,259 100 19,444 100 24,085
rPE3 5 12D 100 41,927 100 14,156 100 22,734 100 29,609
24D 100 74,049 100 20,940 100 29,556 100 34,539
6D 81 49,178 31 17,081 18 157,285 93 28,839
rPE4 5 12D 95 73,920 47 26,372 18 160,185 95 34,766
24D 92 106,009 52 34,856 13 173,166 96 41,556
6D 100 14,482 97 6495 100 15,957 100 11,371
rPE5 4 12D 99 26,104 98 8689 100 17,974 100 14,262
24D 100 40,554 99 13,483 100 23,047 100 19,376
6D 38 31,667 16 9273 100 33,931 100 27,663
rPE6 5 12D 72 87,190 25 14,210 100 39,294 100 34,036
24D 81 149,441 20 20,668 100 44,985 100 38,869
6D 70 19,461 71 8963 78 24,119 92 17,149
rPE7 4 12D 88 36,529 66 11,269 74 27,698 92 19,232
24D 97 66,258 63 16,060 75 31,887 94 24,854
6D 87 20,116 61 9051 100 21,242 91 17,972
rPE8 5 12D 96 51,426 71 13,286 100 24,934 96 21,388
24D 100 95,032 74 20,105 100 32,808 97 28,224

Including local optimisation in both SC1 and SC2 sig­
nificantly increased the SR of GTO.
For rPE3, the performances of all the algorithms in all
cases are pretty similar to the performance in problem rPE2.
However, the performance of GTO was better in rPE3 than
in rPE2.
rPE4 is the most computationally challenging problem out
of all the reactive problems considered because it has a
prominent local minimum point value of − 1.10326 (Bamikole
and Narasigadu, 2023). Most of the algorithms get trapped
against the global maximum point of − 1.10630 shown in
Table 2. In the implementation of SC1 without a local opti­
miser, the average SR of all the algorithms are 7.4 %, 36.6 %,
42.8 % and 62 % for GTO, PGAO1, and POA2, respectively. The
inclusion of a local optimiser for SC1 improved the average
SR to 48 %, 51.4 %, 78 % and 82 % for GTO, PGOA1, and PGOA2,
respectively. The result of implementing SC2 without a local
optimiser is shown in Table 5; the result shows that the
average SR of GTO, PGOA1 and PGOA2 is 43 %, 16 %, 89 % and
94.7 %, respectively. The SR of GTO was better in the im­
plementation of SC2 than in SC1, while in the POA1, it was
otherwise. The inclusion of local optimisation improves the
SR of all algorithms in SC2, but the SR of PGOA1 was not
affected.
In rPE5, the SR of the algorithms was high in all the cases;
the average SR in the implementation of SC1 without a local
optimiser are 81.6 %, 83.8 %, 89.2 % and 92.5 % for POA, GTO,
PGOA1 and PGOA2 respectively. The performance in SC2, as
seen in Table 5 was slightly better than SC1 for all the algo­
rithms.
For rPE6, in the implementation of the SC1 without a local
optimiser, the performance of POA, PGOA1 and PGOA2 look
alike, while that GTO was poor. The average SR of all the
algorithms are 15.4 %, 46.8 %, 70.4 %, and 77.6 % for GTO,
POA, PGOA1 and PGOA2, respectively. When a local optimiser
was included to intensify the result of SC1, the performance
was greatly enhanced for all algorithms. The implementation
of SC2 without a local optimiser is shown in Table 5. While
the SR for POA1 and POA2 were better and higher than that of
SC1, there is no significant improvement in the SR of POA
and GTO.
For rPE7, the result of the implementation of SC1 without
a local optimiser shows that the average SR of all the algo­
rithms 48.3 %, 50.8 %, 58 % and 67.8 % for GTO, POA, PGOA1
and PGO2, respectively. The inclusion of a local optimiser
using SC1 had little effect on the SR of all the algorithms, it
improved the average SR to 60 %, 87.6 %, 72.4 % and 80.8 %,
for GTO, POA, PGOA1 and PGO2, respectively. This improve­
ment was better enhanced for POA than the other algo­
rithms. The effect of implementing SC2 without a local
optimiser can be seen in Table 5; the SR of the algorithms are
66.7 %, 85 %, 75.7 % and 92.7 % for GTO, POA, PGOA1 and
PGO2, respectively. The inclusion of a local optimiser to SC2
led to average SR values of 66.7 %, 93.6 %, 77.3 % and 93 %;
these effects were very negligible in GTO, PGOA1 and PGOA2
but more pronounced in POA.
In rPE8, the implementation of SC1 without including a
local optimiser, the average SR was 65.2 %, 77.4 %, 80.2 % and
87.4 % for the GTO, PGOA2, POA and POA and PGOA1, re­
spectively. The effect of SC2, without a local optimiser,
yielded SR averages of 68.7 %, 94.6 %, 94.3 % and 100 % for the
GTO, PGOA2, POA and PGOA1, respectively. While the SR of
SC2 was more favourable for POA, PGOA1 and PGOA2 than
that of SC1 but GTO had a slight improvement. Including
local intensifiers in SC1 and SC2 increased and equated the
SR of all the algorithms to 100 %.
The overall performance of all the algorithms for all rPE
problems shows that as the number of algorithms increases,
the GSR of all the algorithms increases though at different
rates, as seen in plot of GSR against the number of iterations
in Fig. 5a. The rate increase of POA was the most steady as
 Chemical Engineering Research and Design 194 (2023) 163–178
Fig. 5 – The GSR versus the number of iterations for rPE
Problems with SC1 (a) Stochastic Algorithms only (b)
Stochastic and local optimisation.
the iteration increased. At the 10th iteration, the GSR was 2 %
but increased to the highest GSR of 97.6 % at the 1000th
iteration. At the same time, PGOA2 had a GSR value of 21 % at
the 10th iteration and had a sudden leap to 79.1 % at the 50th
iteration, an additional GSR value of 12 % was added at the
100th iteration. Beyond the 500th iteration, it maintained a
GSR average of 97.5 %. GTO and PGOA1 have a similar rate of
increases in GSR as the iteration increases. Beyond the 10th
iteration, the GSR value was slightly maintained as the
iteration progressed, though the performance of POA1 was
better than GTO. The effect of the local optimisation on SC1
can be seen in Fig. 5b; all the algorithms have similar per­
formance, though the GSR of GTO was slightly lower than the
rest. It was also seen that the effect of the number of itera­
tions was negligible.
The result of the implementation of SC2 without local
optimisation is shown in Table 5. The GSR was fairly con­
stant as SCmax increased from 6D to 24D for most of the al­
gorithms except for POA, in which the increase of GSR was
more significant from SCmax of 6D to 12D. The inclusion of a
local optimiser in SC2 yielded a GSR average of 86.7 %, 92 %,
98.5 % and 97.5 % for PGOA1, GTO, PGOA2 and PAO, respec­
tively.
The performance profile POA and PGOA2 are similar and
better than that of GTO and PGOA1, though the PP of GTO
was slightly higher than that of PGOA1. The convergence rate
of PGOA2 is the fastest and the most consistent for most of
the rPE problems. The accuracy in the obtaining the global
solutions for rPE systems, will in turn yield the correction
composition of all components in the all the phases at
equilibrium, the extent of reaction and the reaction equili­
brium constant.
175
Fig. 6 – The GSR(plot a) and NFE(plot b) of stochastic
algorithms for all problems with SC2.
5.4. The performance of all the algorithms for all
problems
The overall performances of all the algorithms were com­
pared for all 24 problems. The comparison was based on the
SC2, and the plot of the GSR against the different values of
SCmax is shown in Fig. 6a. From the plot, it can be seen that in
the first set of SCmax, the GSR of POA, PGOA1, GTO, and
PGOA2 are 64 %, 69.5 %, 79.2 % and 81 %, respectively; PGOA2
has the highest GSR, which GTO closely followed. As the
SCmax progressed, the previous trend in the GSR of the al­
gorithms changed; though PGOA2 still retained the highest
GSR, the GSR of PGOA1 was slightly better than that of GTO,
while the GSR of POA was the lowest in all the iterations. The
effect of intensification of a local optimiser on the GSR of all
the algorithms led to a similar performance in all cases,
though PGOA2 still retained the highest GSR.
The plot of NFE is shown in Fig. 6b, it shows that GTO has
the lowest NFE, which means that it is computationally less
expensive. The NFE of the PGOA2 is slightly higher than that
of GTO, while the NFE of PGOA1 and POA are higher than that
of PGOA2 and POA.
Without intensification, the PP of PGOA was far above that
of others, followed by that of POA, while GTO and PGOA1
have similar PP. Including a local intensifier improves the PP
of all the algorithms and reduces the difference between the
PP of PGOA2 and others, though PGOA2 still has the
highest PP.
The combination of the GSR, NFE and PP shows that
PGOA2 has the best performance for all problems; though the
NFE of GTO was the smallest, its GSR was lower than that of
PGOA2, which makes the performance of PGOA2 more robust
and reliable than the other algorithms.
176 Chemical Engineering Research and Design 194 (2023) 163–178

Table 6 – Comparison of the studied algorithms with other methods in the literature.
PS PE rPE All Problems

GSR NFE GSR NFE GSR NFE GSR NFE

IDE 87 20,821 99.8 8629 89.4 19,648 92.1 16,366

CS 81 27,167 99 35,208 90 12,161 90.0 24,845
KH 89.5 1406 99 3543 90 3062 92.8 2670
LKH 81 614 98 2506 89 3122 89.3 2081
HB 85.9 211 96.9 254 84.4 299 89.1 255
HH 92.9 235 86.3 338 77.9 364 85.7 312
POA 80.4 197 55.4 230 95.9 932 77.2 453
GTO 96.6 158 81.3 227 67.8 206 81.9 197
PGOA1 79.9 514 96.8 325 86 513 87.6 451
PGOA2 99.3 250 94.1 496 97.3 354 96.9 367

5.5. The comparison with the performance of other
algorithms reported in the literature
It is essential to compare the performance of the applied and
proposed algorithms to other methods available in the lit­
erature. Several algorithms have been used to solve phase
stability and equilibrium problems. In order to have a fair
basis for comparison, the selected algorithms were chosen
because; the same set of problems was solved, the same kind
of problem formulation was used, the same set of stopping
criteria were also used, and the comparison was done based
on the GSR after solving each problem 100 times with a dif­
ferent set of random initialisation. The NFE was also a factor
that was used for comparison, NFE is a good yardstick for
comparison of computational efficiency, and it is in­
dependent of the computer and computation software
(Fateen et al., 2012).
The bases above were used in selecting the following al­
gorithms for comparison with the studied algorithms in this
work. In the work by Zhang et al. (2011), four algorithms,
namely; unified bare-bones particle swarm optimisation,
integrated differential evolution (IDE) and IDE without tabu
list and radius, were studied and used to solve the same set
of phase equilibrium and stability problems. Their finding
shows that IDE has the highest SR and the lowest NFE, and it
was termed the best. In the application of the Covariance
Matrix Adaptation Evolution Strategy (CMAES), Shuffled
Complex Evolution (SCE) and Firefly Algorithms (FA) for sol­
ving the same set of problems, the results were compared
with the performance of IDE, and IDE performed better than
CMAES, SCE and FA. (Fateen et al., 2012). The performance of
IDE surpasses several other algorithms and therefore it was
chosen for comparison with the algorithms in this study.
In the study by Khalil et al. (2016), Gravitational Search,
Monkey, and Krill Herd Swarm Algorithms were studied for
the same set of problems, all the algorithms were compared
with the cuckoo search (CS) algorithms. The result shows
that CS was better than the other algorithms. In a recent
study by Bamikole and Narasigadu (2023), four different al­
gorithms, Pathfinder, Honey Badger, Red Fox and Horse Herd,
were examined, the findings showed that honey badger and
horse herd algorithms were better than the others.
Therefore, in concise but detailed comparison, integrated
differential evolution (IDE), cuckoo search (CS), Krill Herd
(KH), Lévy-Flight Krill Herd (LKH), Honey Badger (HB) and
horse herd (HH) were used for comparison with the present
study. The result presented for IDE, and CS include local
optimisation, while others do not. To have a fair basis for
comparison, the result of stochastic optimisation without the
inclusion of local optimisation in this study were used for
comparison, also the result of stochastic algorithms is sol­
ving the problem without local optimisation indicate the
reliability of the algorithms in find the solutions ( Khalil et al.,
2016). The comparison for the studied algorithms with other
methods in the literature is shown using the SCmax = 50
stopping criteria is shown in Table 6.
The results of the comparison for PS problems are shown
in Table 6. From the result of the ten algorithms presented,
the GSR of PGOA2 was the highest, and this was followed by
that of GTO. The NFE of GTO was the lowest, though the NFE
of HB and POA were lower than that of PGOA2, the GSR of the
latter was relatively higher. This shows that GTO and PGOA2
are very reliable in solving PS problems with low computa­
tional cost and will favourably compete with most methods
without local intensification.
The performance of all the algorithms for the PE problems
can be seen in Table 6. The GSR of PGOA2 with local opti­
misation is 99.9 %, which was similar to the GSR of IDE, and
surpasses that of the other algorithms. The NFE of PGOA2 is
lower than that of IDE and other algorithms with similar GSR,
and this makes PGOA2 to be computationally less expensive
than the others for solving PE problems.
The comparison of the algorithms for solving rPE in
Table 6 shows that PGOA2 has the highest GSR with a small
NFE; therefore, it is highly robust and more computationally
less expensive than most of the algorithms in solving rPE
problems.
The comparison of the performance of the algorithms for
all problems is shown in Table 6. The GSR of the algorithms
shows that the overall performance of PGOA2 surpasses that
of most algorithms in solving all the problems. It is also
computationally less expensive, reliable, and robust in opti­
mising phase stability and equilibrium problems.
6. Conclusion
In this study, two recently developed stochastic global opti­
misation algorithms, POA and GTO, were studied to solve
multidimensional and challenging phase stability, phase and
chemical equilibrium problems. To improve the perfor­
mances of these algorithms, two new hybrid algorithms,
namely PGOA1 and PGOA2 were developed in this study.
These newly developed hybrid algorithms combine the ex­
plorative ability of POA and the exploitative ability of GTO for
improved performance. The effect of different stopping cri­
teria, the number of iterations and local optimiser inclusion
 Chemical Engineering Research and Design 194 (2023) 163–178
were explored. Most of the algorithms studied require a
reasonable number of iterations for optimum performance
and therefore caution should be taken in implementing the
stopping criteria. Their performances vary with the nature of
the problems. Though the performance of GTO and POA is
good, considering the GSR of all the problems, GTO slightly
outperformed POA. The SC2 was more favourable for the
performance of GTO than POA, and the inclusion of a local
optimiser (Sequential Quadratic Program) improved the
performances of both algorithms. The hybrid algorithms,
PGOA1 and PGOA2 were better than that of GTO and POA for
all the problems combined. Though PGOA1 seems to have an
overall performance that is slightly above that of GTO and
POA, the performance seems inconsistent and can be more
computationally expensive than both. For all cases and per­
formance indices, PGOA2 is more robust and reliable, and it
outperforms all the other algorithms in locating the points of
instability, and the composition of all components in all the
phases at Equilibruim. Comparison with other studied algo­
rithms in the literature shows that PGOA2 has a higher
probability than most algorithms in locating the global
minimum with very little deviation from the known global
minimum value, equilibrium compositions and it is less
computationally expensive than most algorithms.
PGOA2 is highly reliable without the presence of a local
intensifier. The performance of PGOA2 without a local opti­
miser surpasses that of several algorithms with local in­
tensification. Therefore PGOA2 is highly reliable, less
computationally expensive, and does not necessarily need
the enhancement of a local optimiser. Its implementation is
quite easy, and its application can be extended to other
global optimisation and multidimensional problems, as such
equipment design, chemical kinetic modelling, parameter
evaluation for thermodynamic models and other forms of
global optimisation problems.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have
appeared to influence the work reported in this paper.
References
Abdollahzadeh, B., Soleimanian Gharehchopogh, F., Mirjalili, S.,
2021. Artificial gorilla troops optimiser: a new nature-inspired
metaheuristic algorithm for global optimisation problems. Int.
J. Intell. Syst. 36, 5887–5958. https://doi.org/10.1002/int.22535
Ammar, M., Renon, H., 1987. The isothermal flash problem: new
methods for phase split calculations. AIChE J. 33, 926–939.
Balogh, J., Csendes, T., Stateva, R.P., 2003. Application of a sto­
chastic method to the solution of the phase stability problem:
cubic equations of state. Fluid Phase Equilib. 212, 257–267.
https://doi.org/10.1016/S0378-3812(03)00266-8
Bamikole, J.O., Narasigadu, C., 2023. Application of Pathfinder,
Honey Badger, Red Fox and Horse Herd algorithms to phase
equilibria and stability problems. Fluid Phase Equilib. 566,
1–17.
Bender, E., Block, U., 1975. Thermodynamische Berechnung der
Flüssig-Flüssig-Extraktion. Verfahrenstechnik 9, 106–111.
Bhargava, V., Fateen, S.E.K.K., Bonilla-Petriciolet, A., 2013. Cuckoo
Search: a new nature-inspired optimisation method for phase
equilibrium calculations. Fluid Phase Equilib. 337, 191–200.
https://doi.org/10.1016/j.fluid.2012.09.018
Bonilla-Petriciolet, A., Bravo-Sánchez, U., Castillo-borja, F.,
Frausto-hernández, S., Segovia-Hernández, J., 2008. Gibbs
177
energy minimization using simulated annealing for two-
phase equilibrium calculations in reactive systems. Chem.
Biochem. Eng. Quart. 22, 285–298.
Bonilla-Petriciolet, A., Rangaiah, G.P., Segovia-Hernández, J.G.,
2011. Constrained and unconstrained Gibbs free energy
minimisation in reactive systems using genetic algorithm and
differential evolution with tabu list. Fluid Phase Equilib. 300,
120–134. https://doi.org/10.1016/j.fluid.2010.10.024
Bonilla-Petriciolet, A., Segovia-hernández, J.G., 2010. A com­
parative study of particle swarm optimisation and its variants
for phase stability and equilibrium calculations in multi­
component reactive and non-reactive systems. Fluid Phase
Equilib. 289, 110–121. https://doi.org/10.1016/j.fluid.2009.11.
008
Bonilla-Petriciolet, A., Vázquez-Román, R., Iglesias-Silva, G.A.,
Hall, K.R., 2006. Performance of stochastic global optimisation
methods in the calculation of phase stability analyses for
nonreactive and reactive mixtures. Ind. Eng. Chem. Res. 45,
4764–4772. https://doi.org/10.1021/ie051081g
Dolan, E.D., Mor, J.J., 2002. Benchmarking Optimisation Software
with Performanc. pp. 201–213.
Elnabawy, A.O., Fateen, S.E.K., Bonilla-Petriciolet, A., 2014. Phase
stability analysis and phase equilibrium calculations in re­
active and non-reactive systems using Charged System
Search algorithms. Ind. Eng. Chem. Res. 53, 2382–2395.
Fateen, S.-E.K., Bonilla-Petriciolet, A., Rangaiah, G.P., 2012.
Evaluation of covariance matrix adaptation evolution
strategy, shuffled complex evolution and firefly algorithms for
phase stability, phase equilibrium and chemical equilibrium
problems. Chem. Eng. Res. Des. 90, 2051–2071.
Fateen, S.E.K., Bonilla-Petriciolet, A., 2015. On the performance of
swarm intelligence optimisation algorithms for phase stabi­
lity and liquid-liquid and vapor-liquid equilibrium calcula­
tions. Period. Polytech. Chem. Eng. 59, 186–200. https://doi.org/
10.3311/PPch.7636
Fernández-Vargas, J.A., Bonilla-Petriciolet, A., Segovia-
Hernández, J.G., 2013. An improved ant colony optimisation
method and its application for the thermodynamic modeling
of phase equilibrium. Fluid Phase Equilib. 353, 121–131.
https://doi.org/10.1016/j.fluid.2013.06.002
Fonseca-Pérez, R.M., Bonilla-Petriciolet, A., Tapia-Picazo, J.C., Jaime-
Leal, J.E., 2021. A reconsideration on the resolution of phase sta­
bility analysis using stochastic global optimisation methods:
Proposal of a reliable set of benchmark problems. Fluid Phase
Equilib. 548. https://doi.org/10.1016/j.fluid.2021.113180
Harding, S.T., Floudas, C.A., 2000. Phase stability with cubic
equations of state: global optimisation approach. AIChE J. 46.
Heidemann, R., Mandhane, J., 1973. Some properties of the NRTL
equation in correlating liquid–liquid equilibrium data. Chem.
Eng. Sci. 28, 1213–1221.
Hua, J.Z., Brennecke, J.F., Stadtherr, M.A., 1998a. Enhanced in­
terval analysis for phase stability: cubic equations of state
models. Ind. Eng. Chem. Res. 37, 1519–1527.
Hua, James Z., Brennecke, J.F., Stadtherr, M.A., 1998b. Reliable
computation of phase stability using interval analysis: cubic
equation of state models. Comput. Chem. Eng. 22, 1207–1214.
https://doi.org/10.1016/S0098-1354(98)00024-6
Jalali, F., Seader, J.D., Khaleghi, S., 2008. Global solution approaches in
equilibrium and stability analysis using homotopy continuation
in the complex domain. Comput. Chem. Eng. 32, 2333–2345.
https://doi.org/10.1016/j.compchemeng.2007.12.001
Khalil, A.M.E., Fateen, S.E.K., Bonilla-Petriciolet, A., 2016.
Gravitational search, monkey, and krill herd swarm algo­
rithms for phase stability, phase equilibrium, and chemical
equilibrium problems. Chem. Eng. Commun. 203, 389–406.
https://doi.org/10.1080/00986445.2015.1004666
Khalil, A.M.E., Fateen, S.E.K., Bonilla-Petriciolet, A., 2016.
Gravitational search, monkey, and krill herd swarm algo­
rithms for phase stability, phase equilibrium, and chemical
equilibrium problems. Chem. Eng. Commun. 203, 389–406.
https://doi.org/10.1080/00986445.2015.1004666
178 Chemical Engineering Research and Design 194 (2023) 163–178
Khalil, A.M.E., Fateen, S.E.K., Bonilla-Petriciolet, A., 2015. MAKHA-
A new hybrid swarm intelligence global optimisation algo­
rithm. Algorithms 8, 336–365. https://doi.org/10.3390/a8020336
McDonald, C.M., Floudas, C.A., 1997. GLOPEQ: a new computa­
tional tool for the phase and chemical equilibrium problem.
Comput. Chem. Eng. 21, 1–23. https://doi.org/10.1016/0098-
1354(95)00250-2
McDonald, C.M., Floudas, C.A., 1995. Global optimisation for the
phase stability problem. Am. Inst. Chem. Eng. J. 41, 1798–1814.
Michelsen, M.L., 1982. The isothermal flash problem. Part I.
Stability. Fluid Phase Equilib. 9, 1–19. https://doi.org/10.1016/
0378-3812(82)85001-2
Moodley, K., Rarey, J., Ramjugernath, D., 2015. Application of the
bio-inspired Krill Herd optimisation technique to phase
equilibrium calculations. Comput. Chem. Eng. 74, 75–88.
https://doi.org/10.1016/j.compchemeng.2014.12.008
Nichita, D.V., Gomez, S., Luna, E., 2002. Phase stability analysis
with cubic equations of state by using a global optimisation
method. Fluid Phase Equilib. 194–197, 411–437. https://doi.org/
10.1016/S0378-3812(01)00779-8
Peng Lee, Y., Pandu Rangaiah, G., Luus, R., 1999. Phase and che­
mical equilibrium calculations by direct search optimisation.
Comput. Chem. Eng. 23, 1183–1191. https://doi.org/10.1016/
S0098-1354(99)00283-5
Rangaiah, G.P., 2001. Evaluation of genetic algorithms and si­
mulated annealing for phase equilibrium and stability pro­
blems. Fluid Phase Equilib. 187–188, 83–109. https://doi.org/10.
1016/S0378-3812(01)00528-3
Srinivas, M., Rangaiah, G., 2007a. A study of differential evolution
and tabu search for benchmark, phase equilibrium and phase
stability problems. Comput. Chem. Eng. 31, 760–2007.
Srinivas, Mekapati, Rangaiah, G.P., 2007b. Differential evolution
with tabu list for global optimization and its application to
phase equilibrium and parameter estimation problems. Ind.
Eng. Chem. Res. 3410–3421.
Sun, A.C., Seider, W., 1995. Homotopy-continuation method for
stability analysis in the global minimisation of the Gibbs free
energy. Fluid Phase Equilib. 103, 213–249.
Tessier, S.R., Brennecke, J.F., Stadtherr, M.A., 2000. Reliable phase
stability analysis for excess Gibbs energy models. Chem. Eng. Sci.
55, 1785–1796. https://doi.org/10.1016/S0009-2509(99)00442-X
Trojovský, P., Dehghani, M., 2022. Pelican optimization algorithm:
a novel nature-inspired algorithm for engineering applica­
tions. Sensors 22. https://doi.org/10.3390/s22030855
Ung, S., Doherty, M.F., 1995. Vapor-liquid phase equilibrium in
systems with multiple chemical reactions. Chem. Eng. Sci. 50,
23–48. https://doi.org/10.1016/0009-2509(94)00180-Y
Vianna Neto, M.R., Oliveira, E.D., 2017. Chemical and phase
equilibrium calculations by Gibbs energy minimisation using
deterministic methods based on globally convergent branch
and bound algorithms. Fluid Phase Equilib. 447, 95–106.
https://doi.org/10.1016/j.fluid.2017.05.020
Wakeham, W.A., Stateva, R.P., 2004. Numerical solution of the
isothermal, isobaric phase equilibrium problem. Rev. Chem.
Eng. 20, 1–56.
Wasylkiewicz, S.K., Li, Y.K., Satyro, M.A., Wasylkiewicz, M.J.,
2013. Application of a global optimisation algorithm to phase
stability and liquid-liquid equilibrium calculations. Fluid
Phase Equilib. 358, 304–318. https://doi.org/10.1016/j.fluid.
2013.08.030
Wasylkiewicz, S.K., Ung, S., 2000. Global phase stability analysis
for heterogeneous reactive mixtures and calculation of re­
active liquidliquid and vapor-liquid-liquid equilibria. Fluid
Phase Equilib. 175, 253–272.
Wolpert, D.H., Macready, W.G., 1997. No free lunch theorems for
optimisation. IEEE Trans. Evol. Comput. 1, 67–82.
Zhang, H., Fernández-Vargas, J.A., Rangaiah, G.P., Bonilla-
Petriciolet, A., Segovia-Hernández, J.G., 2011. Evaluation of
integrated differential evolution and unified bare-bones par­
ticle swarm optimisation for phase equilibrium and stability
problems. Fluid Phase Equilib. 310, 129–141. https://doi.org/10.
1016/j.fluid.2011.08.002