Prediction of Azeotropic Behaviour by the Inversion of

Functions From the Plane to the Plane

Aline L. Guedes, Francisco D. Moura Neto and Gustavo M. Platt*

Instituto Politécnico, Rio de Janeiro State University, Nova Friburgo, Brazil

Azeotropy is a thermodynamic phenomenon where liquid and vapour coexisting phases have the same composition. In binary mixtures, the
azeotropy calculation is represented by a 2
2 nonlinear system of algebraic equations with temperature (or pressure) and one molar fraction as
unknowns. On rare occasions, this nonlinear system exhibits two solutions, characterizing a double azeotrope. In this work, we calculate double
azeotropes with a geometry-based methodology: the numerical inversion of functions from the plane to the plane. We present results for two
mixtures where the double azeotropy phenomenon occurs: the system benzene þ hexafluorobenzene and the system 1,1,1,2,3,4,4,5,5,5-
decafluoropentane þ oxolane. The persistence of double azeotropes across different pressures is made clear by this global geometric approach.
Moreover the vanishing of the existence of a pair of azeotropes is explained by the coalescence of them in just one, as can be easily understood from a
global geometric viewpoint presented of the nonlinear function involved. The results indicate that this methodology can be a powerful tool for a
better understanding of nonlinear algebraic systems in phase coexistence problems.

Keywords: double azeotropy, functions from the plane to the plane, nonlinear algebraic systems

INTRODUCTION methylfuran, 2-methylfuran þ oxolane (tetrahydrofuran, THF), HFC-

4310 mee þ 2-methylfuran þ oxolane. The vapour-liquid equilibrium
measurements obtained by Loras et al.[14] were used to adjust

A
mixture of two or more substances where the coexistence
of liquid and vapour phases occurs concurrently with
equality of composition between phases represents the-
thermodynamic phenomenon called homogeneous nonreactive
azeotropy (henceforth called in this paper simply as azeotropy,
since we just deal with homogeneous and nonreactive azeo-
tropes).[1] The reliable calculation of azeotropes is extremely
important in the chemical engineering context, since the presence
of azeotropic phenomena can produce distillation regions in
separation processes. In binary mixtures, this phenomenon is
represented by a 2
2 nonlinear system of algebraic equations with
temperature (or pressure) and one molar fraction as unknowns.
In some specific (and rare) situations, this nonlinear system shows
two solutions. In these cases, the phenomenon is called double
azeotropy. A detailed review about theoretical double azeotropy
phenomenon is presented by van Konynenburg and Scott.[2] The
polyazeotropic behaviour can be predicted by a g  f modelling, as
pointed by Wisniak et al.[3] and Segura et al.[4] In this context, Wisniak
et al.[3] presented the necessary and sufficient conditions for
polyazeotropy in binary systems with excess Gibbs free energy
models. The influence of association effects in the conditions for
polyazeotropy was detailed by Segura et al.[4] Experimental evidences
of polyazeotropy were presented by several authors[5–9] in the system
benzene þ hexafluorobenzene and by Burget et al.[10] for the system 2-
metylpropyl ethanoate þ ethanoic acid. In this scenario, Montón
et al.[11] showed that the binary system methyl ethanoate þ 1,2-
epoxybutane does not present polyazeotropy; the previous exper-
imental results published indicating the double azeotrope phenom-
enon in this system were incorrect. Aucejo et al.[12] studied the vapour-
liquid equilibrium in the system methanol þ diethylamine at 101.3 and
300 kPa and found a behaviour that indicates the existence of a double
azeotrope at temperatures close to the values reported by Srivastava
and Smith.[13] Loras et al.[14] presented experimental results and
the thermodynamic modelling for the double azeotropy in the
system 1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310 mee) þ 2-
parameters of a Redlich-Kister model for the studied mixtures. The
polyazeotropic behaviour in the mixture formed by HFC-4310 mee þ
oxolane was previously reported by Kao et al.[15] Loras et al.[16] reported
new vapour-liquid equilibrium data for the binary system HFC-
4310 mee þ oxolane. The existence of a double azeotrope in this system
at several pressures was confirmed by Loras et al.[16] Polishuk et al.[17]
applied a Dieterici EOS in order to predict azeotropic behaviour. These
authors identified even three azeotropes for binary mixtures.
Several methodologies have been developed for the reliable solution
of nonlinear algebraic systems (some of them with applications in
azeotropic phenomena); in this scenario, we can cite deflation
techniques,[18] homotopy-continuation methods,[19–21] interval meth-
ods[22] and stochastic optimization approaches.[23] Recently, Platt
et al.[24] used a hyperheuristic framework in the double azeotropy
calculation problem. The same hyperheuristic structure was applied
by Platt et al.[25] in a double retrograde vapourization problem (a hard
nonlinear algebraic system with four roots).
In this work, we present some global geometrical and numerical
aspects to the problem of calculation of homogeneous nonreactive
azeotropes for two systems that exhibit double azeotropes in
narrow ranges of pressures: benzene þ hexafluorobenzene and
1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310 mee) þ oxolane
(THF). Malta et al.[26] introduced a new and geometry-based
numerical methodology to solve 2
2 nonlinear algebraic problems:
the numerical inversion of functions from the plane to the plane. Here,
we extend this methodology in a number of ways to shed light on the
* Author to whom correspondence may be addressed.
E-mail address: gmplatt@iprj.uerj.br
Can. J. Chem. Eng. 93:914–928, 2015
© 2014 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.22152
Published online 20 February 2015 in Wiley Online Library
(wileyonlinelibrary.com).

914 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 93, MAY 2015
global geometric aspects of the double azeotropy calculations in the ^ P ¼ Z Lf
ZiV f
V
^ P; i ¼ 1; 2; :::; c:
L
ð3Þ
i i i
studied systems. This methodology is based on the numerical
calculation of critical curves, the calculation of pre-images of some For two equilibrium phases, we used, as usual, yi instead of ZVi
arbitrary points in order to produce a bank of solved points and, then, (vapour molar fraction) and xi instead of ZLi (liquid molar
the numerical inversion of the function. A detailed explanation of the fraction). Thus, the isofugacity equations can be written as
geometric structure and the basic numerical methodology is
presented by Malta et al.[26] and Saldanha and Tomei.[27] In the ^ ¼ xi f
V
^ ; i ¼ 1; 2; :::; c:
L
yi f i i ð4Þ
next sections, we present the nonlinear algebraic system that
describes the azeotropic phenomenon, a brief description of the ^ a are functions of molar fractions of all
Fugacity coefficients f i
thermodynamic models (a detailed description can be found in
components in a given phase, temperature and pressure, i.e.,
Guedes et al.[28] for the benzene þ hexafluorobenze mixture and in a a
a 
^ ¼f
f ^ Z ; :::; Z a ; T; P . Since we are calculating azeotropes in
Loras et al.[16] and Segura et al.[29] for the HFC-4310 mee þ THF) and i i 1 n
a binary mixture, the system has two components, in which case
the mathematical and numerical tools and concepts involved in the
c ¼ 2. The coexistence problem shows 6 coordinates:
numerical inversion of functions from the plane to the plane. Finally,
xi ði ¼ 1; 2Þ; y i ði ¼ 1; 2Þ, T and P.
in the “Results and Discussion” section, some algorithmic steps and
Thus, we have 2 coexistence equations (Equations (1), (3), or (4))
numerical results are presented. The results permitted – for the P2
studied examples – a better understanding of the phenomenon of and the constraints over molar fraction vectors,
P2 i1 xi ¼ 1,
double azeotropy from a geometrical point of view, in addition to i1 yi ¼ 1, and the number of independent equations is
generating the expected solutions. Moreover, the methodology is 2 þ 2 ¼ 4. Therefore, the number of degrees of freedom of the system
useful for the calculation of azeotropic coordinates at other pressures, is 6  4 ¼ 2. Assuming that the pressure (as we will do) or the
using a unique structure constructed at a single pressure, additionally temperature is previously specified, the number of degrees of freedom
exhibiting the coalescence of azeotropes. reduces to 2  1 ¼ 1.
The main objective of this work is to present a detailed The ordinary (non-reactive) homogeneous azeotrope condition,
description and a global view of a nonlinear problem with expressed by the equalities of compositions in both phases,
industrial interest – the double azeotrope calculation. In this
sense, some graphical details presented illustrate, in a qualitative x1 ¼ y1 ; ð5Þ
way, the range of existence of a double azeotrope, and the
geometric way in which its existence vanishes. must also be considered in the nonlinear system of equations. Only
one azeotropic condition is considered in azeotrope calculations
for a binary mixture since it automatically reduces the number of
THE DOUBLE AZEOTROPY PHENOMENON
degrees of freedom to zero. Thus, we have a new system (under
In a few binary mixtures and for a narrow range of pressures – specified pressure):
such as benzene þ hexafluorobenzene at subatmospheric pres-
sures – it is possible to find two distinct azeotropes when the 8
> ^ V ðy1 ; y2 ; TÞ ¼ xi f
yi f ^ L ðx1 ; x2 ; TÞ; i ¼ 1; 2
>
>P i i
nonlinear system that characterizes azeotropic conditions has two >
< 2 x ¼1
different and physically meaningful solutions. This specific i¼1 i
P2 ð6Þ
phenomenon is called double azeotropy.[1] In the following >
>
> i¼1 yi ¼ 1
>
:
sections, we present the formulation of azeotropic conditions and x1 ¼ y1 ;
the numerical methods used for solving this problem. In our
approach, we used two formulations of vapour-liquid equilibrium: with 5 equations and 5 unknowns, without degrees of freedom.
(i) a f  f approach with an appropriate mixing rule[30] and (ii) a Considering Equation (5), we get that y2 ¼ 1  y1 ¼ 1  x1 and
modified Raoult’s Law modelling. taking x2 ¼ 1  x1 , the fugacity coefficients f ^ a can be seen as
a a i
Problem Formulation ^ ¼f
function of only x1 and T, f ^ ðx1 ; T Þ. Therefore the nonlinear
i i
system can be rewritten in its final form,
The azeotropy (ordinary, nonreactive) is a coexistence phenom-
enon and, thus, is an equilibrium condition between vapour and 8
liquid phases. This equilibrium is usually expressed by isofugacity <f ^ L ðx 1 ; T Þ
^ V ðx 1 ; T Þ ¼ f
1 1
ð7Þ
equations: :f^ V ðx ; T Þ ¼ f ^ L ðx ; T Þ;
2 1 2 1

^f V ¼ ^f L ; i ¼ 1; 2; :::; c; ð1Þ
i i as a 2
2 nonlinear system.
a Alternatively, we can use a g  f approach. In these cases, the
where ^f i refers to the fugacity of ith component in phase a, which phase coexistence equations are described as
can be vapour or liquid phase, denoted, respectively, by a ¼ V and
L, and c is the number of components in the system. ^ P ¼ xi g i f L ; i ¼ 1; 2; :::; c
yi f
V
ð8Þ
i i
The fugacity coefficient of component i in phase a, f^ a is defined by
i
where g i is the activity coefficient and f iL is the fugacity of pure
component in liquid phase. Neglecting the vapour phase non-
^a
^ ai ¼ f i ; i ¼ 1; 2; :::; c and a ¼ L; V;
f ð2Þ idealities and considering Poynting correction factor equal to one,
Pzia we obtain the modified Raoult’s Law:

where P is the system pressure and Zia is the molar fraction of yi P ¼ xi g i Pisat ; i ¼ 1; 2; :::; c ð9Þ
component i in phase a. Using the fugacity coefficient definition,
Equation (1) can be rewritten as where Pisat represents the vapour pressure of pure components.

VOLUME 93, MAY 2015 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 915
 Table 1. Critical Properties, acentric factors, parameters for PRSV EOS[37] and molar volumes[22] for the system benzene þ hexafluorobenzene
 
TC ðK Þ PC ðkPaÞ v k1;i Vi cm3 :mol 1

Benzene 562.2 4898.0 0.20929 0.07019 88.26

Hexafluorobenzene 516.7 3273.0 0.39610 0.02752 114.96

For a binary mixture and considering the azeotropy condition, and is one of the reasons that the methods of Malta et al.[26]
the previous system of equations can be written as partially breaks down on the problem at hand and further ideas
have to be implemented.
(
P ¼ g 1 ðx1 ; T ÞP1sat ðT Þ
ð10Þ Thermodynamic Models
P ¼ g 2 ðx1 ; T ÞP2sat ðT Þ;
In this paper, we present numerical results with a thermody-
which is the final form of the nonlinear algebraic system namic modelling using (i) a f  f approach with appropriated
considering the modified Raoult’s Law. Again, we obtained a 2
mixing and combination rules to predict azeotrope behaviour
2 system. (for more details see Orbey and Sandler),[31] and (ii) a modified
If the unknowns are expressed in a vector form u ¼ ðx1 ; T Þ and Raoult’s Law characterization of phase equilibrium, with
activity coefficients calculated by a Redlich-Kister type model,
F : D ! R2 presented by Segura et al.[29]
ð11aÞ The first example analyzed is the binary mixture formed by
u7!F ðuÞ benzene þ hexafluorobenzene. The fugacity coefficients are cal-
culated through the Peng-Robinson-Stryjek-Vera (PRSV) cubic
is given by equation of state[32] with Wong-Sandler (WS) mixing rules[30] and
 V  the Wilson model for the excess Gibbs free energy.[33] Wong-
F ðuÞ ¼ f ^ L ðx1 ; T Þ; f
^ ðx1 ; T Þ  f ^ V ðx1 ; T Þ  f
^ L ðx1 ; T Þ ; ð11bÞ
1 1 2 2 Sandler mixing rules were previously applied in low-pressure
calculations (as is the present case), for example, Faúndez and
or Valderrama.[34] Segura et al.[35] presented a detailed discussion of
the capabilities of equations of state in the prediction of azeotropic


F ðuÞ ¼ P  g 1 ðx1 ; T ÞP1sat ðT Þ; P  g 2 ðx1 ; T ÞP2sat ðT Þ ; ð11cÞ phenomenon, including the PRSV EOS with Wong-Sandler mixing
rules coupled with the NRTL model. The fugacity coefficients for
where D  R2 is the subset where one can compute FðuÞ, the the PRSV equation of state with WS mixing rules are presented by
nonlinear system can be rewritten as the problem of finding a root Orbey and Sandler.[36] Table 1 contains the values of critical
u 2 R2 of F, i.e., constants, acentric factors, constants for the Stryjek-Vera mod-
ification of Peng-Robinson EOS and molar volumes for pure
F ðuÞ ¼ 0; ð12Þ components in the system benzene þ hexafluorobenzene.
An interesting and useful portion of the thermodynamic model
where 0 is the null vector in R2 . It is stressed that F cannot be used in this work must be detailed: the Wilson model for excess
calculated for all u 2 R2 and that not all u 2 D has physical Gibbs free energies. The excess Gibbs free energy is used in order
meaning. This has theoretical as well as numerical consequences to calculate fugacity coefficients, with Wong-Sandler mixing rules.

Figure 1. Normal form of fold points.

916 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 93, MAY 2015
Figure 2. Critical curves for the system benzene þ hexafluorobenzene. The colour scheme is the same used in Figure 3.

With this approach, the excess Gibbs free energy GE for a binary Here, V 1 and V 2 stand for molar volumes of benzene
mixture is calculated by[33] (1) þ hexafluorobenzene (2), respectively. Also, a12 and a21 are
binary interaction parameters for Wilson model. We used a12 ¼
GE 406:6544 and a21 ¼ 922:6229 cal/mol. These quantities are
¼ x1 lnðx1 þ L12 x2 Þ  x2 lnðx1 L21 þ x2 Þ; ð13Þ tabulated by Maier et al.[22]
RT
Since the excess Gibbs free energy is given in terms of natural
where GE is the molar excess Gibbs free energy, R is the universal logarithms (Equation (13)), their arguments, W1 ¼ ðx1 þ L12 x2 Þ
gas constant, T is the absolute temperature (Kelvin). The and W2 ¼ ðx1 L21 þ x2 Þ, which are functions of x1 and T, must be
quantities L12 and L21 are given by non-negative. However, in the algorithmic process, x1 can
be negative or greater than one. Thus, a careful analysis must be
V2  a  V1  a  conducted in order to guarantee that W1 and W2 are greater than
12 21
L12 ¼ exp  ; L21 ¼ exp  : ð14Þ
V1 RT V2 RT zero. Besides, the cubic equation of state used (PRSV) can
exhibit, in some instances, only one real root (and two complex

Figure 3. Critical images for the system benzene þ hexafluorobenzene. The colour scheme is the same used in Figure 2.

VOLUME 93, MAY 2015 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 917
Figure 4. Domain of the problem. Black and yellow regions: feasible regions with opposite signs for the determinant of Jacobian matrix. Blue region: trivial
solutions (only one real root for PSRV equation). Red regions: thermodynamic model not defined (negative values in logarithms).

conjugate roots). In such cases, the nonlinear system repre-
sented by Equations (7) presents trivial solutions (since the
compositions of both phases are equal and the selected root is
the same). Again, the algorithm (inversion methodology) must
avoid these regions. Finally, even when the cubic equation of
state shows three roots, some of them can be lower than zero, or
lower than the co-volume, introducing negative terms in the
logarithms that appear in the expression of fugacity coefficients.
These three situations – (i) negative arguments for logarithms in
Wilson model, (ii) only one real root for the cubic equation of
state, and (iii) negative roots or roots lower than the co-volume –
will be detailed in the “Results and Discussions” section. It is
remarked that (i) and (ii) represent mathematical restrictions on
the domain where F can be calculated, and properties of the
function F, respectively. On the other hand, (iii) also represents
physical restrictions on the model.
For the second example studied here, the mixture HFC
4310 mee þ THF, the previous analysis is not necessary. However,
the numerical inversion of functions from the plane to the plane is
capable to find infeasible (non-physical) solutions; for instance,
with negative molar fractions. The model parameters and Antoine
coefficients for vapour pressures of pure components are tabulated
by Segura et al.[35]
THE INVERSION METHODOLOGY
The numerical inversion of functions from plane to the plane,[26] is
intended to solve 2
2 nonlinear systems written in the form

Figure 5. Critical curves for the system HFC-4130 mee þ THF. The colour scheme is the same used in Figure 6.

918 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 93, MAY 2015
Figure 6. Critical images for the system HFC-4310 mee þ THF. The colour scheme is the same used in Figure 5.

F ðuÞ ¼ q, where q 2 R2 is a point in the image and u 2 R2 is a way, when dealing with nonlinear systems FðpÞ ¼ q, when
point in the domain. The main idea of this method is to build F : R2 ! R2 , one can restrict the analysis to nice functions.
a global understanding of the function and use it to find For a nice function, the critical set C consists of disjoint union of
numerically all inverse images of a point q in the image. In this smooth isolated curves. Since cusp points are isolated, most points of
paper, we had to depart from the full blown global description of a critical curve are fold points. The critical set gives rise to its image,
the function since the problem we are analyzing, which involves F ðCÞ, and the flower, = ¼ F 1 ðF ðCÞÞ. For a nice function, these sets
function F, Equation (11), does not have all properties required by breaks the domain and the codomain of F in a collection of disjoint
the theory developed by Malta et al.[26] In particular, the domain of subsets, called tiles, xi and Yj , such that C [ xi ¼ R2 , in the domain of
definition of F is not the whole plane as required. We therefore F and F ðCÞ [ Yj ¼ R2 in the codomain of F, respectively. The number
focused on an engineering approach of this technique, but, on the of pre-images of any point q 2 R2 is finite, that is, the nonlinear
other hand, some mathematical insights must be presented and system has only a finite number of solutions. Moreover, the number
discussed. of pre-images is constant across each tile Yj , and for each tile xi that is
Some Theoretical Ingredients of the Inversion of Functions from
the Plane to the Plane
Malta et al.[26] and Saldanha and Tomei[27] analyzed and
constructed algorithms to solve the 2
2 nonlinear systems of
equations FðpÞ ¼ q, when F : R2 ! R2 is a nice function. A nice
function is a proper, excellent function such that the image of
critical points, ðCÞ, satisfy some technical conditions,[27] which we
omit. A function is proper if lim FðxÞ ¼ 1. In particular, Fðx; yÞ ¼
p!1
ðsinðxÞ; cosðyÞÞ is not a proper function while F ðx; yÞ ¼
ðx þ sinðxÞ; xy þ cosðyÞÞ is. Whitney[38] defined the class of
excellent functions, F : R2 ! R2 , as differentiable functions whose
critical points consist of folds and cusps points. The critical points
are those in which the Jacobian, JF, of the nonlinear function F is
non-invertible. We discuss these concepts further below. An
advantage of an excellent function is that it has a topological degree.
A major feature of the class of nice functions is that it is generic in
an adequate topological setting. That is, the class of nice functions
is open and dense. In an informal way, one can say that the set of
nice functions are stable (open): sufficiently close to a nice
function; all functions are still nice. Moreover, nice functions
are pervasive (dense) in all neighbourhoods of a given differ-
entiable function, nice or not. No matter how small the
neighbourhood is, there always exists a nice function approx-
imating the given function. In other words, either a function is Figure 7. Squares of the bank of solved points for the system
nice or can be arbitrarily approximated by a nice function. In this benzene þ hexafluorobenzene (in the image).

VOLUME 93, MAY 2015 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 919
Figure 8. Inversion of q1 ¼ ð0:17; 0:02Þ: (a) Domain: (D) – pre-image of a point in the bank of inverted points, (*) – calculated pre-image of an intermediate
point, () – calculated pre-image of a point to be inverted (b) Codomain: (D) –point in the bank of inverted points, (*) – point intermediate between point in
the bank and the one to be inverted, () – point to be inverted.
transformed by F into a tile Yj , there are the same number of
solutions. More explicitly, for any q 2 Yj , the number of solutions of
the system F ðpÞ ¼ q belonging to xi is the same.[27]
Based on these strong geometric properties, Malta et al.[26]
constructed an algorithm to find the solutions of nonlinear systems
for nice functions. We modified somewhat their approach to solve
the double azeotrope problem presented, as explained below.
The Generation of the Critical Set
The generation of critical set, C, is the first step in the method-
ology. Since the critical points are those in which the Jacobian of
the nonlinear function F is non-invertible, for this task, we
constructed a rectangular grid in the domain of function F (x1
versus T) and then identified opposite signs in detðJF Þ (det refers to
the determinant of a matrix). When different signs of detðJF Þ are
found, this procedure is interrupted. A critical point is found in
the segment that connects two points with opposite signs for the
determinant, through a Newton procedure. Then, using a
continuation method, we obtained a critical curve.[39] After the
generation of this first critical curve, the algorithm re-starts the
search for points in the domain with different signs of detðJF Þ.This
procedure is quite similar to that proposed by Hicks and Young,[40]
for critical point calculations using the plane (temperature,
volume).
These critical points are classified in two well-defined types:
folds and cusps.[41,26] A critical point p is a fold-point if (i)
rðdetðJF ÞÞ 6¼ 0 and (ii) kerðJF Þ and the tangent to the curve are not
coincident [here, kerðJF Þ represents the kernel of JF]. At this point,
we present a more detailed explanation about folds (or fold-
points), since this definition will be explored in the “Results and
Discussion” section.
" #
1 0
JF ¼ : ð15Þ
0 2v
Thus, the critical set satisfies detðJF ðu; vÞÞ ¼ 0 and, therefore,
v ¼ 0. The critical set appears in the form ðu; 0Þ. The critical image
is then calculated by F ðu; 0Þ ¼ ðu; 0Þ. Furthermore, we can
calculate the flower of the function, that is, the inverse image of
920 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
the critical image: = ¼ F 1 ðF ðCÞÞ ¼ F1 ðu; 0Þ ¼ ðu; 0Þ. These
objects are depicted in Figure 1.
The critical image is represented by the u-axis in the codomain
and the critical set and the flower are both represented by the
u-axis in the domain. We can note that (i) points with coordinates
ðu; 0Þ exhibit images ðu; 0Þ (only one pre-image); (ii) points in the
first or second quadrants of the image,  represented
pffiffiffi as ða;pbffiffiffiÞshows
two pre-images, with coordinates a; b and a;  b ; (iii)
points in the third and fourth quadrants of image have no pre-
images; and (iv) crossing the critical set there is a change of 2 in the
number of pre-images (from zero to two or backwards).
There is a similar analysis (but more complicated) for cusp-
points, not presented here. For more details on folds and cusps, see
Malta et al.[41]
Malta et al.[26] used a word criterion in order to decide if a set of
curves C is in fact the critical set or if there are other critical curves.
In this work, we conducted exhaustive searches for critical curves,
instead of applying such tests, since our aim is to illustrate some
interesting features of the double azeotrope problem. On the other
hand, an automatic procedure, as presented by Malta et al.[26] can
be used in this problem.
The Bank of Solved Points and the Euler-Newton Homotopy-
Continuation
The next step in the methodology is the generation of a bank of solved
points, which will be used in the inversion step. In this bank, we have
(arbitrary) points in image and all corresponding inverse images in
the domain. For this procedure, some “squares” in the image (far
from the critical image) were constructed and, using a homotopy-
continuation Euler-Newton method (with steplength adaptation), all
the correspondent pre-images in the domain for each vertex of these
squares were obtained. Details about homotopy-continuation
methods can be found in Allgower and Georg.[39]
Table 2. Inversion of q1 ¼ ð0:17; 0:02Þ at P ¼ 20 kPa
x1 Temperature (K)
Pre-image 1 7.692238 298.463569
Pre-image 2 1.164689 311.957538
Pre-image 3 1.025794 304.093240
VOLUME 93, MAY 2015
Figure 9. Inversion of q1 ¼ ð0:19105; 0:32058Þ: “L” path in the image.

The homotopy used in this work is given by[42] 0; Hðu; 0Þ ¼ FðuÞ  Fðu0 Þ (start point) and when l ¼ 1; Hðu; 1Þ ¼
FðuÞ  q1 (end point).
Hðu; lÞ ¼ FðuÞ  GðlÞ; ð16Þ We also have the 2
3 Jacobian of homotopy function, defined as
2 3
where @h1 @h1 @h1
6 @x1 @T @l 7
JHðu; lÞ ¼ 6
4 @h
7; ð19Þ
GðlÞ ¼ lq1 þ ð1  lÞF ðu0 Þ: ð17Þ 2 @h2 @h2 5
@x1 @T @l
With appropriate substitutions, we have the homotopy function
for the azeotropy problem: where h1 and h2 are the components of homotopy function.
The predictor step used is an Euler-type expression
Hðu; lÞ ¼ FðuÞ  lq1  ð1  lÞFðu0 Þ; ð18Þ
" # " #
v u
where u ¼ ðx1 ; T Þ and q1 is a point in the image for which we want ¼ þ htðJHð ui ; li ÞÞ ð20Þ
to find inverse images (called pre-images). As we can see, the l iþ1
l i
homotopy function is a function from R3 ! R2 , since a parameter
l was added in the domain. Changing the parameter l from 0 to 1, where h > 0 represents the stepsize and tðJHð ui ; lÞÞ is the unitary
a series of solutions of Hðu; lÞ ¼ 0 is obtained, indicating the vector tangent to the solution curve at the point ui , that is, in the
solution path for solving FðuÞ ¼ q1 . In particular, when l ¼ null space of JH, calculated according to the procedure described

Figure 10. Inversion of q1 ¼ ð0:19105; 0:32058Þ: “L” paths in the domain. (a) Global view; (b) Amplification close to the critical curve.

VOLUME 93, MAY 2015 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 921
by Allgower and Georg (a QR decomposition calculated with
Givens rotations; not detailed here).[39]
The corrector step is calculated by a Newton-type expression (but
with a non-square Jacobian matrix), generating the point wiþ1
" # " #
w v
¼  JHðviþ1 ; liþ1 Þþ Hðviþ1 ; liþ1 Þ
l l
iþ1 iþ1
where the superscript þ indicates the Moore-Penrose inverse. For
a matrix P, the Moore-Penrose inverse is defined by
Pþ ¼ Pt ðPPt Þ1 ;
t
where, as usual, P denotes the transpose matrix of P.
It is important to emphasize that homotopy-continuation
procedures were previously used in azeotrope calculations by
Fidkowski et al.[19] and Aslam and Sunol,[20–21] but, in all these
cases, the authors used the pure components (trivial solutions of
the azeotropy problem) as the initial points for the procedure.
Here, the algorithmic structure is totally different, since the bank
of solved points corresponds to real solutions of the problem. In
other words, the thermodynamic model was not changed during
the path.
The Inversion Process
When the construction of the bank of solved points is finished, the
inversion process can be started. In this step, initially an arbitrary
point q1 in image (the point to be inverted) is chosen. Then, the
closest point of the bank to q1 (represented by q0 ) is selected, and a
“L” path connecting q1 to q0 is built.
The segments in the “L” path must have few (or none)
intersections with the critical image. When this path crosses the
critical image (at a point q ), the number of pre-images (in the
domain) increases or decreases by two, if the critical point is a fold
point.[26] When the number of pre-images increases, two new pre-
images appear in the domain. Conversely, two pre-images can
disappear in the domain when the critical image is crossed. The
inversion process continues until we approach the neighbourhood
Figure 11. Inversion of q1 ¼ ð0:19105; 0:32058Þ: the fold point in the domain. Blue arrow: tangent vector. Black arrow: kernel of Jacobian matrix. Vector
lengths are adjusted to permit visualization.
922 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
Table 3. Inversion of q1 ¼ ð0:19105; 0:32058Þ at P ¼ 20 kPa
x1 Temperature (K)
Pre-image 1 0.7442222 303.20058
Pre-image 2 0.7673854 303.20438
ð21Þ
of the desired value, i.e., the neighbourhood of u satisfying
FðuÞ ¼ q1 . In specific case of the azeotropy problem, we will look
to the neighbourhood of u satisfying F ðuÞ ¼ 0, accordingly to
Equation (12).
ð22Þ
RESULTS AND DISCUSSION
The aim of this work is to obtain, in a reliable way, the solutions of
Equation (7) (or Equation (10)) that represent the problem of
calculation of homogeneous nonreactive azeotropes in two
systems that exhibit double azeotropes at low pressures: (a) the
system benzene þ hexafluorobenzene, and (b) the system HFC-
4310 mee þ THF. At a specified pressure (P ¼ 20 kPa), the system
benzene þ hexafluorobenzene shows two azeotropes, one of them
close to pure benzene and another one close to pure hexafluor-
obenzene. The calculated azeotropic coordinates, presented by
Guedes et al.[28] using some modifications of Newton’s method
and C-GRASP (Continuous GRASP, see Hirsch et al.[43]) are
ðx1 ¼ 0:9729; T ¼ 308:5KÞ and ðx1 ¼ 0:0220; T ¼ 310:6KÞ. These
results are fully compatible to that obtained, for instance, by Maier
et al.,[22] using the modified Raoult’s Law with an interval
Newton/generalized bisection algorithm. A phase diagram for this
system (using the same thermodynamic modelling) was presented
by Guedes et al.[28] The two azeotropes in the system HFC-4310
mee þ THF were reported by Segura et al.[35]
Generation of Critical Curves
Benzene þ hexafluorobenzene system
The first step in the inversion methodology is represented by
Figure 2, which is the construction of the critical set C. We found
four critical curves, represented as dashed lines in Figure 2. In
VOLUME 93, MAY 2015
Figure 12. Inversion of q1 ¼ ð0; 0Þ for the system benzene þ hexafluorobenzene: (a) Domain; (b) Image.
order to show how the critical images (Figure 3) behave in relation
to the critical curves, different colours were used in these figures,
since the critical image is obtained through evaluating the function
F in the critical points. We can see that the critical curves and
critical images are open curves and this fact is a consequence of
some characteristics of the modelling of azeotrope problem. These
specific characteristics also make the domain have a large non-
solution region, as we will see. Indeed, for negative molar
fractions ðx1 < 0Þ, we must analyze if the function F is defined,
since the thermodynamic model (Wilson model or even the
expression for the fugacity coefficient) shows logarithmic portions
in their expressions, as pointed out previously. On the other hand,
even for negative or greater than one molar fractions we can solve
(in some instances) the nonlinear algebraic system (with non-
physical roots, obviously). Moreover, in a portion of the domain,
the PRSV equation shows only one real root, providing trivial
solutions. In other words, F defined on Equation (11b), equals 0
across the blue region. These situations are illustrated in
Figure 4. The portions represented by black and yellow colours
indicate regions of the domain with opposite signs of determi-
nant of the Jacobian matrix. Thus, the interfaces between these
regions are the critical curves (null determinant of the Jacobian
matrix), as one can note by comparing Figures 2 and 4. The blue
region represents trivial solutions (only one real root for the
cubic equation of state). Finally, the red portion represents
the region of the domain where the physical problem is not
defined (negative values for argument of logarithms). Clearly, an
analysis of this figure indicates that the azeotrope calculation
problem is not defined for all values of x1 and T since function F
is not defined, not even mathematically, for all values. In view of
the fact that some critical curves are far from the physical region
where the azeotropic phenomenon occurs, we decide to use only
one critical curve, represented as a red dashed line in Figure 2.
Then, in the next figures (after Figure 5), only one critical curve
(and, clearly, one critical image) will appear. Besides, some
critical curves (marked as blue and purple dashed lines in
Table 4. Calculated azeotropes at P ¼ 20 kPa for the system
benzene þ hexafluorobenzene
x1 Temperature (K)
Azeotrope 1 0.0220170 310.55670
Azeotrope 2 0.9726470 308.51220
VOLUME 93, MAY 2015
Figure 2) are separated from the other ones by a region where
the thermodynamic model is not defined (a red region to the left
in Figure 4). Nevertheless, some steps of the methodology
proposed by Malta et al.[26] can be implemented, producing
useful results.
HFC-4310 mee þ THF
For the system HFC-4310 mee þ THF, the analysis of the domain is
not necessary, since the thermodynamic model does not present
logarithms in its expression. On the other hand, the critical curves
are, again, open curves. Two critical curves were identified and
presented in Figure 5. The corresponding critical images are
depicted in Figure 6.
Construction of the Bank of Solved Points
Figure 7 illustrates the second step of the inversion methodology,
for the system benzene þ hexafluorobenzene: the construction of
the bank of solved points. These points are arbitrarily chosen, but
far from the critical image and are represented by the vertices of
the squares in Figure 7. In our adaptation of inversion method-
ology,[26] we made some modifications in the construction of the
squares, considering that the domain has a very large region of
non-solution (trivial solutions and not defined regions), as pointed
out previously.
We performed a scan in the image in order to verify which points
could be inverted and do not cut neither the critical image nor the
critical curve in the process of inversion. Then, we constructed
squares with these points and, by a continuation method, we find
all the inverse images of each vertex, differently of the original
proposal, which used the pre-image of a previous vertex as initial
condition for the pre-image of the next vertex. The generation of
the bank of solved points for the system HFC-4310 mee þ THF was
conducted using the same procedure.
Calculation of Pre-Images of Some Illustrative Points
The bank of solved points permits to conduct the inversion process
of some arbitrary points in the image. Particularly, we are
interested in inverting F at the point q1 ¼ ð0; 0Þ, which correspond
to the solutions of Equations (7) or (10). On the other hand, the
proposal of the methodology is not only to solve a 2
2 nonlinear
system, but also to generate a global view of the problem, in a
neighbourhood of q1 ¼ ð0; 0Þ. Thus, the inversion of F at other
points is also to be considered.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 923
Benzene þ hexafluorobenzene system
Initially, the procedure uses paths in “L” shape, contained in the
codomain, that do not cut the critical image and with points q far
from it. In all cases, the points represented by circles (), in
Figures 8–12 denoted by q1 , are those that we want to find the pre-
images. The points represented by triangles (D) are the solved
points (stored in the bank of solved points) and the points
represented by asterisks (*) are the intermediate points in the “L”
paths. The inversion process starts at a D point, stored in the bank of
solved points. This D point is such that there is a “L” path connecting
it to the point to be inverted having no intersection with the critical
image, and the one whose distance to the point to be inverted () is
the lowest possible. In some instances, we were able to find
three pre-images, although some are located in regions far from the
physical domain (0  x1  1 and T > 0). As an illustration of this
situation, we present results for the inversion of q1 ¼ ð0:17; 0:02Þ.
Figure 8a shows the pre-images of the points of the “L” path while
the “L” path which is in the codomain is represented in Figure 8b.
We remark that two pre-images remain distant from the blue and
red regions (recall that the blue and red regions represent,
respectively, trivial solutions and non-defined model, as previously
detailed), but one “L” path (to the left in Figure 8a) approaches to
the blue portion (trivial solutions). In fact, for points in the image
very close to q1 ¼ ð0:17; 0:02Þ, only two pre-images can be
obtained, inasmuch as one of them tends to the region with trivial
solutions and, consequently, cannot be inverted.
Table 2 contains the coordinates (solutions or pre-images)
obtained for q1 ¼ ð0:17; 0:02Þ. Obviously, none of these three pre-
images corresponds to a physical solution. Nevertheless, the
thermodynamic model provides mathematical solutions for that
point, and the inversion process worked in a robust way.
In other situations, however, we could only find two distinct pre-
images, as it was physically expected (the system shows two
azeotropes at low pressures). Inverting, for instance, the point q1 ¼
ð0:19105; 0:32058Þ – represented by a circle () in Figure 9 – we
verify that in, these conditions (near the upper part of critical image),
the pre-images are converging to the critical curve, i.e., tend to
degenerate as we can see in Figure 10a. Figure 10b presents an
amplification of Figure 10a, in order to illustrate more clearly
the two pre-images. Again, in Figures 10a and 10b, the dashed
curve represents the critical curve. This behaviour of the pre-image is
typical of the inversion of a fold near the image of a fold point.
Table 3 presents the pre-images found by the inversion method
for q1 ¼ ð0:19105; 0:32058Þ. The pre-images are very similar, and
Figure 13. Inversion of q1 ¼ ð0; 0Þ for the system HFC-4310 mee þ THF: (a) Domain; (b) Image.
924 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
Table 5. Calculated azeotropes at P ¼ 35 kPa for the system HFC-
4310 mee þ THF
x1 Temperature (K)
Azeotrope 1 0.0923864 309.45203
Azeotrope 2 0.2552517 309.56669
tend to degenerate, i.e., these two pre-images will disappear at the
critical curve. In fact, the two pre-images collapse at a fold point.
Figure 11 presents an illustration of this fold point: the two vectors
represent the tangent vector to the curve (blue arrow) at the fold
point and the kernel of Jacobian matrix (black arrow). As one can
see, these vectors are not coincident (a necessary condition for a
fold point).
HFC-4310 mee þ THF
The inversion of arbitrary points in the image for the system HFC-
4310 mee þ THF shows similar behaviour to that observed for the
system benzene þ hexafluorobenzene. Thus, for the sake of
conciseness, these graphical results were not presented.
Calculation of Azeotropic Coordinates
In this section, we present the inversion of q1 ¼ ð0; 0Þ, which is
the main objective of our work, since we want to find the roots of
the nonlinear system of algebraic equations (Equations (7) or
(10)), which represents the azeotropic condition for benzene þ
hexafluorobenzene and HFC-4310 mee þ THF, respectively.
Benzene þ hexafluorobenzene system
As we can see in Figure 12, we started from a point of the bank (D),
applied the inversion process and obtained the two solutions of the
nonlinear system, represented by (). In Figure 12a, we can see –
in the domain – two parts of the inverted path, moving towards to
the two distinct azeotropes. Figure 12b shows the correspondent
“L” path in the image. The azeotropic coordinates at 20 kPa are
presented in Table 4.
HFC-4310 mee þ THF
The inversion process for the point q1 ¼ ð0; 0Þ was also conducted
for this system. The coordinates for the azeotropes at P ¼ 35 kPa
were presented in Table 5. Figure 13 shows the paths for the
inversion in the domain (Figure 13a) and in the image
(Figure 13b).
VOLUME 93, MAY 2015
Figure 14. Calculation of azeotropes at several pressures for the system benzene þ hexafluorobenzene: (a) Domain; (b) Image.

CALCULATION OF AZEOTROPIC COORDINATES AT OTHER system, and the double azeotrope disappears at higher pressures
and temperatures when compared to the results obtained by
PRESSURES
this f  f modelling of vapour-liquid equilibrium.

System benzene þ hexafluorobenzene System HFC-4310 mee þ THF

Finally, we present some interesting results for the calculation of
azeotropic coordinates at higher pressures. We are able to
calculate azeotropic points for higher pressures using the bank
of inverted points at the fixed pressure of 20 kPa. In this scenario,
the framework presented here shows useful properties, since the
more expensive step of the methodology (in terms of computa-
tional time and user interference) is the generation of the bank of
solved points. Figure 14 presents the calculation of the azeotropic
coordinates at several pressures and using the same bank of solved
points generated at P ¼ 20 kPa. The legend used in Figure 14b is
identical to the presented in Figure 14a. An analysis of Figure 14b
indicates that the critical images are affected by the pressure. On
the other hand, the critical curves do not show a significant
influence of system pressure. Moreover, the two distinct
azeotropic points get closer and closer with the increase in the
pressure. Azeotropic coordinates for various pressures are
tabulated in Table 6. In fact, for P ¼ 210 kPa, the coordinates of
the azeotropic points are very close (mainly for temperature), as
presented in Table 6. It must be kept in mind that the main
objective of this work is not to perform comparisons between
experimental and calculated azeotropic coordinates. In this
context, Ewing et al.[44] presented experimental results for this
The calculation of azeotropes at several pressures with the same
bank of solved points was also conducted for HFC-4310 mee þ
THF. Accordingly to Segura et al.,[35] this system shows two
azeotropes with pressures in the range 14.55–42 kPa (circa).
Thus, the main idea here is to illustrate the behaviour of the “L”
paths in the domain for this range of pressures. Figure 15 present
the graphical illustration of azeotrope calculations for several
pressures in the interval 15–35 kPa. Since the critical curve is not
a function of the pressure (a consequence of the use of
the modified Raoult’s Law), only one critical curve appears in
Figure 15a. On the other hand, critical images are affected by the
pressure. In this sense, in Figure 15b one can note different
critical images. Furthermore, at low pressures (below 15 kPa),
one of the azeotropes disappears, as pointed by Segura et al.[35]
Since the numerical inversion of functions from the plane to the
plane is a purely mathematical tool, a second azeotrope persists
(but with negative molar fractions, an infeasible solution),
accordingly to Figure 15a. Finally, Figure 16 contains the results
for the inversion process in the range 35–43 kPa, where a
tangent azeotrope is predicted as a limit situation. We used two
figures (Figures 15 and 16) for scale reasons. Clearly, as
indicated by Figure 16a, the two azeotropes collapse at the

Table 6. Calculated azeotropes for the system benzene þ hexafluorobenzene at several pressures

Azeotrope 1 Azeotrope 2

Pressure (kPa) x1 T (K) x1 T (K)

20 0.0220170 310.55670 0.9726470 308.51220

25 0.0542130 315.71827 0.9643848 313.88153
30 0.0814312 320.09521 0.9567451 318.43092
40 0.1265220 327.31408 0.9427124 325.92572
50 0.1638149 333.19594 0.9297469 332.02359
100 0.3011108 353.25405 0.8704135 352.74109
150 0.4130189 366.44124 0.8119503 366.22081
200 0.5476586 376.57334 0.7088309 376.56097
210 0.6035730 378.35547 0.6592681 378.36501

VOLUME 93, MAY 2015 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 925
 Table 7. Calculated azeotropes for the system HFC-4310 mee þ THF at several pressures

Azeotrope 1 Azeotrope 2

Pressure (kPa) x1 T (K) x1 T (K)

15  0.0022512 290.18568 0.3344157 291.23023

20 0.0210864 296.44854 0.3160096 297.14547
25 0.0436142 301.50266 0.2975336 301.94400
30 0.0667583 305.76144 0.2778498 306.01305
35 0.0923864 309.45203 0.2552517 309.56669
36 0.0981076 310.13511 0.2500932 310.22814
37 0.1041482 310.80192 0.2445996 310.87521
38 0.1106066 311.45319 0.2386842 311.50869
39 0.1176113 312.08962 0.2322116 312.12933
40 0.1254008 312.71180 0.2249319 312.73775
41 0.1344148 313.32022 0.2164250 313.33471
42 0.1457548 313.91524 0.2055882 313.92087
43 0.1648448 314.49707 0.1869753 314.49735

critical curve (at a pressure close to 43 kPa) and, thus, the
number of pre-images of the image q1 ¼ ð0; 0Þ is decreased by
two, i.e., the two azeotropes disappear. This situation can
be also observed in Figure 16b; the critical image is very close to
the point q1 ¼ ð0; 0Þ for P ¼ 43 kPa, indicating a variation in the
number of pre-images. The calculated azeotropic coordinates in
the system HFC-4310mee þ THF at several pressures are
presented in Table 7. The negative value for the molar fraction
at 15 kPa indicates that the methodology founds two azeotropes,
but only one with physical significance.

Figure 15. Calculation of azeotropes at several pressures for the system HFC-4310 mee þ THF: (a) Domain; (b) Image.

Figure 16. Calculation of azeotropes at several pressures for the system HFC-4310 mee þ THF in the range 35–43 kPa: (a) Domain; (b) Image.

926 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 93, MAY 2015
CONCLUSIONS x molar fraction in liquid phase
y molar fraction in vapour phase
In this work we solved the double azeotrope problem with a new Zia molar fraction of i in phase a
and robust approach based on geometry: the inversion of
functions from the plane to the plane proposed by Malta et al.[26]
The azeotrope problem was presented, together with the Greek Symbols
thermodynamic modelling. We obtained the critical curves for
a phase (liquid or vapour)
the nonlinear system of equations that represents azeotropic
g activity coefficient
coexistence. A bank of solved points was constructed and some
l homotopy parameter
representative points were inverted. The double azeotrope
Lij parameter of Wilson model, between i and j
coordinates were robustly calculated, with high accuracy, for
c local change of variables (fold point definition)
two binary systems. Moreover, with the same bank of solved
= the flower of F
points, azeotropic coordinates at higher pressures were deter-
v acentric factor
mined. We conclude that general ideas stemming from the
f fugacity coefficient
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Manuscript received March 7, 2014; revised manuscript received

June 5, 2014; accepted for publication June 15, 2014.

928 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 93, MAY 2015