Chemical Engineering and Processing 42 (2003) 475
/485

www.elsevier.com/locate/cep

On the dynamics of nonequilibrium simple batch distillation

processes
J.M.F. Silva a,*, A. Knoechelmann b, Antonio J.A. Meirelles c, M.R. Wolf-Maciel a,1,
C.E. Lopes b
a
Laboratory of Separation Process Development, Faculty of Chemical Engineering, State University of Campinas (UNICAMP), Cidade Universitária
Zeferino Vaz, CP-6066 Campinas, São Paulo CEP-13081-970, Brazil
b
Laboratory of Fermentation Processes, Department of Antibiotics, Federal University of Pernambuco (UFPE), Cep-50670-901 Recife, PE, Brazil
c
Physical Separation Laboratory (LASEFI), Faculty of Food Engineering, State University of Campinas (UNICAMP), PO Box 6121, Campinas, São
Paulo 13083-970, Brazil

Received 20 March 2002; received in revised form 31 May 2002; accepted 31 May 2002

Abstract

The study of the dynamics of a simple batch distillation usually assumes the equilibrium between the liquid and vapour phases. In
contrast to that approach, this work considers the analysis of the dynamic behaviour of a nonequilibrium simple batch distillation.
A simple batch distillation device is similar to an evapouration unit because no reflux is employed. A mathematical model and their
singular points are analysed through the usual technique of linearization followed by the eigenvalues analysis. The stability nature of
those points is presented for ideal solutions. Phase plane plots are made to show the occurrence of some unexpected behaviours such
as ‘dynamic azeotropic points’ and ‘inversion of the distillation order’. The dependence of these phenomena on the vapour
withdrawal flowrate is established for simple batch distillation.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Separations process; Dynamic azeotrope; Nonequilibrium distillation; Dynamic simulation; Stability; Mass transfer

1. Introduction steady states can be found, which do not correspond to

An adequate dynamic description of distillation
devices is important, both in terms of steady state
analysis and in terms of the way the equipment behaves
in a processing situation of dynamic behaviour. This
area of study has attracted the attention of the
researchers since Rosembrock [1] proved that nonideal,
binary, constant molar overflow distillation columns
with nontheoretical plates and neglected vapour hold-
up, have a unique global asymptote stable steady state.
But a more recent research indicates that, for batch
distillation in a column with a middle vessel, additional
* Corresponding author. Fax: /55-19-2894717
E-mail address: jmfs@lopca.feq.unicamp.br (J.M.F. Silva).
1
Fax: /55-19-2894717.
0255-2701/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 5 - 2 7 0 1 ( 0 2 ) 0 0 0 6 4 - 8
pure components [2]. Doherty and Perkins [3,4] started
the dynamic analysis applied to simple batch distillation
processes. Investigations on dynamic analysis applied to
more complex situations are still underway [5
/7].
Distillations are called equilibrium operations because
they are studied by assuming thermodynamic equili-
brium between phases, i.e. the bulk properties of the
vapour and liquid phases (temperatures, pressures and
compositions) are such that the equations of thermo-
dynamic equilibrium are satisfied. These equations are:
T V T L
PV PL
mVi  mLi (i 1; 2; 3; . . . ; c)
where T is the bulk temperature, P the bulk pressure
and m is the bulk chemical potential. The superscripts L
476 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485
and V refer to the liquid and vapour phases, respec-
tively, and the subscript i refers to the components of
the phases. The chemical potential is function of the
system temperature, pressure and phase compositions.
An essential phenomenum in simple batch distillation
devices is the net mass transfer of the component across
the interface. It is impossible for such devices to work
without net mass transfer from liquid to vapour allow-
ing the liquid to vapourise. In this case it would be better
to assume that equilibrium prevails only at the interface
of the system, but not between the phase bulk proper-
ties. The equilibrium between the bulk properties is
closely linked to the process slowness, requiring quasi-
reversibility state conditions to occur.
When a batch distillation is performed under irrever-
sible conditions, equilibrium becomes a local property as
stated by the microscopic reversibility principle and the
bulk properties of the phases are not related by
thermodynamic equilibrium equations [8]. The equili-
brium, and consequently, the thermodynamic equations
for multiphase equilibrium prevail only at the interfacial
region.
Krishnamurty and Taylor [9] picked up this point and
developed a nonequilibrium model for the steady state
simulation of distillation columns, which was later
applied to an industrial column operation [10]. Sec-
ond-generation models, which incorporated the pressure
as a variable, were also developed [11,12]. Koojiman and
Taylor [13] considered the use of this model for the
dynamic simulation of distillation columns and showed
that the back-computed Murphree tray efficiencies are
time dependent and, as a consequence, the equilibrium
model is not suitable for dynamic simulations. In a
recent paper, Luna and Martı́nez [14] analysed the
stability of the drying process in a multicomponent
nonideal mixture and they found interesting results
concerning to the existence of dynamic azeotropes and
the multiplicity of steady states (bifurcation).
The purpose of the present paper is to develop a
qualitative dynamic analysis of a simple batch distilla-
tion by assuming interfacial equilibrium coupled with
mass transfer between the phases. The resulting model
equations, as usual, will be linearized around the
equilibrium points and the asymptote stability analysed.
The results are compared with those obtained by
Doherty and Perkins [3,4].
2. The governing equations
The isothermal multicomponent simple batch distilla-
tions are governed by the following set of material
balance equations [3,4] (see Appendix A):
dxi
xi yi (x) i 1; 2; . . . ; c1
do
where xi and yi are mole fractions of the i component in
the liquid and vapour phases, respectively, and o is the
modified time variable defined by the integral
t
q
o
g N dt
0
(2)
where q is the molar flow rate at which the vapour is
withdrawn from the equipment and N is the molar
amount of the residual liquid within the equipment.
The two-film theory will be used to correlate the bulk
concentrations of the solute in both phases. The liquid
and vapour compositions at interface are given by xi
and yi , respectively. The compositions of the liquid and
vapour in the bulk of the phases are given by xi and yi .
The theory assumes also that all the resistance to the
mass transfer concentrates in the film region. The
schematic representation of the two-film theory is shown
in Fig. 1. As usual, the compositions in the liquid and
vapour sides of the interface are assumed to be in
equilibrium, as required by the thermodynamic of
irreversible processes which imposes stricter requirement
than a continuum theory does. It requires, in addition,
that the infinitesimal subsystems are in equilibrium at
every instant [8].
The material balance equation for the batch distilla-
tion device requires that the mole flow of vapour leaving
the equipment must be equal to the mole flow crossing
the liquid and vapour films. Considering component i,
for the vapour which is withdrawn from the still, the
material balance equation becomes:
(Pyi Pyi ) (Cxi  Cxi)
qyi   (3)
RT =Akgi RT=Akli
where P * is the total pressure at interface, C * the mole
concentration of the liquid at the interface, P the total
pressure in the bulk of the vapour phase, C the bulk
mole concentration of the liquid phase, A the interfacial
area, kgi and kli are the mass transfer coefficients of
component i in the vapour and liquid films, respectively,
R the gas constant and T is the temperature of the
system.
Coulson and Richardson [15] pointed out that when
the components of the vapour are totally soluble in the
liquid, the main resistance to the mass transfer is located
in the vapour film and Eq. (3) becomes:
(1)
Fig. 1. Schematic representation of the two film theory.
 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485 477

Fig. 2. Phase space for the following conditions: T/280 K, q/0 gmol/s; (kg1 /0.001 m/s; kg2 /0.03 m/s kg3 /0.05 m/s).

Pyi Pyi Akgi P

qyi  (4) ai  (7)
RT =Akgi RTq  Akgi P
or Inserting Eq. (7) into the material balance equation
set, it gives
Akgi Pyi
yi  (5) dxi
RTq  Akgi P xi ai y(x); i 1; 2; . . . ; c1 (8)
i
do
and
where yi is the mole fraction of the component i at the
yi  ai y
i (6)
vapour interface, which is in equilibrium with the liquid
where interface. The above set of equations is similar to the

Fig. 3. Phase space for the following conditions: T/280 K; q/0.02 gmol/s, (kg1 /0.01 m/s; kg2 /0.01 m/s; kg3 /0.01 m/s).
478 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485

Fig. 4. Phase space for the following conditions: T/280 K; q /0.02gmol/s, (kg1 /0.01m/s; kg2 /0.03m/s; kg3 /0.05 m/s).

one which is used by Doherty and Perkins [3,4], except where:

by the presence of the ai parameters, which consider the
P0i
mass transfer phenomena. bi (x) ; i 1; 2; . . . ; c1 (11)
Under the Doherty and Perkins [3,4] assumptions, as P(x)
P /P * and q/0, the value of this parameter is unity. P0i is the vapour pressure of component i. According
The reversibility of the process implies absence of net to Doherty and Perkins [3,4], bi has the following
mass transfer. As P "/P * and q "/0, the irreversibility is properties:
closely linked to the existence of the net mass transfer
and the ai? s are usually different from 1. a) bi/(x)/ /0 for all feasible xi i /1. . .c/1;
It is very interesting to point out that ai becomes also b) db/dt /0 i/1, 2, . . ., c/1;
unity when kg is independent of i, i.e. kg1 /kg2 /. . . c) bi (ei )/1 i/1, 2, . . ., c/1 e1 /(1, 0, . . ., 0), e2 /(0,
kgc1. In this case, an irreversible system is similar to a 1, . . ., 0), etc.;
reversible one. As the energy equation is not considered d) bc (0) /1.
here, the above set of equations was developed for
isothermal processes. Nevertheless, as indicated by The steady state are:
Doherty and Perkins [4], the results also apply to
1) /x0;/
isobaric distillation, since the analysis is essentially the
2) /xk ek ;/
same.
3) /xxs when

1
3. Simple batch the distillation of ideal solutions bi (xs )
ai (xs )
The ideal solutions obey the following set of equili- Depending on the process conditions, the nodes can
brium relations: be stable, unstable or saddle points. The stability
P0i characteristics of the nodes will depend on the thermo-
yi xi (9) dynamic and mass transfer interactions of the compo-
P(x)
nents. Owing to this dependence, nodes different from
This set of equations assumes that the vapour phase is those of pure components are called dynamic azeo-
governed by the ideal gas law. Inserting the above tropes, as proposed by Schluender [16]. The third steady
equilibrium equations into Eq. (8), it gives: state condition, mathematically, admits the existence of
a dynamic azeotropic point as a singular point of the
dxi
xi (1ai (x)bi (x)); i 1; 2; . . . ; c1 (10) model. The model of Doherty and Perkins [3,4] does not
do predict this occurrence. The mathematical existence of
 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485 479

Fig. 5. Phase space for the following conditions: T / 280 K; q /0.02 gmol/s, (kg1 /0.001 m/s; kg2 /0.05 m/s; kg3 /0.1 m/s).

this steady state shows an interesting behaviour that can and so

happen with an ideal mixture. The ideal mixture serves 2 3
u11 : : : u1C1
as a limit case for the study of this phenomenon. 6 7
6 : : : : : 7
The Liapounov first theorem starts from the linear- s
J(X ) 6
6 : : : : : 7
7 (16)
ized equation: 4 5
: : : : :
dx u(C1)1 : : : u(C1)(C1)
J(x)(xxs ) (12)

do where: dbi @P dai
uii xi ai ai bi 1xi bi
where: dP @xi T;x? dP
2 3

n @P

  (17)
6 @fi 7 @xi
J(xs ) 6
4





7
5 (13) T;x?
@xj T;x?
n and



and dbi @P dai @P
uij xi ai xi bi (18)
fi xi (1ai (x)bi (x)) i 1; 2; . . . ; c1 (14) dP @xj T;x? dP @xj T;x?



@fi @bi @ai Now, the properties of the Jacobean matrix will be
xi ai xi bi
@xJ @xj T;x? @xj T;x? analysed at the points xs  0 and x xs ; such as:
dij (1ai bi ) (15) 1
bi (xs )
where: ai (xs )
to determine the stability behaviour of these points. The
@xi if i j 1
dij   properties of the Jacobean matrix at the point xk ek
@xj if i "j 0
are given in Appendix B.



@ai dai @P Case 1: for the trivial solution, when xs 0; the
 Jacobean matrix becomes:
@xj T;x? dP @xj T;x?
2 3
1a1 (0)b1 (0)


0
and 6


1a2 (0)b2 (0)


0 7
J(0)6
4 :: 7
5 (19)


 :
@bi db @P 1a(c1) (0)b(c1) (0)
 i
@xj T;x? dP @xj T;x? and the determinant of this matrix is:
480 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485
Fig. 6. Phase space for the following conditions: T /280 K; q/0.02 gmol/s, (kg1 /0.005 m/s; kg2 /0.001 m/s; kg3 /10 m/s).
Y
c1
det J(0) (1ai bi )
i1
The topological nature of this singular point is
determined by the eigeinvalues of the Jacobean matrix
J (0). As it is a symmetric matrix, all the eigenvalues
must be real [17]. The trivial singular point, as a
consequence, is a node or a saddle point and the
eigenvalues are given by:
li 1ai bi
The corresponding possibilities are:
a) A stable node occurs if and only if ai bi /1, since in
this case all the eigeinvalues assume negative values.
As bi (0) obey the relationship:
P0i
bi (0) i 1 . . . c1
P(0)
and as, at the origin, P *(0) /P0c , this implies that:
P0c
P0i  i 1 . . . c1
ai
where P0c is the pure c -component vapour pressure
and, as usual, component c is the heavier one
(which has the smallest value of P0i ). The origin
will be a stable node, if the values of P0c determines
the above inequality. Nevertheless, if the values of
ai are such that break the inequality and the origin
becomes an unstable node, another component, i.e.
one of the other vertices, becomes the stable node.
Otherwise, the dynamic azeotropic point becomes
(20) the stable node, as we will see later. In batch
distillation, there is always at least one stable
node. The existence of a dynamic azeotropic point
does not occur when a1 /a2 /. . .a(c1), which
implies that all the kgi are equal, or when q /0,
i.e. the distillation process is reversible. In both
cases ai /1 for every component. Such situations
seem not likely, since each component would be
(21) usually transferred to the vapour phase with a
different speed.
b) An unstable node occurs at xs 0 only if all
ai (0)bi (0) B/1.
In these conditions, all the eigenvalues are
positive. Following a similar reasoning to the above
item, the condition for an unstable node is:
(22)
P0c
P0i B i  1 . . . c1 (24)
ai
(23)
and there is the possibility that the origin becomes
an unstable node.
c) Finally, it is possible to get a saddle point when one
or more components obey condition Eqs. (23) and
(24) is valid for the other components, simulta-
neously.
Case 2: when xxs ; such as bi (xs ) 1=ai (xs ); then
(@P=@xj )T;x?  0 and the Jacobean matrix becomes:
 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485 481

Fig. 7. Phase space for the following conditions: T /280 K; q/0.02 gmol/s, (kg1 /0.001 m/s; kg2 /0.0015 m/s; kg3 /10 m/s).

2 3
1a1 b1 ... 0 pressure P was calculated using Eq. (26) below. It
6 ... 1a2 b2 ... 0 7
6 7
J(xs ) 6 7 summation over all components, taken into account Eq.
4 :: 5
: (5) given above.
1a(c1) b(c1)
(25)
As this matrix is null, det J(xs )0; this is a none-
lementary singular point or a degenerate singular point.
As it is widely known, degenerate points are not
amenable to mathematical and physical analysis. This
is a necessary but not enough condition for the multi-
plicity of steady states (bifurcation), and a similar result
was also reported by Luna and Martı́nez [14]. So, we
will perform numerical simulations of the phase space to
reach some conclusions on this question.
4. Numerical simulations
To perform the computational experiments, the dis-
tillation of a three-component mixture will be investi-
gated. Component 1 is assumed to be the most volatile
and component 3 the least one. For equilibrium
calculation purposes, it is assumed that component 1
has the properties of propane, and components 2 and 3
of n -butane and n -pentane, respectively. The mass
transfer coefficients were varied in a large range of
values to test all possible situations. The values were
selected in such a way that it is possible to pick up the
important dynamic behaviour, and the exact values are
presented in the captions of the figures. For each
selected set of mass transfer coefficients the bulk
should be noted that this equation corresponds to the
X
3
Akgi Pyi
1 (26)
i1 RTq  Akgi P
The results of the stability studies for all steady states
considered in the present work are reported in Appendix
C. The experiments start by considering the equilibrium
conditions where q/0 and ai /1, Ö/i . This corresponds
to the situation analysed by Doherty and Perkins [4]. As
expected, the phase plane curves converged to the origin,
which corresponds to the least volatile component, as
shown in Fig. 2. In this figure, three different phase
plane trajectories were represented because in the
numerical experiments three different initial points
were selected for describing the system over time. It is
important to note that the mass transfer coefficient
values have no influence because the mass transfer is
very slow.
In a second set of computational experiments, the q
value was assumed to be different from zero and all
components were assumed to have the same mass
transfer coefficient. It is usual in chemical engineering
process design to assume the equality of the mass
transfer coefficients, despite of the fact that this
assumption is not likely to occur. Under these circum-
stances, again ai /1, Ö/i , and we obtained a similar
behaviour to that observed in the first case. It is worth
to point out that the Doherty and Perkins’s model [4] is
still valid at nonequilibrium situation, as is this case and
482 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485
Fig. 8. Phase space for the following conditions: T/280 K; q /0.02 gmol/s, q/0.21 gmol/s; (kg1 /0.003 m/s; kg2 /0.01 m/s; kg3 /0.1 m/s).
can be seen in the curves presented in Fig. 3. The third
set of computational experiments were carried out
assuming that q is different from zero and that all
mass transfer coefficients have different values, and
under these circumstances, ai "/1, Ö/i . Similarly to the
previous situation, the origin remained as a stable point.
The phase plane trajectory, however, became different,
as shown in Fig. 4.
An interesting phenomena occurred when component
3 mass transfer coefficient was assumed to be 2 times
higher than that corresponding to component 2 and 100
times higher than component 1 mass transfer coefficient.
The origin still remains as a stable node, but a
modification of the distillation path occurs, reflecting
the fact that component 2 distillates before component
1, as it is easy to see in Fig. 5. In spite of the large
volatility of component 1, its lower mass transfer
coefficient reduces the transfer velocity to the vapour
phase. This is the reason for the inversion of the
distillation order. In the literature, there are already
reports of a similar inversion of the distillation order.
For example, this behaviour happens in the distillation
of the mixture chloroform, acetone and benzene, in
which the azeotrope acetone-chloroform (boiling point
of 64.5 8C) distils before pure chloroform (61.2 8C) [3].
Obviously, in the majority of the experimental situa-
tions, the higher mass transfer coefficient correspond to
the most volatile component.
Exploring the inversion phenomena through numer-
ical analysis, a very interesting result was obtained when
the mass transfer coefficient of the least volatile
component was assumed to be thousands of times larger
than the mass transfer coefficient of the other two
components. In this case, the origin still remains a stable
node, but component 2 also becomes a stable node. In
Fig. 6, it is shown a situation where the phase plane
trajectories converge to the component with intermedi-
ate volatility (component 2). This fact indicates the
multiplicity of the steady-state of an ideal solution, as it
is suggested by the theory exposed before. In the present
case (ideal solutions) such behaviour was obtained by
using very different mass transfer coefficients for all
components. It might occur that for real solution a
similar behaviour can be obtained without assuming
such a difference between the mass transfer coefficient
values. For example, the consideration of solutions
nonideality would mean the introduction of component
i activity coefficient multiplying the irreversibility factor
ai in the Eq. (23). Activity coefficients lower than 1 in
such equation willl increase the possibility of inverting
the distillation order. It should be noted that the mixture
acetone-chloroform mentioned above exhibits signifi-
cant negative deviation from ideality.
Another phenomena predicted by the model and
obtained in the numerical experiments is the occurrence
of a dynamic binary azeotropic stable point for ideal
mixtures, as shown in Fig. 7. In this case, the theory
shows that the origin is still a stable node and the
vertices, components 1 and 2, are saddle point and
unstable node, respectively, what also suggests the
existence of multiple steady states. The captions of the
above mentioned figures show the values of the para-
meters which induce the above result. In the present
work there is no mathematical restriction to the
 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485 483

existence of a dynamic azeotropic point as occurs in the
Doherty and Perkins [4] equilibrium model. According
to Doherty and Perkins [4], if a binary ideal mixture
possesses an azeotropic point, it would not be an isolate
singular point because it belongs to the straight line yi /
xi , and this violates the hypothesis of an isolated point.
Such restriction does not exist in our model, where a
dynamic azeotropic point appears without any doubt.
It was verified that the Jacobean matrix of the
dynamic azeotrope is null, and this is a necessary
condition to occur multiplicity of steady states. For
this reason, some operational parameters were disturbed
in order to confirm the existence of bifurcation. As ai is
a function of several operational variables, it was tried
to perturb those variables to test the behaviour of the
model. The parameters were the interfacial area, dis-
tillation temperature and flow rate. When we change the
vapour flow rate ten times its initial value, a change in
the phase plane trajectory occurred, as shown in Fig. 8.
We started for a given initial point and in the case of the
lower flow rate (q/0.02 gmol/s), the system converged
to the origin, and for the higher value (q /0.21 gmol/s),
the system converged to the dynamic ternary azeotropic
point. These results show that the final steady state of
batch distillation is dependent on vapour flow rate. This
confirms the existence of steady state multiplicity
(bifurcation) in the simple batch distillation. A similar
result was also reported by Luna and Martı́nez [14] in
their analysis of stability in multicomponent drying of
homogeneous nonideal liquid mixtures.
5. Conclusion
This work considered the distillation of ideal liquid
mixtures in a batch equipment. The mathematical
analysis was carried out for a general n-component
mixture. The numerical experiments were performed
considering a three-component mixture.
The mass transfer was included in the mathematical
model by equating the rate of the vapour that is
withdrawn to the overall mass transfer across the
vapour
/liquid interface. The resulting equation allows
one to relate yi *, the equilibrium concentration of
component i , at interface, to the bulk vapour concen-
tration of this component yi . The insertion of this
relationship in to the main balance equation leads to
the following conclusions:
1) batch distillation equipment are devices that re-
quires that the mass transfer phenomena at the
interface be considered;
2) the nonequilibrium model reproduces the Doherty
and Perkins [4] model when the following condi-
tions are fulfilled:
a) the rate of vapour withdrawn is zero, i.e. the
distillation is performed under reversible con-
ditions (very slow distillation) or
b) the mass transfer coefficients of the compo-
nents have the same values.
Condition (b) is the only one where the Doherty and
Perkins [4] model prevails under irreversible conditions.
In the general case, the nonequilibrium model predicts
that the following system behaviours for ideal mixture
are also possible:
1) The occurrence of a situation in which the residual
liquid curve converges to the component with
intermediate volatility (see Fig. 6).
2) The occurrence of stable dynamic azeotropic points
(see Figs. 7 and 8).
3) A change in the vapour withdrawn rate may result
in a change on the stability of the equilibrium point.
This work considers ideal vapour and liquid phases,
and shows the wealth of phenomena occurring in a
simple batch distillation when mass transfer is taken into
account.
Silva [18] considered also regular quadratic solutions.
This discussion will appear in a future paper.
Acknowledgements
This work was supported financially by research
grants from Fundação de Amparo à Pesquisa do Estado
de São Paulo (FAPESP-99/09944-2/98-12302-0) and
Conselho Nacional de Desenvolvimento Cientı́fico e
Tecnológico (CNPq-521011/95-97 /301309/1996-5).
Appendix A: Balance mass equation
Considering the diagram representation of a batch
distillation shown in Fig. 1A below and performing a
material balance of the component i, it gives:
d(Nxi )
qyi i 1; 2; . . . c1 (1:A)
dt
so
xi d(N) Nd(xi )
 qyi i 1; 2; . . . c1 (2:A)
dt dt
From an overall material balance it gives:
d(N)
q (3:A)
dt
so
484 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485

d(xi ) q(t) K, so that the pressure of saturation of each component

 (xi yi ) i 1; 2; . . . c1 (4:A)
dt N(t) is:

which is not an autonomous system. To convert the P0i 5:83 bar P02 1:33 bar P03  0:33 bar
above equation in an autonomous system, a new time
variable is defined by the equation: Then, the conditions of stability given in the figures
are;
d(o) q(t)
 (5:A)
dt N(t) Figure 2;
Inserting this equation into the above nonautono- 5.83 /1 /0.33 0.33 /1 B/1.33 0.33 /1 B/5.83
mous system, the following system can be obtained: 1.33 /1 /0.33 5.83 /1 /1.33 1.33 /1 B/5.83
d(xi ) Stable node Saddle point Unstable node
(xi yi ) i  1; 2; . . . c1 (6:A)
do
Figure 3;
which is the autonomous form of the material balance
equation. 5.83 /1 /0.33 0.33 /1 B/1.33 0.33 /1 B/5.83
1.33 /1 /0.33 5.83 /1 /1.33 1.33 /1 B/5.83
Stable node Saddle point Unstable node

Appendix B: Analysis on the vertices

2 3




1a1 (ek )b1 (ek )
6 :: 7
6   :   7
6 dbk @P dak @P dbk @P dak @P 7
6a
J(ek ) 6 k b


a b


7 (7:A)
dP @x1 T;X 0
k
dP @x1
k
dP @xk T;X ?
k
dP @xk T;X ? 7
6 :: 7
4 5
:
1ac1 (ek )bc1 (ek )

Figure 4;
in the vertices

 5.83 /0.74 /0.33 0.33 /1 B/1.33 0.33 /1B/5.83
@P
0 i 1 . . . c1 (8A) 1.33 /0.944 / 5.83 /0.74 / 1.33 /0.944 B/
@xi T;xek 0.33 1.33 5.83
Then Stable node Saddle point Unstable node

J(ek )0 (9A) Figure 5;

This is a nonelementary singular point or degenerate
singular point. This result will be investigated by 5.83 /0.18 / 0.33 /1.003 B/ 0.33 /1.003 B/
numerical simulations presented in the paper 0.33 1.33 5.83
1.33 /0.95 / 5.83 /0.18 /1.33 1.33 /0.95 B/5.83
0.33
Stable node Saddle point Unstable node
Appendix C: Condition of stability
Figure 6;
In agreement with the theory exposed in this paper,
the stability is given for: 5.83 /4.515 / 0.33 /732 /1.33 0.33 /732 B/5.83
0.33
P0i ai P0c (10:A)
1.33 /0.907 / 5.83 /4.515 / 1.33 /0.907 B/
The temperature of the simulated systems is T /280 0.33 1.33 5.83
 J.M.F. Silva et al. / Chemical Engineering and Processing 42 (2003) 475
/485 485

Stable node Saddle point Unstable node s singular point value

V, L vapour and liquid phases, respectively
Figure 7;

5.83 /0.99 / 0.33 /2.93 B/ 0.33 /2.93 B/

0.33 1.33 5.83
1.33 /0.55 / 5.83 /0.39 / 1.33 /0.55 B/ References
0.33 1.33 5.83
Stable node Saddle point Unstable node [1] H.H. Rosembrock, Approach to a stable steady state far from
equilibrium, Proc. Phy. Soc. London 80 (1962) 962.
[2] A.G. Davidyan, V.N. Kiva, G.A. Meski, M. Morari, Batch
Figure 8; distillation in column with a middle vessel, Chem. Eng. Sci. 49
(1994) 3033
/3051.
5.83 /0.41 / 0.33 /1 B/1.33 0.33 /1B/5.83 [3] M.F. Doherty, J.D. Perkins, On the dynamics of distillation
0.33 processes */I. The simple distillation of multicomponent non-
reacting homogeneous liquid mixtures, Chem. Eng. Sci. 33
1.33 /0.72 / 5.83 /0.41 / 1.33 /0.72 B/ (1978a) 281
/301.
0.33 1.33 5.83 [4] M.F. Doherty, J.D. Perkins, On the dynamics of distillation
Stable node Saddle point Unstable node processes */II. The simple distillation of model solutions, Chem.
Eng. Sci. 33 (1978b) 569
/578.
[5] P. Rouchon, Y. Creff, Geometry of the flash dynamics, Chem.
Eng. Sci. 48 (18) (1993) 3141.
[6] M. Barolo, G.B. Guarise, S.A. Rienzi, A. Trotta, Understanding
Appendix D: Notation the dynamics of batch distillation column with a middle vessel,
Comput. Chem. Eng. 22 (Supl. S) (1998) S37
/S44.
C number of components in a multicomponent [7] L.U. Kreul, A. Gorak, P.I. Barton, Dynamic rate-based for
mixture multicomponent batch distillation, AIChE J. 45 (9) (1999) 1953
/
1962.
EI unit vector in ith orthogonal direction [8] G.D.C. Kuiken, Thermodynamics of Irreversible Processes:
J Jacobean matrix of first partial derivatives Application to Diffusion and Reology, Wiley, Chichester, 1994.
P total pressure (bar) [9] R. Krishnamurty, R. Taylor, A nonequilibrium stage model of
P0i saturated vapour pressure of pure component i multicomponent separation process part */I: model description
(bar) and method solution, AIChE J. 31 (3) (1985) 449
/455.
[10] R. Taylor, M.F. Powersa, A. Vickery, A. Arehole, A none-
Q flow rate (gmol/s) quilibrium stage model of multicomponent separation process */
R gas constant (m3 bar/g mol K) V: computational methods for solving the model equations,
T temperature (K) Comput. Chem. Eng. 12 (12) (1988) 1229
/1241.
/x/ vector of mole fraction in the liquid phase [11] R. Taylor, H.A. Kooijman, J.S. Hung, A second generation
/x/ vector of liquid mole fraction in equilibrium with nonequilibrium model for computer simulation of multicompo-
nent separation process, Comput. Chem. Eng. 18 (3) (1994) 205
/
vapour at interface 217.
y
/ / vector of mole fraction in the vapour phase [12] M.H. Pescarini, A.A.C. Barros, M.R. Wolf-Maciel, Development
y/
/ vector of vapour mole fraction in equilibrium of a software for simulating separation processes using a none-
with liquid at interface quilibrium stage model, Comput. Chem. Eng. 20 (1996) S279
/
284.
[13] H.A. Kooijman, R. Taylor, A nonequilibrium model for dynamic
Greek symbols simulation of tray distillation collumns, AIChE J. 41 (8) (1995)
ai irreversibility factor 1852
/1863.
dij kronecker delta [14] F. Luna, J. Martı́nez, Stability analysis in multicomponent drying
l eingeinvalue of homogeneous liquid mixtures, Chem. Eng. Sci. 54 (1999) 5823
/
5837.
uij component of the Jacobean matrix
[15] A. Coulson, Q. Richardson, Unit Operations, vol. 2, Pergamon
Press, Oxford, UK, 1968.
Subscripts [16] E.U. Schluender, Einführung in die Stoffübertragung, Verlag,
i, j, c components Stuttgart, 1984, pp. 56
/77.
T temperature [17] M. Marcus, H. Mink, A Survey of Matriz Theory and Matriz
x? vector of x1. . .xj1, xj1,. . .xc1 hold constant Inequalities, Allyn & Bacon, New York, 1964.
[18] J.M.F. Silva, Dynamic of an irreversible simple batch distillation
(in portuguese), M.Sc. thesis, Department of Chemical Engineer-
Superscripts ing, Federal University of Pernambuco, Recife, Pernambuco,
O pure component quantity Brazil, 1996.