Separation and Purication Technology 132 (2014) 616626

Contents lists available at ScienceDirect

Separation and Purication Technology

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

Transport of p-nitrophenol in an agitated bulk liquid membrane system

Experimental and theoretical study by network analysis
Piotr Szczepanski a,, Szidonia K. Tanczos b, Lucian D. Ghindeanu b, Romuald Wdzki a
a
Nicolaus Copernicus University, Faculty of Chemistry, Gagarin Str. 7, 87-100 Torun, Poland
b
Faculty of Applied Chemistry and Material Science, University Politehnica of Bucharest, Polizu Str. 1-7, 011061 Bucharest, Romania

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

Article history: A predictive mathematical model has been developed to simulate the pertraction of phenolic compounds
Received 3 March 2014 in the agitated bulk liquid membrane system (ABLM). A bond-graph method, based on pseudo-
Received in revised form 10 June 2014 thermodynamic network analysis, was applied for the detailed description of the three steps pertraction
Accepted 11 June 2014
mechanism, i.e., extraction, diffusion, and re-extraction with the neutralization reaction in the stripping
Available online 20 June 2014
solution. The corresponding mathematical model (a set of ordinary differential equations) was solved to
predict the time evolution of local uxes and concentrations of p-nitrophenol (PNP) in the experimental
Keywords:
system: PNP aq. soln.|tolunene|NaOH soln. The calculations were carried out mainly with the data
p-Nitrophenol
Pertraction
accessible in literature (diffusion coefcients, thickness of diffusion layers) or measured in independent
Liquid membranes experiments (extraction and re-extraction kinetic constants, equilibrium distribution coefcient). The
Transport prediction results of numerical calculations were compared with the experimental PNP transport data. It was found
Bond-graph model that the model and calculation procedures allow the prediction of time dependent-concentration or
uxes proles of the transported species in the feed, membrane, and stripping solution as a function
of operating parameters (volumes, concentrations), as well as pertraction mechanism parameters
(distribution coefcients, diffusion coefcients, kinetic constants).
2014 Elsevier B.V. All rights reserved.

1. Introduction liquid membranes with an alkaline stripping solution have been

Phenol and its derivatives, produced from a number of indus-
trial processes, are well-recognized, dangerous contaminants
found in wastewaters, the disposal of which is highly restricted,
i.e. typically, the content of various phenolic compounds should
be maintained below 10 ppm [1,2]. For this reason, various meth-
ods of their elimination from waste and/or recovery as valuable
chemicals have been studied and implemented for many years.
Among wastewater treatment techniques, liquid membranes are
expected to be most appropriate as their applicability results from
fundamental studies performed for over forty years. Those studies
dealt with the transport and separation of phenol or phenolic com-
pounds [311], amines, aminoacids, metallic ions, and pharmaceu-
ticals [12]. Three groups of pertraction methods, namely, emulsion
liquid membranes (ELM), supported liquid membranes (SLM), and
bulk liquid membranes (BLM) including such practical construc-
tions as the creeping lm (CFP) [13] and rotating lm pertractors
(RFP) [1416], have been intensively researched in recent years.
For example, the studies on the recovery of phenol using emulsion
Corresponding author. Tel.: +48 566114306.
E-mail address: piotrs@chem.uni.torun.pl (P. Szczepanski).
reported by several authors [1722]. The ELMs can be replaced
by more stable supported liquid membranes in which an organic
phase is immobilized in the micropores of a polymer foil
[6,23,24]. Also, bulk liquid membranes were applied for this
purpose, especially in the case of the studies of the fundamental
character [2528]. Other phenolic compounds such as cresols,
chlorophenols, and nitrophenols [26,2937] can be separated by
the pertraction technique in the way analogous to the phenol case.
It was also recommended to adjust the initial pH to the value lower
than 4 in order to obtain an efcient phenol removal. An excessive
amount of the stoichiometric NaOH used to neutralize phenol is
required in order to achieve a phenol removal rate as high as
possible. Note that the stripping solution can be further treated
with electrodialysis or diffusion dialysis with the use of Naon
membranes to convert phenoxides into undissociated species [38].
The simplest pertraction process is represented by a sequence
of extraction, diffusion, and re-extraction steps classied also as
the liquid membrane transport occurring according to the solu-
tiondiffusion mechanism [39]. However, pertraction design is
hindered by signicant uncertainties regarding the prediction of
mass transfer rates. For this reason, various mathematical
models for the pertraction of phenolic compounds were proposed,

http://dx.doi.org/10.1016/j.seppur.2014.06.016
1383-5866/ 2014 Elsevier B.V. All rights reserved.
 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626
Nomenclature
A contact area between the membrane and external
solutions (cm2)
j s
DS diffusion coefcient of S = PNP, PNPNa and NaOH in the
membrane (m), feed (f) or stripping solution (s) (cm2/s)
JS ux of S (mol/cm2 s)
Jmax output maximum ux of S (mol/cm2 s)
k1 k1 extraction an re-extraction rate constant (cm/s) at the
f|m interface
k2 re-extraction rate constants (cm/s) at the m|s interface
l(j) thickness of membrane or diffusion layers (cm) for j = f,
m and s
j
li thickness of sublayer (local diffusion distance) (cm)
for j = f, m and s
n(j) number of sub-layers for j = f, m and s
j
PS permeability coefcient of S (cm/s)
j
PNPb concentration of PNP in the bulk solution phase, for j = f
and m (mol/cm3)
j
PNPi local concentration of PNP for j = f and m (mol/cm3)
s
PNPNab concentration of neutralized PNP in the bulk stripping
solution phase, (mol/cm3)
i.e. Cahn and Li [3] presented a very simplied model for the
extraction of phenol in the ELM system, whereas Szczepanski
and Diaconu [35] used the consecutive irreversible rst order
chemical reaction model for the PNP pertraction analysis in the
ABLM system. Also, the stationary model for the transport of
phenol through SLM containing benzene or benzene and a carrier
with or without the stripping reaction was described in detail
by Park et al. [40]. In general, these models are based on the
resistances-in-series model in which particular elements of the
membrane system can contribute to the overall transport resis-
tance. They were used to simulate the membrane-based extraction
and integrated membrane-based extractionstripping processes
[34,4147], or true pertraction transports [4850]. However, all
these models need some parameters (adjusted by data tting),
the correctness of which is related to the problem of model
adequacy and assumptions concerning the transport mechanism
or its state. In our opinion, a more general and exact solution can
be achieved by the application of a network thermodynamic anal-
ysis of diffusion and reaction systems [5153]. Therefore, the main
goal of this study is to model the ABLM functioning in the frame-
work of the network analysis, respective numerical simulations,
and their validation by the experimental study of PNP pertraction
in the system undergoing evolution in time. On the other hand,
despite its evident advantages, the thermodynamic network
analysis still remains an emerging method of membrane systems
modelling or description. Namely, the papers published since
the year 2000 are not frequent and concern mainly problems such
as general modelling of physicochemical processes (including
membrane systems) [5457], modelling in chemical engineering
[5862], and electrochemistry [6365]. Other, previously published
papers concerning transport in synthetic and biological membranes
were referenced elsewhere in [66,67].
2. Theoretical-membrane system description
All the fundamental formulations concerning the practical
application of the bond-graph analysis were described in our
previous papers [6668]. They concern the formulation of: (i) the
phenomenological model, (ii) compartmental model, (iii) network
model, and (iv) mathematical description represented by a set of
ordinary coupled differential equations as presented below.
617
s
PNPNai local concentration of neutralized PNP in the
stripping solution (mol/cm3)
NaOHb concentration of NaOH in the bulk stripping solution
phase, (mol/cm3)
s
NaOHi local concentration of NaOH in the stripping solution
(mol/cm3)
j
fSgi local capacitance for S = PNP, PNPNa, NaOH and j = f, m
or s
t time (s)
V(j) overall volume (cm3)
j
Vi volume of sub-layer (cm3)
a(m|f) distribution constant for extraction
b PNP dissociation degree
Superscripts
j = f, m, s indices for feed, membrane, and stripping solution
m|f and m|s membrane|feed and membrane|stripping solution
interface
2.1. Phenomenological model
The pertraction of PNP or other phenolic compounds represents
the transport from the aqueous phase through a bulk liquid mem-
brane into the second aqueous phase. This transport is driven by
means of a prompt PNP reaction with a strong base in the stripping
solution and the insolubility of p-nitrophenolate in the organic
phase. Usually, an effective transport of PNP and others phenolic
compounds occurs from an acidied feed solution (pH < 4),
through an organic hydrophobic liquid membrane, into a stripping
solution of pH = 1012. Such conditions result in the most efcient
PNP removal from the feed or p-nitrophenolate concentration in
the receiving phase, although other conditions for the transport
are possible dependently on its task. The phenomenology of the
transport is then classied as the diffusionsolution process with
the neutralization reaction in the stripping phase. Consequently,
the overall process of the PNP pertraction can be divided into the
following steps [69]:
1. transport of PNP from the bulk feed solution to the feed|mem-
brane (f|m) interface region; diffusion step,
2. permeation of PNP across the interface, from the aqueous to the
organic phase; kinetic step,
3. transport of PNP across diffusion layers located in the liquid
membrane at the membrane|feed (m|f), and membrane|
stripping solution (m|s) interfaces, outside the intensively
agitated bulk organic phase; diffusion steps,
4. re-extraction of PNP from the liquid membrane associated with
prompt neutralization of PNP to PNPNa in the stripping
solution; this kinetic step is coupled with the diffusion of a
neutralizing agent (e.g. NaOH) across the diffusion layer in the
stripping solution at the (m|s) interface,
5. transport of PNPNa across the diffusion layer at the (m|s)
interface to the bulk phase of the stripping solution; diffusion
step.
Step 4 should be additionally commented on as the one appear-
ing also in conventional extraction processes and sometimes being
the subject of speculation and controversy concerning the type and
spatial location of the reaction. According to the fundamentals of
the liquidliquid extraction [70], fast and instant neutralization
618 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626

reaction takes place in the plane or small volume element located

in the stripping phase near the m|s interface, which should be
taken into account while constructing the compartmental model.
Consequently, in this place, the concentration of PNP can be
assumed zero valued, i.e. this compound does not diffuse to the
bulk stripping solution whereas the concentration of the neutraliz-
ing agent is maintained at a high and nearly constant level. Such
phenomenology of the PNP pertraction is consistent with a model
for mass transfer with the instantaneous chemical reaction as
described by Grosjean and Sawistowski [71] and elsewhere applied
to the membrane extraction by Basu [24]. Another aspect of the
m|s inerfacial phenomena in PNP re-extraction and neutralization
is the concentration of a neutralizing agent in the bulk stripping
solution, or more exactly, in the reaction compartment. In this case,
two situations are possible, i.e.:
(1) when the stripping phase contains a sufcient amount of
base a chemical reaction takes place at the interface
between the membrane and the stripping phase. The free
PNP concentration at the interface of the stripping side and
in the stripping solution is close to zero and the compound
is present mainly in the form of p-nitrophenolate (e.g. in
the case of pH = 12),
(2) when the stripping phase contains insufcient amount of
base the chemical reaction front is not at the phase inter-
face but it is located in the lm of the aqueous phase. In this
case, the existence and diffusion of both PNP and PNPNa in
the stripping solution should be taken into account.
2.2. Compartmental and network model
Fig. 2. Graph for neutralization reaction R3.
J sNaOH
2 !s1
and PNPNa, J sPNPNa
1 !s2
are coupled by a very fast neutralization
reaction R3 represented by a graph of chemical equilibrium (Fig. 2).
The specied diffusion, extraction, re-extraction, and reaction
bond graphs can be added using 0-junctions (dened by KCL
Kirchhoff current law), and the nal network for the PNP pertrac-
tion and its neutralization is represented by the full network
shown in Fig. 3. Note that the arrows indicate the direction in
which the ux is considered positive.
The diffusion modules used in the network presented in Fig. 3
are equivalent to diffusion graphs dened and discussed previously
[68].
2.3. Mathematical model
The set of differential equations describing the properties of the
membrane system, local uxes, and its other characteristics is
listed in Table 1.
The local input and output uxes (J, mol/s cm2) are dened
using the phenomenological transport equation (from i sub-layer
to i + 1 sub-layer):

j
The compartmental model for the PNP pertraction (Fig. 1) is DS
J i!i1
S j
Si  Si1 for S  PNP and PNPNa;
similar to that published elsewhere [68] for benzoic acid and bro- li
mothymol blue pertraction. The main difference results from the j f and s; respectively 1
fact that the neutralization reaction (R3) in the receiving solution
occurs as one of the stages of the above described pertraction
and for NaOH
process.
All the local processes such as feed PNP depletion, PNP accumu- s
DNaOH
lation in the membrane, PNPNa accumulation, and NaOH con- J i1!i
NaOH s
NaOHi1  NaOHi 2
sumption in the stripping solution can be represented by a basic li
thermodynamic network analysis in the bond-graph version The interfacial extraction and re-extraction uxes (mol/cm2 s)
[52,53]. are described by the following equations:
For modelling the interfacial phenomena, i.e. extraction and
re-extraction of PNP, it was assumed that these processes are rep-
J fPNP
m
n !m1
k1 PNPnf  PNP1 =amjf 3
resented by unimolecular reactions (R1 and R2) with respective
bond graphs [67]. According to the compartmental model, these
processes occur between the f10 and m1 or mn and s1 sublayers Jmn !s1
PNP k2 PNPm
n 4
and are characterized by kinetic rate constants k1, k1, and k2 for
the forward and reverse process of R1 and irreversible R2, respec- where k (cm/s) and a(m|f) denote kinetic constants and equilibrium
tively. Obviously, the conditions for extraction and reextraction distribution coefcients for PNP (between the membrane and aque-
are different which means that k1 k2. At the m|s interface, the ous feed phase). Note that the input ux of PNPNa is equal to Jm n !s1
PNP
re-extraction ux of PNP, J m n !s1
PNP , and diffusional uxes of NaOH, because of the assumed fast and irreversible neutralization reaction.

Fig. 1. Compartmental model of the solutiondiffusion pertraction in an agitated bulk liquid membrane system (ABLM) with postulated concentration proles in diffusion
layers: PNP p-nitrophenol, PNPNa sodium p-nitrophenolate.
 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626 619

Fig. 3. Network for the p-nitrophenol pertraction.

Table 1
Mathematical model and data for model calculations.

Feed solution (f) Stripping solution (s)

Time evolution of local concentrations (mol/cm3 s)
s s
dPNPb =dt J fPNP
f b !f 1
A=V b
f
dPNPNa1 =dt Jm n !s1
PNP  JsPNPNa
1 !s2
A=V 1
s si !si1 s
f
dPNP1 =dt JfPNP
b !f 1
 JfPNP
1 !f 2 f
A=V 1 dPNPNai =dt JsPNPNa
i1 !si
 JPNPNa A=V i ; i 2 . . . n  1
f i !f i1 sn1 !sn sn !sb
f
dPNPi =dt f i1 !f i
JPNP  J PNP A=V i ;
f
i 2 . . . n  1 dPNPNans =dt JPNPNa  JPNPNa A=V s n

JfPNP  JfPNP
s
J sPNPNa
s
dPNPf
n =dt n1 !f n n !m1
A=V nf dPNPNab =dt n !sb
A=V b

Membrane (m)
m m m !mk1
dPNPb =dt J m
m m
dPNP1 =dt JfPNP
n !m1
 Jm 1 !m2
PNP A=V 1 k !mb
PNP  J PNP
b
A=V b
m mi !mi1 mb !mk1 mk1 !mk2
Jm i1 !mi m m m
dPNPi =dt PNP  J PNP A=V i ; i 2 . . . k  1 and i k 2:::n  1 dPNPk1 =dt J PNP  JPNP A=V k1
m mk1 !mk mk !mb m m  mn1 !mn mn !s1  m
dPNPk =dt JPNP  JPNP A=V k dPNPn =dt J PNP  J PNP A=V n

Fluxes (mol/s cm2)

s !s s s s
JfPNP
b !f 1 f f f
2P PNP PNPb  PNP1 a J PNPNa
i i1
P PNPNa PNPNai  PNPNai1
si1 !si s s s
J NaOH P NaOH NaOHi1  NaOHi ; i 1 . . . n  1
f !f f f f sn !sb s s s
JPNP
i i1
P PNP PNPi  PNPi1 ; i 1 . . . n  1 J PNPNa 2P PNPNa PNPNan  PNPNab a
J sNaOH
b !sn s s
2P NaOH NaOHb  NaOHs
n a

f|m interface m|s interface

JfPNP
n !m1
k1 APNPnf  PNP1 =amjf
m
Jm n !s1
PNP k2 APNPnm

Membrane (m) Denitions

mi !mi1 m m m f f f m m m
JPNP P PNP PNPi  PNPi1 ; i 1 . . . k  1 and i k 1 . . . n  1 P PNP DPNP =li ; P PNP DPNP =li
s s s s s s
P PNPNa DPNPNa =li ; P NaOH DNaOH =li ; cm/s
 
f f m m s s
Jm k !mb m m m a
PNP 2P PNP PNPk  PNPb li l =n; li 2l =n; li l =n; cm
f f m m s s
V i li A; V i li A; V i li A
m !mk1 m m m f f m m s s
JPNP
b
2P PNP PNPb  PNPk1 a V b V f  l A; V b V m  2l A; V b V s  l A; cm3
output sn !sb 2
J PNPNa JPNPNa ; mol/cm s

Data for calculations:

V(f) = 200, V(s) = 200, V(m) = 50, cm3, l(f) = 0.0025, l(s) = 0.0025, l(m) = 0.0025, cm, A = 17 cm2
a(m|f) = 1.2, k1 = 3.8  104, k2 = 2.2  103, cm/s, Df s
PNP DPNPNa 9:2  10
6 s m
; DNaOH 2  105 ; DPNP 1:48  105 cm2 s1
number of sub-layers (n): feed 10, membrane 20, stripping solution 10
Initial conditions:
[PNP](f) = 2.0154  107, [PNP](m) = 0, [PNPNa](s) = 0, [NaOH](s) = 1  105; mol/cm3
a
The coefcient equal to 2 means that the diffusion distance from the centre of edge diffusion sub-layers to the feed, stripping or membrane bulk phase equals to one half
of that between diffusion sub-layers.

3. Experimental and calculations 3.2. Pertraction experiments

3.1. Reagents The scheme of a glass-made pertractor with ABLM is presented

in Fig. 4. Aqueous solutions were stirred with two Teon-coated
The reagents used in the experiments dealing with pertraction magnetic bars (375 rpm). The membrane phase was agitated with
through the liquid membrane and the studies of extraction and two mechanical stirrers (375 rpm).
re-extraction were p-nitrophenol (PNP) and toluene. The hydro- The experimental pertraction system suited for the verication
chloric acid was used for the pH adjustment of the feed phase (f), of the model adequacy was composed of aqueous solutions of
and NaOH was used for preparing the stripping solution (s). All 200 cm3 each. The volume of the liquid membrane was 50 cm3.
the reagents (supplied by POCh, Gliwice, Poland) were of analytical The contact area between the liquid membrane and the aqueous
grade and used without further purication. phases (f|m and m|s) was 17 cm2.
620 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626
Fig. 4. Scheme of the experimental agitated bulk liquid membrane system: f feed
solution, m liquid membrane, s stripping solution.
The feed and stripping solutions were prepared from distilled
water previously equilibrated with toluene. The initial feed con-
centration was 2.015  104 mol PNP/dm3, and its starting pH
was 2 (adjusted with HCl) or 6.5 (acid free solution). The initial
concentration of NaOH in the stripping solution was 0.01 mol/
dm3. The liquid membrane was composed of toluene equilibrated
previously with distilled water. The concentrations of PNP or
PNPNa in aqueous solutions were determined as the function of
time using a UVVis spectrophotometer (UV-2101PC Shimadzu).
The absorbances of the samples were measured at 317 (PNP) or
404 nm (PNPNa or dissociated PNP) wavelength. The concentra-
tion of PNP in the membrane was calculated from the mass
balance rule. The pH of the feed and stripping solutions was con-
trolled using an Elmetron CX-721 pH meter with a combined
glass electrode. In some experiments carried out to check the
predictive power of the model, the operational conditions such
as the composition of the feed or the volume of the liquid mem-
brane were changed. All experiments were carried out at
25 1 C.
3.3. Extraction and re-extraction experiments
Distribution coefcients for PNP between toluene and aque-
ous solutions were determined by conventional solvent extrac-
tion at 25 1 C. For this purpose, 20 cm3 of aqueous PNP
solutions at concentrations: 0.64  104 mol/dm3 were shaken
for over 2 h with 20 cm3 of toluene. The PNP concentration in
the aqueous phases before and after extraction was analyzed
by UV spectroscopy. The PNP concentration in the organic phase
was then calculated using the mass balance rule. The corre-
sponding equilibrium distribution coefcient was calculated as
the following ratio:
org:
amjf PNPeq: =PNPaq:
eq:
The kinetics of the PNP extraction into toluene was studied in the
experimental system (half-cell used in the pertraction experiments)
composed of the feed solution and organic phase of volumes and
concentrations applied in the pertraction experiments. The PNP con-
centration values in the both phases were determined in the func-
tion of time by the method described above. The re-extraction
experiments were carried out in a similar way, i.e. from the organic
phase (liquid membrane) into the aqueous stripping solution of the
composition the same as used in pertraction experiments. To carry
out the re-extraction experiment, a toluene solution of PNP of
1.695  104 mol/dm3 was prepared and contacted with 0.01 mol/
dm3 NaOH solution. In both cases, the samples were taken out for
an analysis from the aqueous solutions at dened time intervals.
The required constants, e.g. apparent permeability coefcients (Pf,
Ps), or kinetic constants (k1, k1, k2) necessary to solve the pertraction
model were then calculated as described below.
3.4. Calculations
To evaluate the predictive ability of the model derived from the
bond-graph analysis, the operational parameters (volumes, contact
area, etc.) and other system characteristics listed in Table 1 were
used. Their values correspond with the experimental system under
study, as far as possible. The thickness of interfacial diffusion layers
(l(j), j = f, s, m) was assumed to be 2.5  103 cm, after taking into
account reliable data reported by Arana et al. [11]. Note that sim-
ilar values were postulated in literature for interfacial layers in dif-
ferent extraction and transport systems [72]. However, it should be
emphasised that the value of a diffusion layers thickness is a weak
point of this approach as this quantity is practically impossible to
be immediately experimentally veried. In more advanced calcula-
tions, the differentiation of this parameter as dependent on the
phase composition, viscosity, temperature, and agitation speed
should be taken into account.
In the pertraction process, PNP diffuses throughout the aqueous
and liquid membrane diffusion layers with respective diffusion
f m s
coefcients (DPNP ; DPNP ; DPNPNa ) the values of which were taken from
literature [73] or evaluated by applying the WilkeChang equation
[74] with the dependence of diffusion coefcient on the medium
viscosity only, i.e. 0.891 and 0.554 mPa s (298 K) for water and tol-
uene, respectively. At concentrations ranging from 0.69  102 to
3.4  102 mol/dm3, and temperature of 298.2 K, the PNP diffusion
coefcients vary from 0.919 to 0.93  105 cm2/s. Consequently,
f
DPNP was assumed to be 9.2  106 cm2/s for aqueous solutions
and 1.482  105 cm2/s for toluene forming the liquid membrane.
f s
It was also assumed that DPNP  DPNPNa . For model calculations, the
diffusion coefcient of NaOH in the aqueous media of 0.01 mol/
dm3 concentration was used as reported by Noulty and Leaist
s
[75], i.e. DNaOH = 2.0  105 cm2/s.
PNP permeates through the f|m and m|s interfaces with the
kinetic constant k1 or k2 (cm/s), respectively. Note that for the cal-
culation of interfacial permeablility fn|m1 and mn|s1, the immediate
experimental data for extraction and re-extraction (Pf, Ps) cannot
be employed because they combine diffusion and interfacial
extraction phenomena. Therefore, the respective k1 and k2 values
were evaluated by the modication of a compartmental model
and tting reduced model to the extraction or re-extraction exper-
imental data by setting k2 = 0 or k1 = 0, respectively.
Numerical calculations were carried out using the Berkeley
Madonna programme v. 8.1 [76] and the fourth-order RungeKutta
method. The initial conditions and other system characteristics
necessary to carry out the calculations are listed in Table 1. In other
case studies these values were modied in an appropriate way.
The calculation module for Berkeley Madonna v. 8.1, according
to the model presented in Table 1, is accessible from the authors on
5
personal request.
 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626
4. Results and discussion
4.1. Partition coefcients and kinetic data
At the acidic pH, the undissociated species of PNP predominates,
and only this compound is distributed between the feed and organic
phase. The results of experiments indicate that the distribution coef-
cient am|f, dened as the equilibrium concentrations ratio, does not
practically depend on the concentration and amounts the mean
value of 1.20 with the standard deviation sa = 0.01. This value, found
experimentally, was then applied in all the calculations with the
mathematical model presented in Table 1.
Two series of experimental kinetic data for PNP extraction pro-
cess are presented in Fig. 5 as the plot of PNP concentration in the
feed aqueous phase stripping solution vs. time.
Usually, the extraction kinetic data are interpreted as the kinetic
rst order process resulting in the determination of apparent perme-
ability coefcients (mass transfer coefcients) Pf, as already
described by Yoshida and Hayano [77]. The application of this proce-
dure allows the determination of Pf as equal to (3.05 0.05) 
104 cm/s. This value is comparable with Pf reported elsewhere for
PNP extracted into toluene (4.17 0.08)  104 cm/s calculated by
the application of the model of consecutive reactions [35]. However,
this quantity is inapplicable for the calculations involved in the
network model because it evidently results from the combination
of diffusion and interfacial permeation phenomena. Therefore, the
evaluation of a true kinetic rate constant at fn|m1 interface, denoted
in the model by k1, was achieved by tting the reduced model from
Table 1 (k2 = 0, and nm = 10) to the experimental extraction data. The
best t results corresponding with k1 = 3.6  104 cm/s are
presented in Fig. 5 as a continuous line. The value of the kinetic con-
stant of the reverse interfacial process was evaluated from a simple
relationship (6):
k1 k1 =amjf 6 dashed line. The results of calculations are in a fairly good agree-
To complete the set of data necessary to predict PNP pertrac-
tion, the independent re-extraction experiments were carried
out. The results of two experimental series are presented in Fig. 6.
Fig. 5. Extraction of PNP from acidied aqueous solution (pH = 2) into toluene: d,s
two separate experimental series, line calculated with reduced network model
using adjusted value of k1 = 3.6  104 cm/s.
621
Applying a procedure similar to the one used in the case of
extraction [77], the apparent interfacial permeability coefcient
for re-extraction Ps was calculated. Its value is equal to
(1.083 0.04)  103 cm/s, i.e. it is comparable with that evaluated
elsewhere [35] from the model of consecutive reactions for the
pertraction process amounting the value of (1.33 0.22) 
103 cm/s. To evaluate the kinetic constant k2, the reduced pertrac-
tion model (k1 = 0, k1 = 0, without the diffusion layer in an organic
phase at f|m interface) can be applied. The tting procedure results
in the k2 value equal to 1.4  103 cm/s and calculated the re-
extraction curve presented in Fig. 6 as a continuous line.
4.2. Experimental pertraction results and their model interpretation
The main role of predictive models is to reconstruct the depen-
dencies which are observed immediately from experiments. In the
case of PNP pertraction, the following phenomena should be taken
into account:
f
(a) the removal of PNP from the feed, PNPb f t;
(b) the accumulation of neutralized PNP in the stripping
s
solution, PNPNab f t;
(c) the accumulation of PNP in the membrane phase,
m
PNPb f t;
(d) the depletion of NaOH in the stripping solution,
s
NaOHb f t.
The three series of experimental results of PNP pertraction
illustrating the above a and b tasks are presented in Fig. 7 together
with the corresponding curves representing numerical solutions of
the model from Table 1.
The calculations of the PNP concentration in the feed and
PNPNa in the stripping solution were carried out using indepen-
dently evaluated rate constants and presented in Fig. 7 as the
ment with the experimental points; however, it can be concluded
that the use of k1 = 3.6  104 cm/s and k2 = 1.4  103 cm/s from
extraction and re-extraction experiments allows the prediction
of the lower and upper limit of the feed and stripping phase
Fig. 6. Re-extraction of PNP from toluene solution into alkaline aqueous solution
(pH = 10): N,4 two separate experimental series, line calculated with reduced
network model and adjusted value of k2 = 1.4  103 cm/s.
622 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626

Fig. 8. Experimental points: (d) total, (s) undissociated, and (h) dissociated PNP
concentration in the feed solution; (N) PNPNa concentration in the stripping
Fig. 7. Three experimental series: d,s, feed solution, N,4,} stripping solution,
solution; lines calculated with pertraction model and adjusted k1 = 3.8  104 and
and predicted pertraction of PNP: dashed line calculated using kinetic constants
k2 = 2.2  103 cm/s.
from extraction and re-extraction experiments, continuous line adjusted kinetic
constants.

degree of dissociation approximated by the above empirical

equation. From the presented data, one can conclude that the
concentration, respectively. The results are even better after a
model allows fairly good prediction of the feed and stripping phase
slight correction of kinetic constants by their optimization
composition in the pertraction process studied.
(adjusting), which is presented in Fig. 7 as the continuous line
calculated with k1 = 3.8  104 and k2 = 2.2  103 cm/s.
4.4. Retention of PNP in the liquid membrane phase
4.3. Transport of PNP from nonacidied feed
To compare the pertraction of PNP in the ABLM of different
One can imagine a situation when a tank containing PNP (or volumes, two additional experiments, i.e. with V(m) = 100 and
similar compounds) cannot be acidied to maintain the maximum 150 cm3, were carried out. The results are presented in Fig. 10 as
concentration of undissociated species. In this case, assuming that the plots of the percentage of PNP contained in the feed, mem-
the kinetics of dissociation can be neglected, the concentration of brane, and the stripping solution. The lines predicted with the
species undergoing extraction at the f|m interface is dependent model well correspond with the experimental data. One can also
on PNP concentration and its pKa. The problem, as described by
Jnsson [78], can be formally solved by the application of
HendersonHasselbach equation to predict the concentration of
undissociated species or their degree of dissociation (b). To check
the network model applicability for predicting transport in such
a system, i.e. with PNP degree of dissociation changeable in time,
the experiment of conguration the same as previously but with-
out acidication of the feed was carried out, and the experimental
results are presented in Fig. 8. The model calculations were then
performed after evaluating the interfacial concentration of undis-
sociated PNP resulting from the total PNP concentration and its
degree of dissociation. As pointed out above, this can be made
using a well-known relationship between pH, pKa, and b. However,
it requires very precise pH measurement to achieve data sufcient
for the use in calculations. Thus, we decided to determine b by the
spectrophotometric method in the time of pertraction process, and
thereafter, to correlate b with the total concentration of PNP in the
way presented in Fig. 9. The corresponding correlation polynomial
was as follows:

b a0 a1 ln PNPtotal 7

with a0 = 0.358 0.015, a1 = 0.0451 0.0016, and squared corre-

lation coefcient (r2) equal to 0.9659.
The calculated lines in Fig. 8 result from the model solution
with k1 = 3.8  104 and k2 = 2.2  103 cm/s and a changeable Fig. 9. Dependence of PNP dissociation degree on its total concentration in the feed.
 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626 623

Fig. 10. Distribution of PNP in the feed (s), membrane (r) and stripping solution (4) as dependent on ABLM volume: (a) V(m) = 50, (b) V(m) = 100, (c) V(m) = 150.

Fig. 11. Input (a) and output (b) uxes vs time of transport. ABLM of 50 (1), 100 (2), 150 cm3 (3).

conclude that, according to expectations, the PNP retention in the the bulk phase and its experimental value can be calculated as this
membrane phase increases with its volume. Another difference is ux corresponding with the time going to zero (Eq. (8)) The
that the processes occur at different rates, the analysis of which maximum output ux is dened as the maximum observed on
requires the discussion of uxes as presented below. the output ux vs. the time of transport curve (Eq. (9))
f
f f
dPNPb;t!0
4.5. Fluxes J b;t!0 V b 8
dt
An alternative interpretation of the experimental transport data s
s s dPNPb
can be made using uxes instead of concentrations in the function Jb V b f t 9
of time. Two characteristic uxes for the system of nite volumes dt
can be taken into account as the ones most frequently discussed by The experimentally found initial input ux of PNP reaches the
many authors. The rst one is the input ux and the second one is mean value of 6.39  1011 for ABLM of 50, 100 and 150 cm3
the output ux, both of which are observed at the extraction and whereas its value predicted by the model varies from
re-extraction interface, respectively. As presented in Fig. 11, these 6.56  1011 to 6.57  1011 mol/cm2 s. Thus, these values are
both uxes are time dependent. Therefore, it is accepted to charac- slightly differentiated (Fig. 11a) and do not depend practically on
terize the system using the initial input ux or maximum output the membrane volume. The second transport characteristics taken
ux. The initial input ux of PNP is represented by the ux from into consideration is the maximum ux of PNPNa observed in the
624 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626

m f
Fig. 12. Maximum output ux dependence on the liquid membrane volume: Fig. 13. Interfacial concentration ratio of PNP1 to PNP10 for the ABLM system
} experimental, line calculated with model and Eq. (10). with V(m) = 50 (1), 100 (2), 150 (3), and distribution coefcient value for PNP in
water toluene system (4).

curves 13 drawn in Fig. 11b, the value of which decreases with an

[68], we postulated that the dependence of maximum output
increase in the liquid membrane volume from 4.92  1011 to
uxes on the liquid membrane volume fulls the following polyno-
4.21  1011 for the ABLM of 50 and 150 cm3, respectively. These
mial relationship:
values can be compared with the experimental ones (from
4.78  1011 to 3.82  1011 mol/cm2 s) as calculated according X
n
i
s
to the method described elsewhere [35]. In our previous paper log J b;max ai log V m 10
i0

Fig. 14. Calculated concentration proles in the ABLM system after: a 0.5 h, b 1.5 h, c 8.25 h, and d 50 h operation. For data in Table 1.
 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626
The respective curve calculated with the use of Eq. (10) with
n = 4 is presented in Fig. 12 and compared with the experimental
data points. One can conclude that the coincidence of the experi-
mental data with the calculated values is high (50, 100 cm3) or
fairly good (150 cm3).
After verifying the model adequacy by the comparison of the
experimental and calculated results, we would like to show how
to gather some information which can be valuable for a researcher
but is inaccessible immediately from the experiment. Namely, in
the membrane science, there is a widespread method of data anal-
ysis with the assumption that interfacial processes are very fast
when compared with the diffusional ones. In this case, the bound-
ary membrane conditions are governed by the equilibrium values,
which substantially simplies the transport mathematics [79]. To
diagnose this problem for the transport of PNP in the ABLM system,
m f
the plot of PNP1 =PNP10 ratio vs. time was drawn in Fig. 13. It is
noticeable that this value depends on the liquid membrane volume
and amounts only 2025% of its equilibrium value, i.e. 1.21. This
result conrms that the ABLM system for PNP pertraction cannot
be described by a simple solution diffusion model with interfacial
processes at equilibrium.
According to its nature, the network model enables the calcula-
tion of local concentrations or uxes of each species appearing in
the transport system. This property can be used for the verication
of a very popular assumption on the linearity of concentration pro-
les in diffusion layers as the basis for approximate steady state
solutions of mathematical models. For this reason, four characteris-
tic times of transport were selected, i.e. (a) short time of transport
(0.5 h), (b) the time at which the maximum of the output ux
appears (1.5 h), (c) the time when the concentrations of PNP in the
feed and PNPNa in the stripping solution are equal, i.e. after this time
the transport becomes quasi-up-hill. (occurring against the concen-
tration difference), and (d) long time at which the majority of PNP
was transferred into the stripping solution (50 h). The results of
the calculations are presented in Fig. 14 as the diagrams illustrating
the concentration proles. It is seen that nearly linear concentration
proles are calculated, which justies the application of the resis-
tance-in-series model as a good approximation for phenolic com-
pounds transport under comparable conditions.
5. Conclusion
It can be concluded that the presented network analysis and
pertraction modelling or data analysis is an efcient and reliable
tool for the theoretical description of the PNP pertraction phenom-
ena in the ABLM system operating under conventional conditions,
i.e. with a fast neutralization reaction in the stripping solution. One
can suppose that the same model can be applied for describing the
pertraction process of other phenolic compounds and phenol itself.
The model accurately predicts the time-dependent PNP concentra-
tion proles and local uxes involved in the pertraction process
under study. It takes into account the operation parameters such
as volumes, concentrations, contact area, and pertraction mecha-
nism parameters such as distribution and interfacial mass transfer
coefcients established in independent experiments. The calcula-
tions can be made without special tting procedures (except for
extraction and re-extraction kinetics rate constants) by applying
accessible data characterizing the membrane system, e.g. diffusion
coefcients and the thickness of diffusion layers, reported in liter-
ature. The model elaborated is the predictive one as derived from
the general system simulation theory and seems feasible for
designing and optimizing the corresponding membrane systems
or predicting the effects which are not observed immediately by
experiments, e.g. concentration proles, local concentrations and
uxes, etc. It should be noted that the above model, after some
625
modication, is applicable for describing the ABLM transport of
weak bases from an alkaline solution into an acidic stripping solu-
tion, e.g. the transport of pyridine.
References
[1] I. Diaconu, G. Nechifor, A.C. Nechifor, E. Ruse, E.E. Totu, Membranary
techniques used at the separation of some phenolic compounds from
aqueous media, U.P.B. Sci. Bull., Ser. B 71 (2009) 6170.
[2] G. Busca, S. Berardinelli, C. Resini, L. Arrighi, Technologies for the removal of
phenol from uid streams: a short review of recent developments, J. Hazard.
Mater. 160 (2008) 265288.
[3] R.P. Cahn, N.N. Li, Separation of phenol from wastewater by the liquid
membrane technique, Sep. Sci. Technol. 9 (6) (1974) 505519.
[4] T. Kataoka, T. Nishiki, S. Kimura, Phenol permeation through liquid surfactant
membranes, J. Membr. Sci. 41 (1989) 197209.
[5] X.-J. Zhang, J.-H. Liu, Q.-J. Fan, Q.-T. Lian, X.-T. Zhang, T.-S. Lu, Industrial
applications of liquid membrane separation for phenolic wastewater
treatment, in: N.N. Li, H. Strathman (Eds.), Separation Technology, Engineers
Foundation, New York, 1988, pp. 190203.
[6] R. Prasad, K.K. Sirkar, Dispersion-free solvent extraction with microporous
hollow ber modules, AIChE J. 34 (1988) 177188.
[7] C.C. Wang, A.L. Bunge, Multisolute extraction of organic acids by emulsion
liquid membranes. I. Batch experiments and models, J. Membr. Sci. 53 (1990)
71103.
[8] C.H. Yun, R. Prasad, K.K. Sirkar, Membrane solvent extraction removal of
priority organic pollutants from aqueous waste streams, Ind. Eng. Chem. Res.
31 (1992) 17091717.
[9] S. Schlosser, I. Rothova, H. Frianova, Hollow-bre pertractor with bulk liquid
membrane, J. Membr. Sci. 80 (1993) 99106.
[10] F.F. Zha, H.G.L. Coster, A.G. Fane, A study of stability of supported liquid
membranes by impedance spectroscopy, J. Membr. Sci. 93 (1994) 255271.
[11] G. Arana, G. Borge, N. Etxebarria, L.A. Fernandez, Permeation of mixtures of
four phenols through a supported liquid membrane in NaCl 1.0 mol dm3,
medium, Sep. Sci. Technol. 34 (1999) 665681.
[12] V.S. Kislik, Liquid membranes. Principles and Applications in Chemical
Separations and Wastewater Treatment, Elsevier, Oxford, 2010.
[13] L. Boyadzhiev, E. Bezenshek, Z. Lazarova, Removal of phenol from waste water
by double emulsion membranes and creeping lm pertraction, J. Membr. Sci.
21 (1984) 137144.
[14] D. Bobok, . Schlosser, E. Kossaczky, Method of separation of solutions and
related equipment for realisation of this method (in Slovak), Patent CSR
235362 (1984).
[15] K. Dimitrov, D. Metcheva, L. Boyadzhiev, Integrated processes of extraction
and liquid membrane isolation of atropine from Atropa belladonna roots, Sep.
Purif. Technol. 46 (2005) 4145.
[16] A. Raszkowska-Kaczor, P. Adamczak, R. Wdzki, Hybrid rotating pertractor for
Zn(II) recovery and separation, Desalination 257 (2010) 6672.
[17] P.F.M.M. Correia, J.M.R. de Carvalho, Recovery of phenol from phenolic resin
plant efuents by emulsion liquid membranes, J. Membr. Sci. 225 (2003) 4149.
[18] S. Schlosser, E. Kossaczky, Emulsion properties inuence on pertraction of
phenol from water, in: paper Proceedings CHISA 78, Prague, 1978.
[19] S. Schlosser, E. Kossaczky, Comparison of pertraction through liquid
membranes and double liquidliquid extraction, J. Membr. Sci. 6 (1980) 83
105.
[20] W. Halwasch, E. Flaschel, K. Schgerl, Liquid membrane transport a highly
selective separation process for organic solutes, J. Membr. Sci. 6 (1980) 3344.
[21] M. Teramoto, H. Matsuyama, Effect of facilitated diffusion in internal aqueous
droplets on effective diffusivity and extraction rate of phenol in emulsion
liquid membranes, J. Chem. Eng. Japan 19 (1986) 469472.
[22] R.D. Noble, J.D. Way, A.L. Bunge, Liquid membranes, in: J.A. Marinsky, Y.
Marcus (Eds.), Ion Exchange and Solvent Extraction, Marcel Dekker, New York,
1988, pp. 63103.
[23] A. Sengupta, R. Basu, K.K. Sirkar, Separation of solutes from aqueous solutions
by contained liquid membranes, AIChE J. 34 (1988) 16981708.
[24] R. Basu, R. Prasad, K.K. Sirkar, Non dispersive membrane solvent back
extraction of phenol, AIChE J. 36 (1990) 450460.
[25] W. Cichy, S. Schlosser, J. Szymanowski, Extraction and pertraction of phenol
through bulk liquid membranes, J. Chem. Technol. Biot. 80 (2005) 189197.
[26] I. Diaconu, G. Nechifor, A.C. Nechifor, E.E. Totu, E. Ruse, The transport of
nitrophenols through liquid membranes, Rev. Chim. Bucarest 60 (2009)
12431246.
[27] I. Diaconu, H.Y. Abdoul-Enein, M.A. Al-Omar, G. Nechifor, E. Ruse, A.A. Bunaciu,
E.E. Totu, Separation of nitrophenols. Equilibriums in bi- and tri-phasic
systems, Arabian J. Chem. 4 (2011) 99103.
[28] Y.S. Ng, N.S. Jayakumar, M.A. Hashim, Behavior of hydrophobic ionic liquids as
liquid membranes on phenol removal: experimental study and optimization,
Desalination 278 (2011) 250258.
[29] R.E. Terry, N.N. Li, W.S. Ho, Extraction of phenolic compounds and organic
acids by liquid membranes, J. Membr. Sci. 10 (1982) 305323.
[30] M. Teramoto, H. Takihana, M. Shibutani, Extraction of phenol and cresol by
liquid surfactant membrane, Sep. Sci. Technol. 18 (1983) 397419.
[31] T. Kakoi, M. Goto, S. Natsukawa, K. Ikemizu, F. Nakashio, M. Matsumoto, T.
Hano, Recovery of phenols using liquid surfactant membranes prepared with
newly synthesized surfactants, Sep. Sci. Technol. 31 (1996) 107124.
626 P. Szczepanski et al. / Separation and Purication Technology 132 (2014) 616626
[32] P.F.M.M. Correia, J.M.R. Carvalho, Recovery of 2-chlorophenol from aqueous
solutions by emulsion liquid membranes: batch experimental studies and
modelling, J. Membr. Sci. 179 (2000) 175183.
[33] P.F.M.M. Correia, J.M.R. Carvalho, A comparison of models for 2-chlorophenol
recovery from aqueous solutions by emulsion liquid membranes, Chem. Eng.
Sci. 56 (2001) 53175325.
[34] C.J. Tompkins, A.S. Michaels, S.W. Peretti, Removal of p-nitrophenol from
aqueous solution by membrane supported solvent extraction, J. Membr. Sci. 75
(1992) 277292.
[35] P. Szczepanski, I. Diaconu, Transport of p-nitrophenol through an agitated bulk
liquid membrane, Sep. Sci. Technol. 47 (2012) 17251732.
[36] Y. Park, A.H.P. Skelland, L.J. Forney, J.-H. Kim, Removal of phenol and
substituted phenols by newly developed emulsion liquid membrane process,
Water Res. 40 (2006) 17631772.
[37] A. Balasubramanian, S. Venkatesan, Removal of phenolic compounds from
aqueous solutions by emulsion liquid membrane containing Ionic Liquid
[BMIM] + [PF6]- in tributyl phosphate, Desalination 289 (2012) 2734.
[38] S. Bandini, Naon membranes for conversion of sodium phenoxides into
undissociated phenols, J. Membr. Sci. 207 (2002) 209225.
[39] . Schlosser, E. Kossaczky, Pertraction through liquid membranes, J. Radioanal.
Nucl. Chem. 101 (1986) 115125.
[40] S.W. Park, C.F. Kaseger, J.B. Moon, J.H. Kim, Mass transfer of phenol through
supported liquid membrane, Korean J. Chem. Eng. 13 (1996) 596605.
[41] M. Rodriguez, R.M.C. Viegas, S. Luque, I.M. Coelhoso, J.P.S.G. Crespo, J.R.
lvarez, Removal of valeric acid from wastewaters by membrane contactors, J.
Membr. Sci. 137 (1997) 4553.
[42] Z. Lazarova, B. Syska, K. Schgerl, Application of large-scale hollow ber
membrane contactors for simultaneous extractive removal and stripping of
penicylin G, J. Membr. Sci. 202 (2002) 151164.
[43] M. Vajda, E. Sabolov, . Schlosser, E. Mikulov, Membrane-based extraction
joined with membrane-based stripping in a circulating arrangement II.
Extraction of organic acids, Chem. Pap. 57 (2003) 310.
[44] M.J. Gonzlez-Muoz, S. Luque, J.R. lvarez, J. Coca, Simulation of integrated
extraction and stripping processes using membrane contactors, Desalination
163 (2004) 112.
[45] M.J. Gonzlez-Muoz, S. Luque, J.R. lvarez, J. Coca, A predictive model for the
extraction and simultaneous stripping of phenylglycine from alkaline
solutions using membrane contactors, J. Membr. Sci. 255 (2005) 133140.
[46] A.G. Asimakopoulou, A.J. Karabelas, Mass transfer in liquidliquid membrane-
based extraction at small ber packing fractions, J. Membr. Sci. 271 (2006)
151162.
[47] S.F. Shen, K.H. Smith, S. Cook, S.E. Kentish, J.M. Perera, T. Bowser, G.W. Stevens,
Phenol recovery with tributyl phosphate in a hollow ber membrane
contactor: experimental and model analysis, Sep. Purif. Technol. 69 (2009)
4856.
[48] A.M. Urtiaga, M.I. Ortiz, E. Salazar, J.A. Irabien, Supported liquid membranes for
the separationconcentration of phenol. 1. Viability and mass-transfer
evaluation, Ind. Eng. Chem. Res. 31 (1992) 877886.
[49] K. Trivunac, S. Stefanovic, M. Mitrovic, Pertraction of phenol, in hollow-ber
membrane contactors, Desalination 162 (2004) 93101.
[50] M.T.A. Reis, O.M.F. de Freitas, M.R.C. Ismael, J.M.R. Carvalho, Recovery of
phenol from aqueous solutions using liquid membranes with Cyanex 923, J.
Membr. Sci. 305 (2007) 313324.
[51] G.F. Oster, A.S. Perelson, A. Katchalsky, Network thermodynamics: dynamic
modelling of biophysical systems, Quart. Rev. Biophys. 6 (1973) 1134.
[52] J. Schnakenberg, Thermodynamic Network Analysis of Biological Systems,
Springer Verlag, Berlin, 1977.
[53] A.R. Peacoke, Introduction to the Physical Chemistry of Biological
Organisation, Clarendon Press, Oxford, 1989.
[54] D.C. Mikulecky, Network thermodynamics and complexity: a transition to
relational systems theory, Comp. Chem. 25 (2001) 369391.
[55] R.C. Srivastava, S.K Saha, A.K. Jain, Thermodynamics: A Core Course, Network
Thermodynamics, third ed., Prentice Hall of India, New Delhi, 2007. pp. 274
295, (Chapter 10).
[56] F. Couenne, Ch. Jallut, B. Maschke, M. Tayakout, P. Breedveld, Structured
modeling for processes: a thermodynamic network theory, Comp. Chem. Eng.
32 (2008) 11201134.
[57] W. Borutzky, Bond graph modelling and simulation of multidisciplinary
systems an introduction, Simul. Model. Practice Theory 17 (2009) 321.
[58] C. Heny, D. Simanca, M. Delgado, Pseudo-bond graph model and simulation of
a continuous stirred tank reactor, J. Franklin Inst. 337 (2000) 2142.
[59] J. Ceynowa, P. Adamczak, Analysis of the bond graph network model of
membrane reactor for olive oil hydrolysis, Sep. Purif. Technol. 2223 (2001)
443449.
[60] F. Couenne, Ch. Jallut, B. Maschke, M. Tayakout, P. Breedveld, Bond graph for
dynamic modelling in chemical engineering, Chem. Eng. Proc. 47 (2008) 1994
2003.
[61] E. Sosnovsky, B. Forget, Bond graph representation of nuclear reaction point
kinetics and nearly incompressible thermal hydraulics, Ann. Nucl. Energy 68
(2014) 1529.
[62] M. Abbes, A. Farhat, A. Mami, G. Dauphin-Tanguy, Pseudo bond graph model of
coupled heat and mass transfers in a plastic tunnel greenhouse, Simul. Model.
Practice Theory 18 (2010) 13271341.
[63] A.A. Moya, J. Horno, Stationary electrodiffusionadsorption processes in
membranes including diffuse double layer effects. A network approach, J.
Membr. Sci. 194 (2001) 103115.
[64] R. Saisset, G. Fontes, Ch. Turpin, S. Astier, Bond graph model of a PEM fuel cell,
J. Power Sources 156 (2006) 100107.
[65] J.J. Esperilla, J. Felez, G. Romero, A. Carretero, A model for simulating a lead-
acid battery using bond graphs, Simul. Model. Practice Theory 15 (2007) 82
97.
[66] R. Wdzki, G. Szczepanska, P. Szczepanski, Unsteady state pertraction and
separation of cations in a liquid membrane system simple network and
numerical model of competitive M2+/H2+ counter-transport, Sep. Purif.
Technol. 36 (2004) 116.
[67] P. Szczepanski, G. Szczepanska, R. Wdzki, Bond-graph description and
simulation of membrane processes: permeation in a compartmental
membrane system, Chem. Pap. 66 (2012) 9991009.
[68] P. Szczepanski, R. Wdzki, Bond-graph description and simulation of agitated
bulk liquid membrane system  dependence of uxes on liquid membrane
volume, J. Membr. Sci. 435 (2013) 110.
[69] S. Durand-Vidal, J.-P. Simonin, P. Turq, Solute transfer kinetics at a liquid/liquid
interface, in: Electrolytes at Interfaces, Kluwer Academic Publishers, New York,
2002, pp. 235250.
[70] C.I. Koncsag, A. Barbulescu, Liquidliquid extraction with and without a
chemical reaction, in: M. El-Amin (Ed.), Mass Transfer in Multiphase Systems
and its Applications, InTech, Rijeka, Croatia, 2011, pp. 207232.
[71] P.R.L. Grosjean, H. Sawistowski, Liquid/liquid mass transfer accompanied by
instantaneous chemical reaction, Trans. Inst. Chem. Eng. 58 (1980) 5965.
[72] P.R. Danesi, Solvent extraction kinetics, in: J. Rydberg, M. Cox, C. Musikas, G.R.
Choppin (Eds.), Solvent Extraction Principles and Practice, CRC Press, 2004, pp.
206256.
[73] R. Nieser, A. Heintz, Diffusion coefcients of aromatics in aqueous solution, J.
Chem. Eng. Data 45 (2000) 11211124.
[74] R.C. Reid, T.K. Sherwood, The Properties of Gases and Liquids, McGraw-Hill,
New York, 1966.
[75] R.A. Noulty, D.G. Leaist, Activity coefcients and diffusion coefcients of dilute
aqueous solutions of lithium, sodium, and potassium hydroxides, J. Solution
Chem. 13 (1984) 767778.
[76] Berkeley Madonna, Modeling and Analysis of Dynamic Systems, http://
www.berkeleymadonna.com.
[77] S. Yoshida, S. Hayano, Kinetics of partition between aqueous solutions of salts
and bulk liquid membranes containing neutral carriers, J. Membr. Sci. 11
(1982)
0
157168.
[78] J.
A. Jnsson, Membrane extraction in preconcentration, sampling, and trace
analysis, in: A.K. Pabby, S.S.H. Rizvi, A.M. Sastre (Eds.), Handbook of
Membrane Separations. Chemical, Pharmaceutical, Food, and
Biotechnological Applications, CRC Press, Boca Raton, 2009, pp. 345369.
[79] J.-P. Behr, M. Kirch, J.-M. Lehn, Carrier-mediated transport through bulk liquid
membranes: dependence of transport rates and selectivity on carrier
properties in a diffusion-limited process, J. Am. Chem. Soc. 107 (1985) 241
246.