Separation and Purification Technology 22-23 (2001) 643– 654

www.elsevier.com/locate/seppur

Transport number of counterions in ion-exchange

membranes
S. Koter *
Faculty of Chemistry, Nicolaus Copernicus Uni6ersity, 7 Gagarin Street, PL-87100 Toruń, Poland

Abstract

The transport number of counterions in ion-exchange membranes (Nafion, Neosepta) has been predicted using the
homogeneous and capillary models of transport. In the case of capillary model, two distributions of ions — described
by the traditional and modified by Gur Boltzmann equations — have been applied. It has been found that the
homogeneous model based on the experimental sorption and the capillary model, with the traditional Boltzmann
equation, predict the transport number relatively well. The only exception is the anion-exchange membrane Neosepta
AM1 in HCl solutions, because of facilitated transport of protons through that membrane. It has been proved that
the sorption given by the Boltzmann equation is always higher than that given by the modified Boltzmann equation
and than the Donnan sorption. The modified Boltzmann equation, successful in predicting partition coefficient in
Nafion 117 membrane equilibrated with H2SO4 solutions and salt mixture solutions, as reported by other authors,
failed here. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Ion-exchange membrane; Transport number; Capillary model; Sorption

Nomenclature

Ai hydration constant of ion i (J/mol)

Bik transport coefficient (mol2/J m s)
c̄i mean concentration of species i in the pore solution (mol/m3)
c̄i,r concentration of species i depending on the radial coordinate (mol/m3)
Ji flux of species i (mol/m2s)
lik, Lik transport coefficient (mol2/J m s)
Mi molar mass of species i (kg/mol)
r dimensionless radial coordinate ( r(dimen.)/R) ( − )
R radius of capillary (m)
t( i transport number of species i ( − )

* Tel.: + 48-566-114525; fax: + 48-566-42477.

E-mail address: skoter@chem.uni-torun.pl (S. Koter).

1383-5866/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 3 - 5 8 6 6 ( 0 0 ) 0 0 1 6 0 - X
644 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654
6̄i partial molar volume of species i (m3/mol)
Vp volume fraction of pores (− )
zi valency of ion i ( − )
Greek letters
m permittivity of vacuum (m = 8.8542·10-12 C/vm)
mr dielectric constant (− )
p viscosity (N s/m2)
v0 chemical potential of water (J/mol)
ṽi electrochemical potential of ion i (J/mol)
z density (kg/m3)
„ potential (V)
1. Introduction
The transport number of counterions, the mea-
sure of selectivity of ion-exchange membranes, is
the basic parameter determining the efficiency of
electromembrane separation processes. For the
prediction of the transport number the following
models of ion-exchange membranes can be used:
(1) the homogeneous model, assuming the uni-
form distribution of ions in the membrane pores
[1]; and (2) the capillary model, in which the pores
are approximated by a charged capillary [2 – 4] of
different geometries [5]. The homogeneous model
has been verified by some authors [6 – 9]. How-
ever, because of the incorrect equations they used,
this model should be re-examined. In spite of
numerous papers on the capillary model of ion-
exchange membranes, practically no comparison
with experiment regarding the transport number
has been made.
Special attention has been focused on the pe-
rfluorosulfonic acid Nafion membranes because of
their exceptional properties. Applying various
techniques, e.g. small-angle X-ray scattering, elec-
tron microscopy (see Ref. [10]), an ion cluster
structure of those membranes has been stated and
a cluster-network model has been developed [11].
With that model Gierke and Hsu could success-
fully describe the current efficiency (CE) of
Nafion in a chlor –alkali electrolysis, whereas CE,
based on the Donnan exclusion [11], was too low.
Using the Donnan equation, Reiss and Bassig-
nana [12] attributed the increased CE to the
nonuniform distribution of fixed charges (a series
of layers of high and low concentration of fixed
charges). Eventually it was shown that that
nonuniform distribution had negligible effect on
CE [13,14]. The transport of OH− ions through
Nafion was also modelled by the capillary model
[15], however no relation to the experimental re-
sults was given.
The aim of this paper is to verify both the
homogeneous and capillary models using the dif-
ferent membrane/electrolyte systems and to state
whether the more sophisticated transport theories
are needed.
2. Theory
The considerations are restricted to a mono-
monovalent electrolyte. The fixed charges of
membrane are also monovalent. Subscript 1 de-
notes counterion, subscript 2 denotes the coion
and subscript 0 denotes the solvent. Two types of
transport number of counterions are commonly in
use — the real transport number t( 1 is defined as:
t( 1 = Fz1
J1
(1)
I Dc,Dp = 0
and the apparent transport number t( 1,app given by:
t( 1,app = t( 1 − (cs/c0)t( 0 (2)
where t( 0 is the electroosmotic transport of solvent:
t( 0 = F
J0
(3)
I Dc,Dp = 0
 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654 645

where Ji is the flux of species i; I is the current

c̄2(c̄2 + c̄m)=
 f9 2
c2 (11)
density; and cs, c0 are the concentrations of elec- f( 1f( 2 s
trolyte and solvent in a solution bathing a
where f( i is the activity coefficient of ion i in the
membrane.
pore solution. According to Eq. (9) for the condi-
tion t( 0 = 0 the lower limit of t( 1 is:
2.1. Homogeneous model
(1+s̄)ū 01 Eq. 8 1+ s̄
t( 1,min = (t( 1)t( 0 = 0 = “ (12)
In this model it is assumed that ions and sol- (1+s̄)ū 01 + s̄ū 02 1+ s̄/t1
vent are uniformly distributed in the cross-section In the past t( 1,app was identified with Eq. (12)
of pores in a membrane. t( 1 and t( 0, expressed in [6–8]. Indeed, it has been checked that the differ-
terms of the concentrations of ions and solvent ence between Eq. (12) and Eq. (2) is B10% for
inside the membrane, c̄i and their mobilities with the systems discussed here. The positive verifica-
respect to the membrane, ūi, are given by: tion of Eq. (12) for the cation-exchange mem-
c̄1ū1 branes in the H+-form [9] results from the fact
t( 1 = , (4) that for such systems the electroosmotic transport
c̄1ū1 + c̄2ū2
number of water is very small and thus, t( 1,min :
c̄0ū0
t( 0 = (5) t( 1,app : t( 1. However, these equations cannot be
c̄1ū1 + c̄2ū2 regarded as identical. Such an assumption would
The concentration of counterions, c̄1, is the sum lead to false expression relating t( 1,app with the
of concentrations of coions c̄2 and fixed charges non-transport properties of membrane only
c̄m: (s̄, N( m) [8]. Certainly, the transport number also
c̄1 = c̄2 +c̄m (6) depends on the ion mobilities.

Because of electroosmotic flow of solvent directed 2.2. Capillary model

towards the counterions, the ion mobilities can be
written as [16]: In this model, the pores of membrane are ap-
ū1 = ū (0)
+ū0, ū2 = ū (0)
−ū0 (7) proximated by a charged capillary of radius R
1 2
with the uniform surface density of fixed charges
(0)
where ū is the mobility of ion i with respect to
i | related to their mean concentration c̄m in the
solvent. Usually it is assumed that ū (0) (0)
2 /ū 1 is the pore solution by:
same as in a free solution [7,9]:
|= c̄mR/2 (13)
ū (0) (0) (0) (0)
2 /ū 1 = u 2 /u 1 =(1 −t1)/t1 (8)
Discussing this model, the transport numbers t( 1
where t1 is the transport number of counterions in and t( 0 will be expressed in terms of the phe-
the free solution. Combining Eqs. (4) and (5) and nomenological coefficients Lik from the transport

  
Eq. (7) yields: equations of irreversible thermodynamics:
(1+ s̄)ū 01 s̄ ū 0 Ji = Li1(− 9ṽ1)+ Li2(− 9ṽ2)+ Li0(− 9v0)
t( 1 = 1+ 1 + 20 t( 0
N( m
 
0 0
(1+ s̄)ū 1 + s̄ū 2 ū 1
i= 0, 1, 2 (14)
(1+ s̄)
Eq. 8 s̄t(
“ 1+ 0 (9) In Eq. (14), Ji is the flux of species i; 9ṽi is the
(1+s̄/t1) N( mt1
gradient of electrochemical potential of ion i; and
where 9v0 is the gradient of chemical potential of sol-
s̄ =c̄2/c̄m N( m =c̄0/c̄m (10) vent. The Lik coefficients fulfil the Onsager re-
ciprocity Lik = Lki. Using the definitions Eq. (1)
To estimate t( 1 from Eq. (9), the solvent content and Eq. (3), t( 1 and t( 0 can be expressed as:
and the sorption of electrolyte have to be mea-
sured. The sorption can also be calculated from L11 − L12
t( 1 = , (15)
the Donnan equation: L11 − 2L12 + L22
646 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654

L01 −L02
t( 0 = (16) In Eq. (22) c̄i is the mean concentration of ions i
L11 − 2L12 +L22
in the pore solution, calculated from:
The Lik coefficients, averaged over the cross-sec-
tion of a capillary, are the sum of two compo- c̄i = 2
& 1
c̄i,rrdr i= 1, 2 (23)
nents [17]: 0

The mean concentration of fixed charges c̄m is

Lik = Bik + l( ik, i,k = 0, 1, 2 (17)
determined from the experimental data (see Ap-
In Eq. (17), Bik is the contribution of the move- pendix A). The method of calculating the l( ik co-
ment of the mass center of pore solution, defined efficients is given in Appendix B. The capillary
by: radius R is determined in such a way that the

Bik = 2R 2
& & &
1
c̄i,rr
1
1 r
c̄k,rrdr 3 i,k= 0, 1, 2
electroosmotic transport number of water calcu-
lated on its basis (Eqs. (16) –(18)), t( 0(R), is equal
0 r pr 0 to the experimental one, t( 0(experimental) [20]:
(18)
t( 0(R)= t( 0(experimental) (24)
It depends on the capillary radius, R, the radial
distribution of species, c̄i,r and on the viscosity of
pore solution, p. The second term in Eq. (17), l( ik, 3. Membranes
describes the transport relative to the center of
mass of pore solution. All the coefficients are The investigated membranes are the cation-ex-
symmetrical, i.e. l( ik =l( ki, Bik =Bki and Lik =Lki. change membranes Nafion 120 (Du Pont de
To calculate Lik, two equations describing the Nemours) and Neosepta CM2 (Tokuyama Corp.),
distribution of ions are chosen. and the anion-exchange membrane, Neosepta
(1) The Boltzmann equation:
 
AM1. Their chemical composition and the basic
F properties (volume fraction of pores, Vp, concen-
c̄i,r = ci exp −zi „ (19) tration of fixed charges in the pore solution, c̄m,
RT
water content, N( m) are shown in Table 1.
(2) The Boltzmann equation modified by Gur et The dependence of the experimentally deter-
al. [18]:
  
mined concentration of sorbed electrolyte in the
pore solution c̄2, the real transport number of
F A 1 1
c̄i,r = ci exp −zi „− i − (20) counterions t( 1 and the electroosmotic transport
RT RT mr,r mr,0
number of water t( 0 on the molality of external
In Eq. (20), Ai denotes hydration constant (ANa+ electrolyte are shown in Figs. 1–3. The method of
= 431, ACl− = 296 kJ/mol [18], AH + =555 kJ/ calculating c̄2 is described in Appendix A. t( 1 was
mol [19]), mr,0 is the dielectric constant at r= 0, calculated from t( 1,app and t( 0 using Eq. (2). The
where the gradient of electric potential is zero. experimental data needed to calculate c̄2, t( 1 and t( 0
The dependence of dielectric constant on the elec- were taken from: Nafion 120 membrane [21,22],
tric field in the charged capillary is described by AM1 [23] and CM2 [24].
the Booth equation [3,4]. The concentration profi- Compared to Nafion 120, the Neosepta mem-
les, needed for the calculation of Bik and c̄i, are branes are highly charged — their concentration
found by solving the Poisson equation: of fixed charges exceeds approximately two times
that of Nafion (Table 1). Therefore, the transport
F number of counterions in those membranes is
9(mr 9„)= − %z c̄ (21)
m i i i,r much higher and closer to one (Fig. 2). The
with the boundary and electroneutrality exception is the anion-exchange membrane AM1
conditions: in HCl solutions, which rapidly looses its selectiv-
ity when the concentration of HCl increases. Two
((„/(r)r = 0 =0 z1c̄1 +z2c̄2 +zmc̄m =0 (22) factors responsible for that effect are: the high
 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654 647

Table 1
Characteristics of ion-exchange membranes

Membrane Chemical composition Ionic form Vp c̄m (mol fixed N( m (mol

charge/dm3 pore sol.) H2O/mol fixed
charge)

Nafion 120 Saponified copolymer of sulphonyl fluoride Na+ 0.39 3.1 17.1
vinyl ether and tetrafluoroethylene
Neosepta CM2 Strongly acidic cation-exchange membrane Na+ 0.33 5.4 10.2
prepared by paste method [29]
H+ 0.27 7.3 7.5
Neosepta AM1 Strongly basic anion-exchange membrane Cl− 0.27 6.4 7.8
prepared by paste method [29]

mobility of H+ ions and higher concentration of 4. Comparison of theory with experiment

sorbed electrolyte than in other membrane/elec-
trolyte systems (Fig. 1). Comparing the concentra- Applying the capillary model to the transport
tions of fixed charges it should be noted that the description in charged membranes, usually the
high sorption of HCl into AM1 is in contradiction values of viscosity and the mobilities of ions in the
with the Donnan equation according to which the infinitely dilute solution are used [2,4]. However,
higher concentration of fixed charges the lower the concentrations of ions in the pore solutions of
sorption of electrolyte. Nafion and Neosepta membranes are high. There-
Because of low water content, the electroos- fore, here the calculation of l( ik is based on the l( (0)
ik
motic transport number of water, t( 0, is lower in coefficients for cs = 3 M — the highest concentra-
Neosepta membranes than in Nafion (Fig. 3). tion for which the values of l( (0)
ik are available [26]
Plotting t( 0/t( 1 divided by the water content ex- (Table 2). Because of the lack of data for NaOH
pressed as c̄0/c̄1 (in Fig. 4) one notices that :40 – solutions, the cross coefficient l (0) 12 has been ne-
60% of water is moving electroosmotically glected and the coefficients l (0)
11 and l (0)
22 have been
towards the counterions. The lowest value, ca. estimated from t1 and the molar conductance of
10% observed for the system CM2/HCl, results
from the hopping mechanism of transport of pro-
tons, discussed in detail in [25]. Comparing
Nafion/NaCl and Nafion/NaOH, it is seen (Fig.
3) that t( 0 (NaOH) is slightly lower than t( 0(NaCl),
whereas the decrease of t( 1(NaOH) comparing to
t( 1(NaCl) is significant (Fig. 2). This effect can be
explained by the different mechanism of transport
of OH− ions, according to which the movement
of OH− is connected with ‘hopping’ of H+ in the
opposite direction. In that case, the movement of
water molecules, forced by Na+ counterions
would be less hampered by OH− than Cl−. How-
ever, the analogous situation is not observed in
the anion-exchange membrane AM1 with Na+
and H+ coions, where t( 0(HCl) B t( 0(NaCl). Here,
the transport number of Cl− counterions in AM1/
HCl decreases to a much higher extent than in Fig. 1. Concentration of sorbed electrolyte in the pore solution
AM1/NaCl. of membrane versus the molality of external electrolyte.
648 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654
Fig. 2. Real transport number of counterions, t( 0 versus the
molality of external electrolyte.
Fig. 3. Electroosmotic transport number of water, t( 0 versus the
molality of external electrolyte.
NaOH solution \, according to the equations
given in [26]. The relative viscosity of electrolyte
solutions, p/p0, ranges from 1.3 (HCl) to 2.2
(NaOH) (Table 2). In the calculations of all the
systems p/p0 =1.4 has been used.
All the calculations have been performed using
Mathematica® 3.0 (Wolfram Research, Inc.,
USA). In the case of the modified Boltzmann
equation Eq. (20) the results for CM2/HCl and
AM1 will not be presented because of numerical
problems.
4.1. Equi6alent radius of membrane pores
According to the Boltzmann distribution the
pores of Nafion membrane are characterised by
the radius of magnitude 1.2 –1.4 nm in dilute
solutions (Fig. 5a), which is smaller than the
radius of clusters (ca. 2–2.5 nm) and greater than
the radius of channels connecting clusters (B 0.5
nm), determined by other methods [11]. It de-
creases with concentration, as the content of wa-
ter decreases. The radius of AM1 is similar to that
of Nafion, whereas the pores of CM2 are the
narrowest (R= 0.8 nm). Comparing with the
Boltzmann distribution, the modified distribution
yields : 10–15% smaller values of radius (Fig.
5b).
4.2. Sorption
The ratio of the calculated to the experimental
concentration of electrolyte in the pores of mem-
branes, c̄2/c̄2,exp, is presented in Fig. 6a–c.
The general feature of the Donnan equation
and the capillary model is that the calculated
sorption of electrolyte is too small in dilute solu-
Fig. 4. ((t( 0/t( 1)/(c̄0/c̄1) versus the molality of external electrolyte.
 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654 649

Table 2
The l (0)
ik coefficients, used to calculate l( ik (see Appendix A), and the relative viscosity of aqueous electrolyte solutions; cs =3 M,
T = 298 K

Electrolyte l (0)
11 (10
−10
mol2/J ms) l (0)
12 (10
−10
mol2/J ms) l (0)
22 (10
−10
mol2/J ms) p/p0 (10−10 mol2/J ms) [30]

NaCl 10.1 2.6 16.2 1.38

HCl 69.3 4.7 16.7 1.26
NaOHa 8.1 0 32.0 2.20

a (0)
l ik were estimated from t1 and \ only; l (0)
12 has been assumed to be zero.

tions. With the increase of external concentration modification. This statement results from the
it increases and can exceed the experimental sorp-
tion. The modified Boltzmann equation gives the
worst estimation of the concentration of sorbed
electrolyte (Fig. 6c). This is in contradiction with
the results reported in literature [19]. For the
membrane Nafion 117 in the wide concentration
range of H2SO4 (0.1 – 3 M), Verbrugge and Hill
[19] found a good agreement between the experi-
mental and calculated partition coefficient based
on the modified Boltzmann equation, whereas
that obtained using the Boltzmann equation was
about two times higher. The discrepancy between
their results and the results presented here is
probably caused by the much higher diameter of
pores assumed by those authors, equal to the
Bragg spacing 5.5 nm, as reported by Gierke [27].
One can conclude that the sorption is governed by
clusters, whereas the transport by channels con-
necting clusters. Using the modified Boltzmann
equation Bontha and Pintauro [28] also calculated
correctly the concentration of counterions in
Nafion 117 equilibrated with a mixture of alkali
metal chlorides (total external concentration 0.1
M). They used the diameter of pores the same as
in [19], whereas the hydration constant for Na+
ions, estimated from their model for ion-solvent
energies in a membrane pore, was two times lower
than that used in this paper (ANa+ =209 com-
pared to 431 kJ/mol [18]). However, they did not
present the concentrations of sorbed electrolytes,
much smaller in magnitude, whose deviation from
the experimental values would be much higher
than that of counterions.
It should be noted that the concentration of
sorbed electrolyte given by the Boltzmann equa-
tion is always higher than that calculated by its
comparison of the product c̄1,rc̄2,r (z1= z2= 1):
Boltzmann
c̄1,rc̄2,r =
c 2s \ c 2s exp −
(A1 + A2) 1
−
1 
RT mr mr,0
mod.Boltzmann
= c̄1,rc̄2,r (25)
remembering that A1 + A2 \ 0 and mr,0 \ mr. Also
the Donnan equation (constant electric potential)
yields lower sorption than the Boltzmann equa-
tion (variable electric potential), as it is seen in
Fig. 6a,b. The proof of inequality:
Donnan
c̄1c̄2(Boltzmann)\ c 2s = c̄1c̄2 (26)
is given in Appendix C.
4.3. Transport number of counterions
The concentration dependence of the ratio of
calculated real transport number of counterions
to the experimental one, t( 1/t( 1,exp, is shown in Fig.
7 (homogeneous model) and Fig. 8 (capillary
model).
In the case of Nafion 120 membrane, both
models predict t( 1 reasonably well. The exception
is the modified Boltzmann equation, which signifi-
cantly overestimates t( 1 because of too low sorp-
tion predicted by that distribution (Fig. 6c). A
good agreement of the simple homogeneous
model with the experiment suggests that more
elaborated theories of transport through Nafion
membranes are not necessary for estimating t( 1.
Using the Donnan equation Gierke and Hsu [11]
calculated ca. 20% too low CE of Nafion mem-
branes in the chlor-alkali electrolysis, whereas in
this work the deviation of t( 1 is still within 5% for
4 m NaOH solution (Fig. 7b). The higher devia-
tion observed in [11] probably results from the
650 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654
applied higher concentration of NaOH. Unfortu-
nately, the authors did not state for which concen-
tration of NaOH CE was determined.
Regarding the cation-exchange membrane CM2,
the transport number of H+ counterions estimated
by both models agrees very well with the experi-
mental one, which is close to 1 in the investigated
concentration range. This agreement results from
the high mobility of H+, which is the dominating
factor influencing t( 1. In the case of NaCl solutions,
Fig. 5. Equivalent radius of pores calculated from the condi-
tion 9240; (a) CD, the Boltzmann equation Eq. (19); 9B0
BDH, the modified Boltzmann equation Eq. (20).
the homogeneous model underestimates t( 1, whereas
the capillary model gives satisfactory results — the
deviation of t( 1 does not exceed 2%.
In the case of the anion-exchange membrane
AM1, equilibrated with NaCl solutions, both mod-
els only slightly overestimate t( 1 (B 3%), whereas
when the membrane is in contact with HCl solu-
tions, the calculated transport number of Cl−
counterions is much too high. Even t( 1 based on the
experimental sorption, which is larger than in other
systems, exceeds : 30% the experimental value of
t( 1 in 1-m solution of HCl. Evidently, the mobility
of H+ is much higher than that of Cl− in compari-
son to their mobilities in a free solution. Certainly,
the mobility of Cl− in that membrane can also be
to some extent reduced, because also for NaCl
solutions the calculated t( 1 is slightly too high.
However, this effect should be rather small. Taking
into account the Grotthus mechanism of proton
migration [25], one can suppose that the electroos-
motic movement of water forced by Cl− counteri-
ons has a negligible influence on the mobility of
protons. Thus, assuming for H+ coions: ū2 : ū (0)2 ,
Eq. (9) would be changed to:
(1+s̄)ū 01 s̄ ū 02
t( 1 = 1+ t( (27)
(1+s̄)ū 01 + s̄ū 02 N( m ū 01 0
However, the transport numbers of Cl−, calculated
according to Eq. (27). is only a few percent (B
2.5%) smaller than that given by Eq. (9). Thus, it
should be concluded that the migration of H+ in
AM1 is facilitated.
5. Conclusions
The transport number of sodium ions in Nafion
120 membrane in contact with the solutions of
NaCl and NaOH can be predicted by the homoge-
neous model with a good accuracy for the concen-
trations up to 4 M. No special model taking into
account the ion cluster morphology of that mem-
brane is needed.
The capillary model with the Boltzmann distri-
bution of ions yields better results for the cation-ex-
change membranes (Nafion 120, Neosepta CM2)
equilibrated with NaCl solutions than the homoge-
neous model.
 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654 651

2
Fig. 6. c̄2/c̄2,exp versus molality of external solution; (a) the Donnan equation Eq. (11), f 9 /(f( 1f( 2) =1; (b) CD, the Boltzmann equation
Eq. (19); (c) BDH, the modified Boltzmann equation Eq. (20).

Neither homogeneous nor capillary model
can predict the transport number of Cl−
counterions in the anion-exchange membrane
Neosepta AM1 in HCl solutions because of the
facilitated migration of H+ coions in that mem-
brane.
The equivalent pore radius of membrane pores
estimated from the electroosmotic transport of
water, ranging from 0.8 nm (CM2) to 1.3 nm
(Nafion 120), is too small to predict correctly the
sorption at low concentrations of external elec-
trolyte (B0.5 M).
It has been proved that the sorption given by
the Boltzmann equation is always higher than
that given by the modified Boltzmann equation
and the Donnan equation.
652 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654

Fig. 7. Homogeneous model: t( 1/t( 1,exp versus the molality of

Fig. 8. Capillary model: t( 1/t( 1,exp versus the molality of external
external electrolyte, calculated using the concentration of
electrolyte, according to (a) CD, the Boltzmann equation Eq.
sorbed electrolyte: (a) experimentally determined; (b) calcu-
(19); (b) BDH, the modified Boltzmann equation Eq. (20).
lated from the Donnan equation.
z̄m̄i
c̄i =
Acknowledgements 1+ M1m̄1 + M2m̄2
z̄c̄ (m)
i
This work was supported by the Project INCO = (m)
i= 0, 1, 2, m
M c̄
0 0 + M1c̄ (m) (m)
1 + M2c̄ 2
COPERNICUS IC 15 CT 96-0826.
(A1)

Appendix A. Calculation of the mean

concentrations of components in the pore solution
The concentrations of species i, expressed in
moles per unit volume of internal solution, were
calculated from the formula:
where c̄ (m)
i is the concentration of species i ex-
pressed in moles per unit volume of membrane.
The density of pore solution, z̄, usually taken
as the density of bulk solvent, was evaluated
from:
 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654 653

M0c̄ (m) (m)

0 +M1c̄ 1 +M2c̄ 2
(m)
Appendix C. Proof of inequality (26)
z̄ = (A2)
6̄0c̄ 0 +6̄1c̄ 1 +6̄2c̄ 2
(m) (m) (m)

Let us write the integral Eq. (23) as:

assuming that the partial volumes of ions and
n
water are known. Eq. (A2) has been obtained by
c̄i = 2 % rkc̄i,k Dr i=1, 2 (C1)
the substitution of Eq. (A1) into the equation k=1
c̄06̄0 +c̄16̄1 +c̄26̄2 = 1. The membrane porosity, Vp, Substituting Dr= 1/n, rk = Dr/2+(k− 1)/n, into
was calculated from: Eq. (C1) one obtains:
c̄ (m)
i
eq.(A1) 1
1 n
Vp = = (M0c̄ (m) (m) (m)
0 +M1c̄ 1 +M2c̄ 2 ) c̄i = % (2k − 1)c̄i,k i= 1, 2 (C2)
c̄i z̄ n 2 k=1
(A3)
Locally, at a given point r, the Boltzmann
Appendix B. Calculation of l( ik in the mass frame equation is equivalent to the Donnan equation
of reference with the assumption that the ratio of activity
coefficients of ions inside the membrane and in
From the assumption analogous to Eq. (8) it is the solution is equal to 1:
not possible to obtain all the l( ik coefficients.
Therefore, it has been assumed that: c̄1,rc̄2,r = c 2s (C3)
l( ii lii l( ik lik Thus, for each k it can be written:
= and = i,k= 1, 2 (B1)
c̄i ci
c̄ic̄k
ci ck c̄1,kc̄2,k = c 2s (C3a)
The lik coefficients of electrolyte solution, in the Applying Eq. (C2) and Eq. (C3a) the product
mass frame of reference, were calculated from l (0)
ik c̄1c̄2 is as follows:
in the solvent frame of reference, taken from [26],
1 n n
% (2j −1)c1, j % (2k − 1)c̄2,k
   
according to the formulas [29]: c̄1c̄2 = 4
n j=1 k=1
z1 2
M 2 z1 z
l11 = 1− l (0)
11 − 2 1 − 1 l (0) 1 n c̄
z M1 z z 12 % (2j −1)(2k − 1) 2,k
 
= c 2s


n 4 j,k = 1 c̄2, j
M2 z1 2
+ l (0) 1 1
M1 z 22

 
= c 2s n(2n − 1)(2n + 1)

 
n4 3
z 20 + 2z1z2 + z0(z1 +z2) (0) n
l12 = l 12 c̄2,k c̄2, j
z2 %
   
+ (2j −1)(2k − 1) +
j = 1,k = j + 1 c̄2, j c̄2,k
M 1 z2 z M z z (C4)
− 1− 1 l (0) − 2 1 1 − 2 l (0)
M2 z z 11 M1 z z 22

l22 = 1−
z2  2
l (0)
22 − 2
M 1 z2
1−
z2 (0)
l
  In Eq. (C4) the last term fulfils the following
relation:
z
 M1 z2 2
M2 z z 12
 c̄2,k c̄2, j
+
! = 2 for c̄2, j = c̄2,k
(C5)
+ l (0) (B2) c̄2, j c̄2,k \ 2 for c̄2, j " c̄2,k
M2 z
11

In Eq. (B2), zi is the density of ion i, z is the In the case of nonuniform distribution of ions
density of solution. c̄2, j " c̄2,k (the Boltzmann equation) the following

 
The l( 0k coefficients were calculated from: inequality is fulfilled:
n
2 c̄2,k c̄2, j
% Mil( ik = 0 k = 0,1, 2 (B3) % (2j −1)(2k − 1) +
i=0 j,k = j + 1 c̄2, j c̄2,k
Eq. (B3) results from the definition of flux relative 1
\ (n− 1)n(3n 2 − n−1) (C6)
to the center of mass of solution. 3
654 S. Koter / Separation/Purification Technology 22-23 (2001) 643–654

From Eq. (C6) and Eq. (C4) it results that c̄1c̄2 \ [12] H. Reiss, I.C. Bassignana, J. Membr. Sci. 11 (1982) 219.
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[14] S. Koter, J. Membr. Sci. 108 (1995) 177.
function which locally fulfils the Donnan Eq.
[15] W.H. Koh, H.P. Silverman, J. Membr. Sci. 13 (1983) 279.
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121.
[17] S. Koter, Pol. J. Chem. 71 (1997) 1305.
[18] Y. Gur, I. Ravina, A.J. Babchin, J. Coll. Interf. Sci. 64
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