j o u r n a l of MEMBRANE SCIENCE

ELSEVIER

Journal of MembraneScience 123 (1997) 121-131

Chronopotentiometric response of an ion-exchange membrane in the underlimiting current-range. Transport phenomena within the diffusion layers
Philippe Sistat, G6rald Pourcelly *
Laboratory of Materials and Membrane Processes, CNRS, UMR 5635 BP 5051, 34033 Montpellier Cedex, France

Received 18 April 1996;revised 12 July 1996; accepted 15 July 1996

Abstract
The chronopotentiometric response of a cation exchange membrane in contact with a symmetrical 0.01 M NaC1 solution was investigated as a function of the applied current density below the limiting one. Taking into account classical assumptions such as the variation of concentrations associated to the Teorell-Meyer-Sievers (TMS) segmentation model, the concept of the Nemst layer model, the quasi-electroneutrality condition within the diffusion boundary layers (DBL) and the validity of the Donnan equation at the solution-membrane boundaries, theoretical values of the transmembrane potential difference were obtained which fit very well the experimental V - t responses. Moreover, this method allows the calculation of the DBL thickness. In addition, a decrease of the DBL thickness was observed when the current density increases. This result was attributed to the occurrence of convection effects inside the DBL.
Keywords." Chronopotentiometry;Ion-exchangemembrane;Diffusion layers; Donnan conditions

I. Introduction
The passage of an electric current between two dilute solutions separated by an ion-exchange membrane possessing a good selectivity gives rise to concentration polarization in the vicinity of the membrane. In the DBLs, this concentration polarization leads to the establishment of concentration gradients which depend on time before a dynamic equi-

Abbreviations:IEM, ion exchange membrane;DBL, diffusion boundary layer; TMS, Teorell-Meyer-Sievers * Corresponding author. Fax: + 33-467042820; e-mail: pourcell@admcnrs.cnrs-mop.fr

librium was reached (steady-state). If polarization of the interface between an ion-exchange membrane (IEM) and dilute electrolyte solution has been extensively treated at steady-state [1-11], the description of the s o l u t i o n - m e m b r a n e - s o l u t i o n system has been less explored in the transient state, i.e., immediately after the application of a current. To this end, chronopotentiometry seems to be one of the most suitable techniques. Since the early works done by Sand, chronopotentiometry has became a common technique for the observation of the variation in time of a concentration at the interface between a solution and an electrode or a solid electrolyte [12]. When an electrolyte is in contact with homopolar IEMs like those employed in electrodialysis, the studies re-

0376-7388/97/$17.00 Copyright 1997 Elsevier Science B.V. All rights reserved. PH S0376-7 3 8 8(96)00210-4

122

P. Sistat, G. Pourcelly/Journal of Membrane Science 123 (1997) 121-131

ported in literature are less numerous. In this case, chronopotentiometry has been used to compare the transport properties of commercial IEMs [2,13,14] to quantify their heterogeneity [15], to study fouling by organic molecules [16] or scaling by mineral deposits [17], or to point out the contribution of conductivity of the heterogeneous surface of the membrane to the ion-transfer, in the overlimiting current range [18]. Chronopotentiometry also appears well-suited for studying multi-layer membranes, particularly bipolar membranes [19]. Besides, both the time-dependence and the current density-dependence of the parameters of the diffusion layers at IEM have been investigated by means of a laser interferometric method [20,21]. The aim of this work is to show that chronopotentiometry can be used for the study of the time-dependence of the concentration gradients in the DBLs. Stress will be put on the study of both the potential drop in the DBLs and the current-dependence of the DBL thickness.

f~

~c--"
t

2. Theoretical Chronopotentiometry is an electrochemical technique which enables the study of the time-dependence of the electrode potential produced by a controlled current. When the electrode is replaced by a permselective IEM, the difference is that the measured total potential drop includes not only the ohmic drop through the membrane, but also the ohmic and diffusional potential drops due to the concentration polarization, and the Donnan potentials at both membrane-solution interfaces. In the case of a system composed of an IEM clamped between two solutions of the same electrolyte at the same concentration, the transfer of an electric current causes a decrease in counter-ion concentration in the solution becoming depleted at the membrane surface and an increase in the other one which gets concentrated [9]. In the case of dilute solutions under a high current density and without stirring, the counter-ion concentration can reach a value close to zero in the depleted compartment. Let us consider a selective IEM in contact with a binary unstirred 1:1 electrolyte solution of sufficiently low concentration to be in good Donnan exclusion conditions under an applied electric field.

Fig. 1. Shape of intensiostatic current density-voltage curves. (a) Current density-time curve; (b) resulting pd-time curve with different overvoltages: Vss: steady-state voltage; r/n: ohmic overvoltage; r/x: total overvoltage; r/c: concentration overvoltage.

The membrane being flat, migration and diffusion take place perpendicular to the plane of the membrane and the typical steady-state current-voltage responses with the three regions are well known [9]. Under galvanostatic control, as the current is applied, with a time-lag of about 10 -3 s to reach a constant value, a vertical jump of the transmembrane potential difference (pd) corresponds to the ohmic drop ~)n, as shown in Fig. 1. Due to the high concentrations in fixed sites, no significant concentration gradient occurs in the membrane bulk, so that the electrical conductivity of the membrane remains constant and, therefore, the ohmic drop through the membrane can be also considered as a constant. Then, a plateau is reached in a few seconds and a term named the total overvoltage r/T Can be evaluated. After switching-off the current, the concentration overvoltage ~7c can be evaluated either from the recording. The I - V responses of the IEM can be reconstituted from the constant values of the potential drop when steady-state is reached.

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

interfacial Donnan interfacial Donnan layer

123

layer

~1 =.~]
/:~

left DBL

',: , e~1 t' ', V'

,[',
I I

right DBL

_~ol
__

,1',
,,j:
i i i i i i i i

=~

Co

~ ~

Co

~51~

d+5~

d + 5 ~ + 8 , i ~ ,,t X

/+1

/+2

It X

Fig. 2. The different zones of the membrane transfer according to the TMS theory. (X and x are dimensioned and dimensionless parameters, respectively).

counter-ion migration only, and the potential drop through the membrane is only of ohmic nature. (v) The Nernst layer concept based upon a boundary ideally defined between the homogeneous bulk solution and the unstirred layer in which all the concentration gradients appear. This assumption splits the complex convective diffusion-migration problem of transport in solution into a two-step process: a transport through a bulk solution followed by a diffusion-migration through an immobile layer of fluid. The thickness of the diffusion layers on both sides of the membrane are assumed not to vary with time. All the considerations relative to the character of the fluid flow, the geometrical conditions and other factors are supposed to be taken into account by the Nernst layer assumption. (vi) The electroosmotic transport of solvent through the membrane is assumed to be negligible.
2.1. Evolution of the concentration profiles with time in the diffusion layers

With respect to the main goal of this work, which is the study of the time-dependence of the concentration in the diffusion layers by the chronopotentiometry technique, the following assumptions have been made to simplify the resolution of the problem: (i) The membrane is considered as ideally permselective, i.e., with a transport number of the counterion equal to unity. (ii) The total potential drop between the bulk solutions on both sides can be analysed according to the TMS model [22]. The variation of concentration associated to this segmentation is illustrated in Fig. 2. Within the DBLs, the electroneutrality condition is checked when the applied current density is lower than the limiting, and the residual charge is therefore negligible with respect to concentrations in the two ions [23,24]. Nevertheless, this electroneutrality is not valid within the thin layers on both sides of the membrane-solution interface which are zones of space charges. (iii) Donnan equilibrium is assumed at the boundary between membrane and solution even under non-zero flux conditions [1-8,24]. (iv) The exchange capacity of the membrane is sufficiently high to neglect the phenomenon of concentration polarization in the membrane material. In other words, the electric charges are carried by the

We start from the diffusion-migration equations of Nernst-Planck (Eq. (1)) and the continuity equations giving the molar ionic fluxes (Eq. (2)). These equations are written in their dilute solution forms, i.e., with all the activity coefficients taken equal to unity. We have also taken into consideration the current flow relation (Eq. (3)) and the electroneutrality condition (Eq. (4)). With k referring to the ionic species (k = 1 for the cation and 2 for the anion), we have:
Jk = - Dk aC k -~ aJ k

a--t- -

0X

(2) (3) (4)

I= F~ZkJ k
k

~_~Z,C k = 0

k X is taken on the x-axis, perpendicular to the membrane plane with X = 0 corresponding to the outer boundary of the unstirred layer. Ck, D k, Jk and zk are the concentration, diffusion coefficient, ionic molar flux and valency of the 'k' species, respec-

124

P. Sistat, G. Pourcelly/Journal of Membrane Science 123 (1997) 121-131

Eq. (9) can be reduced to the quasi-electroneutrality condition according to:
C 1 -- C2 ~ 0 ( C 1 -- C2) << ( C l ; C 2 ) (10)

tively, E is the electric field, I the current density, t the time. In Eq. (1), only the diffusion in the unstirred layer and the migration in the exterior electric field are taken into consideration for the concentration shift in a volume element at the membrane surface. However, for high current density and long period of current flow, other transport processes occur in addition, due to concentration gradient in the diffusion layer and also to convection phenomena. For solving the system of Eqs. (1)-(4), it is easier to use dimensionless variables. To this end the following classic relations are used:

where subscripts 1 and 2 refer to the cation and the anion, respectively. Introducing c = c 1 = c 2, this electroneutrality condition reduces the Nemst-Planck equation (6) to: Jl
-

0c

dl
J2

Ox
0c

ce
(lla,b)

---=--+ce d 2 Ox
With the help of the continuity relation (Eq. (7)) and combining Eq. (lla,b), we get an equivalent of the second Fick law: Oc
07"

X
x=--

FE6
e=--

16
i

RT

FDoC o

(5a,b,c)

Ck Jk ,5 ck= ~ jk = CoD---~o Dk dk= oZ tD o r = d2

(5d,e) (5f,g)

O2c
0X 2

(12)

where C0, D 0, 6 are arbitrary scaling factors, taken as characteristic values of the system studied. C o is equal to the salt concentration of the bulk solution, 6 is the diffusion layer thickness. We affect the value of the salt diffusion coefficient D s to the scaling factor D o according to: D~ 2D1D 2 (D, +D2) (5h)

Eq. (12) can be solved taking into account the following boundary conditions, for instance for the left DBL: x=0 r>0 c(0,'r)=l J2 = 0 Jl=i T=0 c(x, 0)=l (13a) (13b) (13c) (13d)

x= 1 r> 0 x=l 0<x<l r>0

where D 1 and D 2 are the ionic diffusion coefficients. The system of Eqs. (1)-(4) gives:

jk = --dk( ~OCk ZkCke)

Ock Ojk 0---~-= - 0--~i = Y'~ Zk Jk
k

(6)

Condition (13a) expresses the fact that the concentration of the bulk solution is a constant at any time; Eq. (13b) expresses the nullity of the co-ion flux through the membrane; Eq. (13c) expresses that the current is only transported by the counter-ion through the membrane, and Eq. (13d) is the initial concentration in the DBL, equal to the bulk concentration before the current application.With conditions (13b) and (13c), Eq. (1 la,b) can be reduced to: 0c 0x i - - , for x = 1 2d 1 (14)

(7)
(8) (9)

Zk Ck = 0
k

Eq. (12) with the boundary conditions written in Eqs. (13a), (13d) and (14) is solved by help of the Laplace transformation method. From the solution in the Laplace plane, for the concentration: - i sinh(v~s x) 1 (15)

For the following, we consider a 1:1 electrolyte only. The resolution for a multivalent Zl:Z2 electrolyte is given in the Appendix.

C(x, s) = 2dlSf~cosh(v~s ) + -s

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

125

we get by inverse Laplace transformation:

c(x't)=12d, + d - ~ E
x (2n-

/x

4i

( - 1 ) "-1

n=l

s i n [ ( 2 n - 1)~-x/2] 1) 2 (16)

Xexp[ (2n --1)27rzT 1

picted in Fig. 3. Diffusion constants d I and d 2 have been taken constant, equal to those in the bulk solution and not-dependent on concentration in the diffusion layer as in most of the papers dealing with ion transfer through IEMs. Indeed, the variation range of d I and d 2 remains lower than 4% for NaC1 concentrations ranging from 0.001 to 0.01 M [25]. Moreover, introduction of a diffusion constant-concentration dependence, leads to an impossibility to solve Eq. (16) analytically.

The two first terms represent the steady-state (c versus x becomes a linear relationship rapidly), the third one consists in vanishing exponentials. We have therefore obtained the concentration profiles versus x and r, in the diffusion layer. The dimensionless value of the limiting current density i l, is equal to 2d 1. With a value of 0.5 for the ratio of the current density to the limiting one (or i = d 1) and the values of 0.835 and 1.246 for d 1 and d 2 (representing a 0.01 M NaC1 solution), respectively, the representation of the time and spatial-dependence of the dimensionless concentration c(x, r) is de-

2.2. Potentialand electricfield in the diffusion layer

With

i=jl -J2,

Eq. (lla,b) gives:

i=-dl(~x-Ce ) + d2( ~x + Ce)

,

(17)
(18)

e =

[ dl- d2) Oln(c)

kdl+d 2 Ox

~,dl+d2, c+

The potential drop for the left diffusion boundary layer (DBL) is given by:
uDBL= -left

foledx
i 11
d2) f0

(19)

\b
0.9 . ~
\

and therefore: c
. DBL Vleft = (dl+

C dx -- (2tl -- 1)
(20a)

t 01n(c)

0.8

X fo

Ox

dx

0.7

f g

with t 1 = d2) , being the migrational transport number of the ion ' 1' in solution. One can easily integrate the second integral involved in the last expression:
DBL
Vleft (dl+

dl/(d 1+

0.6

]hi
k

d2) Jo c

:1 1
d x - ( 2 t l - 1)In(Cleft)

0.5

0.6 1 X Fig. 3. Calculated concentration profiles c(x, r) in the depleted diffusion boundary layer: (a) without current; (1) at steady-state (0.01 M NaC1; cation-exchange membrane; underlimiting current range). Ordinate: values of time (s): (a) 0; (b) 0.01; (c) 0.04; (d) 0.09; (e) 0.16; (f) 0.25; (g) 0.36; (h) 0.49; (i) 0.64: (j) 0.81; (k) 1: (1) ~.

', . . . . ', 0.2 0.4

',

'. . . . . 0.8

(20b) The first term of Eq. (20b) is the ohmic contribution to the potential. It contains a sum of vanishing exponentials and is therefore not easy to integrate. It must be evaluated from a numerical integration. The second is the contribution of the diffusion potential c(x, r) and is directly evaluated from the value of Cleft(T) = C ( X = 1, r).

126

P. Sistat, G. PourceUy / Journal of Membrane Science 123 (1997) 121-131

2.3. Potential drops through the two diffusion layers

Eq. (16) gives the expression of the concentration profile c(x, "r) in the left diffusion layer (the depleted). To obtain c(x, r) in the right diffusion layer (the concentrated), corresponding to x ranging from l + 1 to 1 + 2 (Fig. 2), we only have to substitutes by x - 2 - l in Eq. (16), l being the dimensionless thickness of the membrane equal to d~ 6.To obtain the potential drop VDB through the two diffusion L layers, we have to sum the two conditions, which gives:
UDB L -- f l --1

resistance, the total potential drop vv between the system boundaries is given by:
U y = UDB L "~ U D --

ri
1 1

(25)

VT

(d,~_dz) f _ , c d X + 2 ( 1 - t l ) Xlnl Cleft [--ri

[ Cfight J

(26)

2.5. Concentration overvoltage

When the steady-state is reached, i.e., when c(x, ~-) depends no more on time, the interruption of the current suppresses the ohmic drops and Eq. (26) becomes:

edx

(21)

the electric field being evaluated from Eq. (18), one obtains:
UDB L --

VT=2(1--tl)ln[C'eftht J lCrig

(27)

(dl+d2) f , c d X - ( 2 t l - 1 ) l n [
-

1 1

c'at] I_ cri ht .]
(22)

which is the dimensionless concentration overvoltage vc. At the steady-state, just before the current cut-off, c(x, T) is given by:

with Clat and Cright the concentrations in solution at the two solution-membrane interfaces.

ix c(x, z) = 1 - - 2d~
SO,

(28a)

2.4. Domain potentials at the two membrane-solution interfaces

With Fleft and Fright t h e concentrations in the membrane at the left and right solution-membrane interfaces (bars referring to the membrane), the sum of the two Donnan potentials gives: vo = In cleft

i qeft = 1 - - -d 1 and Cright= 2

1 +

i 12d--

(28b)

From Eqs. (27), (28a) and (28b), one can deduce the value of the concentration overvoltage: [ i --2dl i 1 + 2d--T (29)

vc =

2( 1 -

t 1)ln

(23)

Cright Cleft ]

Assuming that there is no appreciable concentration gradient in the membrane bulk and by there that Cleft = Fright , w e get:

3. Experimental
The experimental cell was the four-electrodes cell depicted in Fig. 4 and already used for voltammetric studies of IEM [9]. Two plane Ag/AgC1 electrodes permitted current injection since two Ag/AgC1 electrodes were used to scan the transmembrane potential. The membrane (cation-exchange membrane CRA from Solvay; exchange capacity: 2.14 mmol g - i ; area 0.785 c m 2) w a s clamped between two 100

UD = ln[ cleft ]
[ Cright J

(24)

With r including both the ohmic membrane resistance and the non-compensated electrolyte ohmic

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

127

V1

"l

ICathodel

Fig. 4. The polarization measurement cell. (a) Ag/AgC1 probes; (M): membrane; (b) bulk solution.

ml 0.01 M NaC1 solutions. Solution in the cell is under free natural convection conditions, no stirring was provided. All measurements were carried out at 25C using an AUTOLAB PGSTAT-20 potentiostat/galvanostat from EcoChemie (The Netherlands).

4. Results and discussion Fig. 5 shows the variation in time of the measured transmembrane potential difference when 500 s wide

square pulses of current are applied to the cell. After a potential jump due to the non-compensated ohmic resistance, the potential difference reaches a plateau after about two-hundred seconds. After 500 s, when the current is switched off, the concentration overvoltage Vc can be evaluated. From the theoretical expression of the total potential drop VT between the system boundaries (Eq. (26)), and using dimensioned parameters ( D 1, D 2, C O and 6), given previously in Section 2, V~ can be calculated for different values of current densities I

160mV

140mV

120mV experimental 100mV ..... simulation

data

80mY

60mV

f
~ . . . . v"

40mY

20mY OV 0

S
, I 200 , I 400 600 ' 800 , _ I 1000

Time Is]
Fig. 5. Chronopotentiometric responses of the membrane system. Comparison between experimental values (continuous lines) and calculated ones (dotted lines) for different values of the current (mA): (a) 0.1; (b) 0.2; (c) 0.3; (d) 0.4. (Membrane area: 0.785 cm 2, 0.01 M NaC1.)

128

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

480460. 440 .I~ [.. ~1 420 4000',1 012 0',3 0'.4 015 016

C u r r e n t density 1 mA-em'2 ] Fig. 6. Variation of the DBL thickness with current density (calculated values).

and non-compensated ohmic resistances R, in the 0-500 s time range. Experimental data are fitted for each value of the applied current with respect to free variables which are 6 and R, all the other variables occurring in the calculations being fixed. In a first step, 6 is fixed and R is adjusted to fit the initial value of the ohmic drop. Using a bracketing method, this procedure is repeated to fit V x for different values of 6 to reach a minimum in the merit function defined by the classical least square method. The comparison between the calculated and the experimental values is satisfactory as shown in Fig. 5. The DBL thickness evaluated from fitting the theoretical voltage-time curve to experimental data decreases with the current density as shown in Fig. 6. In order to check that this method gives reliable values of 6, the results have been compared with those obtained using the classical expression of the limiting current:
z~DkFCk

[21]. The consequence of this convection is the regeneration of the diffusion layer. Besides, the possibility of ionic transport to induce additional convection near the membrane surface was also previously mentioned in the literature [26,27] and is the principal explanation for the evolution of 6 with the current density. The main reason is the convection created by passing an electric current through an electrolyte solution. Density gradient appears which are in conjunction with gravitational forces. Two types of mechanism can occur, concentration free convection and thermal free convection [26]. Those effects can be invoked to explain the decrease in the Nernst layer thickness measured by chronopotentiometric experiments under free convection conditions. Moreover, the relative contribution of the concentrated layer potential to the total potential decreases with the current density and the effects we have measured can mainly be attributed to the depleted layer.

5. Conclusion
Chronopotentiometry is a valuable tool for the measurement of DBL thickness under current flow conditions. The thickness of the DBL can be evaluated for each value of the current density, which is not the case for values deduced from the interpretation of I - V curves [9,28]. This method of determination, which is easier to perform than radiotracer or laser interferometric ones [10,20,21], allows to point out the contribution of natural convection or electroconvection to the variation of the DBL thickness with the current. Moreover, the validity of both the Nemst-Planck and the Donnan formalisms has been shown, even in the transient state. An interfacial equilibrium state can be assumed under an applied current at the solution-membrane interface which can be described by the Donnan equations.

6(}k _ tk )

(30)

where t k is the transport number of the counter-ion (the cation), C k is the concentration of the bulk solution and where bars refer to the membrane. From experimental I - V curves obtained for 0.01 M NaC1, I = 4.82 mA cm -z. With ?k = 1 and t~ = 0.39, the calculated value of 6 is 410 + 5 p~m, which is close to that deduced from Fig. 6 for the same current density. The phenomenon of the DBL thickness decrease has already been observed in similar experimental conditions. It should be attributed to the natural convection in diffusion layers at vertical membranes

6. List of symbols
Cg ck d concentration of the 'k' ion (mol m - 3 ) dimensionless value thickness of the membrane (m)

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

129
= c, Eqs. ( A l l a ) and

Dk dk Do E e F I i J~ Jk l R R r t T V v x X zk 6 ~7 r

diffusion coefficient (m 2 s - z ) dimensionless value arbitrary scaling factor for D k electric field (V m -1) dimensionless value Faraday constant (96 500 C) current density (A m -2) dimensionless value ionic flux (mol m -2 s - l ) dimensionless value dimensionless value gas constant (J mo1-1 K -1) resistance (f~) dimensionless value time (s) temperature (K) voltage (V) dimensionless value abscissa (m) dimensionless value (perpendicular to the membrane plane) valency thickness of the DBL (m) overvoltage (V): (c: concentration; l-l: ohmic; T: total) dimensionless value

and therefore: c 1 = ( z 2 / z l ) c 2 (A11b) lead to: Jl dl

~c

Ox

zl ce

(A1 lc)

J2
d2

Oc zl + zl ce
~x z2

(A1 ld)

To take into account the continuity relation (Eq. (12) in the text), we calculate: 1 Oc1 dZ ~---~--- d 10"r

10c ( c)
~x -~x - zlce
~Jx Z 2 ~Jx

(A12a)

zl Oc 1 Oc2 d--~- ~---~-= -z- d 2 ~"t" 2

And, as:

O ( zl Oc ) - - - - + zlce

(A12b)

(1 zl,)oc t zl)o2c
--+---dl z 2 d2 ~

1+--

z2

~x 2

(A12c)

The boundary conditions are: x= 0 r> 0 c(0, r ) = 1 _ J_L = 0 d:

Jl ------ Zl

(A13a) (A13b)

x= 1 r> 0

Appendix A

7" >

(A13c) (A13d)

The numerotation of Eqs. corresponds to that in the text, except for the A letter, corresponding to the Appendix.

0<x<l

r=0

c(x,0)=l

Conditions (A14b,c) can be reduced to: ~c ~x

i z2 1 dl zl ( z l + z 2 ) ' f r x = l

A.1. Expression of c(x, r) for a Zl:Z 2 electrolyte

All diffusion coefficient are normalized to D s = 1 + z 2 D 2 ) , z 1 refers to the cation, z2 to the anion. In the following z 2 is taken as Iz21. Eq. (1 la,b) gives: Jl dI J2

(g14)

((Zl + z 2 ) D 1 D 2 ) / ( Z l D

Using the Laplace transformation, the solution of Eq. (12) gives:

c(x,'r)=ldlzl(z
co

1+z2) +

dl~2Zl(Zl +Z2)

0cl 3x 0c2
--

zlcle

(Alla)

E ( - 1 ) n-1 s i n [ ( 2 n - 1 ) r r x / 2 ] n=l (2n1) 2 (a16)

d2

Ox

-+-Z2C2 e

(Allb)

exp[-(2n-1)2"rr2r]

The electroneutrality condition gives: ZlCl = z2 c2,

130

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

cation exchange membrane, J. Electroanal. Chem., 336 (1992) 171. G. Pourcelly, I. Tugas and C. Gavach, Electrotransport of HC1 in the special anion exchange membranes for the recovery of acids. Part II: Kinetics of ion transfert at the membrane-solution interface, J. Membrane Sci., 85 (1993) 195. A. Chapotot, G. Pourcelly, F. Lebon and C. Gavach, Electrotransport of proton and divalent cations through modified cation exchange membranes, J. Electroanal. Chem., 386 (1995) 25. P, Delahay, In: I. Kolthoff and P. Elving (Eds.), Treatise on Analytical Chemistry, Interscience, New York, 1963. V.Ya Bartenev, A.M. Kasputin, N.M. Voznaya, G.M. Sorokina and A.A. Filonov, Electrochemistry properties of ion exchange membranes, Elektrokhimiya, 12 (6) (1976) 967. R. Audinos and G. Pichelin, Characterization of electrodialysis membranes by chronopotentiometry, Desalination, 68 (1988) 251. K.R. Brennen and G.J. Hills, Chronopotentiometric evaluation of membrane performances, Experientia Suppl., 18 (1971) 183. R. Audinos, F. Jacquet-Battault and M. Moutounet, Study of the variation in time of the transport properties of electrodialysis permselective membranes fouled by polyphenols of grape must, J. Chim. Phys., Chim. Biol., 82 (10) (1985) 969. E.I. Ivakina, Polarization of ion exchange membranes in the absence of convecting mixing of an electrolyte solution, Tr. Voronezh Univ. Zh. Khim., 94 (1971) 65. H.W. Boesler, F. Maletzki and E. Staude, Ion transfer across electrodialysis membranes in the overlimiting current range, J. Membrane Sci., 72 (1992) 171. N. Gnusin, V. Zabolotski, N. Shel'Deshov and N. Krikunova, Investigation of bipolar membrane MB-1 in the salt solutions by chronopotentiometry, Elektrokhimiya, 16 (1980) 49. D. Lerche and H. Wolf, Quantitative characterisation of current-induced diffusion layers at cation-exchange membranes. I. Investigations of temporal and local behaviour of concentration profile at constant current density., Bioelectrochem. Bioenerg., 2 (1975) 293. D. Lerche, Quantitative characterisation of current-induced diffusion layers at cation-exchange membranes. II. Determination of diffusion layer thickness and concentration polarisation in dependence on current density., Bioelectrochem. Bioenerg., 2 (1975) 304. N. Lakshminarayanaiah, In: Transport Phenomena in Membranes, Academic Press, New York, 1969. M.Kh. Urtenov and V.V. Nikonenko, Analysis of the boundary-value problem solution of the Nernst-Planck-Poisson equations 1:1 electrolytes, Elektrokhimiya, 29 (2) (1993) 239. J.A. Manzanares, W.D. Murphy, S. Maf6 and H. Reiss, Numerical simulation of the non-equilibrium diffuse double layer in ion exchange membranes, J. Phys. Chem., 97 (1993) 8524. R.A. Robinson and R.H. Stockes, In: Electrolyte Solutions, 2nd edn., Butterworths, London, 1959, p. 513.

A.2. Expressions of the electric field and the potential in the diffusion layers From both i = zlJl - z2J2 and Eqs. (A1 l a) and (A1 lb), we get:

[10]

[11]

i=

-Zldl

~XX-- zlce

+ z2d2

----Z2Ox + zlce

(A17) i
e =

[12] [13]

( e 1 - de)
q-

Bin(c) Ox (A18)

Zl( Zldl + z2d:)c

( Zld~ + z:d2)

[14]

Integration of the electrical field according to Eq. (19) gives the expression of the potential: i
v = -

[15]

cdl
C]o

Z l ( Z l d l - + z2d2 )

cdX
(A23)

[16]

( zldl +

In-z2d2)

c(d,
C0

[17]

References
[1] H.P. Gregor and M.A. Paterson, Electrodialytic polarization of ion-exchange membrane systems, J. Phys. Chem., 68 (8) (1964) 2201. [2] M. Block and J.A. Kitchener, Polarization phenomena in commercial ion-exchange membranes, J. Electrochem.Soc., 113 (1966) 947. [3] T. Yamabe and M. Seno, The concentration polarization effect in ion-exchange membrane electrodialysis, Desalination, 2 (1967) 148. [4] K.S. Spiegler, Polarization at ion exchange membrane-solution interfaces, Desalination, 9 (1971) 367. [5] A.A. Sonin and G. Grossman, Ion transport through layered ion exchange membranes, J. Phys. Chem., 76 (26) (1972) 3696. [6] I. Rubinstein and L. Shtilman, Voltage against current curves of cation exchange membranes, J. Chem. Soc., Faraday Trans. 2, 75 (1979) 231. [7] Y. Tanaka, Concentration polarization in ion-exchange membrane electrodialysis, J. Membrane Sci., 57 (1991) 217. [8] V.M. Aguilella, S. Mafe, J.A. Manzanares and J. Pellicer, Current-voltage curves for ion-exchange membranes. Contributions to the total potential drop, J. Membrane Sci., 61 (1991) 177. [9] M. Taky, G. Pourcelly, F. Lebon and C. Gavach, Polarization phenomenon at the interfaces between an electrolyte solution and an ion exchange membrane. Part I. Ion transfer with a

[18]

[19]

[20]

[21]

[22] [23]

[24]

[25]

P. Sistat, G. Pourcelly / Journal of Membrane Science 123 (1997) 121-131

[26] I. Rubinstein and F. Maletzki, Electroconvection at an electrically inhomogeneous permselective membrane surface, J. Chem. Soc., Faraday Trans., 87 (13) (1991) 2079. [27] V.I. Zabolotsky and V.V. Nikonenko, Electrodialysis of dilute electrolyte solutions, International Conference on Mem-

131

brane Electrochemistry, Proc. of the 20th Spring Meet., May 1994, Anapa, Russia. [28] K. Kontturi, S. Maf6, J.A. Manzanares, L. MurtomSki and P. Viinikka, Limiting currents and sodium transport numbers in Nafion membranes, Electrochim. Acta, 39 (1994) 883.