2 SIMCO
3 Laboratoire
dEtudes et de Recherches sur les Materiaux 23; rue de la MadeleineBP 136 13631 Arles Cedex; France
SUMMARY
The main features of a numerical model aiming at predicting the drift of ions in electrolytic solutions are
presented. The mechanisms of ionic diusion are described by solving the NernstPlanck system of equations.
The electrical coupling between the various ionic
uxes is accounted for by the Poisson equation. Two
algorithms using the nite element method for spatial discretization are compared for simple test cases. One
is based on the Picard iteration method while the other is based on the NewtonRaphson scheme. Test results
clearly indicate that the range of application is broader for the algorithm based on the NewtonRaphson
method. Selected examples of the application of the algorithm to more complex 1D and 2D cases are
given. Copyright ? 1999 John Wiley & Sons, Ltd.
KEY WORDS:
1. INTRODUCTION
In many engineering problems, the behaviour of porous materials is directly aected by the transport of ions under a concentration gradient. For instance, it has been shown that the swelling
of clays is predominantly controlled by the penetration of ions by diusion in their interlayer
spaces [1]. Given their in
uence on various phenomena such as the ltration by ion exchange
membranes and the transport of pollutants in soils, the mechanisms of ionic diusion in porous
media has also received a great deal of attention from chemical and geological engineers [2; 3].
The process of ionic diusion remains of primary importance in many civil engineering problems
since the longterm durability of many building materials, such as concrete, is directly aected by
the transport of chemical species [4].
Over the years, it has been established that the mechanisms of ionic diusion can be adequately
modelled by the NernstPlanck= Poisson set of equations [2; 4]. These equations take into account
the electrical coupling between the dierent ions present in an ideal solution (i.e. no chemical
activity eects are considered). According to this model, the drift of an ionic species strongly
in
uences that of all other ions dissolved in the electrolytic solution.
Correspondence to: J. Marchand, CRIBDepartment of Civil Engineering, Laval University, Quebec, Canada G1K 7P4
CCC 00295981/99/36204318$17.50
Copyright ? 1999 John Wiley & Sons, Ltd.
2044
E. SAMSON ET AL.
Although the electrical coupling between the various ionic
uxes is well known to electrochemists and engineers, most existing models aiming at describing the mechanisms of ionic
diusion tend to neglect this phenomenon [3; 5]. Furthermore, a comprehensive bibliographical
review has recently shown that the proposed analytical or numerical ionic transport models are
unsatisfactory, all of them being limited to unidimensional and steadystate cases. A summary of
this literature survey is given in the following section.
In order to extend the application of the NernstPlanck= Poisson set of equations, two algorithms
were tested. The rst one is based on the Picard iteration method. The second algorithm uses a
NewtonRaphson scheme. Both rely on the nite element method for spatial discretization.
After this comparison, selected examples of calculations are presented to illustrate the application of the second algorithm to the treatment of steadystate and transient problems involving an
important number of multivalent ionic species. An example of application of the algorithm to the
resolution of 2D cases (axisymmetrical geometries) is also given.
2. MATHEMATICAL MODEL
The NernstPlanck model, which describes the
ux of an ionic species i in solution, is given by
zi F
ci grad (V )
(1)
ji = [Di ] grad (ci ) +
RT
where ji stands for the
ux of the species i, [Di ] is the diusion coecient tensor of the species, ci
is the ionic concentration of the species, zi is the valence number of the species, F is the Faraday
constant, R is the perfect gas constant, T is the temperature, and V is the electrical potential that
is locally induced in the electrolytic solution by the movement of all ionic species.
It should be emphasized that the presence of this electrical potential is probably the most
important feature that distinguishes ionic diusion from molecular diusion. In an ionic solution,
the local electroneutrality shall be preserved at any point. The conservation of electroneutrality
requires that the transport of all diusing species should be coupled. During the diusion process,
all ions are not drifting at the same speed. Some ions tend to diuse at a higher rate. However,
any excess charge transferred by the faster ions builds up a local electric eld (Valso called the
diusion potential) which slows down the faster ions, and reciprocally accelerates the slower ionic
particles. The diusion potential has to be accounted for even in cases where an external electrical
eld is applied to the system. In that case, the diusion potential is superimposed to the external
eld.
It should also be underlined that equation (1) does not consider any chemical activity eects
or the transport of ions by convection of the liquid phase in the pore system. The in
uence of
activity phenomena on the mathematical treatment of the diusion problem is discussed elsewhere
[6]. A detailed discussion on the limits of equation (1) is given by Helerich [2].
For each of the ionic species present in solution, the mass conservation law is given by
@ci
+ div( ji ) = 0
@t
(2)
This equation does not account for any chemical or physical interactions that can develop between
the solid and the various ionic species in solution. A comprehensive discussion of the in
uence
Copyright ? 1999 John Wiley & Sons, Ltd.
2045
of chemical reactions and physical interaction phenomena on the mathematical treatment of ionic
diusion problems is given in [7; 8].
By replacing equation (1) in equation (2), one nds the complete NernstPlanck equation:
zi F
@ci
div [Di ] grad (ci ) +
ci grad (V )
(3)
@t
RT
In order to complete this system of equations, one has to dene one last relationship that will
couple the transport of all ionic species to one another. Over the past decades, numerous authors
have chosen to simplify the problem by assuming that the electroneutrality of the solution is
preserved at any points:
N
P
i=1
zi ci + w = 0
(4)
where N is the number of species and w is a xed charge density over the domain. For most
porous materials, the xed charge density is not a relevant parameter. It is, however, often used
in the description of biological systems like thin membranes.
In many cases, it is also assumed that the global
ow of all ions across the membrane yields a
nil current:
N
P
i=1
zi ji = 0
(5)
However, as will be discussed in the following section, these assumptions are not always valid.
A more rigorous way to treat the problem [2] is to dene the variation of the electric potential
according to the spatial distribution of the electric charges. This relationship is given by the Poisson
equation
2 V +
=0
(6)
where is the electrical charge density and is the dielectric constant of the surrounding medium.
The electrical charge density is a function of the concentration of the various ions in solution and
can be calculated using the following equation:
P
(7)
= F( zi ci + w)
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E. SAMSON ET AL.
on both sides of the domain. The solution was obtained using the electroneutrality and nil current
assumptions. The geometry and boundary conditions of this problem, although simple and very
idealized, still remain about the only ones for which an analytical solution is possible.
Later on, Schlogl [10], Helerich [2] and Teorell [11] developed other solutions for the treatment
of unidimensional steadystate problem. Schlogl [10] derived an analytical solution using the same
boundary conditions as Planck. Schlogls solution was developed in such a way that it could
account for any number of ions, whatever their valence number. Once again, the electroneutrality
and nil current assumptions were at the basis of the development of his solution.
The application of all previous analytical solutions was limited to steadystate cases. Always
using the electroneutrality and nil current assumptions, Conti and Eisenman [12] proposed a different solution that could be applied to the treatment of unsteadystate problems. They developed
an expression for the variation of the electrical potential through a membrane but could not obtain
neither the concentration nor the electrical potential proles. Furthermore, the validity of their
solution was solely restricted to electrolytic solutions made of monovalent ions.
It should also be emphasized that all the previous analytical solutions were developed on the
basis of the electroneutrality and nil current assumptions. In 1943, Goldman [13] presented a
solution for the steadystate case assuming a constant electric eld across the membrane (i.e. a
linear variation of the electrical potential across the system). This simplication of the problem
allowed the author to integrate directly the NernstPlanck equation.
The considerable diculty of developing analytical solutions for this system of equations has
led researchers to use numerical methods. In 1965, Cohen and Cooley [14] presented an algorithm
that allows solving the NernstPlanck equation for transient cases. Their solution was obtained
using a predictorcorrector scheme. But the predictor step uses Plancks analytical solution, thus
limiting the application of the algorithm to very simple cases.
More recently, Hwang and Helerich [15] developed an algorithm that can be used to solve the
NernstPlanck equation for any number of ions, for any valence number, and for transient problems,
with a nitedierence discretization. The discretization is not directly performed on equation (3).
The system of equations rst has to be transformed according to the electroneutrality and nil current
hypotheses. This transformation introduces two new terms that are used as iteration coecients
in the algorithm. However, after being transformed, the equations become very complex, which
makes the conversion in two or three dimensions extremely dicult. Moreover, the transformation
of the equations complicates the treatment of the boundary conditions. Patzay [16] modied the
approach by using three iteration coecients instead of two. In this case, no modication in the
treatment of the boundary conditions is required.
Harden and Viovy [17], who worked on membranes subjected to a current of variable intensity, have directly discretized the conservation equation (3) using the nitedierence method. An
explicit Euler scheme is used for time discretization. For a case with N ionic species, the concentration proles of N 1 ions are calculated using the concentration and potential calculated at
the preceding time step. For the remaining species, the concentration is calculated using the electroneutrality condition. The new electric eld is determined knowing that the current introduced
in the membrane must be equal to the internal current. The advantage of this method, compared
to all those previously described, is that it can be easily transposed in two or three dimensions.
This solution, however, still relies on the electroneutrality assumption.
All the previous numerical models are based on the assumption that the coupling of the Nernst
Planck equation with either the electroneutrality condition or the constant eld relationship yields
a reliable description of the ionic diusion mechanisms. Even if these hypotheses may constitute
Copyright ? 1999 John Wiley & Sons, Ltd.
2047
a good choice in some practical cases, Helerich [2] mentions that the Poisson equation should be
used in a more rigorous approach of the problem. MacGillivray and Hare [18; 19] have demonstrated that the electroneutrality and constant eld hypotheses are, in fact, nothing but particular
applications of the Poisson equation. The electroneutrality assumption is applicable only when the
concentrations are high while the constant eld hypothesis is rather valid for low concentrations.
Some researchers have tried to couple the NernstPlanck equation to the Poisson equation.
For instance, James et al. [20] coupled both equations to the Stokes equation to model the
ow
of a liquid containing charged particles in a cylinder. Their analysis was limited to steadystate
cases. The conservation equations were discretized using the nite element method and a Galerkin
residual weighting. The algorithm consists in solving the equations one after the other starting
from an initial concentration prole (Picard iterations), the values obtained being used as starting
points for the following iterations, until convergence is reached.
Kato [20] has proposed a numerical method to solve the NernstPlanck= Poisson system of
equations for unidimensional steadystate cases. Knowing that, once the steady state is reached,
the
uxes are constant, a rst analytical integration of the NernstPlanck equation can be performed. The solution obtained has to be discretized afterwards by the nitedierence method. The
numerical scheme used is similar to that of James et al. [20], the main dierence being that the
starting point is a potential prole, which is subsequently used to calculate the concentrations.
As can be seen, the development of numerical solutions clearly appears to be the most promising
approach for the treatment of the NernstPlanck= Poisson system of equations. It should however
be emphasized that transient problems with any number of species for 1D or 2D cases with a
nite element discretization have never been investigated. As previously discussed, all attempts to
develop numerical solutions for this set of equations were limited to simpler cases. The object of
this paper is to compare the ability of two numerical algorithms to treat complex ionic diusion
problems using the NernstPlanck= Poisson equations.
3.2. First algorithm: uncoupled equations
The rst algorithm proposed is based on the Picard iteration technique, also known as the successive substitution technique [21]. It is a rstorder method, thus having a low rate of convergence.
The algorithm is similar to the numerical resolution proposed by James et al. [22] and Kato [20],
in which the equations are solved one after another.
The equations are discretized separately following the standard nite element method. The results
are thus presented without much detail. The weighted residual form of the NernstPlanck equation
(3) over the domain
is given by
Z
zi F
@ci
div [Di ] grad (ci ) +
ci grad (V )
d
= 0
(8)
W=
@t
RT
where is the weighting function. From that point on, an axisymmetrical case with an orthotropic
material is considered. Performing an integration by parts on W yields the following weak form:
Z
Z
@ci
zi F
c
V; r
r dr dz + h ; r ; z i [Di ] i; r +
ci
r dr dz
(9)
W=
c
V
@t
RT
i;
z
;z
The boundary terms are omitted, since all the simulations will be performed considering Dirichlet
conditions. Equation (9) is discretized according to the Galerkin method. The unknown ci is
Copyright ? 1999 John Wiley & Sons, Ltd.
2048
E. SAMSON ET AL.
, according to
ci = hN i{cin }
(10)
= hN i{ n }
(11)
where hN i are the shape functions and the subscript n indicates node values. The elementary
matrices are written as
Z
[B]T [Di ] [B] + [B]T [Ei ] [N N ]r dr dz
(12)
[Kie ] =
Z
[Mie ] =
{N }hN ir dr dz
(13)
Dri zi F @V
0
RT @r
[Ei ] =
Dzi zi F @V
0
RT @z
The matrices [B] and [N N ] are dened as
@
@r hN i
[B] =
@
hN i
@z
hN i
[N N ] =
hN i
(14)
(15)
(16)
The various integrals are calculated using a Gaussian quadrature method. The terms @V=@r and
@V=@z in the matrix [Ei ] are evaluated at the integration points.
The Poisson equation is discretized using the same technique. The elementary matrices are
Z
[B]T [B]r dr dz
(17)
[K e ] =
e
P
Z
zi ci
r dr dz
(18)
{N }
{F e } =
e
Z
w
e
{Fs } =
(19)
{N } r dr dz
e
where {Fse } is the solicitation vector coming from the xed charge density w. The concentrations
in equation (18) are calculated at the integration points.
The resolution steps for a steadystate problem are presented. For a transient problem, a standard
method [21] could be used.
1. An initial concentration is assumed for each ionic species.
2. The Poisson equation is solved using the concentration of the previous iteration level.
3. A loop is performed on all the ionic species:
(a) The gradient potential is calculated on the integration points from the numerical solution
of the Poisson equation. The results are used to build the matrix [Ei ].
Copyright ? 1999 John Wiley & Sons, Ltd.
2049
(b) The solution of the NernstPlanck equation is obtained for the species i using the elementary matrices (12) and (13).
4. The L2 norm of the vector u = hc1 c2 : : : V ik hc1 c2 : : : V ik1 is calculated where k stands
for the iteration level.
5. If the norm is higher than a tolerance threshold , go back to step 2 by using the concentration
just calculated. The loops are performed until convergence is reached.
The main advantage of this algorithm is that the same calculation code can be used, whatever
the number of ionic species. Only the number of loops (step 3) is dierent.
3.3. Second algorithm: coupled equations
In the second algorithm, the NernstPlanck and Poisson equations are coupled and solved simultaneously. A classical NewtonRaphson method [21; 23] is used to solve the nonlinear set of
equations. As it is a secondorder scheme, convergence is expected to be faster than what is
obtained for Picard iteration method. Once again, the discretization follows the standard nite
element procedure.
The weighted residual form is written as [23]
Z
R1
h1 2 : : :i R2 d
= 0
(20)
W=
..
.
where the Ri s are the residuals associated to each of the equations and the i s are the corresponding weighting functions. For each of the ionic species, the residual is
@ci
zi F
Ri =
div [Di ] grad (ci ) +
ci grad (V )
(21)
@t
RT
and for the Poisson equation,
F P
( zi ci + w)
(22)
For a case limited to ionic species, the integration by parts leads to the following weak form:
Z
c1
W = hc1 c2 V i c2 r dr dz
Dr1 z1 F
c
c
+
V
D
r1 1; r
1 ;r
RT
D
z
F
z1
1
D c +
c1 V; z
z1 1; z
RT
Dr2 z2 F
c
D
c
+
V
r2
2;
r
2
;
r
r dr dz
+ hc1; r c1; z c2; r c2; z V; r V; z i
RT
D
z
F
z2 2
c2 V; z
Dz2 c2; z +
RT
;r
V; z
RV = 2 V +
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E. SAMSON ET AL.
Z
hc1 c2 V i
1
1
r dr dz
F
z 2 c2
0
r dr dz
(23)
+ hc1 c2 V i
F w
The weak form is discretized using a Galerkin weighting. The vector of the unknown variables
is written as
c1
c2
= [N ]{Un }
(24)
..
N2
NG
N1
N1
N2
NG
(25)
[N ] =
..
..
..
.
.
.
N2
NG
N1
+
(26)
where G is the number of nodes in the element. The small dots (: : :) indicate the terms to add
when considering more ionic species, whereas the big dots ( ) stand for the missing shape
function terms. The subscripts i and j designate the species i and the node j. The elementary
matrices can thus be expressed as
T
[B] [D1 ][B] + [N ]T [D2 ] [N ] + [B]T [D3 ] [N N ]r dr dz
(27)
[K e ] =
{z
} 
{z
} 
{z
}

e
e
[KDe ]
[KPe ]
KNP
Z
[N ]T [D4 ][N ]r dr dz
(28)
[M e ] =
0
..
r dr dz
(29)
[N ]T
{F e } =
.
Fw
The matrix [K e ] is divided into three parts. The rst part, KDe , includes all the diusion terms. The
two other parts
are related to the coupling between the concentration and the electrical potential.
The matrix KPe comes from the discretization of the Poisson equation (the third line in equation
e
(23)) and KNP
is related to the coupling between the concentration and the electrical potential
Copyright ? 1999 John Wiley & Sons, Ltd.
2051
N2
NG
N1
N1
N
NG
2
N1
N2
NG
N
N
NG
1
2
[N N ] =
..
..
.
.
N2
N1
N1
N2
For an axisymmetrical case, the matrix [B] corresponds to
NG; x
N1; x
N1;y
NG;y
N1; x
NG; x
NG;y
1;y
[B] =
..
N1; x
N1;y
The matrices [D1 ][D4 ] are given by
Dr1
[D1 ] =
..
NG
NG
(30)
..
NG; x
NG;y
(31)
Dz1
Dr2
Dz2
..
(32)
[D2 ] =
Dr1 z1 F @V
RT @r
[D3 ] =
0
0
..
.
Fz1
Dz1 z1 F @V
RT @z
Fz2
(33)
Dr2 z2 F @V
RT @r
Dz2 z2 F @V
RT @z
..
.
0
(34)
0
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2052
E. SAMSON ET AL.
[D4 ] =
1
..
(35)
0
The tangent matrix is obtained by calculating the rst variation of the weak form W (Equation
(20)) [23]:
R1
(36)
W = h1 2 : : :i R2 d
= 0
..
.
For a transient case solved with an implicit Euler scheme ( = 1), the elementary tangent matrix
is given by
Z
e
e
e
[BT ] [D5 ] [B] r dr dz
(37)
[KT ] = [M ] + t[K ] + t
where
[D5 ] =
:::
Dr1 z1 F
c1
RT
0
Dr2 z2 F
c2
RT
0
..
.
0
0
Dz1 z1 F
c1
RT
Dz2 z2 F
c2
RT
..
0
0
(38)
In contrast to the preceding numerical scheme, the characteristics of the various matrices vary
with the number of ionic species accounted for. Furthermore, larger matrices have to be stored.
V=
(39)
(40)
Int. J. Numer. Meth. Engng. 46, 20432060 (1999)
Di = D i D0
2053
(41)
c0 D0
j
L i
ci = c0 ci
ji =
(42)
(43)
where the subscript 0 designates a reference value and L is the length of the domain. Equations (1) and (6) are rewritten as
Di d ci
Di d V
zi ci
(44)
ji =
D0 d x
D0 d x
d 2 V
+ 2 =0
2
d x
(45)
with
RT
c0 F 2 L2
P
= zi ci + (w=c0 )
2 =
(46)
(47)
2054
E. SAMSON ET AL.
Figure 2. First algorithm: norm vs. number of iterations for dierent values of 2
{u}k1 + {u}k2
2
(48)
This modication allowed us to break the 025 limit, but only to nd the same problem for a
value of about 015. For such values of 2 , only thin membrane problems can be solved. This is
what justied the development of the coupled equation algorithm, in an attempt to broaden the
eld of application of the NernstPlanck= Poisson set of equations.
4.2. Results obtained with the second algorithm
The same tests were carried out for the second algorithm, and proved to provide much better
results. For the second algorithm, there is no evidence of a critical value of 2 for which divergence
occurs. The number of required iterations is lower and limited to approximately four. Furthermore,
this number varies very little according to 2 .
Copyright ? 1999 John Wiley & Sons, Ltd.
2055
To illustrate the superior behaviour of the second algorithm, the same problem was solved,
but this time with 2 = 00001. The results are shown in Figure 3, and were obtained with 100
elements. More elements are needed to avoid oscillations near the boundaries, due to high gradient
values. Comparisons with the results of Kato [20] are impossible since the author did not perform
any tests for low values of 2 .
Following these results, it is clear that the second algorithm is much more robust. It was used
to obtain the results that will be presented afterwards.
Various other cases were considered to test the second algorithm. The rst example was inspired
from Helerich [2]. It consists in a 1D steadystate problem where four species are present:
+
+
Mg2+ , SO2
4 , Na and K . Dimensionless variables were used in the treatment of the problem.
2+
The diusion coecients were 10 for SO2
and Na+ , and 167 for K+ . At x = 0, the
4 , Mg
2
2+
boundary conditions were 10 for SO4 , 05 for Mg and zero for the other species. At x = 1,
2+
+
+
the conditions were 08345 for SO2
4 , 00 for Mg , 0169 for Na and 05 for K . The potential
was established at 00 at x = 0 and 50 at x = 1. The xed charge density in the membrane, w=c0 ,
was equal to 10. The only remaining unknown variable was the value of 2 .
The solution obtained analytically by Helerich [2] for that same problem was developed on
the basis of the electroneutrality hypothesis. Considering that MacGillivray and Hare [18; 19]
have demonstrated that the validity of this assumption is restricted to very low values of 2 , the
calculations were performed with 2 = 1 1010 .
The solution, computed with 50 elements, is shown in Figure 4. The dierence with the analytical
solution presented by Helerich [2] is about 3 per cent, which conrms the results of MacGillivray
and Hare [18; 19] concerning the value of 2 .
The other example concerns a transient diusion problem. It was selected to evaluate the in
uence of the 2 parameter for a xed length domain. The calculations were performed using
an implicit Euler scheme. The dimensionless variables were once again used with the addition
of t= D0 t=L2 as a time variable. Two species were considered, with z1 = + 1 and D 1 = 3 for the
rst one, and z2 = 1, D 2 = 1 for the second. Initially, the concentrations were set equal to zero
over the entire domain, which consisted of a bar of length 1. At t= 0, a unit concentration was
imposed at x = 0 for both species. The concentrations were set at zero at x = 1.
Copyright ? 1999 John Wiley & Sons, Ltd.
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E. SAMSON ET AL.
Two simulations were performed for values of 2 equal to 1 102 and 1 104 respectively.
This implies that, for a given domain length, the concentrations involved in the second case were
a hundred times higher than in the rst one. Results are given in Figures 5 and 6. These results
were obtained at t= 001 and reached after 200 steps of 5 105 . All calculations were performed
with 50 elements. As a comparative basis, the solutions computed without taking into account any
electrostatic eect, thus derived on the sole basis of Ficks law, are also given in Figures 5 and 6.
In Figure 5, the in
uence of the electrical coupling between the species is clearly noticeable.
On the one hand, results indicate that the progression of the fastest ion is slowed down by the
electrical potential. On the other, the slowest ion, with a diusion coecient being three times
lower, is accelerated. In the case of higher concentration (Figure 6), this phenomenon is even
more obvious. Both concentration proles are so close that they became superposed.
These results conrm, once more, the conclusion of MacGillivray and Hare [18; 19], who suggested that the electroneutrality is gradually approached as the value of 2 decreases. Figure 7
shows that the electrical charge density tends toward zero as 2 is reduced.
Copyright ? 1999 John Wiley & Sons, Ltd.
2057
The last example shows the use of this numerical scheme for a transient problem with an
axisymmetrical geometry. The simulations were performed to investigate the eect of the presence
of electrical charges on the inner surface of a pore. In this case, ions are diusing in and out of
the pore space. The pore, presented in Figure 8, has a radius of 1 m and a length of 10 m.
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E. SAMSON ET AL.
the electrical potential on the inner surface of the pore was set equal to 10 mV as shown in
Figure 8. The system was considered to remain in isothermal conditions (i.e. at 22 C ) over
the entire duration of the process. The dielectric constant of the system was xed at 70823
1010 C=V m. The two simulations were performed in ve time steps of 00002 s. For the spatial discretization, a regular mesh of 10 50 linear threenode triangles was used, as shown in
Figure 8.
According to the numerical simulations, the potential on the inner surface of the pore has no
signicant eect on the concentration proles. Its in
uence is limited to a small region at the
vicinity of the surface. Hence, the
ux of ions in the pore is the same for both simulations.
For the electrical potential, the situation is however dierent. The potential on the inner surface
tends to lower the dierence of potential between both ends of the pore. For the case without any
electrical charges on the pore wall, this dierence has a value of 5 mV. In the other case, this
value drops to 31 mV.
Copyright ? 1999 John Wiley & Sons, Ltd.
2059
5. CONCLUSION
The comparison between a numerical scheme based on the Picard iteration technique and another
scheme based on the NewtonRaphson method has clearly showed that the former, even though it
has already been used in some recent papers, cannot be used to solve the NernstPlanck= Poisson
system of equations for all cases.
By coupling all the equations and using the NewtonRaphson method, the NernstPlanck= Poisson
system of equations could be solved for problems with a high number of ionic species with dierent valence number, either for steady state or transient cases. Furthermore, the numerical scheme
works for 1D geometry as well as 2D and axisymmetrical ones, and could easily be extended
for 3D cases.
This work opens the way for the treatment of complex multiionic species models of transport
in porous media involving chemical reactions between the species and the solid matrix, while
considering the electrical coupling.
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