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Abstract
The membrane potential, the pressure difference, and the concentration difference induced by an applied concentration gradient through samples
of compact clay were measured as functions of sodium chloride concentration and of porosity. The results of some previous numerical predictions
are recalled to be functions of a characteristic length scale which can be derived from conductivity and permeability. Generally, the experimental
data were in agreement with these numerical predictions. Therefore, nondiagonal coupling coefficients can be derived with acceptable precision
from the diagonal coefficients.
2005 Elsevier Inc. All rights reserved.
1. Introduction write
The ability of clay soils to act as “perfect” or “ideal” mem- I = γ11 · E + γ12 · (−∇P ) + γ13 · (−∇n), (1a)
branes that inhibit the passage of electrolytes is of great value U = γ21 · E + γ22 · (−∇P ) + γ23 · (−∇n), (1b)
for some possible storage of toxic wastes. Clays exhibit mem-
brane properties when charged ionic species are excluded from Jd = γ31 · E + γ32 · (−∇P ) + γ33 · (−∇n), (1c)
the pores, while uncharged species have a relatively free move- where k is the Boltzmann constant (=1.38 × 10−23 m2 kg
ment. s−2 K−1 ). A distinction is generally made between the diago-
The major purpose of this work was to experimentally de- nal phenomenological coefficients γij with i = j , and the non-
termine the coefficients which characterize coupled transports diagonal ones with i = j . Because of the Onsager symmetry
in compact clays and to compare them to some numerical pre- properties, the nondiagonal coefficients are not all independent.
dictions derived by [1,2] for various kinds of porous media. A literature search shows that measurements of these co-
More precisely, consider a porous medium filled by an elec- efficients for clays (and especially for compact clays) were
trolyte solution with a concentration n (defined as the number not frequently performed. Interesting contributions concerning
of molecules per m3 ). When a pressure gradient ∇P , an electric electrokinetic coefficients were made by Kemper and Quirk [4],
field E and a concentration gradient ∇n are simultaneously ap- Elrick et al. [5], Groenvelt et al. [6], and Sherwood and Cras-
plied to the porous medium, three fluxes are generated, namely, ter [7]. A recent review of all of these coefficients was written
a flow characterized by the seepage velocity U (m s−1 ), a solute by Horseman et al. [8].
flux Jd which is the number of molecules per unit surface and This paper is organized as follows. Section 2 summarizes the
per unit time (m−2 s−1 ) and a current density I (A m−2 ). Close theoretical determination of the coupling coefficients. The lo-
to equilibrium, when gradients are not too large, the problem is cal transport equations corresponding to the electrical potential,
linear and fluxes are proportional to these gradients (see [3]). the ionic concentrations, and the velocities are the Poisson–
Then, with respect to the solvent-fixed reference plane, one can Boltzmann, the convection–diffusion, and the Stokes equations,
respectively. Numerical results for various porous media corre-
* Corresponding author. spond to the analytical solutions valid for circular Poiseuille
E-mail address: adler@ipgp.jussieu.fr (P.M. Adler). flows when the capillary radius is replaced by a suitable length
0021-9797/$ – see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.10.026
354 M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364
scale. The material, the experimental procedure and the data are Marino et al. [2] (and references therein),
described in Section 3. Two samples of argilite extracted from
γ11 µe2
a Callovo–Oxfordian formation were characterized. Section 4 γ11 =
is devoted to the analysis of the effective diffusion coefficient, (el kT κ)2
osmotic coefficient and coefficient related to “membrane poten- 1 ζ
= D1 + D2 − D1 − D2 I1 (κRc )
tial.” Results are considered as functions of solute concentration 2 κRc I0 (κRc )
and porosity in isothermal conditions. Data relative to the elec-
λ
trokinetic coefficients are compared to numerical and analytical + 2ζ 3
− I1 (κRc ) , (6a)
κRc I0 (κRc )
results derived by [1,2]. The paper ends with some concluding
γ21 µ 2I1 (κRc )
remarks. γ21 = = γ 12 = ζ − 1 , (6b)
el ζ Kκ 2 κRc I0 (κRc )
γ13 µe I1 (κRc )
2. Theoretical background γ13 = 2
= D1 − D2 − 2ζ D1 + D2 ,
el (kT ) κRc I0 (κRc )
2.1. Analysis on the pore scale (6c)
γ23 µκ 2 2I (κR )
= 4ζ
1 c
γ23 = −1 , (6d)
The coefficients γij defined by (1) can be derived by ana- kT κRc I0 (κRc )
lyzing the phenomena on the pore level. Such an analysis was
γ33 µe2 1 I1 (κRc )
performed in [2]. If no temperature gradient is imposed on γ33 = 2
= D1 + D2 − ζ D1 − D2 ,
el (kT ) 2 κRc I0 (κRc )
the medium, the transport is governed by three types of cou-
(6e)
pled equations. First, the concentration ni (R, t) of each ith ion
species is the solution of a convection–diffusion equation where κ −1 is the Debye–Hückel length. The dimensionless val-
ues γij (i, j = 1, . . . , 3) are defined by the first equalities and
∂ni Di marked with a prime.
+ ∇ · −Di ∇ni − ezi ni ∇ψ + ni u = 0,
∂t kT It is important to note that most numerical results obtained
i = 1, 2, . . . , N, (2) for various types of porous media were shown to be very close
to the analytical results (6) when the radius of the tube is re-
where t is the time, Di the diffusion coefficient of ion i, e the
placed by the characteristic length Λ , defined by
absolute value of the electron charge, zi the valency, ψ the elec-
tric field, and u the fluid velocity. N is the number of ionic 12.5Kσ ∞ 1/2
species; it is equal to 2 in this paper. Λ = , (7)
σ
Since the Reynolds number is in most cases much less than
unity, u and the pressure P (R, t) are governed by modified where σ ∞ is the fluid conductivity, σ the macroscopic conduc-
Stokes equations, tivity of the medium filled by the electrolyte, and K the perme-
ability of the porous medium. The definition of this length scale
∇ · u = 0, µ∇ 2 u = ∇P + ρ∇ψ, (3) was inspired by the length scale Λ introduced by [9]. Note that
Λ is homogeneous to a length. The use of Λ was already ex-
where µ is the fluid viscosity and ρ the charge density. perimentally justified for electroosmotic phenomena in [10].
Finally, ψ(R, t) is the solution of the Poisson–Boltzmann Therefore, the major purpose of this work is to check this
equation property with data obtained for compact clays.
e
N
ρ
∇ 2ψ = − =− ni zi (4) 2.2. Analysis on the macroscopic scale
el el
i=1
where el is the fluid permittivity. Consider now an experiment performed on a porous sam-
ple of thickness 2l and cross-sectional area S separating two
To be solved, the set of Eqs. (2)–(4) is subject to the bound-
compartments each of volume V filled by aqueous solutions at
ary conditions on the solid/fluid interface Si
different concentrations n10 and n20 of the same electrolyte.
ν · ji = 0, u = 0, and ψ = ζ, (5) The system of Eqs. (1a)–(1c) must be completed by the one
dimensional continuity equations
where ν is the outward normal to the solid surface, and ζ the
zeta potential. ∂I
= 0, (8a)
These equations were linearized around equilibrium, made ∂x
dimensionless, and solved by [2] (and the references therein) ∂
· U = 0, (8b)
for spatially periodic porous media. The coefficients γij (i, j = ∂x
1, . . . , 3) can be derived by integrating the local fields over the ∂n ∂
+ · JL = 0. (8c)
unit cell. ∂t ∂x
The only cases which can be solved analytically, are the ones The initial concentrations are
of a plane channel or of a circular tube of radius Rc . Let us recall
the coefficients given in the latter case by Coelho et al. [1] and n(x = −l, t = 0) = n10 , n(x = l, t = 0) = n20 . (9)
M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364 355
In addition, we used the boundary conditions at x = ±l Neither ω nor τ depends on the formation factor F . However,
∂n it is important to note that ω is a nondimensional parameter,
±a = JL , (10a) whereas τ is expressed in A−1 s−1 m3 .
∂t
We interpreted ω by considering the flow of solvent to be a
P = Pa , (10b)
consequence of the interplay of the applied concentration gra-
where Pa is the atmospheric pressure and the parameter a is dient of the solute and the interaction forces between the solute
defined as and the charged pore surfaces, which causes both the pressure
V gradient and the electrical field [11]. When the clay is a “per-
a= . (11) fect” or “ideal” membrane, i.e., totally impermeable to the
S
solute, ω is unity and the solute flux is equal to zero. For a clay
Let V be the common volume of the two reservoirs and S
that is completely permeable to the solute, ω = 0. However, in
the cross section of the porous medium.
most real systems, the solute permeates the clay to some ex-
tent and ω falls within the range 0 < ω < 1. Thus, the clay is
2.2.1. General case where U (t) = 0
considered as a “nonideal” membrane [12].
Let us assume that the processus is mostly one-dimensional,
The degree to which the clay prevents ions from entering
along the x-axis.
into the pore space is termed its “efficiency.” Hence, if a clay is
Since no external electric field is applied and since both solu-
an ideal membrane, its efficiency is 100%.
tions in the reservoirs are insulated from each other, the current
Moreover, substitution of Eqs. (16) and (17), after rearrange-
density derived from (8a) is equal to zero,
ment with relations (18a) and (18b), into Eqs. (1b) and (1c)
I (t) = 0. (12) yields the set of coupled equations
Therefore, Eq. (1a) can be written as ∂P ∂n
U = −K + 2kT ωK , (19a)
∂ψ γ12 ∂P γ13 ∂n ∂x ∂x
=− − . (13) ∂n
∂x γ11 ∂x γ11 ∂x Jd = D̄ − − nωU, (19b)
∂x
Integrating Eqs. (13) and (1b) along the x-direction and as-
where K is given by
suming as a first approximation that the coefficients γij do not
depend on x yields γ12 γ21
K = γ22 − . (19c)
γ12 γ13 γ11
ψ = − P − n, (14a)
γ11 γ11 D̄, which was called the dispersion coefficient in [6], is defined
lU (t) = −γ21 ψ − γ23 n. (14b) by
With the help of Eqs. (1a) and (1b), one obtains D̄ = (γ33 − nτ γ13 ) + nωγ23
∂ψ ∂P ∂n = (γ33 − 2kT τ γ31 ) + 2kT ωγ32 . (19d)
γ11 + γ12 = −γ13 , (15a)
∂x ∂x ∂x K contains the contribution of self-induced electroosmosis
∂ψ ∂P ∂n
γ21 + γ22 = −U (t) − γ23 . (15b) to the water flow. D̄ contains the effect of salt sieving formu-
∂x ∂x ∂x lated by ωγ32 , due to the presence of a hydrostatic pressure
Rearrangement of Eqs. (15a) and (15b) yields the follow- difference and the contribution to Jd of self-induced electrod-
ing expressions for the electrical potential gradient ∂ψ
∂x and the iffusion, formulated by τ γ31 . Recall that an ideal membrane
pressure gradient ∂P
∂x in terms of the concentration gradient and completely prohibits the passage of solutes. Thus, by definition,
seepage velocity, D̄ must approach zero for an ideal membrane.
The governing one-dimensional partial differential equation
∂ψ (−γ13 γ22 + γ12 γ23 ) ∂x
∂n
+ γ12 U is obtained by substituting Eq. (19b) into the mass balance ex-
= , (16)
∂x γ11 γ22 − γ12 γ21 pression (8c),
∂P (−γ13 γ21 + γ11 γ23 ) ∂x
∂n
+ γ11 U
=− . (17) ∂n ∂ ∂n
∂x γ11 γ22 − γ12 γ21 + D̄ − − nωU = 0. (20)
∂x ∂x ∂x
The membrane behavior of the clay, i.e., its ability to be par-
tially or totally impermeable to the solutes, is generally quan- 2.2.2. Special case where U (t) = 0
tified by two parameters ω and τ , commonly referred to as the Since the electric current through the pore must be zero in
“reflection coefficient” and the “charge fluidity,” respectively. the absence of any externally applied electrical field and since
They are defined as (see [6]) U (t) is assumed to be zero, Eqs. (15a) and (15b) reduce to
1 P 1 γ21 γ13 − γ23 γ11 ∂ψ ∂P ∂n
ω= = , (18a) γ11 + γ12 = −γ13 , (21a)
2kT n I =0,U =0 2kT γ22 γ11 − γ12 γ21 ∂x ∂x ∂x
1 ψ 1 γ22 γ13 − γ23 γ12 ∂ψ
+ γ22
∂P ∂n
= −γ23 .
τ =− = . (18b) γ21 (21b)
2kT n I =0,U =0 2kT γ22 γ11 − γ12 γ21 ∂x ∂x ∂x
356 M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364
σ γ12 γ13
γ11 γ12 γ13 tivity measurements made with a pair of platinum electrodes
γ21 γ22 γ23 = γ12 K
µ γ23 . (26) related to a Consort P407 conductimeter by means of a cali-
γ31 γ32 γ33 n n
2kT γ13 2kT γ23 γ33 bration curve. The voltage across the reversible Ag/AgCl elec-
trodes was measured using a Keitley 175A multimeter (from 1
3.1. Materials to 200 mV full scale). We observed an asymmetry potential of
about 0.5 mV between the electrodes when zero concentration
The material, supplied to us by ANDRA, is a compact was imposed across the clay. We treated this potential as an ex-
argilite extracted in east France from a Callovo–Oxfordian for- perimental error. The hydrostatic pressure difference between
mation. The wellbore, referred to as EST104, was sampled at both sides of the clay sample was measured continuously with
two different levels, 483.6 m (EST104/2364) and 505.15 m a Kimo 25 differential pressure transducer (from 0 to 600 Pa
(EST104/2487). Both cores were used to obtain powder or solid full scale). Solute conductivity σf , voltage differences ψmeas ,
cylinders of thickness 3 mm and diameter 12 mm. A SEM and pressure difference P were measured once a day.
analysis of the argilite powder shows a heterogeneous compo-
sition; owing to the careful crushing process to obtain powder 3.3. Ag/AgCl electrodes
from the original block, the average grain radius ranges from
1 to 10 µm. The cation exchange capacity (CEC) of argilite 3.3.1. Electrode potential
was found (data from ANDRA) to be 25 meq 100 g−1 for The absolute potential ψm/s of an electrode is defined as
EST104/2364 and 17 meq 100 g−1 for EST104/2487. the potential difference between the metal (m), when immersed
M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364 357
ψm/s = ψm − ψs . (28)
One cannot measure the equilibrium potential of a metal
with respect to a given solution, but only the potential difference
between the metals (m1) and (m2) of two electrodes immersed
in the same solution,
(a) (b)
(c)
Fig. 3. A typical example of the evolution with time of the measured parameters: (a) C = C1 − C2 , (b) P , (c) ψ(=ψmeas − ψN ). (!) obtained by
subtracting from the measured potential difference ψmeas (∗) the electrode potential difference ψN (1).
(a) (b)
In the limit of extremely low concentration, the co-ions are almost the entire pore volume is electrically neutral. Thus, the
almost completely excluded from the pores, because of the large potential that arises across the medium is nothing but the “free
double-layer repulsion. Therefore, assuming ideal behavior, diffusional potential” given by
kT
ψmax = − ln(C1 /C2 ) = −2.57 × 10−2 ln(C1 /C2 ). (37) kT D1 − D2
e ψmin = − ln(C1 /C2 )
e D1 + D2
On the other hand, in the limit of large concentrations, the
electrical double layers formed in the pore are compressed and = 5.18 × 10−3 ln(C1 /C2 ), (38)
M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364 359
where D1 and D2 are the diffusion coefficients in a free medium To take into account the dependence of ψ on C1 /C2 , C̄,
of cations and anions, respectively. and , ψ/ ln(C1 /C2 ) is plotted in Fig. 6 as a function of κΛ
In the intermediate concentration range, the induced poten- for both samples EST104/2487 and EST104/2364. The accu-
tial has values between the two former limits. racy on ψ/ ln(C1 /C2 ) is about 10–30%.
Generally, the membrane potential ψ can be expressed in Results seem to be independent of the clay sample, but de-
terms of the transference number t± of the cations (t+ ) and the pend on C1 /C2 and C̄. |ψ| increases as C1 /C2 increases.
anions (t− ) as follows: ψ/ ln(C1 /C2 ) displays asymptotic behavior at large and
kT small κΛ , while it varies quite rapidly in the intermediate range
ψ = − (t+ − t− ) ln(C1 /C2 ). (39) of κΛ . With increasing κΛ , ψ/ ln(C1 /C2 ) increases and be-
e
The transference number t+ (=1 − t− ) can be deduced from comes positive for κΛ ≈ 7.
the quotient of ψm and ψN [15], The two former limits are plotted in Fig. 6. The membrane
1 ψm potential tends to the free diffusional potential at large κΛ ,
t+ = . (40) indicating that ψ is only related to the diffusion difference be-
2 ψN
tween anions and cations. The surface effects do not influence
The transference number t + gives information about the solute diffusion and the clay efficiency is close to zero. More-
ability of a medium to restrict solute transport. For a nonse- over, for κΛ < 7, the negative sign of ψ indicates that the
lective medium, t + is equal to 0.4 for NaCl. However, if there double layer effects play a role. The clay efficiency increases as
is a total exclusion of ions from the pores, t + is equal to 1. κΛ decreases. The lowest value of κΛ obtained experimen-
In Fig. 5, we display the induced potential ψ of samples tally is equal to 0.51 with an associated value of ln(Cψ equal
EST104/2487 and EST104/2364 as functions of the initial con- 1 /C2 )
−2
to −1.35 × 10 V, which corresponds to a clay efficiency of
centration ratio C1 /C2 and the porosity for different average
concentrations C̄. Results seem to be independent of the clay
sample, but depend on C1 /C2 , , and C̄. |ψ| increases as
C1 /C2 increases.
For C̄ > 10−3 mol l−1 , the dependence of ψ on C1 /C2 can
be approached by a logarithmic relation (see Fig. 5a),
ψ = 5.07 × 10−3 ln(C1 /C2 ). (41)
This relation is very close to relation (38), indicating that ψ is
only related to the diffusion differences of anions and cations.
Therefore, there is no anionic exclusion.
For C̄ < 10−3 mol l−1 , the negative sign of ψ indicates
that the double-layer effects play a role. The dependence of ψ
on C1 /C2 can also be approximated by a logarithmic relation,
ψ = −6.3 × 10−3 ln(C1 /C2 ), (42)
with a correlation coefficient r equal to 0.7. Such a bad value of Fig. 6. ψ/ ln(C1 /C2 ) as a function of κΛ . Data are for EST104/2487 (")
r can be explained by experimental errors; moreover, porosity and EST104/2364 (2). Solid line: Eq. (44). The broken lines are the two limits
is varying slightly in these experiments, as shown by Fig. 5b. corresponding to Eqs. (37) and (38).
(a) (b)
Fig. 5. The induced potential ψ as a function of C1 /C2 (a) and of (b) for various C̄. Data are for EST104/2487 for C̄ > 10−3 mol l−1 (") and C̄ < 10−3
mol l−1 (!); EST104/2364 for C̄ < 10−3 mol l−1 (1) and C̄ > 10−3 mol l−1 (2).
360 M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364
60%. The clay efficiency E is defined by The agreement between predictions and experiments is good
for large κΛ , except for some experimental errors. The analyt-
(ψ − ψmin )
E= × 100. (43) ical results display asymptotic behaviors both at very low and
(ψmax − ψmin ) very large κΛ . The minimum close to 0.4 indicates no surface
As it is very difficult experimentally to obtain values of κΛ effects, and thus E = 0. The maximum close to 0.88 indicates
lower than 1, we cannot conclude that this value corresponds to a maximum efficiency E = 80%.
the maximum efficiency.
In order to estimate the maximum efficiency, we have also 4.2. Transport coefficients
displayed in Fig. 6 the analytical values of ψ/ ln(C1 /C2 ).
Analytical values were obtained by integrating Eq. (13) and In the present experimental setup, the seepage velocity u(t)
writing it in a dimensionless form, is forced to be zero. Moreover, since there is no externally ap-
plied electrical field and since the electrical circuit is open, the
current density I (t) is equal to zero.
ψ kT 1 γ13
=− . (44) In this section, attention is focused on the coefficients related
ln(C1 /C2 ) e 2 γ11
to the concentration gradients, namely γ13 (γ31 ), γ23 (γ32 ), and
The method for deriving the coefficients γ13 and γ11 will be γ33 .
explained in the next section. The values of the γ13 and γ23 coefficients were calcu-
Fig. 6 indicates qualitative agreement between analytical ψ
lated from the experimental constant values P C and C using
predictions and experiments. When compared with the numer- Eqs. (21a) and (21b),
ical value for κΛ = 0.51, for example, the experimental value
P ψ
of ψ/ ln(C1 /C2 ) is underestimated by about 20%. However, γ13 = −γ12 − γ11 , (46a)
the minimum and the maximum seem to correspond to the ex- n n
perimental values. Therefore, the analytical results help us to P ψ
γ23 = −γ22 − γ21 . (46b)
conclude that the maximum value of ψ/ ln(C1 /C2 ) reached n n
for κΛ ≈ 0.4 is close to −1.84 × 10−2 V, which corresponds to The coefficients corresponding to electrokinetic phenomena,
a maximum efficiency of 77%. Argilite only partially restricts namely γ11 , γ22 , and γ21 (or γ12 ), were measured separately in
the passage of NaCl and it cannot be considered as an “ideal another series of experiments described in [17].
membrane,” as can be expected for natural clays. Next, γ33 was derived from Eq. (23) when D̄ is known. The
The cation transference number t + in both clay samples is measured concentration difference C(t) yields D̄ by means
plotted as a function of κΛ in Fig. 7. The same comments as of an elementary program described in [13].
for ψ can be made. t+ decreases from 0.75 to 0.4 when κΛ
increases from 1 to 30. For large κΛ , t+ is equal to 0.4, i.e, 4.2.1. Analysis of γ13 and γ31
essentially the same as in the bulk solution, indicating that E The coefficient γ13 , related to the membrane potential ψ,
is equal to zero. For the small experimental values of κΛ , i.e., can be analyzed more precisely with the help of (6) in order to
1, t+ reaches a value of 0.75. Again, the experimental values eliminate the bulk effects; it may be written in dimensionless
were compared to the values obtained by combining Eqs. (39) form as
and (44),
γ13 γ13 (ζ = 0)
1
α13 =
−
1 1 γ13 D̄1 − D̄2 D̄1 − D̄2 ζ
t+ = 1 + . (45)
2 2 γ11 (D1 + D2 ) I1 (κΛ )
= −2 (47a)
(D1 − D2 ) κΛ I0 (κΛ )
with
Di
D̄i = , i = 1, 2. (47b)
F
by (D − D ) and by the electric for-
Hence, division of γ13 1 2
mation factor F cancels the influence of the molecular diffusion
coefficients and of the restricted geometry, respectively.
as a function of κΛ and compares exper-
Fig. 8 displays α13
imental results to the analytical solution for circular Poiseuille
flows. The experimental data are seen to cluster around the an-
alytical expression. By standard techniques, the experimental
errors on κΛ and α13 are estimated to be equal to 46 and 60%.
only geometric effects are taken into account. Moreover, in the surface effects influences D̄ by generating electroosmosis and
free medium D2 > D1 . Therefore, the best comparison of γ33 electrodiffusion. Moreover, as shown in Fig. 12, the comparison
with analytical results is obtained when Eq. (50) is modified as with analytical data is qualitatively successful.
γ33 γ33
1 I1 (κΛ ) 4.3.2. The conversion efficiency
α33 = − ζ = 0 = . (51)
D̄1 D̄1 ζ κΛ I0 (κΛ ) Let us follow the development of Gross and Osterle [16] con-
The experimental values of α33 and the analytical expression cerning the conversion efficiency of the clay. The maximum
(51) are displayed in Fig. 11 as functions of κΛ . For large κΛ , value of the conversion efficiency ηij is related to the “figure
approaches zero indicating that the anionic mobility (i.e.,
α33 of merit” βij by
increases
Cl− ) has a negligible effect on γ33 . For small κΛ , α33 (1 + βij )1/2 − 1
up to 1, indicating that surface effects delay the cation diffusion. (ηij )max = , (55)
(1 + βij )1/2 + 1
4.3. Discussion where βij is given by the relationship
−1
γii γjj
4.3.1. The dispersion coefficient βij = −1 . (56)
γij γj i
Relation (19d) can be made dimensionless as
Equations (1a)–(1c) imply that there are three dissipative
D̄ γ32 γ31 processes coupled together in clay. They are osmosis, elec-
D33 = − 1 = 2kT ω −τ . (52)
γ33 γ33 γ33 troosmosis, and electrodialysis, described by β23 , β21 , and β31 ,
Since ω is close to zero, the first term on the right-hand side respectively. The results are displayed in Fig. 13 as functions of
of (52) is negligible; therefore, κΛ together with the analytical data.
In osmosis, the maximum value of β23 is close to 0.006, cor-
γ31
D33 = −2kT τ . (53) responding to a maximum efficiency of 0.2% for κΛ ≈ 1.7.
γ33 Then, β23 decreases from this value down to zero for larger and
Hence, by using the condition γ11 γ22 γ12 γ21 and by sub- smaller values of κΛ .
stituting Eq. (49) into Eq. (18b), D33 can be expressed as β21 contains the contribution to the water flow of self-
induced electroosmosis. The maximum value of β21 is about
γ31 γ13 γ21 γ12
D33 = − 1− . (54) 0.04 at κΛ ≈ 3–4, which corresponds to a maximum efficiency
γ33 γ11 γ22 γ11
of the clay with respect to electroosmosis about 1%.
Thus, D33 contains contributions of the self-induced elec- β31 contains the contribution of electrodialysis to the solute
troosmosis term (γ12 γ21 /γ11 ) and of the selfinduced electro- flux. β31 decreases monotonically as κΛ decreases from a
diffusion term (−γ13 γ31 /γ11 ) to the water flow and the solute maximum value of approximatively 5.9 corresponding to an ef-
flux, respectively. ficiency of 45%. The efficiency is rather small, which is due
In Fig. 11, D33 is plotted against κΛ for both clays. One to the small surface charges. The data are in poor agreement
can observe that D33 is close to zero for large κΛ (>7), indi- with (56).
cating that D̄ approaches γ33 , which, for large κΛ , represents
the diffusion coefficient of cations (Na+ ) without any surface 4.3.3. Comparison with the analytical predictions
effects. Hence, D̄ is essentially dominated by geometrical ef- The experimental data were compared with the analytical
fects and is independent of the self-induced electroosmosis and predictions (6) obtained for a circular tube where the radius Rc
electrodiffusion. However, for small κΛ (<7), the presence of is replaced by the length Λ given by (7).
M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364 363
(a) (b)
(c)
Fig. 13. Figures of merit of (a) osmosis, (b) electroosmosis, and (c) electrodialysis. Solid lines: Eq. (56).
In most cases, the nondiagonal coefficients (see Figs. 6–9) Such estimations can be very useful since the non diagonal
are in agreement with the analytical formulae. Generally speak- coefficients are quite difficult to measure.
ing, the agreement is better for large κΛ , i.e., for large con-
centrations. For these values, the discrepancies are seen to be 5. Conclusion
random in character and the average is very close to the ana-
lytical predictions. This provides an order of magnitude for the The objective of this study was to measure the coupling
experimental errors. transport coefficients of NaCl solutions through a compacted
However, in most cases, for small κΛ , the data deviate from natural clay submitted to concentration gradients and to com-
pare the experimental coupling coefficients with the analytical
the analytical predictions. This is probably due to the fact that
solutions obtained for circular Poiseuille flows. There are three
the experiments corresponding to these values had to be per-
processes coupled together: osmosis, described by γ23 , elec-
formed with very low concentrations and thus were more diffi-
troosmosis, described by γ21 , and electrodialysis, described by
cult and uncertain than the other ones.
γ31 .
This property is also valid for diagonal coefficients such as The coefficients were measured as functions of C and and
γ33 where surface effects can be important. When bulk effects represented in a dimensionless form as functions of κΛ .
are removed from γ33 , the resulting dimensionless coefficient The maximum efficiencies related to osmosis and electroos-
is seen to verify the previous property in Fig. 11; the same
α33 mosis were found to be lower than 1%. The maximum effi-
comments apply for the variations of the quality of the compar- ciency related to the self-induced electrical field (electrodial-
ison with κΛ . ysis) was found to be 45% for κΛ < 1.
This property is practically very important, since it can be Thus, an important result is that the major contribution to
used to estimate all these coefficients when diagonal properties solute transport is due to the concentration gradient and the self-
such as K and σ/σ ∞ are known. (7) implies Λ . When the elec- induced electrical field. Moreover, convection, osmosis, and
trolyte concentration and ζ are known, all the coefficients can electroosmosis do not have a strong effect on solute and water
be estimated from (6). transports. The efficiency, delaying the passage of ionic species
364 M. Rosanne et al. / Journal of Colloid and Interface Science 297 (2006) 353–364
by the charged clay pores increases with decreasing κΛ and [5] D.E. Elrick, D.E. Smiles, N. Baumgartner, P.H. Gronevelt, Soil Sci. Soc.
the maximum efficiency was found for κΛ < 1. Since the abil- Am. J. 40 (1976) 490–491.
[6] P.H. Gronevelt, D.E. Elrick, T.J.M. Blom, Soil Sci. Soc. Am. J. 42 (1978)
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671–674.
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