Fundamental theoretical study of nanoscale ion transport through charged

porous rocks: Part II diffusion-advection

P. Pivonka, D. Smith & B. Gardiner

Department of Civil and Environmental Engineering, The University of Melbourne, Parkville,
Melbourne, Australia

ABSTRACT: Depending on the rock permeability, different mass transport mechanisms have to be distin-
guished. Whereas mass transport through porous rocks characterized by low permeabilities is governed by
diffusion, mass transport through highly permeable rocks is governed by advection. Coupled diffusive-advective
mass transport then plays an important roll in many geoengineering systems, such as mineralization, ore body
genesis and pollutant migration (including the transport of bacteria, viruses and other microorganisms). Addi-
tionally a large number of porous materials are characterized by the presence of surface charge which affects
the permeability of the porous medium.
In this paper the fundamental equations describing micro-scale multi-ion transport (i.e., the generalized
Nernst-Planck equations are coupled with the Navier-Stokes equations describing advective mass transport and
the Poisson equation of electrostatics) are given. Various effects such as (i) pore size, (ii) concentration of ionic
species, and (iii) the size of particle charge on solvent transport are studied at the nanoscale by means of finite
element simulations. The nanoscale findings provide insight into events encountered at the macroscale.

1 INTRODUCTION electro-hydrodynamics. The governing partial differ-

It is recognized that the permeability of a large num-
ber of porous media is not only dependent on the pore
morphology (i.e., the porosity and tortuosity of the
material), but also on the concentration of ions in the
pore fluid saturating the porous space, and the permit-
tivity of the pore fluid (Hueckel, 2002) (Shackelford
et al., 2000). This phenomenon is typical for porous
media including clays, shales, polymer gels, and bio-
logical tissues (Hunter, 2001). An important property
inherent to these materials is the positive/negative
charge of their surface. In the case of clay minerals neg-
ative surface charges are a consequence of isomorphic
substitutions of certain atoms in the clay crystal lat-
tice and the presence of crystal imperfections (defects
or broken bonds) (Sposito, 1989) (Iwata et al., 1995).
The presence of surface charges leads to formation
of diffuse double-layers characterized by high con-
centrations of anions/cations depending of the sign
of the surface charge, respectively. In the presence
of diffuse double-layers the dissipation of power in
a flowing fluid is not only due to friction within the
pore fluid, but also due to friction of the pore fluid and
the ions pinned in the diffuse double-layer by means
of electrical forces (Smith and Pivonka, 2003).
In this paper an explanation for the experi-
mentally observed concentration dependence of the
permeability will be given in the framework of coupled
ential equation describing this phenomenon is the
generalized Nernst-Planck (G-N-P) equation (Cussler,
1997). In order to obtain the fluid velocity encoun-
tered in the G-N-P, this equation is coupled with the
Navier-Stokes (N-S) equation. Finally, to describe the
behavior in the diffuse double-layer the Poisson equa-
tion is employed. This system of equations will be
solved for a 2D slit problem. Effects such as ion con-
centration, charge density of the porous medium, and
porosity will be investigated.
2 GOVERNING EQUATIONS AT THE
MICROSCALE
The key constitutive equation describing microscale
multi-ion transport in the presence of electrochemi-
cal forces is the generalised Nernst-Planck (G-N-P)
equation (Cussler, 1997):
where ji , ci , and ci is the molar flux density, the
concentration of the i-th ion, and the concentration gra-
dient of the i-th ion, respectively. Di is the free-solution
diffusion coefficient of the i-th ion. There are several
refinements that may be incorporated in the estimated

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Copyright 2005 Taylor & Francis Group plc, London, UK
diffusion coefficient, for example, taking into account
the activity of the ions in solution arising from corre-
lated spatial movements of ions, see (Cussler, 1997)
for details. The quantities zi and are the valence
of the i-th ion and the voltage gradient. vf is the fluid
velocity and F, R and T are the Faraday constant, gas
constant, and the absolute temperature, respectively.
The first term inside the brackets results in transport
of the i-th ion species along minus of the chemical
potential gradient (assuming an ideal solution). The
second term inside the brackets results in transport
along the voltage gradient. Note that the direction of
transport depends on the charge zi of the ion. The
G-N-P Eqn. (1) is a generalisation of Ficks law, tak-
ing into account electrical effects on charged solutes,
and taking into account the movement of the fluid. The
voltage appearing in Eqn. (1) is made up of two dis-
tinct parts. The first part of the voltage arises from any
external potential applied to the system (for example,
the external voltage may result from the accumulation
of excess ions on one side of a clay barrier membrane).
The second part of the voltage arises from the potential
generated by the diffusion coefficients of the individ-
ual ions being different, leading to the formation of
ion-pair dipoles. This second potential is known as the
diffusion potential. However, the ions in solution are
influenced by the electric potential irrespective of its
origin, so the two voltages arising from either process
may be summed and represented by a single .
The transport Equations (1) are supplemented by
mass conservation equations. Mass conservation for
each conservative ion species is expressed by,
where ji is the divergence of the flux vector of the
i-th ion and t is the time. Substitution of the
G-N-P Eqn. (1) into the mass conservation Eqn.
(2) leads the governing partial differential equation
for mass transport. Finally, charge conservation of
ions in solution exerts an important constraint on
the behaviour of a multi-ion
 system by enforcing
electroneutrality (i.e., zi ci = 0) of the system at
all times. Electroneutrality is observed in all solu-
tions except in a thin diffuse double-layer near
electrodes and charged particle surfaces (Newman,
1991). Some other commonly applied constraint con-
ditions are given in the first part of the paper (see
Eqn. (4)(6)). In order to rigorously describe the above
mentioned interface phenomena the space charge den-
sity (q) must be related to the electric potential. This
constraint can be expressed by means of the Poisson
equation of electrostatics for a system consisting of
N ions:
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Copyright 2005 Taylor & Francis Group plc, London, UK
where the permittivity is the product of the permit-
tivity of free space,0 , and the relative permittivity of
water w . Eqns. (1),(2) and (3) can be employed in
order to gain information on the structure of the dif-
fuse double-layer for any ion composition of the pore
fluid and solid geometry. Further, these equations are
suitable for the analysis of ion diffusion through a
charged porous medium containing a stationary fluid,
i.e., vf = 0. For these reasons, it is clear that the equa-
tions constitute a very powerful model, and can solve
many problems dealing with colloidal domain pro-
cesses and the chemomechanical behaviour of clays.
However, for systems characterized by movement of
the pore fluid (i.e., vf = 0), an additional equation
describing the fluid flow is required. In this case, there
are couplings between the flow of fluid in the pore
spaces and the movement of ions in the pore fluid (e.g.
as occurs in clay soils or charged biological tissues).
When pore fluid motion occurs relative to the coun-
terions (i.e., the ions required to maintain electroneu-
trality at the charged particles) in the pore fluid, there
is initially a drift of counterions in the direction of fluid
flow. However soon after this drift begins, large elec-
trical and chemical forces comes into play, effectively
pinning the counterions in solution. The counteri-
ons are pinned in a spatial location in a time-averaged
sense (there are thermally induced fluctuations about
the mean position). Counterions pinned in the pore
fluid can contribute significantly to the dissipation of
energy in the fluid (the counterions can be imagined
to be small spheres suspended in the fluid, interrupt-
ing the flow). In clay soils with a high cation exchange
capacity, calculations made here show that this may be
the principal means for energy dissipation during fluid
flow. Assuming no source or sink terms are present, the
governing equations required for the analysis of this
system are the continuity equation (Slattery, 1999),
and the generalized Navier-Stokes (N-S) equation
describing electrohydrodynamic flow ((Eringen and
Maugin, 1990), pp. 553),
where f is the fluid density. The form of the N-S
Eqn. (4) assumes f and f are constant, though these
restrictions may be relaxed. Fm , Fe , F , and Fg are the
force vectors of mechanical, electrical, viscous, and
gravitational origin. These forces can be expressed for
an incompressible homogeneous fluid as (Smith and
Pivonka, 2003),
 Parameters used for the coupled generalized Nernst-
PlanckNavier-StokesPoisson equation are given in
Table 1.
The geometric dimensions of the slit and the bound-
ary conditions are shown in Figure 1. The length of
the slit (a) is 150 nm, whereas the the slit width (b)
is 10 nm.
Use of the Poisson Eqn. (3) assumes ions are rep-
p denotes the fluid pressure in the pore fluid within resented as point charges. It was recognized that this
the porous medium, f is the fluid viscosity. vi is the assumption considerably overestimates surface con-
velocity of the i-th ion and ui denotes the ion mobility. centrations obtained in the Gouy-Chapman model
It is noted that Eqn. (7) accounts for both electrical of the diffuse double-layer (see e.g., (Shainberg and
and chemical forces. This equation differs from pre- Kemper, 1966), (Iwata et al., 1995), pp. 94).
viously proposed electrohydrodynamic equations by Rather than to introduce a hydration potential, a
means of the gradient of concentration term (see for phenomenological correction term may be applied to
example Gross and Osterle, 1968, Fair and Osterle,
1971). It was shown that this equation is necessary
Table 1. Model parameters used for
for the investigation of coupled fluid flow and diffu- the numerical analyses.
sion through uncharged and charged porous media (see
Smith and Pivonka, (2003) for details). Symbol Value Dimension
The total power (energy/time) dissipated per unit
volume of fluid in this system is the sum of the 0 8.85e12 C 2/(J m)
power dissipated due to fluid viscosity and the power w 78
dissipated by friction between the pore fluid and coun- D+ 1.5e09 m2/s
terions pinned in the fluid. The energy dissipated in D 1.5e09 m2/s
the fluid must be equal to the rate of work done on the F 96500 C/mol
system by pressure-volume work on the system bound- T 293 K
aries. For two-dimensional flow the power dissipated R 8.31 J/(K mol)
f 0.001 kg/(m s)
due to fluid viscosity is given by (Slattery, 1999),
f 1000 kg/m3

while the power dissipated due to the counterions

pinned in the pore fluid under steady-state conditions
is given by (ions fixed in position):

Finally the power dissipated under transient conditions

by counterions pinned in the pore fluid is given by (ions
moving):

3 NUMERICAL ANALYSES

In the following, the consequences of the proposed

theory will be demonstrated for fluid flow of a charged
slit opening containing an electrolyte. This problem Figure 1. Navier-Stokes flow through a slit: geometric
deals with 2D stationary fluid flow (i.e., vf /t = 0). dimensions and boundary conditions (figure not at scale).

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Copyright 2005 Taylor & Francis Group plc, London, UK

Figure 2. Navier-Stokes flow through a slit: dependence of
solvent flux on the hydration parameter ko .
either the concentration of the electric potential in the
GNP Eqn. (1):
Figure 3. Navier-Stokes flow through a slit: cation dis-
tribution in a cross-section for c = 1000 mol/m3 and
= 0.2 C/m2 for various values of the hydration con-
stant ko .

where ko represents a hydration parameter. In the limit

case of ko Eqn. (13) returns the G-N-P Eqn. (1).
Investigation of the functional dependence of Eqn. (13)
has shown that replacement of the exponential function
by means of a linear function, i.e., f (ci , ko ) = 1 ci /ko
only had minor influence on the numerical results.
Only for low values of ko deviations of the numerical
results were obtained.
The first investigation deals with the value of
ko used in Eqn. (13). Dependence of the solvent flux
on the concentration of background electrolyte and
the hydration constant for a negative surface charge
= 0.2 C/m2 is shown in Figure 2. Figure 4. Navier-Stokes flow through a slit: dependence of
solvent flux on the concentration of background electrolyte
Increasing the hydration constant ko from 250 to
and surface charge density.
10000 leads to a strong increase of the solvent flux (see
Figure 2). This increase of solvent flux is more pro-
nounced for high concentrations of background elec- solvent flux as a consequence of the compression of
trolyte. The distribution of cations in a cross-section the diffuse double-layer. Increasing the surface charge
of the slit (y = 75 nm) for a background electrolyte on the slit leads to a considerable reduction of solvent
concentration of 100 mol/m3 is given in Figure 3. flux because of an increase of energy dissipation by
Increasing the hydration parameter ko (decreasing the ions pinned in the pore solution.
ion size) leads to a strong increase of surface concen- The final study deals with the influence of the slit
tration from approximately 7000 mol/m3 for the case width b on the solvent transport for a surface charge
of ko = 1000 to 1000 mol/m3 for the case of ko = 250. density of 0.2 C/m2 . Increasing the slit width leads to
In the following a hydration constant ko = 2500 is a strong increase of solvent flux. Whereas the solvent
employed. flux for b = 5 nm is almost constant the solvent flux
The second investigation deals with the influence for b = 20 nm shows a strong increase with increas-
of surface charge density () on the solvent flux. ing concentration. For the latter case dissipation is
Figure 4 shows the solvent flux at various concen- governed due to friction in the fluid and, hence, the
trations of background electrolyte. From this figure portion of friction in the diffuse double-layer plays
it can be concluded that increasing the background only a minor role. However, for small slit widths dis-
electrolyte concentration leads to an increase of the sipation is mainly due to friction of the fluid and ions

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Copyright 2005 Taylor & Francis Group plc, London, UK

Figure 5. Navier-Stokes flow through a slit: dependence of
solvent flux on slit width for = 0.2.
located in the diffuse double-layer. It should be noted
that the continuum description of ion transport through
the slit opening breaks down for a slit width in the range
of the Debye length characterizing the size of double
layers. For such cases molecular dynamic simulations
where motions of both ions and water molecules are
traced (Roux and Karplus, 1994) or Brownian dynamic
simulations (Moy et al., 2000) must be applied.
4 CONCLUSIONS
From the numerical results obtained from the
coupled generalized Nernst-PlanckNavier-Stokes
Poisson system of equations the following conclusions
can be drawn: The fluid flux through a charged porous
medium strongly depends on the slit width (porosity)
and on the particle surface charge. The latter leads
to the development of diffuse double-layers which
significantly contribute to energy dissipation in the
fluid. For high surface charges ( = 0.5 C/m2 ) an
almost three fold reduction of fluid flux (permeabil-
ity) was found. This reduction of fluid flux strongly
depends on the surface charge density and the concen-
tration of background electrolyte. However, changes
in porosity (slit width) showed even more pronounced
influence on the permeability. It was found that a four
fold increase of the slit width led to approximately
a two order of magnitude increase of solvent flux.
At small slit widths energy dissipation is dominated
by energy dissipation in the diffuse double-layer, on
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Copyright 2005 Taylor & Francis Group plc, London, UK
the other hand for large slit width energy dissipation
is mainly due to the viscosity of the fluid. Finally,
the investigation of cation concentration in the diffuse
double-layer showed very high surface concentrations
which stem from the assumption of zero ion size
(point charges). Introduction of a correction term in
the generalized Nernst-Planck equations led to a more
realistic description of concentration distribution in
the diffuse double-layer.
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