The Hydroelectric Problem of Porous Rocks: Thermodynamic Approach and Introduction of A Percolation Threshold
The Hydroelectric Problem of Porous Rocks: Thermodynamic Approach and Introduction of A Percolation Threshold
The Hydroelectric Problem of Porous Rocks: Thermodynamic Approach and Introduction of A Percolation Threshold
RESEARCH NOTE
André Revil
CNRS-CEREGE, Department of Hydrogeophysics and Porous Media, BP 80, Cedex 4, 13545 Aix-en-Provence, France. E-mail: [email protected]
SUMMARY
An electrical field is produced in response to groundwater flow in porous materials such as
soils and permeable rocks. This electrical field is due to the relative displacement between the
charged mineral grains and the pore water, which drags the excess of electrical charge located
in the close vicinity of the pore water/mineral interface in the so-called electrical double layer.
In this note, I take the hydroelectric problem back to its thermodynamic roots by showing
how the hydroelectric equations can be derived from the Gibbs-Duhem equation. In addition,
I suggest that the introduction of a percolation porosity may improve the description of the
material properties of granular porous materials entering the coupled hydroelectric problem at
the macro-scale. Comparison between the proposed model and a set of laboratory data available
from the literature are in agreement for a reasonable choice of specific parameters.
Key words: electrical transport, percolation, permeability, porous medium, streaming
potential.
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Hydroelectric coupling 945
surrounding environment. One of the pillars of ‘generalized’ linear tion equation for entropy. In isothermal conditions, the dissipation
thermodynamics is the existence of a local equilibrium assump- function of the system D ≡ T ≥ 0 is given by:
tion, which is characterized by the use of the classic Gibbs-Duhem
equation. Indeed Prigogine (1949) showed that the Gibbs-Duhem D = −j(+) ∇ µ̃(+) − j(−) ∇ µ̃(−) − jw ∇µw . (11)
equation remains valid in the vicinity of equilibrium to the Dissipation is zero at thermodynamic equilibrium. In linear ther-
first-order of perturbation of the state variables. Neglecting defor- modynamics, the choice of thermodynamic forces and fluxes is
mation of the porous plug (e.g. poro-elastic effects) and assuming arbitrary to a certain extent as long as the product of any pair of
that the pore water is composed by a multicomponent (N species) conjugated flows and thermodynamic forces have the dimension of
electrolyte (N-1 ionic species plus the solvent), this yields: an entropy-production rate and the sum of all products leave the en-
N tropy production rate invariant. In addition needless to say that the
du = T ds + µ̃i dn i , (1) material fluxes and scalar potentials are not uniquely defined and
i=1 only the divergence of a flux and the gradient of a scalar potential
where µ̃i represents the electrochemical potential of the species have a physical meaning. This usually means that for experimen-
i, n i represents the concentration (in mol m−3 ) of species i per unit
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946 A. Revil
the ratio between the intrinsic permeability k (in m2 ) and the dy- ξ = σ S /σ f is the ratio between surface to pore fluid electrical con-
namic shear viscosity of the pore water η f (in Pa s), and . The ductivity (dimensionless), σ S represents the surface conductivity (in
conservation equations for electrical charge is obtained combining S m−1 ), and t(+) is the Hittorf number of the cations in the electrolyte
eq. (4) with (dimensionless), which represents the fraction of electrical current
transported by the cations in the pore water (t(+) = 0.38 for NaCl
j = e j(+) − j(−) , and 0.51 for KCl). Surface conductivity corresponds to an electrical
conduction mechanism located in the close vicinity of the pore wa-
∇ · j = −dρ/dt, (15) ter/mineral interface in the so-called electrical double layer coating
where ρ = e(n (+) − n (−) ) represents the free charge density per unit the mineral water interface (e.g. Revil & Leroy 2001). In eq. (20),
volume of the porous rock. Eq. (5) and u = w jw (and n w w = φ χd ≡ (ε f kb T /2e2 I )1/2 is the Debye screening length (approximately
for a water saturated porous medium) yields: half the thickness of the electrical double layer coating the pore wa-
ter/mineral interface), kb is the Boltzmann constant, I is the ionic
∇ · (ρ f u) = −d(ρ f φ)/dt, (16) strength in mol L−1 (∼salinity) of the pore water, ε f is the dielectric
constant of water ∼(80 × 8.84) ×10−12 F m−1 , and ζ is the so-called
2φ d
εf ζ 2χd → . (25)
≈− 1− , (20) 9(1 − φ)
ηf F
Eq. (24) represents the well-known Hashin-Shtrikman lower bound
d2 and (25) is similar to eq. (24c) of Kostek et al. (1992). The Hashin-
k= , (21)
α F(F − 1)2 Shtrikman lower bound is known to be fairly accurate in the limit of
dilute suspensions of spherical particles whatever its geometry. At
where eqs (18) and (19) result from the application of a differen-
high fractional connected porosity (φ φ p , say φ > 0.40) F can
tial effective medium approach (Revil et al. 1998), eq. (20) results
be replaced by its asymptotic limit and (21) reaches a well-known
from a volume-averaging approach (Pride 1994), and eq. (21) from
asymptotic limit:
a combination of both methods (Revil & Cathles 1999). In (18)
and (19), σ f represents the electrical conductivity of the pore wa- 8 d 2φ3
k≈ , (26)
ter (in S m−1 ), F is the electrical formation factor (dimensionless), 27α (1 − φ)2
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948 A. Revil
1
σ = [σ f + (1 − F)σ S ]. (28)
F
According to volume averaging arguments, the electrical conduc-
tivity of a porous material σ in the high salinity limit is also given
by (e.g. Pride 1994),
1 2
σ = σ f + S + · · · , (29)
F
where the specific surface conductivity S is related to σS by
σS = 2 S /R where R = 2 d is the radius of the grains. Com-
parison between eqs (28) and (29) yields = d/[2(F − 1)], which
result is slightly different from eq. (23). A relationship between the
permeability and the length scale is given by k = 2 /a F with
εf ζ
CHS ≡ , (31)
ηf σf
Figure 2. (a) Permeability versus electrical formation factor (data from
where CHS is the streaming potential coupling coefficient corre- Spangenberg et al. 1998, their Fig. 6, and corresponding to salt rocks).
sponding to the Helmholtz-Smoluchowski (HS) formula. The HS The initial mean grain diameter of the samples is in the range 0.5–2 mm
formula is widely used in an important number of publications to in- for the coarse-grained samples and 0.1–0.5 mm for the fine-grained sam-
terpret electrokinetic laboratory experiments or field data. It predicts ples. (b) Comparison between the model and the data from Chilindar (1964,
that the streaming potential coupling coefficient does not depend on Fig. 2, p. 73) (fine and silty-grained natural sandstone naturally compacted).
Parameter used: m = 1.5, φ p = 0.025 and the best fit of the model with the
the microstructure of the porous medium. Actually, experimental
experimental data yields d = 116 µm for the fine-grained sandstone (filled
data reported in the literature showed that the streaming potential circles) and 46 µm for the silt (filled squares).
coupling coefficient depends quite strongly on the microgeometry
of the porous medium at porosity below 0.30 (e.g. Bull & Gortner
1932). Actually the HS formula is valid only at very high salin- low porosity. For the Fontainebleau sandstone, this yields a perco-
ity and/or high porosity where the two conditions H(ξ 1) = 1+ lation porosity ∼0.035 ± 0.10, quite similar to the value reported in
O(ξ ) + · · · and χd d/[4(F − 1)] are simultaneously satisfied. Sections 3 and 4 (0.025).
According to eqs (30) and (31), the streaming potential coefficient
depends generally on the porosity. The normalized streaming po-
7 CONCLUDING STATEMENTS
tential coefficient C/CHS is shown as a function of the porosity
in Fig. 3(a). The model predicts that the ratio C/CHS increases In this paper, I show (1) how the hydroelectric equations result
strongly with the porosity, especially at low salinity. This prediction from the Gibbs-Duhem equation and (2) that the three materials
is very well confirmed by the experimental data reported by Jouniaux properties (electrical conductivity, permeability, and electrokinetic
& Pozzi (1995) (Fig. 3b). The surface conductivity determined from coupling coefficient) entering the hydroelectric equations exhibit a
eqs (30) and (31) and the data by Jouniaux & Pozzi (1995) is similar percolation porosity. For sandstones and granular materials,
σ S = 0.84×10−4 S m−1 , which is in good agreement with that deter- the percolation porosity is in the range 0.02–0.04, which is quite
mined independently from electrical conductivity data in Fig. 1(a) small. For other types of porous rocks like vesicular basalts, it is
(σ S = 1.03 × 10−4 S m−1 ). In addition the data of Fig. 3(b) show a expected that this percolation porosity could be much higher than
good agreement with a model including a percolation threshold at the previous value owing to their different texture.
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Birch, F.S., 1998. Imaging the water table by filtering self-potential profiles,
Ground Water, 36, 779–782.
Bull, H.B. & Gortner R.A., 1932. Electrokinetic potentials, X. The effect of
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