Environ Earth Sci (2013) 70:303–314
DOI 10.1007/s12665-012-2128-7
ORIGINAL ARTICLE
Novel procedure for the estimation of swelling pressures
of compacted bentonites based on diffuse double layer theory
Tadikonda Venkata Bharat • Puvvadi Venkata Sivapullaiah
Mehter M. Allam
Received: 31 January 2012 / Accepted: 15 November 2012 / Published online: 13 December 2012
Ó Springer-Verlag Berlin Heidelberg 2012
Abstract Bentonite clays are proven to be attractive as
buffer and backfill material in high-level nuclear waste
repositories around the world. A quick estimation of
swelling pressures of the compacted bentonites for differ-
ent clay–water–electrolyte interactions is essential in the
design of buffer and backfill materials. The theoretical
studies on the swelling behavior of bentonites are based on
diffuse double layer (DDL) theory. To establish theoretical
relationship between void ratio and swelling pressure
(e versus P), evaluation of elliptic integral and inverse
analysis are unavoidable. In this paper, a novel procedure is
presented to establish theoretical relationship of e versus P
based on the Gouy–Chapman method. The proposed pro-
cedure establishes a unique relationship between electric
potentials of interacting and non-interacting diffuse clay–
water–electrolyte systems. A procedure is, thus, proposed
to deduce the relation between swelling pressures and void
ratio from the established relation between electric poten-
tials. This approach is simple and alleviates the need for
elliptic integral evaluation and also the inverse analysis.
Further, application of the proposed approach to estimate
swelling pressures of four compacted bentonites, for
example, MX 80, Febex, Montigel and Kunigel V1, at
T. V. Bharat (&)
Department of Civil and Geological Engineering,
University of Saskatchewan, Saskatoon, SK S7N 5A9, Canada
e-mail: tvbharat@gmail.com
T. V. Bharat  P. V. Sivapullaiah  M. M. Allam
Department of Civil Engineering, Indian Institute of Science,
Bangalore, Karnataka 560012, India
Present Address:
T. V. Bharat
Department of Civil Engineering, Indian Institute of Technology
Guwahati, Guwahati, Assam 781039, India
•
different dry densities, shows that the method is very
simple and predicts solutions with very good accuracy.
Moreover, the proposed procedure provides continuous
distributions of e versus P and thus it is computationally
efficient when compared with the existing techniques.
Keywords Bentonite clays  Swelling pressures  Diffuse
double layer theory  Gouy–Chapman method
Introduction
Bentonites are receiving great attention as buffer and
backfill materials in toxic waste disposal and high-level
nuclear waste repositories all around the world (Butcher
and Müller-Vonmoos 1989; Ishikawa et al. 1990; Japan
Nuclear Cycle Development Institute 1999; ENRESA
2000; Pusch and Yong 2006; Zheng et al. 2011). The
ability of the bentonite material to resist migration of
contaminants due to very low permeability, high-ion
adsorption capacity and high-swelling abilities are some of
the attractive features, which are useful in the repositories
(Schanz and Tripathy 2009). The performance assessment
of these repositories for radioactive waste requires physi-
cochemical understanding of the bentonite material
(Mitchell 1993). Thus, theoretical study on the determi-
nation of swelling pressures of the bentonites for given
compacted densities is crucial for safe design of buffer and
backfill materials in the nuclear waste disposal facilities.
Bentonites are the clays that are composed of mineral
crystals of montmorillonite. The double-layer repulsive
pressures, described by theories of diffuse double layer
(DDL), are dominant in these clays and they contribute to
swelling pressures (Verwey and Overbeek 1948). Thus,
123
304
DDL theories play a very important role in understanding
the swelling behavior of bentonite clays.
Bentonites experience volume changes due to clay–
water–electrolyte interactions (Bolt 1956). The DDL theory
proposed by Gouy–Chapman (Gouy 1910; Chapman 1913)
is the most commonly used theory which can relate swelling
behavior of bentonite with variations in the clay–water–
electrolyte systems. Thus, this theory has been widely used
in geotechnical and geoenvironmental sciences for estab-
lishing relationships between swelling pressure and void
ratio (Yong and Mohamed 1992; Sridharan and Choudhury
2002; Tripathy et al. 2004; Gratchev and Towhata 2011).
According to DDL theory, the interaction pressures
between two diffuse double layers depend on the electric
potentials at the midway between two adjacent parallel clay
platelets and is equal to the osmotic pressure in that plane
(Bolt 1956). Therefore, for any given separation distance
between two clay platelets the osmotic pressure can be
determined using DDL theory by knowing electric potential
in the central plane between the platelets and vice versa. To
establish e versus P, using this theory, it is necessary to
calculate the midway potential in the diffuse part of the
interacting diffuse layers by evaluating an elliptic integral.
On the other hand, estimation of swelling pressures for a
given electrolyte system and compaction dry densities
requires inverse analysis. Several researchers (Overbeek
1952; van Olphen 1977; Sridharan and Jayadeva 1982;
Sridharan and Choudhury 2002) circumvented this problem
by using indirect methods in the past to establish e versus P
relationship. It will be shown later in this paper that these
methods have several limitations and can often be too
approximate (Bharat 2004).
This paper establishes a new relationship between
electric potentials of interacting and non-interacting diffuse
clay plates for a given clay–water–electrolyte system. The
influence of electrolyte concentration, valence and clay
properties is verified to explore the generalizing capabili-
ties of the proposed relation between potentials. A novel
and simple procedure is proposed based on the predicted
relation between potentials for establishing theoretical e
versus P relationship. Further, it will be shown in this paper
that the proposed approach eliminates the need for integral
evaluation, in obtaining void ratio (or dry density) from
known swelling pressure values of the bentonite, and
inverse analysis, in obtaining swelling pressure for known
void ratios. Moreover, the proposed approach is computa-
tionally efficient and accurate.
Gouy–Chapman DDL theory
The Gouy–Chapman (GC) theory has been widely used for
understanding swelling characteristics of expansive soils at
123
Environ Earth Sci (2013) 70:303–314
low electrolyte concentrations. GC theory yields a number
of useful relations for calculating swelling pressures of
bentonites at different clay–water–electrolyte systems.
According to this theory the system can be viewed as an
array of single electric charged plates held at an average
distance of 2d. The equilibrium in the system is reached
between electrostatic attractive forces, that attract oppo-
sitely charged ions to the surfaces of the platelets, and
repulsive forces, that back-diffuse the ions from the
neighborhood of the surfaces into the bulk solution at this
distance (van Olphen 1977). This prompts the formation of
DDL around clay plates which is a common phenomenon
observed in clay–water–electrolyte systems. This concept
plays an important role in the prediction of swelling
characteristics of bentonite clays.
According to GC theory, the electrostatic potential in
DDL of a single clay platelet varies from surface potential,
/0 at the surface of the charged particle, to zero at the
interface of DDL and bulk solution. This electrostatic
potential distribution is described by a nonlinear form of
Poisson–Boltzmann equation as shown below:
 
expðjxÞ þ tanðzÞ
y ¼ 2 ln ð1Þ
expðjxÞ  tanðzÞ
where, y is the scaled potential ðy ¼ me0 /=KT ¼ mF/=RT Þ
at any distance, x, from the clay surface of a single plate,
z is the scaled potential at the clay surface
   
z ¼ me0 /0 KT ¼ mF/0 RT , 1/j is thickness of the
qffiffiffiffiffiffiffiffiffiffiffi
0 m2 n 0
DDL or Debye length in which j ¼ 8pe eKT , e is the
elementary electric charge (4.77910-10 esu), v is valance
of ions, n is ion concentration in bulk fluid, e is dielectric
constant, KT is thermal energy per ion, F is Faraday
constant and / is the electric potential at x. The graphical
representation of this equation for describing potential
distribution in the DDL of a single clay platelet is shown in
Fig. 1. Estimation of this distribution in the DDL for non-
interacting clay plate is fairly simple. However, the diffuse
layers of the clay plates overlap each other when the
particles come closer under external pressures, resulting in
a highly non-linear distribution of the potential as shown in
the same figure. This distribution between the plates (2d)
resembles hyperbolic function. The electrostatic potential
at midway (also called mid-plane potential) at a distance d
from either of the clay surface is represented by /d. The
potential of interacting system is computed according to:
Zu
dy
jd ¼  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð2Þ
2 coshðyÞ  2 coshðuÞ
z
where u is the scaled mid-plane potential, me0 /d =KT, of
interacting clay plates. The integral in Eq. (2) is elliptic in
nature. Further, it requires iterative analysis for determining
Environ Earth Sci (2013) 70:303–314 305

scaled potential, u (or swelling pressure), for known value
of half-space distance, d (or void ratio). The useful
equations involved in determining swelling pressure from
void ratio can be arranged as shown below:
e ¼ Gqw Sd
Zu
jd ¼  ð2 coshðyÞ  2 coshðuÞÞ1=2 dy ðfromð2ÞÞ
z DDLs can be neglected. Therefore, the midway potential of
 
dy
¼ ð2 coshðzÞ  2 coshðuÞÞ1=2
dn x¼0
rffiffiffiffiffiffiffiffiffiffiffi
 
dy B 2p
¼
dn x¼0 S enKT
P ¼ 2nRTðcosh u  1Þ
where B is the base exchange capacity (meq/100 g), S the
specific surface area of soil (m2/g), qw the density of water
(Mg/m3), T the absolute temperature, P the swell pressure
(kPa), G the specific gravity of soil particles, e the void
ratio, R the gas constant, and n is the scaled distance (jx).
Determination of swelling pressure using Langmuir’s
Eq. (6) for any given soil–water–electrolyte system
requires the computation of scaled midway potential, u.
However, determination of u is computationally expensive
because of the elliptical form of the integral in Eq. (2) and
also it involves inverse analysis. Thus, several methods
have been established in the past to relate u and jd to
establish e versus P relationship. The existing methods are
summarized in the following section.
Existing approaches for the estimation of e versus P
Several approaches for the estimation of e versus P relation
using DDL theory have been proposed to simplify the
computation. However, they all are subjected to limita-
tions. Some of the popular approaches and their limitations
are summarized here.
Verwey and Overbeek method
The first simplified approach was provided by Verwey and
Overbeek in 1948 by establishing u versus jd relationship
ð3Þ based on GC theory. Explicit analytical solutions were
proposed for weak and strong ion interactions separately. If
the interaction of the diffuse plates is weak (jd  1), the
overlap effect of electric potentials due to interaction of
the central plane is assumed to be built up additively from
ð4Þ the electric potentials of two separate double layers. Hence
substitution of u for 2yd in the potential distribution
equation results,
ð5Þ
u ¼ 8cejd ð7Þ
ð6Þ       
where c ¼ exp z=2  1 exp z=2 þ 1 .
Similarly, analytical equation for strong interactions
(u  1) is derived by neglecting exp (-y) and exp (-u) in
Eq. (2), when the electric potential between the two plates
is large, which can be written as:
 z  u
jd ¼ 2 expðu=2Þ arccos exp  ð8Þ
2
The approximate u versus jd relationship can, thus, be
predicted for weak and strong interactions separately from
the Eqs. (7) and (8).
Limitations
(i) Though the equations are simple, they are approxi-
mate and applicable only to particular range of
interactions.
(ii) The obtained values with this approach show that the
deviation from the actual solution is significant in the
neighborhood of jd = 1; according to the approxi-
mation for small interactions, the computed u is too
high.
Van Olphen’s approach

Van Olphen (1977) has presented tables by giving sets of

values of u and z, for various values of jd and at specific

dy
values of dn . This enables one to determine the
x¼0
midway potential, u, by reading-off the values from the
tables.

Limitations

Fig. 1 Schematic representation of electric potential distribution of dy
(i) Tables were given for only few values of dn x¼0 and
interacting and non-interacting diffuse clay–water–electrolyte system
according to GC theory in between values have to be interpolated.

123
306

(ii) Even for a given value of dy
the values of jd, u
dn x¼0 ,
and z need to be either interpolated or extrapolated.
Hence the tables given by van Olphen (1977) may act
at best as a guide rather than to give correct
relationship between void ratio and repulsive pressure
(Sridharan and Jayadeva 1982).
Sridharan and Jayadeva’s approach
Sridharan and Jayadeva (1982) presented a graphical
method for the estimation of relation between swelling
pressure and void ratio from the numerical solution of Eq.
(2). In this approach, the relationships between jd,
je0 =Gcw S; jm=cw S and P=neT for various values of u have
been presented in the form of figures and tables. From
the known soil and fluid properties, viz. P=neT and jd, the
non-dimensional parameter, u could be determined. The
value of P=neT could be determined by knowing u using
presented figures or tables. The tables and figures can also
be used to determine the void ratio for a given swelling
pressure of the soil.
Limitations
(i) Some of the values of u need to be interpolated
between the curves for known values of P=neT and jd
which involves considerable error.
(ii) In-between values of u or jd have to be calculated by
interpolation method.
In summary, all the existing approaches suffer from various
limitations as discussed above. Thus, a simple approach is
required for the estimation of e versus P relationship.
Proposed approach
As mentioned before, the electrostatic potential distribution
within the DDL of non-interacting system estimated by Eq.
(1) predicts non-linear distribution, in which, the potential
drops from /0 at x = 0 to zero potential at x = ?. Simi-
larly, it will be shown in the following section that the
changes in the midway potential of an interacting system
with variation in the distance between the particles are
analogous. Thus, the similarities between these two
potential distributions are used to derive simple equations
to compute swelling pressures.
Electrostatic potential distribution of non-interacting
DDLs
It is worth noting that the counter-ions of the double layer
subject to two opposing tendencies. The electrostatic forces
123
Environ Earth Sci (2013) 70:303–314
attract them to the charged clay surface whereas the dif-
fusion due to concentration gradients of the ions tends to
bring them away from the surface toward bulk solution.
The electric potential distribution at equilibrium in the
DDL described by Poisson–Boltzmann equation requires
/0. The surface potential in turn depends on the soil
properties such as base exchange capacity (B) and specific
surface area (S). Thus, the surface potential of a clay
platelet in a given fluid system can be expressed after
solving the equation for surface charge density as (van
Olphen 1977)
 
T 1 1256:81  P
0
/0 ¼ 0:1725 sinh pffiffiffiffiffiffiffiffi ð9Þ
m neT
where P0 is the ratio of B (meq/100 g) and S (m2/g), and
surface potential is expressed in mV. The scaled surface
potential, z, can be obtained by the following relation:
mF/0
z¼ ð10Þ
RT
The potential at any given distance from the surface of
the clay plate, thus, can be obtained by substituting (10)
into (1). This potential for different electrolyte
concentrations with distance is given in Fig. 2 when P0 is
assumed to be 0.125. This figure shows that the electric
potential at any given distance from the clay surface
decreases with increase in the electrolyte concentration
which supports the earlier findings (van Olphen 1977).
Electrostatic potential distribution of interacting DDLs
It is worth mentioning that swelling characteristics of
clayey soils can be understood from the interaction of the
diffuse plates. As mentioned earlier, the diffuse layers of
φ
Fig. 2 Plot representing electric potential distribution in the DDL
from the Boltzmann distribution at different electrolyte
concentrations
Environ Earth Sci (2013) 70:303–314 307

the particles overlap each another when two particles come

together and result in a hyperbolic distribution of the
potential. This potential at any given distance from the clay
surface increases with decreases in the distance between
the particles. Thus, it is interesting to study the changes in

φ
the mid-plane potential due to variation in the distance
between the particles. The relation between /d and d is
obtained using the following procedure:
(i) Input swelling pressure, P in kPa,
(ii) Compute scaled midway potential, u, using Lang-
muir’s formula given in (6) as
P ¼ 2nRTðcosh u  1Þ:
(iii) Obtain midway potential, /d in mV, from u using
0
u ¼ meKT/d :
Fig. 3 Plot representing variation of midway potential of the
(iv) The slope of the potential curve, dy/dn, at the surface interacting DDLs with distance between clay plates at different
of the clay plate is calculated from: electrolyte concentrations
 
dy 2513:6P0
¼ pffiffiffiffiffiffiffiffi The potential curves showing the variation of /d with
dn x¼0 enT
half-space distances for different electrolyte concentrations
(v) The scaled surface potential, z, is then obtained by: and P0 value of 0.125 meq/100 m2 are shown in Fig. 3. It
 
dy can be observed from this figure that the variation of mid-
¼ ð2 cosh z  2 cosh uÞ1=2 plane potential with distance between the particles appear
dn x¼0
to be similar to the potential distribution of the non-inter-
(vi) The scaled mid-plane distance, jd, is obtained by acting diffuse clay plates obtained by Poisson–Boltzmann
numerical evaluation of the following integral from u equation. However, comparison between Figs. 2 and 3
to z: reveals that the midway potential is higher than the
Zu potential of non-interacting system (/x=d) at an equal dis-
jd ¼  ð2 cosh y  2 cosh uÞ1=2 dy tance, x = d, from surface of the clay particle due to
z overlapping of the diffuse layers. The similarity between
variations of these two potentials with distance is further
(vii) Furthermore, the mid-plane distance in Å is confirmed by plotting the mid-plane potential curve
 02 2 1=2
calculated from d ¼ jd ; where j ¼ 8pne m
: (d - /d) and non-interacting potential distribution (x - /)
j eKT
at x = d for electrolyte concentrations of 0.01 and
This approach is termed as ‘integral evaluation tech- 0.00001 N and presented in Figs. 4 and 5, respectively.
nique’ in this work. The integration, in step (vi), is eval- These potential variations are nearly logarithmic with a
uated numerically using the ‘‘quad’’ MATLABÒ routine, regression coefficient, R2, varies between 0.997 and 0.999
featuring the adaptive Simpson quadrature approach. as shown in the figures. It is interesting to note that
However, finite value cannot be obtained by numerical deriving several relationships between /d and /x=d for
analysis because of elliptic nature of the integral. Thus, this different electrolyte concentrations is not practical.
integration is evaluated from u þ 1 to z instead of u to z;
where 1 is a small positive number and a value of 1 9 10-5
is chosen in this work. The above steps are coded in Relationship between potentials of interacting
MATLABÒ for the repeated calculations of half-space and non-interacting diffuse systems
distances from different swelling pressures. It is worth
repeating that the calculation of swelling pressure, how- A relationship between midway potential of interacting
ever, from a known value of either mid-plane distance or diffuse plates and electric potential of non-interacting dif-
void ratio (or dry density) is not possible by the above fuse plate system at x = d is obtained here. To obtain these
approach. This can only be solved by inverse analysis that distributions, mid-plane distances are computed from the
requires repeated calculations of the above-mentioned known values of /d using integral evaluation technique.
steps at assumed swelling pressures and then matching the The electric potentials of the non-interacting system are
obtained d with the known values. computed at distance, x = d, using Poisson–Boltzmann

123
308
φ
φ
φ dependency of these potentials do follow linear relationship
φ
Fig. 4 Logarithmic distributions of electric potential variation and
potential curve of non-interacting and interacting systems corre-
spondingly at the electrolyte concentration of 0.01 M
φ
φ
φ and potential of non-interacting system on y axis in Fig. 7b.
φ system with corresponding interacting diffuse system for
Fig. 5 Logarithmic distributions of electric potential distribution and
potential curve of non-interacting and interacting systems corre-
spondingly at 1 9 10-5 molar concentration
equation as described before. These two potentials are
computed at the same distances, x = d, from particle sur-
faces and plotted on the same graph as shown in Fig. 6 for
different electrolyte concentrations. The electrolyte con-
centrations are varied in the range of 10-3 to 10-5, in
which DDL theory is usually valid and used (Bharat 2004;
Tripathy et al. 2004; Bharat et al. 2008). A value of 0.125
for P0 and v = 1 are considered in this computation.
Interestingly, the data points follow nearly a straight line
indicating existence of a unique relationship between these
potentials. Further, it can be observed that potential rela-
tionship is not influenced by the electrolyte concentration.
This enables to obtain a unique relation between the
potentials between /d and /x=d. A linear fit is explored
123
Environ Earth Sci (2013) 70:303–314
initially to represent this relationship and is given in Fig. 6.
The obtained linear relationship is given by
/d ¼ 1:043/x¼d þ 14:769 ð11Þ
where /x¼d is the electric potential of non-interacting system
at distance, x = d, obtained by Poisson–Boltzmann
distribution. It is evident from this figure that the
only in the range of 20 mV \ /x=d \ 240 mV, even though it
predicts very good coefficient of determination (R2 = 0.997).
Thus, a second order polynomial equation is used to relate
these potentials as shown in Fig. 7a. It can be observed from
this figure that polynomial equation provides an excellent fit to
the data. Thus, the equation for computing mid-plane potential
from the potential of non-interacting system is obtained by:
/d ¼ 6:24  104 /2x¼d þ 1:205/x¼d þ 8:582 ð12Þ
This equation is useful for obtaining swelling pressures
from known values of void ratios or dry densities.
Similarly, the equation representing potential of non-
interacting diffuse clay–water–electrolyte system in terms
of mid-plane potential of interacting system is:
/x¼d ¼ 5:62  104 /2d þ 0:7934/d  6:1507
ð13Þ
which is obtained by plotting mid-plane potential on x axis
The derived relations are not only simple, but very powerful
for relating non-interacting diffuse clay–water–electrolyte
swelling pressure calculations as shown in the next section.
However, it can be noted that these relationships are derived
by assuming v = 1 (monovalent system) and P0 to be 0.125.
The predominant exchangeable cations in the compacted
bentonites of high-level nuclear waste repositories are either
monovalent or divalent or combination of these two (Japan
Nuclear Cycle Development Institute 1999; ENRESA
2000). Thus, the influence of valence of exchangeable cat-
ions on the potential relation is studied and is shown in
Fig. 8. It can be observed that the mid-plane potentials in the
presence of divalent ions plot above the potentials obtained
when monovalent system is assumed. However, this influ-
ence of valence on the potential relation is only significant at
higher values and can be ignored in the swelling pressure
calculations as will be shown later. To understand the effect
of P0 on the proposed equations, potentials of interacting and
non-interacting systems are plotted at different values of P0 ,
varied from 0.125 to 0.8, and presented in Fig. 9. It can be
observed that P0 influences the potential relation only at high
potential values similar to the effect of valence. The influ-
ence of valence and P0 on the derived potential relations is
ignored in this work as the DDL theory is not valid at large
mid-plane potentials (or large dry densities). Further, it will
Environ Earth Sci (2013) 70:303–314 309

Fig. 6 Linear fit to the

relationship between midway
potential of the interacting and
potential of non-interacting φ φ
systems

be shown in the following section that these assumptions are /x¼d ¼ /d  20:34
not significant for the prediction of swelling pressures of
commonly used bentonites. Thus, the derived potential or the following polynomial form of potential relation
relations in (12) and (13) are general equations representing from Eq. (13)
dependency of potentials of interacting and non-interacting /x¼d ¼ 5:62  104 /2d þ 0:7934/d  6:1507:
clay–water–electrolyte systems. Further, it will be shown in
the following section that this simple equation will eliminate (iv) Scaled surface potential, z, is then calculated using:
 
not only the need for evaluation of elliptic integration but dy 2513:6P0
also the need for inverse analysis in the estimation of ¼ pffiffiffiffiffiffiffiffi ¼ ð2 cosh z  2 cosh uÞ1=2 :
dn x¼0 enT
swelling pressures from void ratio or dry densities of the
compacted bentonites. (v) Then the scaled distance is calculated from (1):
"   ! #
exp y=2 þ 1 z
jd ¼ ln   tanhð Þ :
exp y=2  1 4
Proposed procedure for the estimation of e versus P
relationship (vi) Mid-plane distance, d (Å), is then computed from:
jd
As mentioned before, the estimation of swelling pressures of d¼ :
j
compacted bentonites at different dry densities and vice
versa is a common practice in the design of high-level (vii) Void ratio is calculated from:
radioactive waste repositories (Madsen 1998; Japan Nuclear e ¼ Gqw Sd:
Cycle Development Institute 1999; ENRESA 2002). The
(viii) The dry density of the compacted bentonite is given
following procedure is proposed in design for the estimation
by:
of e versus P relationship based on the derived equations in
(11)–(13). The important steps involved in obtaining swell- Gqw
qd ¼ ð14Þ
ing pressures of bentonites from dry densities are: 1þe
(i) Obtain scaled midway potential, u, from the know where G is the specific gravity of soil solids, qd is the
swelling pressure using Langmuir’s formula: dry density, and qw is the density of water.
P ¼ 2nRT ðcosh u  1Þ: The estimation of swelling pressure from void ratio
using the proposed approach is a similar exercise except
(ii) Calculate midway potential, /d (mV), using
me0 /d
the use of /d as a function of /x=d from Eq. (12) or Eq. (11)
u¼ KT : in step (iii). It can be observed from this procedure that the
(iii) Estimate electric potential of a non-interacting integral evaluation is eliminated by replacing integral
system at distance x = d [obtained by rearranging equation in Eq. (2) with simple algebraic equations relating
Eq. (11)], electrostatic potentials. This procedure further eliminates

123
310 Environ Earth Sci (2013) 70:303–314

Fig. 7 a Polynomial fit to the (a)

relationship between midway
potential of the interacting and φ φ φ
potential of non-interacting
systems. b Polynomial fit to the
relationship between potential
of the non-interacting and

φ
midway potential of interacting
systems

(b)
φ φ φ
φ

the need for inverse analysis. Moreover, theoretical esti-

mation of e versus P relationship using the proposed
approach can be obtained by simple hand calculations.
φ

Thus, the proposed approach is computationally efficient.

To determine the accuracy of the proposed approach with
the integral evaluation method, swelling pressures of the
compacted bentonites are estimated from these two meth-
ods and compared with experimental data in the following
section. The example calculation is given in Appendix 1.

Application of the proposed method to experimental

data
φ
Varieties of compacted bentonites have been used as backfill
Fig. 8 Dependency of potential relationship on valence and buffer materials of high-level nuclear waste repositories

123
Environ Earth Sci (2013) 70:303–314
Fig. 9 Dependency of potential
relationship on soil property
Table 1 Properties of the compacted bentonites
Parameter MX80a
Specific gravity, G 2.76
Specific surface area, S (m2/g) 562
Base exchange capacity, B (meq/100 g) 73
Valence, v 1 2
a
Data from Müller-Vonmoos and Kahr (1982) (cited by Tripathy et al. 2004)
b
Data from ENRESA (2000)
c
Data from Japan Nuclear Cycle Development Institute (1999)
all around the world. Four such bentonites, for example,
MX80, Febex, Montigel, and Kunigel V1, have been
extensively investigated in the past. These bentonites have
different properties and contain different contents of
exchangeable cations. The properties of these bentonites are
given in Table 1. The valences of the exchangeable cations
for different bentonites are considered based on the presence
of predominant cation in the exchangeable state. The
experimental swelling pressures of these bentonites were
determined by subjecting them to distilled water under
constant-volume condition. The experimental details of
these bentonites are given elsewhere (Bucher and Spiegel
1984; Butcher and Müller-Vonmoos 1989; Madsen 1998).
The experimental swelling pressures of bentonites are
compared with the theoretical counterparts obtained by
integral evaluation and proposed approaches. Figures 10,
11, 12 and 13 show experimental and theoretical swelling
pressures of the bentonites with increasing dry density.
Comparison of experimental and theoretical values indicates
that the experimental swelling pressures are generally less
than their theoretical counterparts at low dry densities,
whereas the opposite tendency is apparent at higher densities
(Tripathy et al. 2004). Thus, only limited experimental data
with maximum densities varying between 1.6 and 2.0 Mg/
311
Febexb Montigela Kunigel V1c
2.70 2.85 2.70
725 ± 47 493 525
102 62 104.4
2 2
m3 are used for different bentonites in this work. The devi-
ation of the theoretical swelling pressures from the experi-
mental counterparts can be attributed to the assumptions
made in the GC theory such as (1) homo-valent ionic system
(either monovalent or divalent) and (2) ignoring the effect
due to size of the ion. The figures clearly show that the
swelling pressures obtained by the proposed approach
exactly match the values obtained by integration evaluation
method. However, the swelling pressures for MX80 ben-
tonite in Fig. 10, obtained by proposed approach, slightly
deviates from integral evaluation approach at densities,
qd C 1.5 Mg/m3. This is mainly because of the considered
assumptions for obtaining unique potential relationship for
different P0 and valance. However, this deviation is not
significant as the theory usually under-predicts the swelling
pressure values at high compacted densities. Thus, the pro-
posed approach is not only computationally efficient but also
accurate in the estimation of swelling pressures of com-
pacted bentonites within the validity range of GC theory.
Summary and conclusions
Swelling pressures of compacted bentonites, used as barrier
and buffer material in the nuclear waste repositories, are
123
312
Fig. 10 Experimental and
theoretical swelling pressures
against dry densities for MX80
bentonite
Fig. 11 Experimental and
theoretical swelling pressures
against dry densities for Febex
bentonite
commonly predicted against void ratios or dry densities
using DDL theory. However, the computation requires the
solution of an elliptic integral. Moreover, the prediction of
swelling pressures of the bentonites at different compacted
dry densities (known jd values) requires an inverse anal-
ysis since the parameter u in Eq. (2) is unknown. Thus, it
requires either repeated calculations of jd with various
assumed u to match the known values or requires rigorous
optimization techniques. Several existing techniques to
circumvent this problem and their limitations are discussed.
A unique relation between mid-plane potentials of the
interacting clay–water–electrolyte system and electrostatic
potential of non-interacting diffuse system is established in
123
Environ Earth Sci (2013) 70:303–314
this work with an aim to propose computationally efficient
method for obtaining swelling pressures of the compacted
bentonites. Simple generalized relations are derived by
relating these potentials of interacting and non-interacting
systems. The derived relations are validated for electrolyte
concentrations of 10-3 to 10-5 M, for both monovalent and
divalent exchangeable cations, and for all values of P0 . A
novel method is proposed for estimating e versus P based
on the established potential relationship. Comparison with
the existing methods shows that the proposed method
alleviates all the limitations of the existing procedures such
as need for interpolation or extrapolation to read-off the
values from tables and graphical representations. The
Environ Earth Sci (2013) 70:303–314 313

Known

Specific surface, S = 800 m2/g; base exchange capacity,

B = 100 meq/100 g (P0 = 0.125 meq/100 m2); n = 0.001
M; v = 1; e = 78.54 T = 298 K; and d = 50 Å

Calculation

Step 1. Surface potential of single clay particle (Eq. 9),

 0
T 1256:81  P
/0 ¼ 0:1725 sinh1 pffiffiffiffiffiffiffiffi
m neT
¼ 214:554 mV

Step 2. Scaled surface potential,

Fig. 12 Experimental and theoretical swelling pressures against dry mFu0 1  9:6487  107  0:214554
z¼ ¼ ¼ 8:3556
densities for Montigel bentonite RT 8:314  103  298

Step 3. The dimensionless parameter, n, at x, which

equals to the half-space distance d, where the
mid-plane potential is to be calculated
n ¼ j  x ¼ j  d ¼ 106  50  108 ¼ 0:5
Step 4. Scaled potential at any distance from the particle
surface,
 
expðnÞ þ tanhð4z Þ
y ¼ 2  ln
expðnÞ  tanhð4z Þ !
expð0:5Þ þ tanhð8:3556
4 Þ
¼ 2  ln ¼ 2:6997
expð0:5Þ  tanhð8:3556
4 Þ

Step 5. Electric potential of a single non-interacting plate

at distance, x, which equals to half-space distance
Fig. 13 Experimental and theoretical swelling pressures against dry
d, where the midway potential is to be calculated,
densities for Kunigel V1 bentonite RT
/x¼d ¼ y ¼ 2:6997
mF
8:314  103  298
  1000 ¼ 69:319 mV
proposed method predicts continuous distribution of the 1  9:6487  107
potentials. Further, it eliminates the need for inverse
analysis for the prediction of swelling pressure from void Step 6. The mid-plane potential is calculated using (12),
ratios. Thus, the proposed method is superior to all the /d ¼ 6:24  104 /2x¼d þ 1:205/x¼d þ 8:582
existing approaches of swelling pressure determination in ¼ 89:113 mV
terms of computation. Further, the proposed method pre-
dicts a continuous distribution of e versus P. Comparison Step 7. Scaled mid-plane potential
of the proposed method with integral evaluation approach
mF/d
for the prediction of swelling pressures of four compacted u¼
bentonites shows that the proposed techniques predict RT
1  9:6487  107  89:113
accurate solutions. ¼  103 ¼ 3:47
8:314  103  298

Step 8. The swell pressure corresponding to the half-space

Appendix 1 distance 50 Å is calculated using the Langmuir’s
formula (5).
Calculation of swelling pressure from half-space distance
P ¼ 2nRTðcosh u  1Þ ¼ 74:77 kPa
by the proposed approach:

123
314 Environ Earth Sci (2013) 70:303–314

References the 9th international clay conference, Strasbourg, 28 Aug–2 Sept

1989. Université de Strasbourg, Strasbourg, France, pp 107–115
Japan Nuclear Cycle Development Institute (1999) H12: project to
Bharat TV (2004) Simplified methods of evaluation of diffuse double
establish the scientific and technical basis for HLW disposal in
layer parameters employed in geotechnical engineering. M. Sc.
Japan: supporting report 2 (respiratory design and engineering
Dissertation, Indian Institute of Science, India
Technology). Japan Nuclear Cycle Development Institute,
Bharat TV, Sivapullaiah PV, Allam MM (2008) Novel algorithm for
Tokyo
estimation of swell pressure of fine grained soils based on diffuse
Madsen FT (1998) Clay mineralogical investigations related to
double layer (DDL) theory. In: The 12th international conference
nuclear—wate disposal. Clay Min 33:109–129
of international association for computer methods and advances
Mitchell JK (1993) Fundamentals of soil behavior. Wiley, New York
in geomechanics (IACMAG), 1–6 October, Goa, India
Müller-Vonmoos M, Kahr G (1982) Bereitstellung von bentonit fur
Bolt GH (1956) Physico-chemical analysis of the compressibility of
laboruntersuchungen. Nagra Technischer Bericht. 82-04
pure clays. Géotech 6(2):86–93
Overbeek JThG (1952) Electrochemistry of double layer and the
Bucher F, Spiegel U (1984) Quelldruck von hochverdichteten
interaction of colloidal particles. In: Kruyt HR (ed) Colloid
bentoniten. Nagra Technischer Bericht. 84-18
science, vol 1. Elsevier, Amsterdam
Butcher F, Müller-Vonmoos M (1989) Bentonite as a containment
Pusch R, Yong R (2006) Microstructure of smectite clays and
barrier for the disposal of highly radioactive waste. Appl Clay
engineering performance. Taylor and Fracis, New York
Sci 4(2):157–177
Schanz T, Tripathy S (2009) Swelling pressure of a divalent-rich
Chapman LA (1913) Contribution to the theory of electrocapillarity.
bentonite: diffuse-double layer theory revisited. Wat res res
Phil Mag Ser 6, 25(148):475–481
45(5)
ENRESA (2000) FEBEX project—full scale engineered barriers
Sridharan A, Choudhury D (2002) Swelling pressure of sodium
experiments for a deep geological respiratory for high level
montmorillonites. Géotech 52(6):459–462
radioactive waste in crystalline host rock. Final report, Publica-
Sridharan A, Jayadeva MS (1982) Double layer theory and com-
ción téechnica 4/2002, Empresa Nacional de Residuos Radiac-
pressibility of clays. Geotech 32(2):133–144
tivos SA (ENRESA), Madrid, Spain
Tripathy S, Sridharan A, Schanz T (2004) Swelling pressures of
ENRESA (2002) Thermo-hydro-mechanical characterisation of a
compacted bentonites from diffuse double layer theory. Can
bentonite from Cabo de Gata—a study applied to the use of
Geotech J 41:437–450
bentonite as sealing material in high level radioactive waste
van Olphen H (1977) An introduction to clay colloid chemistry.
repositories. Publicación téechnica 4/2002, Empresa Nacional de
Interscience, New York
Residuos Radiactivos SA (ENRESA), Madrid, Spain
Verwey EJW, Overbeek JTG (1948) Theory of the stability of
Gouy G (1910) Sur la constitution de la charge electrique a la surface
lyophobic colloids. Elsevier, Amsterdam
d’un electrolyte. J Phys Theor Appl Ser 4(9):457–468 (in
Yong RN, Mohamed AMO (1992) A study of particle interaction
French)
energies in wetting of unsaturated expansive clays. Can Geotech
Gratchev I, Towhata I (2011) Compressibility of natural soils
J 29:1060–1070
subjected to long-term acidic contamination. Environ Earth Sci
Zheng L, Samper J, Montenegro L (2011) A coupled THC model of
64:193–200
the FEBEX in situ test with bentonite swelling and chemical and
Ishikawa H, Amemiya K, Yusa Y, Sasaki N (1990) Comparison of
thermal osmosis. J Contam Hydrol 126(1–2):45–60
fundamental properties of Japanese bentonite as buffer materials
for waste disposal. In: VC Farmer, Y Tardy (eds) Proceedings of

123