PHYSICO-CHEMICAL ANALYSIS OF THE COMPRESSIBILITY

OF PURE CLAYS
by
G. H. BOLT, Ph.D.

SYNOPSIS
It has been shown that the presence of exchange- On a montre que la presence d’ions interchange-
able ions in clay systems leads to the presence of ables dans des constitutions d’argile provoque
long-range repulsion forces between the particles. I’apparition de forces repulsives a grande distance
A comparison between the compression curves as entre les particules. Une comparaison entre les
observed and as calculated from theoretical con- courbes de compression observees et calcultes
siderations indicates that in the case of suspensions d’apres des considerations theoriques indique que
of pure clays the compressibility can be accounted dans le cas de suspensions d’argiles pures on peut
for quantitatively by the consideration of these &valuer la compressibilitk quantitativement par la
long-range forces only. seule consideration de ces forces a grande distance.

INTRODUCTION
If the load on a laterally confined specimen of soil is increased, the volume of the specimen
decreases. In coarse-grained soils, part of the volume decrease is due to a deformation
(including breakage) of the soil particles and the balance to rotational displacement of the
soil particles, involving slippage at the points of contact.
The compressibility of coarse-grained aggregates composed of equi-dimensional particles,
such as round quartz grains, is due almost entirely to rotational displacement of the grains
(Terzaghi, 1925). On the other hand, if the aggregate contains a high percentage of flaky
material (e.g., mica), the compressibility of the aggregate is due chiefly to a deformation of
the flaky constituents by bending. This conclusion is corroborated by the fact that the
compressibility of dry mixtures of sand and ground mica increases very rapidly with increasing
mica content of the aggregate (Redlich, Terzaghi, and Kampe, 1929).
The compressibility of fine-grained soils containing a high percentage of clay minerals also
depends on the chemical composition of the interstitial liquid which will be referred to as the
soil solution. For instance, the replacement of Ca in the soil solution of a bentonitic clay by
Na increases the compression index of the clay many times. Yet the mechanical properties
of the solid soil constituents remain unchanged (Salas and Serratoso, 1953). The compressi-
bility of such systems depends, therefore, not only on the mechanical properties of its con-
stituents, but also on physico-chemical factors.
It will be shown that the physico-chemical interaction between clay particles and the
surrounding liquid phase leads to the existence of a repulsive force between the particles
which can extend over considerable distances. Terzaghi and Peck (1948) discuss the exist-
ence of such a repulsive force between clay particles, which is attributed to “ an increase
in the thickness of the adsorbed layers which separate the grains “. This is correct if it is
understood that the “ adsorbed layer ” refers to the presence of exchangeable cations in the
immediate vicinity of the clay particles. As a result, the ionic concentration in this region
exceeds the concentration of the “ free ” solution that is pressed out from the clay upon
compression. In turn this implies that the osmotic pressure of the clay with the exchangeable
ions is larger than the osmotic pressure of the extracted pore liquid. Since the exchangeable
cations are bound to stay with the clay, a specimen consisting of pure clay can actually be
regarded as an osmometer, the semi-permeable membrane of which is formed by the
clay particles themselves. Upon applying a load to this system a certain amount of pore
liquid is pressed out until the difference between the osmotic pressure of the system and of
the free liquid phase pressed out equals the loading pressure. The significance of this difference
in osmotic pressure becomes clear if one considers the magnitude of the ionic concentration
86
 PHYSICO-CHEMICAL ANALYSIS OF THE COMPRESSIBILITY OF PURE CLAYS 87
close to the clay plates. For most clays this concentration is about 2.5 to 5 molar. This
means that if the plates come very close, the osmotic pressure of the system might reach a
value of SO-100 atm (or tons per square foot). It can also be proved that the repulsive force
arising from the osmotic pressure effect extends over a long range (corresponding to a change
in void ratio of 1 to 20, depending upon the specific surface of the clay). Contrary to the
situation in coarse-grained soils this repulsion between clay particles does not therefore depend
on a direct contact between the particles. As a result, the compressibility of pure
clays will be large, and reversible to a high degree. The magnitude of the compressibility
will be a function of the nature of the clay involved and the electrolyte content of the
system.
It has been suggested (Terzaghi and Peck, 1948) that in addition to the factors deter-
mining the compressibility already discussed, swelling and shrinking could occur within the
clay particles (“ expanding-lattice ” clays). It is thought that this distinction between
expanding and non-expanding clays is a matter of degree rather than a difference in nature.
The basic unit of the montmorillonitic and the illitic clays is a sheet, which is roughly 10 A in
thickness ; this unit will never expand. In montmorillonite the clay particles may consist
of single sheets of 10 8, and as a result the swelling, which implies an increase of the distance
between the particles, is very large. In illitic clays the particles consist, in general, of several
(520) sheets of 10 A each which are bonded by chemical forces. The swelling of such a clay
is comparatively much less than the swelling of montmorillonite, although the cause of both
is the same, namely, the excess osmotic pressure in the adsorbed layer of ions. The distinction
between “ expanding ” and “ non-expanding ” should, therefore, probably be replaced by a
classification according to an average particle thickness or specific surface of the clay.
Natural soils are mixtures of clay particles and coarse-grained soil constituents. Therefore
part of their compressibility is determined by the mechanical properties of the soil particles
and the balance by the physico-chemical interaction between the clay particles and the soil
solution. Experience has shown that the relation between load and compression for dry
sand-mica mixtures is very similar to that of pure clays. Furthermore, the phenomenon of
swelling of precompressed soil specimens can be explained on the basis of both the purely
mechanical concept of the capillary pressure (Terzaghi and Peck, 1948) and of the theory set
forth in this Paper. Therefore it is very difficult to decide a priori which portion of the com-
pressibility of a natural clay soil is due to the mechanical properties of its constituents and
which portion to the interaction between the soil solution and the clay particles. Neverthe-
less, the mechanical concept involves the hypothesis of a shape and an arrangement of the
clay plates susceptible to elastic deformation (bending) to an extent corresponding to the
observed decrease in void ratio upon loading. On the other hand, the physico-chemical
interaction can be regarded as a fact, since there are independent methods to show that
clay plates are charged and are surrounded by exchangeable ions.
In addition, there is one important difference between highly compressible coarse-grained
aggregates and pure clay, The ratio :

a=- G
G
between the swelling index, Cd, and the compression index, C,, of highly compressible coarse-
grained aggregates can be as low as 0.1, whereas the corresponding value for pure clay and
other Colloids is close to unity. Hence, the value a should, in a general way, be indicative
for the relative importance of the influence of the osmotic forces on the resistance of clay soils
against compression. Natural clay soils with an a-value of more than 0.3 are very rare.
The relative importance of the osmotic forces is also disclosed by the influence of base exchange
on the value of the compression index, C,, of a natural clay soil in a remoulded state. How-
ever, statistical data concerning these properties of natural clay soils are not yet available.
88 G. H. BOLT

Finally, since the physico-chemical interaction forces can be calculated, a comparison

between the measured compressibility and the one calculated from this type of interaction
should show the relative importance of both the mechanical and the physico-chemical inter-
action forces with regard to the compressibility of field soils.
The Paper deals exclusively with the compressibility of pure clay, with a close to unity.
It will be shown that it can be accounted for, both qualitatively and quantitatively, by
osmotic forces. However, the theory does not account for the thixotropy of pure clays, for
secondary time effects and other clay properties of outstanding practical importance which
cannot be explained on the basis of purely mechanical concepts. Therefore it represents
only a first step toward a deeper understanding of the interaction between the soil solution
and the clay-fraction of natural clay soils.

THEORETICAL CONSIDERATIONS

Due to ionic substitutions in the crystal lattice, clay particles carry, in general, a negative
charge. The exchangeable cations which accompany the clay particles are attracted to the
particle as a result of this negative charge. This attraction is opposed by the tendency of
the ions to distribute themselves evenly throughout the system. As a result, a diffuse type
of distribution of the ions is formed. Since the negative charge of the particle and the
positive charge of the counter ion are spatially separated, this system can be regarded as an
electric double layer. In order to indicate the diffuse character of the counter charge, the
term “ diffuse double layer ” is used. Although the osmotic pressure within the double
layer decreases continuously with the distance from the solid surface, it can be proved that
the effective osmotic pressure of the system is determined by the concentration of the ions
in the central plane between the plates (Verwey and Overbeek, 1948). This follows from the
consideration that the hydrostatic pressure-gradient force in the double layer, arising as a
result of the gradient in the osmotic pressure, is balanced by the electric forces acting on the
space charge formed by the counter ions. In the central plane the potential gradient (or
electric field strength) is zero and, therefore, no electric forces are acting in this location.
This implies that in a clay system, in equilibrium with an electrolyte solution situated outside
the range of influence of the clay plates, the hydrostatic pressure in the central plane acts as
a net pressure pushing the plates apart. The “ swelling pressure “, therefore, equals the
difference between the osmotic pressure in the central plane and the osmotic pressure in the
equilibrium solution. In practice, such an equilibrium solution is provided by the solution
which is pressed out upon loading of the clay specimen.
Thus the swelling pressure of the system is caused by the tendency of the liquid phase
to re-enter the system. The mechanical concept mentioned before gives a similar explanation
of the swelling of flaky materials, except that in this theory the tendency of the liquid to
re-enter the system is the result of the existence of a deficit in hydrostatic pressure between
the particles, and not of an excess osmotic pressure. In comparing the “ osmotic ” and the
“ mechanical ” theories one should bear in mind that the deficit in hydrostatic pressure
between the grains can exist only if the grains are kept apart by mechanical forces. Such
mechanical forces imply a direct contact between the particles, which seems unlikely in pure
clays, unless a very advanced stage of desiccation has been reached (Bolt and Miller, 1955).
Since in the mechanical theory the swelling of a soil system is directly related to the inter-
granular force, this theory implies a relation between the swelling pressure and the shear
strength. In the osmotic theory such a relationship will not exist ; even systems with zero
shear strength can still exhibit a swelling pressure.
In considering the applicability of the theories mentioned to practical systems it should
be stressed that the osmotic swelling will occur if the ionic distribution is favourable (which
can be calculated). The mechanical swelling, if occurring, will take place in addition to the
 90 G. H. BOLT

3. In saturated pure clays the distance between the clay plates can be expressed in
the void ratio of the system by the approximate expression :
e=y,Sd . . . . . . . . * (3)
in which yc = density of the clay ; 2d is the distance between the plates, and S = specific
surface of the clay.
The relationship between vd/gco(x,,+ e/y$) and log PJRTc, obtained from the com-
bination of equations (l)-(3) has been tabulated in Table 1. It should be noted that for
large values of e/y&Sthis relationship becomes linear, according to :
log PJRTc, = log 64 - 0~4343{2vl/~,(x, + e/y&) . . . . . (4) *
The above theory is based on a number of assumptions ; namely, (a) the validity of the
Gouy theory, (b) parallel alignment of the clay plates, (c) the validity of van’t Hoff’s relation
(equation (2)), and (d) the validity of the calculation of the void ratio. The first of these
assumptions has been dealt with (Bolt, 1954, and Bolt, 1955) and it could be proved that the
Gouy theory is definitely satisfactory for the purpose of the above calculations. The second
assumption means, in fact, that the minimum load-bearing capacity is calculated. In the
pressure range between O-1 to 100 atm, parallel arrangement of the particles corresponds to the
position of minimum free energy of the system and deviations from this minimum value that
could occur should certainly be very small, at least in remoulded systems.
The validity of the van’t Hoff relation is rather doubtful, but since the expected devia-
tions from this law are partly offset by the effect of non-ideal behaviour of the ions in the
double layer, the relative magnitude of the error involved will probably not exceed 10%.
Actually, the applicability of the relation (d) seems the most uncertain factor in this
theory. It follows from the theory that a basic relation exists only between the thickness
of the liquid layer on the clay plates and the swelling pressure. Only in saturated systems
containing perfectly flat clay particles the relation (d) applies. If the clay surface has a
terraced nature (which is very likely even for pure clays), the actual void ratio will be larger
than the one calculated from equation (4).

EXPERIMENTAL
In order to test the validity of the relations presented in the section entitled “ Theoretical
considerations,” a number of compression curves were determined of suspensions of mont-
morillonite and illite. Since the presence of coarse fractions could introduce complications
with regard to the calculation of the plate distance from the moisture content, the fractions
< 0.2~ of these materials was used.
The montmorillonite used was a Wyoming bentonite, obtained from the American Colloid
Company under the proprietary name KWK Volclay. The volclay was electrodialized
and subsequently saturated with Na ions by the addition of NaOH. The sodium clay so
obtained was fractionated by means of a Sharpless centrifuge. The fraction < 0.2~ was
retained and used for the determination of the compression curve. The clay used for the
determination of the Ca curve was obtained by passing a portion of the Na clay through a
column of Ca-saturated exchange resin. The illite sample consisted of the fraction < 0.2~
of the American Petroleum Institute reference clay mineral H35 (Fithian illite). This clay
was saturated with Na ions by repeated treatment of the sample with concentrated NaCl
and subsequent washing with distilled water.
The compression data were obtained by means of a miniature compression apparatus,
which covered a pressure range from approximately 0.1 to 100 atm. In this apparatus the
* Equation (4) is comparable to the qualitative relation between J!Jand e given by Salas (Salas and
Serratoso, 1953). Salas’s relation, valid only under the conditions specified above, also contains a van
der Waal’s term. Unless the electrolyte content of the system is very high, this term can be safely neglected
(Kruyt, 1952).
 PHYSICO-CHEMICAL ANALYSIS OF THE COMPRESSIBILITY OF PURE CLAY 91

sample is contained in a pocket formed by a rubber membrane. The “ open ” side of the
pocket is formed by a cellophane membrane, which is supported by a porous stone. Pressure
is exerted on the outside of the rubber membrane by means of compressed nitrogen gas.
The liquid phase of the sample can escape through the cellophane and the porous stone, and
is collected in a system of calibrated capillaries. A detailed description and diagram of the
apparatus can be found in Bolt and Miller (1955). The accuracy of the determination of the
volume of the expelled liquid, expressed in the corresponding change of the distance between
the clay plates, was approximately 4 A.
The compression data of the montmorillonite samples are plotted in Fig. 1, together with
a theoretical compression curve calculated according to Table 1. The specific surface used in
these calculations was 8 x 102 me/g, as is found from the known thickness of montmorillonite

! F
I I la
.
. COMPRESSION i
5: \ lO-3 NaCl I I
Ide- 8 RECOMPR.

CaCle ( COMPR.)
- loo
3-

10m3 Na ‘, ‘-
,

-.
---_ A - ‘-2 .
--__ ---_
---_ ---- __
---_ --a_
I
I *O
I IO P, atm

Fig. 1. Compression curves of Na-montmorillonite and Ca-montmoril-

lonite, fraction < 0.2~, in equilibrium with 1O-J molar NaCl and
CaCl,, respectively. The dashed lines represent the theoretical curves
for S = 800 rn’lg. The moisture content is indicated both as void
ratio and as average thickness of the liquid layer D = (d + x0)

plates. Comparing the experimental data with this theoretical curve it is found that the
initial compression curve deviates somewhat from the expected curve. Initially it was
thought that the sample might possibly have a specific surface somewhat larger than the
calculated one, as a result of the presence of aluminium hydroxides introduced in the pre-
paration of Na clay by means of electro-dialysis. A check run with a Na-montmorillonite
sample prepared by resin exchange, which was known to be free of these hydroxides, indicated,
however, that this was not the case. It would seem more likely, therefore, that certain
92 G. H. BOLT

structural effects are the cause of these deviations. This implies that during the first com-
pression parallel arrangement is only gradually completed. Upon decompression this
parallel arrangement is not disturbed, which is understandable since non-parallel arrangement
corresponds to a higher energy state of the system than the parallel arrangement. As a
result the decompression curve deviates from the compression curve. Recompression, how-
ever, follows exactly the same pattern as the decompression. Nevertheless, it still has to be
explained why the decompression curve is not identical with the theoretical curve. A
possible interpretation of this is that since the cellophane membrane is somewhat permi-
selective, a certain retention of salts takes place in the sample upon compression. As a result
the decompression curve follows the path of a theoretical curve at a higher salt level ; using
the Table it is found that the decompression data follow roughly the curve corresponding to
5 x 10-s molar NaCl.*
In addition to the curves for Na-montmorillonite, the compression curve of a sample of
Ca-montmorillonite was determined. Although the same (probably structural) effect was
noted as in the case of the Na samples, the observed effect of the introduction of divalent
exchangeable ions agrees very well with the theoretical expectations.
The illite sample (Fig. 2) shows a reasonable agreement between theory and experiment.

e I I I D
0 0 0.001 M NaCl %
0-

!oo

‘;, ,”
3- . . P 100
I\ ‘+, i.0
-\ \ .
-. \ -0
\ *so . .
A
2- \ -.
/IO_ . . \ X\ .B 0.
--__ --__ -- wiNx,
\ "P
--_ ---_ N.- z . 8
I- ----_ ---_ -a- -_
---_- -z-__
--_ ---_a_
Q. I I I 3‘
0.1 I IO PI atm
Fig. 2. Compression curves of Na-illite, fraction < 0.2~ in equilibrium with different
concentrations of NaCl, given as molarity. The dashed lines represent the
theoretical curves for S = 120 m”/g.

* A strong support for this interpretation of the decompression curve was provided by data obtained
by Mr B. P. Warkentin at Cornell University, who showed that the decompression and recompression curve
of a Na-montmorillonite sample that was very carefully freed from NaCl followed exactly the theoretical
curve for very low electrolyte concentration.
 PHYSICO-CHEMICAL ANALYSIS OF THE COMPRESSIBILITY OF PURE CLAY 93

Since not sufficient material was present to determine the specific surface of this sample by
means of negative adsorption (cf. Schofield and Talibuddin, 1948) an estimate was made by
assuming that the specific surface of the fractions < 0.2~ and < 2~ was proportional to the
exchange capacity of these fractions. The specific surface of the fraction < 2~ was deter-
mined directly by means of negative adsorption and found to be equal to 78 mz/g. The
surface area of the fraction < 0.2~ was then calculated to be approximately l-2 x 102 ms/g.
Using this value the theoretical curves of Fig. 2 were obtained.
The apparent shift of 3040 A between the theoretical curve and the experimental data
can be explained by the presence of a “ dead ” volume of liquid in this sample resulting from
the terraced nature of the surface. An electron microphotograph revealed that the particles
had an average thickness of approximately 100 A, the surface being terraced. Such a surface
would lead to a certain volume of liquid which could not be expelled even upon very close
approach. In view of the average thickness of 100 8, 30 A seems very reasonable for the
depth of the layer of non-removable liquid. At the same time the existence of this shift
indicates that in case of natural soils, it cannot be expected that the distance between the
clay plates can be calculated from the knowledge of the specific surface and the moisture
content. The changes in the compression curve of the illite sample upon an increase of the
concentration of salt solution in equilibrium with the sample seems in good agreement with
the theoretical predictions.
In conclusion, it can be stated that the compressibility of pure clay suspensions and pastes
can be accounted for very well by the consideration of the interaction between the electric
double layers formed on the clay particles.

ACKNOWLEDGEMENT
The research conducted in connection with this Paper was supported in part by funds
from Regional Research Project NE-11 under the provisions of Section 9b3 of the Research
and Marketing Act of 1946. The Author gratefully acknowledges the valuable suggestions
offered by Professor Karl Terzaghi and Dr Arthur Casagrande in the course of the preparation
of the manuscript.

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