CRITICAL REAPPRAISAL O F COLLOIDAL ACTIVITY

OF C L A Y S
By N. S. Pandian 1 and T. S. Nagaraj 2

ABSTRACT: Soil properties and their behavior, apart from stress history, are in-
fluence markedly by physicochemical characteristics of the constituent clay and
nonclay minerals and their relative proportions. Atterberg limits and Skempton's
colloidal activity, which are simple quantitative parameters, reflect the composite
effects of the soil constituents and their interactions with pore fluid. Microme-
chanistic interpretations of these parameters have been provided in this paper. It
has been shown that, in general, the liquid limit of fine-grained soils reflects the
physicochemical potential and that each of the factors of Skempton's colloidal ac-
tivity are interdependent. It has been illustrated that property correlations with col-
loidal activity, as well as with Atterberg limits, result in involved interrelationships
due to the interdependence of the parameters.

INTRODUCTION

The fact that even a small fraction of clay in a soil may decisively influ-
ence its engineering behavior, despite the remainder being sand and silt, has
been very well established. It has also been realized that the type of clay
mineral may cause extreme variations in engineering properties of soils, even
though the clay percentage remains the same. Therefore, neither the clay
percentage nor the type of clay alone suffices to characterize the physico-
chemical activity of soils. If it were possible to identify a single valued
parameter that would reflect the total physicochemical activity of a soil, then
such a parameter would help both in soil classification and in the prediction
of soil behavior. Two possible approaches towards the characterization of
the physicochemical activity of soils can be traced in the development of
soil mechanics.
First, Atterberg (1911) realized that in the progressive transition from liq-
uid to solid states, soil undergoes sudden changes in its consistency. The
liquid, plastic, and shrinkage limits of soils reflect the changes in consistency
with moisture content. These limits are determined by relatively simple tests.
Terzaghi (1926) noted that the results of these simplified soil tests depend
precisely on the same physical factors that determine the mechanical behav-
ior of soils in a far more complex manner. Consistency limits of soils and
their derived parameters such as plasticity index and liquidity index are, to
date, the most widely used indices of soil behavior.
Second, Skempton (1953) observed a direct relationship between plasticity
index PI and clay content (C) (percentage by weight of particles finer than
two micrometers). He defined the colloidal activity of clays (ACT) as the
ratio of plasticity index to clay fraction. The activity index has been regarded
as a single-valued parameter for any particular clay. For soils of a given
'Asst. Prof., Dept. of Civ. Engrg., Indian Inst, of Sci., Bangalore 560 012, India.
2
Prof. and Chmn., Dept. of Civ. Engrg., Indian Inst, of Sci., Bangalore 560 012,
India.
Note. Discussion open until July 1, 1990. To extend the closing date one month,
a written request must be filed with the ASCE Manager of Journals. The manuscript
for this paper was submitted for review and possible publication on July 15, 1988.
This paper is part of the Journal of Geotechnical Engineering, Vol. 116, No. 2,
February, 1990. ©ASCE, ISSN 0733-9410/90/0002-0285/$1.00 + $.15 per page.
Paper No. 24370.
285
geological origin, with an increase in clay content, both plasticity index, PI,
and percentage finer than micrometers increase, maintaining a constant value
of activity index. Currently, it has become a routine practice to indicate the
activity index of soils as well as the index properties in soil test reports.
In this paper, a micromechanistic interpretation of the Atterberg limits and
colloidal activity has been made. Based on this, the role played by these
parameters in the interpretation of test data has been identified.

LIQUID AND PLASTIC LIMITS

The liquid limit represents a state of a soil at which the separation distance
between the particles or their aggregated units are in equilibrium under the
influence of interparticle forces (Warkentin 1961). The water-holding ca-
pacity of soils under the influence of surface forces at the liquid and plastic
limits has been found to be due to suction pressures of 5 and 1,112 kPa,
respectively (Russell and Mickle 1970). Soils at their liquid limit possess
small but definite measurable shearing resistances. Casagrande (1932) de-
duced that the liquid limit corresponds to a water content at which the soil's
shear strength is approximately 2.5 kPa. Norman (1958) reported a shear
strength of 2 kPa at the liquid limit. Wroth and Wood (1978), based on the
test results of Youssef et al. (1965), concluded that the shear strength at the
liquid limit is unique and has a value of about 1.7 kPa. Wroth (1979) from
critical state concepts, has demonstrated the existence of a unique consoli-
dation pressure of 6.3 kPa at the liquid limit for all soils, i.e., if the soil is
initially in a slurry state and if it is subjected to a consolidation pressure of
6.3 kPa, the resulting equilibrium water content equals the liquid limit water
content. Whyte (1982), based on extensive test data, showed the shear strength
at the liquid limit to be approximately 1.6 kPa. This review suggests the
existence of a relationship between equilibrium consolidation/suction pres-
sure and shear strength for soils at their liquid and plastic limit water con-
tents.
Micromechanistically, if a parallel plate model is assumed for interaction
between clay particles, there exists a relationship between water content w
(in percent), specific surface s (in cm 2 /gm), and half-space distance between
particles (d in A° units) of the form (Nagaraj and Jayadeva 1981)
w = O.Olsd (1)
Sridharan and Jayadeva (1982) showed that for a given physicochemical en-
vironment, the relationship between d and log (R - A) is unique regardless
of the type of clay mineral, where R and A = the forces of interparticle
repulsion and attraction, respectively. Since comparable equilibrium con-
solidation/suction pressures (R - A) are needed to reach liquid and plastic
limit states of fine-grained soils, micromechanistically, these states can be
represented as
LL = 0.01*4 (2a)
and
PL = 0MsdP (2b)
where dL and dP = d-values at the liquid limit and plastic limit water con-
tents, respectively.
286
 MOISTURE CONTENT %
AT 40k N / m 2

160 K N / m '

[1978]
40 60 80
LIQUID LIMIT %

FIG. 1. Moisture Content versus Liquid or Plastic Limit and Liquid Limit versus
Moisture Content

Variations in the liquid and plastic limits of fine-grained soils can thus be
attributed to variations in specific surface, since dL and dP are of the same
order of magnitude for the physicochemical model of diffuse double-layer
interactions.
It can be seen in Fig. 1 that for the data given (Dennehy 1978), the mois-
ture content of a fine-grained soil is proportional to its liquid/plastic limit
for the soil to attain a particular level of undrained shear strength. For a
particular strength, the ratio of water content to liquid or plastic limit is
constant, provided the soil is devoid of any cementation bonding. From this
observation and the micromechanistic interpretation of Eqs. 2, it is reason-
able to assume that, although the plasticity index PI is different for a wide
spectrum of fine-grained soils, at the microlevel the differences in dL and dP
distances are the same. The manifestation of different magnitudes of plas-
287
ticity indices for different fine-grained soils can be attributed to differences
in the specific surfaces of the soils. Since (dL - dP) varies over a very limited
range, the plasticity index alone cannot be an inferential parameter to de-
scribe the engineering properties of fine-grained soils.

RELATION BETWEEN PI AND LL

A relationship of the form

PI = 0.74(LL - 8) (3)
was obtained by Nagaraj and Jayadeva (1983) based on the following as-
sumptions:

1. For saturated soils, an equilibrium stress condition and a certain shear strength
can be associated with LL and PL water contents.
2. There exists a linear relationship between the void ratio e and the logarithm
of pressure p, as well as undrained strength qu.
3. All soils tend to reach the same specific volume (1 + e) at high consoli-
dation pressures.
4. Eq. 3 is based on the statistical analysis of extensive published data of
consistency limits, as well as the examination of the relationship between PI and
LL from critical state concepts.

The data, which were analyzed to develop Eq. 3, pertain to clay minerals
having a sheet structure. Despite the possibility of getting different values
for the constants when larger data are analyzed or when clay minerals de-
parting from the assumed sheet structure are encountered (Halloysite), it is
clearly indicated that the plasticity index of soils bears a functional rela-
tionship with the liquid limit.

COLLOIDAL ACTIVITY OF CLAYS

Fig. 2 shows the plots of plasticity index versus clay fraction that Skemp-
ton (1953) presented for Shellhaven, London, Weald, and Horten clays. The
plot for each clay is a straight line, the slope of which represents the activity
index. The variation of plasticity index along the line is expected to reflect
the effect of both the amount and type of clay. The involvement of the clay
fraction in the expression for ACT is an indication of the variation of the
physicochemical potential of soil in terms of the plasticity index as the clay
fraction increases.
The following micromechanistic interpretation of ACT is made to assess
its potential role in the prediction of soil behavior. As discussed earlier, the
plasticity index is different for different soils. Micromechanistically, the PI
represents the same difference in the interparticle separation distance (dL —
dp) at their liquid and plastic limit states. Further, according to a recent
analysis (Nagaraj and Jayadeva 1983), a relationship between liquid and plastic
limits exists.
It is necessary to assess the role of the clay fraction in the expression for
ACT. As the clay fraction decreases, the plasticity index also decreases.
Whether this reduction is linearly proportional and if so, what reasons can
288
 100
Legend ACT LL PL
e Shellhaven 1-33 97 32
i London 0.95 73 25
A Weald 063 43 18
~o Horten 0.42 30 16

SUempton [1953]

20 40 60 80
Clay f r a c t i o n « 2u) , %

FIG. 2. Plasticity Index versus Clay Fraction

be attributed to the proportionate reduction merits consideration.

Generally, there is agreement that the liquid limit depends on the base
exchange capacity and the specific surface of a fine-grained soil (Farrar and
Coleman 1967). The presence of a nonclay coarse fraction reduces the spe-
cific surface. Seed et al. (1964) and Lupini et al. (1981) found that the
variation of liquid limit with clay fraction is linear. Whether the coarse frac-
tion has any direct influence on the flow behavior of a soil can be assessed
by the changes, if any, in the flow lines with changes in the coarse fraction's
surface characteristics. Fig. 3 (Srinivasa Murthy et al. 1987) shows the flow
curves of red earth, red earth-sand, red earth-glass, and red earth-glass-sand
mixtures. Although there is a twofold variation in surface frictional char-
acteristics between sand and glass, the flow curves are identical for a par-
ticular percentage of admixture. For example, when red earth is diluted either
by 20% sand or by 20% glass, the flow line remains the same. The red earth
contains mostly kaolinite with traces of quartz and mica. If there were to be
any contact between the constituent particles, the liquid limit water contents

289
 1. Red earth
2. Red earth : Glass =80:20
3. Red earth: Sand = 80:20
4. Red earth : Glass = 60:40
5. Red earth : Sand = 60:40
6. Red earth Glass Sand:
60: 20:20
60
c
c
o
o

o 40
5

, Sn'nivasamurthy etal[l987]
2 ol 1 1 3 ±J
15 20 25
Penetration depth D.mm
FIG. 3. Flow Curves

would have been markedly different. It is inferred that due to the large total
surface area of the clay sized fractions, the clay matrix provides a sheath
over the sand or glass particles, thereby inhibiting direct interactions between
them. In this eventuality, it should be possible to compute liquid limits of
the soil for various percentages of the clay fraction. In the expression for
ACT, the numerator plasticity index PI can be regarded as a function of LL.
The influence of the clay fraction, a parameter in the denominator, is sub-
dued in the value of the liquid limit itself.

REEXAMINATION OF COLLOIDAL ACTIVITY OF CLAYS

In Fig. 2, the slopes of the lines represent the colloidal activity, ACT.
When the effect of the clay fraction is incorporated into the modified liquid
limit due to dilution by coarse fraction added to the clay, the plasticity index
versus liquid limit relationship is uniquely defined. It is known that the liquid
limit of a given soil varies linearly with the amount of clay fraction present
in that soil. Thus for a given soil with a known clay content, if the liquid
limit value is known, the liquid limit value for any other clay content can
be estimated using a linear relation. The so-estimated liquid limit is known
as the modified liquid limit. In this paper, the liquid limit values reported
by Skempton and Northey (1952) are modified using the clay contents ob-
tained from Fig. 2. This is evident from Fig. 4, wherein the data of Skemp-
ton (1953) shown in Fig. 2 are replotted using the modified values of liquid
290
 PI > 0-689 (Liquid limit -6-05
Corr. coefficient = 0-980A
100 Standord error= 4-032
Legend: as in Figure 2

50

100 200
Liquid limit

FIG. 4. Liquid Limit versus Plasticity Index

limit. Clays of different activity fall into a zone along the same line. This
implies that the variation of PI with LL not only takes care of the type of
clay mineral of the soil, but also the percentage of clay in it. If it is accepted
that for clay minerals with sheet structure there exists a relationship between
the PI and the LL, then the LL itself reflects indirectly the colloidal activity
of the soil. As such, Skempton's colloidal activity parameter together with
the consistency limits cannot be used as an inferential parameter to predict
soil behavior.
The linear relationship between modified liquid limit and plasticity index
obtained from Skempton's (1953) data is of the form
PI = 0.689(LL - 6.05) (4)
It has a correlation coefficient of 0.9804 and a standard error of 4.032; the
number of points = 40.
The data of Seed et al. (1964) were also reexamined. They presented the
Atterberg limits for kaolinite-bentonite-sand mixtures and illite-bentonite-sand
mixtures. They also reported different linear relationships between plasticity
index and liquid limit for soils having different activities. Their data together
with those of Skempton (totalling to 103) are shown in Fig. 5. The rela-
tionship takes the linear form
PI = 0.9416(LL - 20.61) (5)
with a correlation coefficient of 0.9978 and a standard error of 6.36. This,
once again, confirms the fact that activity is a parameter that is a function
of liquid limit.
Seed et al. (1962), using test data from soils artificially prepared in the
laboratory, proposed a relationship between percentage of clay sizes present
in a soil, the activity of the clay, and the percentage of swell under one psi
surcharge of a sample compacted at optimum water content to maximum
density in the standard AASHTO compaction test. It is of the form
291
 300

?20O
Plasticity

- o /

N = 103
- y 0 P I = 0.9416(LL-20-6l)
100 Corr. coefft =0-9978
S t d . error = 6.36

SUempton [1953] and

Seed et al [1964]
_ W i i i 1 1 1 1 i i i i 1 i l . i i, 1. i ..
100 200 L i q u i d , i m i 1 300 400

FIG. 5. Liquid Limit versus Plasticity Index

S = kACT2MC3M ! (6)
5
where k = 3.6 X 10~ ; ACT = the activity; and C = the percentage of clay
sizes. Since ACT = PI/C - n, where PI = the plasticity index; and n =
the percentage of clay sizes for zero plasticity index
S = kPl2A4N (7a)
where
j-3.44
N = 77; {lb)
(C - ri)2M
The same data are plotted on a log-log scale in Fig. 6, which shows the
percentage of swell versus liquid limit. This is seen to give a linear relation
of the form
log 5 = 2.658(log LL - 1.289) (8)
with a regression coefficient of 0.88 and a standard error of 1.63; the number
of points = 19. Eq. 8 can be written as
5 = 3.75 x 1(T4LL2-658 . . . (9)
Thus it is possible to express the percentage of swell in terms of liquid
limit alone instead of the function given in Eq. 6, wherein the percentage
292
 100
N = 19
-LogS = 2.658(logLL-1.289)
r = 0-88
50 S td error = 1.63
2-658
S =3.75x10"* LL

01

w
01
O)
IO
o
c
01
o
01
CL-

Seed et al
[1962]
1 ' I ' l l
10 50 100
Liquid limit

FIG. 6. Liquid Limit versus Plasticity Swell

of swell is expressed in terms of both the activity of the soil and the per-
centage of clay sizes. It can also be seen from Eq. 9 that there exists a direct
relationship between the percentage swell and the liquid limit which, in turn,
reflects the influence of clay fraction and the plastic limit.
Fig. 7 shows a plot of the percentage of swell versus the activity of the
same data given by Seed et al. (1962). It can be seen that there is no trend
in the variation, indicating that activity cannot be an independent parameter
to explain the engineering behavior of a clay-water system.
Most recently, Carrier (1985) used a power function relationship between
void ratio and effective stress and related the empirical coefficient of the
power function with the index properties and activity of the soil to develop
an empirical relationship for compression ratio of the form
1 + 0.0133PI(1.192 + ACT"1) - 0.027PL"1
C = = 0.329 . . . . (10)
1+e 1 + 0.027w
where PI = plasticity index (in percent); PL = plastic limit (in percent);
ACT = the activity of the clay; and w = water content (in percent).
293
 9
50 _ m

- «

9
9 9
9

. m
w
Ol . 9 9

2 5 — e •
c 9
(V "
U
(V
0_
•
m
Seed et al
9 .[1962]
1 1 1 l 1 1 1 1 1 i i 1 i | i i

0.3 05 1.0 5.0 10

Activity

FIG. 7. Activity versus Percentage Swell

While discussing this paper, Koppula (1986) highlighted the need for sim-
ple relations. Since some of the properties appearing in Eq. 10 are interre-
lated, it can be simplified as Cc = 0.009w + 0.005 LL after excluding the
PL and ACT terms.
From the minimum air voids line and the generalized compressibility
equation for normally consolidated saturated soils, a generalized simple
equation for the compression ratio (Nagaraj et al. 1988) is of the form

C' = = 0.003 LL (11)

1+e
where LL = the liquid limit (in percent).
The given illustrative examples indicate that when index properties and
colloidal activity are regarded as independent parameters, involved func-
tional relationships are needed to predict the soil behavior. On the other
hand, direct simple relationships can be developed when the liquid limit of
a soil is regarded as reflecting its physicochemical activity.

CONCLUSIONS

The following conclusions are made from the present analysis:

294
 1. The liquid limit of soils is a reflection of their surface activity. It is dom-
inantly influenced by the specific surface area and the associated physicochem-
ical potential. The liquid limit is a measure of the water-holding capacity of soils
under the influence of interparticle forces. At the liquid limit, the soils have
comparable strength. The combined effects of the physicochemical properties
are, to a large extent, reflected by the liquid limit.
2. Skempton's activity index ACT is a function of the plasticity index and
the clay fraction. Note, however, that plasticity index is a function of liquid
limit and liquid limit itself depends upon clay fraction. Thus, any attempt to
predict engineering properties of soils in terms of activity, plastic limit, and
plasticity index is bound to be involved because they are dependent parameters.
Since all these parameters are functions of the liquid limit, it should be possible
to predict engineering behavior primarily in terms of the liquid limit.

APPENDIX I. REFERENCES

Atterberg, A. (1911). "The behavior of clays with water, their limits of plasticity
and their degrees of plasticity." International Reports for Soil Science, 1, 10-43.
Carrier, W. D., III. (1985). "Consolidation parameters derived from index tests."
Geotechnique, 35(2), 211-213.
Casagrande, A. (1932). "Research on the Atterberg limits of soils." Public Roads,
13(8), 121-130.
Dennehy, J. P. (1978). "The remolded undrained shear strength of cohesive soils
and its influence on suitability of embankment fill." Proc. Clay fills, Institution
of Civil Engineers, London, U.K., 87-94.
Farrar, D. M., and Coleman, J. D. (1967). "Correlation of surface area with other
properties of 19 British soils." J. Soil Sci. Soc, 18(1), 118-124.
Koppula, S. D. (1986). Discussion of "Consolidation parameters derived from index
tests," by W. D. Carrier, m . Geotechnique, 36(2), 291-292.
Lupini, J. F., Skinner, A. E., and Vaughan, P. R. (1981). "The drained residual
strength of soils." Geotechnique, 31(2), 181-213.
Nagaraj, T. S., and Jayadeva, M. S. (1981). "Reexamination of one point methods
of liquid limit determination." Geotechnique, 31(3), 413-425.
Nagaraj, T. S., and Jayadeva, M. S. (1983). "Critical reappraisal of plasticity index
of soils." / . Geotech. Engrg., ASCE, 109(7), 994-1000.
Nagaraj, T. S., Joshi, R. C , and Srinivasa Murthy, B. R. (1988). "Generalized
equation for compression ratio." / . Test. Eval., ASTM, 16(1), 86-89.
Norman, L. E. J. (1958). "A comparison of values of liquid limit determined with
apparatus having bases of different hardness." Geotechnique, 8(1), 79-83.
Russell, E. F., Mickle, J. L. (1970). "Liquid limit values of soil moisture tension."
J. Soil Mech. and Found. Engrg. Div., ASCE, 96(3), 967-987.
Seed, H. B., Woodward, R. J., and Lundgren, R. (1962). "Prediction of swelling
potential for compacted clays." / . Soil Mech. and Found. Engrg. Div., ASCE,
88(3), 53-87.
Seed, H. B., Woodward, R. J., and Lundgren, R. (1964). "Clay mineralogical as-
pects of Atterberg limits." J. Soil Mech. and Found. Engrg. Div., ASCE, 90(4),
107-131.
Skempton, A. W. (1953). "The colloidal activity of clays." Proc, III Int. Conf. on
Soil Mechanics and Foundation Engineering, 1, 57-61.
Skempton, A. W., and Northey, R. D. (1952). "The sensitivity of clays." Geo-
technique, 3(1), 30-53.
Sridharan, A., and Jayadeva, M. S. (1982). "Double layer theory and compressibility
of clays." Geotechnique, 32(2), 133-144.
Srinivasa Murthy, B. R., Nagaraj, T. S., and Bindumadhava (1987). "Influence of
coarse particles on compressibility of soils." Proc, Int. Symp. on Prediction and
Performance in Geotechnical Engineering, Calgary, Canada, 195-200.

295
Terzaghi, K. (1926). "Simplified soil tests for subgrades and their physical signifi-
cance." Public Roads, 7(8), 153-162.
Warkentin, B. P. (1961). "Interpretation of the upper plastic limit of clays." Nature,
190(4772), 287-288.
Whyte, I. L. (1982). "Soil plasticity and strength—A new approach using extru-
sion." Ground Engrg., 15(1), 16-24.
Wroth, C. P. (1979). "Correlations of some engineering properties of soils." Proc,
II Int. Conf. on Behaviour of Offshore Structures, London, U.K., 121-132.
Wroth, C. P., and Wood, D. M. (1978). "The correlation of index properties with
some basic engineering properties of soils." Can. Geotech. J., 15(2), 137-145.
Youssef, M. S., El-Ramle, A. H., and El-Demery, M. (1965). "Relationships be-
tween shear strength, consolidation, liquid limit and plastic limit for remolded clays."
Proc, Int. Conf. on Soil Mechanics and Foundation Engineering, 1, 126-129.

APPENDIX II. NOTATION

The following symbols are used in this paper:

ACT = colloidal activity, activity index;

C = percentage of clay fraction;
cdc = compression index;
= half space distance;
dL = d at liquid limit;
dp = d at plastic limit;
e = void ratio;
k = constant;
LL = liquid limit;
n = percentage clay fraction for zero plasticity index;
PI = plasticity index;
PL = plastic limit;
P = consolidation pressure;
qu = undrained strength;
R,A = interparticle forces of repulsion and attraction;
ss = percentage of swell;
= specific surface; and
w = water content.

296