Professional Documents
Culture Documents
R,.rtQrch,
YQl. 5, No.1,
1986
28-32.
CLAY-ORGANIC
MOLECULE
INTERACTION:
P. V. SIVAPULLAIAH,
Department
Abltract:
Conventional
been done
correlation
water
holds
with
exists
shrinkage
a series
between
coefficients.
promise for
of Civil
tests
T. G. SITHARAM
Engineering,
for
Indian
commercially
of organic
solvents
the shrinkage
void
The use of
partition
the better
understanding
with
ratio
Studies
of
clay-organic
available
coefficients
in the
of the interaction
molecule
swelling
cf clays
(Barshad,
tions
1952:
were
observed
and cation
appear
formation
of
been studied
Recently,
the swelling
organic
When
occurs.
pore water
with
But
soil,
Shrinkage
the
data
to organic
Green et al.
(1983}
solvents
clayey
The
is not
is evaporated
of
have caused
erent
the
have
well
from
clays
of
saturated
or shrinkage
caused
damage
by
loss
have
organic
compounds
particles.
clays.
In semi-arid
thus
regions
the clay
shrinks
clay swells
opening
clay
to
closing
and closing
become
explained
of shrinkage
fissured.
the
the shrinkage
cracks
Sridharan
phenomenon
modified
effective stress concept.
of dielectric
constant
and surface
pore
pore
medium
were
brought
cracks.
out by
of
causes
and Rao
shrinkage
The importension of
using
diff-
fluids.
phenomenon
Shrinkage
limit is expressed as the water
content at which there is no further volume decrease with further evaporation of porewater. Yong
and Warkentin
(1966) summarized the characteristics affecting
the shrinkage
as per cent clay
in the soil, the kind of clay minerals, the mode
of geological deposition, the depositional environment which determines the particle
arrangement
and overburden
pressure, and the degree of
of shrinpresence
gel
are
studied
understood.
decrease
enormous
bulk
soils in presence
in the
hydroxide
has
liquids
periods
Shrinkage
different
on
force of
with
clay
on or with
exists
aluminium
In this investigation
an attempt is made to
relate the shrinkage
behaviour of extreme types
of clays in the presence of organic solvents with
the octanol-water
partition
coefficients.
The
mechanism
of clays
a volume
the
of swelling
Ca-montmorillonite
and
dry periods
forming
cracks
that
extend
distances
below
the surface
and during the
(1971 }
using
tance
these trends
of
exposed
types
water
compressible
complexes
solvents.
of different
solvent
clay
the
correla-
solvent-dependent.
of some natural
of hydrophobic
various
be
in detail.
of clays
scarce.
kage
to
interlamellar
compounds
properties
the extent
in a given
where
This
compounds
Although
built
Bangalore
The
result3 show
that a significant
basis and the
logarithm
of octanol-
study
of intermolecular
of organic
molecules
wet
interactions
of organic
bentonite
groups.
by
volume
tures
BEHAVIOUR
K. S. SUBBARAO
of Science,
kaolinite,
during
some
by Theng
(1974}.
done on interlayer
1980}.
between
properties
themselves
organic
in presence
Brindley,
AND
Institute
different
functional
or shrinkage
limit
SHRINKAGE
of
weathering.
to struc-
28
..
;-
Clay-organic
ternal
During
load
a conventional
is zero and
clay
can
be
with
the
intensity
and
considered
forces
of
of
be
negative.
oves
to
the
capillary
water
towards
evaporation
must
"as evaporation
rem-
shrinkage,
the
surface,
a meniscus
pores
resulting
tension
in
water.
difference
The
by
the
shrinkage
effective
stress
Ua
mass)
becomes.
required
for
surface
tension
Uw
an
the
modifiej
and
Rao, 1971
saturated
the normal
be
the
upon
the
pore
water
dielectric
the.
net
of
clay
an
pressure
repulsive
force.
is
the
Denoting
the
effective
stress
menon
attractive
controlling
the
as
of
uTS the
shrinkage
water
the
For
any
resistance
surface
at
tension
the
particles.
gre3ter
change.
These
normal
forces
is
acting
force.
particle
shear
the
contacts
resistance
resistances
between
with
(2)
greater
the
shear
and/or
between
against
volume
are
particles
particles
at
by
equation
2,
stress
is seen
to
which
pore
been
layer.
the
the
pore
solvent
depend
medium.
the
the
will
di~l~ctric
than that of
the.
be
As
such
explaining
the
dielectric
higher.
the
intermolecular
hold
promise
the
interaction
of
the
the
of
phenomenon
Octanolcontrary,
forces
for
than
use
has limitations.
on
solvent
possessing
lower
layer,
coefficients,
of
pore spaces
of
Since
fluid
in
the
clays
is
itself.
of
better
organic
in
organic
under-
molecules
particles.
The octanol-water
used to measure
molecules
are
of
n-octanol
and
and,or
at
index
of
the
adsorbed
interaction
of
clay
of
solvent
functions
29
enters
constant
account
partition
standing
R
soil
coefficients
water
clay-fluid
compounds,
= urs
of the
solvent
constant
the. .study
reads,
be bro-
resistance
forces
organic
in
of
of
water
pheno-
O:l
of
dielectric
forces
constant
organic
adsorbed
that
tension
effective
electrical
partition
altered
the
and
force.
surface
the
This
controlled
constant
A
can
tension
constant
is
The
dipole
moment,
dielectric
constant,
the solubility
parameter
and the molar attraction constant hqve each been useful in establishing a scale for solvents
in certain applications.
gets
is
is
of
Octanol-water
soil
Uw
forces.
contacts.
modified
a function
When
u:
when
equal
between
particle
level
wherein
(1
and
repulsive
phenomenon
offered
the
interparticle
where
is
and
the shrinkage
resistance
and or
water .
using
frictiona.l_properties,
with
+ A
-R
in
outward
of
the
attractive
adly explained
as being injtiated
by the capillary
forces
due to- surface
tension
of the
pore fluid,
the hydro-
the
initially
Hence
begins
surface
Hence,
(Sridharan
(for
= (7
at the
phenomenon
concept
when
acting
contacts,
electrical
forces.
surface
pressure
from
caused
the
particle
the
hydrostatic
During
stress
for
surface
the
is
required
shrinkage
Shrinkage
reaches
its limit
shear resistance
becomes
Since
the
of
the
hydro-
fhe
each of
static
the
and
the
forces
clay is zero.
is
in
flow
and
difference
of
water
form
capillary
stress
evaporation,
vicinity
of the
in comparison
(i.e..
forces),
in the interior
the
the
forces
electrical
a hydrostatic
flow
negligible
of
interparticle
static
shrinkage
test,
the dead weight
inter8ction
apt to
partition
water.
molecular
partition
coefficients
the degree to which
It
transfer
themselves
has
been
from
the
have
solute
between
used
as
an
solvent
to
Sivapullaiah,
the
water
(Leo
between
their
soil
et
at.,
1971
adsorption
octanol-water
of
).
simple
organic
partition
Sitharam
relation
chemicals
and
has
been
coefficients
Table
and
established
by Briggs
relationship
with
organic
Physical properties
Subbarao
, who
found
for
a good
series
of
solvents.
of the clays.
Kaolinite
Properties
(1973)
Jog K adsorption
Bentonite
Aluminium
hydroxide
gel
"
Liquid
limit.
Plastic
limit.
Plasticity
51.10
216.0
34.00
188.0
17.10
28.0
386.60
261
2.50
2.87
560
26.73
12.50
index. %
446.60
55.60
18.80
Specific gravity
solids
Natural
of
water
the
of
content
clay,
~~
MATERIALS
AND
METHODS
Clay:
Commercially
available
extreme types of
clays kaolinite and bentonite together with aluminium hydroxide gel were studied. Table 1 summarises the properties of the clays. Their liquid
limits were in order kaolinite < aluminium hydroxide gel < bentonite and ranged from 51.1 for
kaolinite to 441.6 for bentonite.
Fluids:
Water
anol.
as
ethanol.
pore
and
of
the
benzene
to
about
ithm
partition
of
+ 2.13
ected.
for
the
directly
in
and
this
80
solvents.
benzene.
were
for
from
water.
coefficients
(Jog
benzene
to
-1.15
for
dielectric
constant
and
used
Dielectric
ranged
2.28
Also
the
Kow
water.
log
As
Kow
are
from
expnot
related.
The conventional
on
the
clays
AND
tests
with
DISCUSSION
of
shrinkage
different
were consolvents
of low boiling
point.
organic solvents along with selected solvent physical properties. The shrinkage limit by weight,
WSl is the ratio of weight of pore fluid to the
weight of solids at minimum soil volume conditions. The shrinkage limit by volume, SLv, is defned as the ratio of the volume
of pore fluid to
the volume of solids expressed as a percentage.
Shrinkage void ratio, eSL. is defined as the void
ratio at at the shrinkage limit.
Since fluids of
different specific
gravities were used, shrinkage
limit by volume
basis, SLy, and shrinkage void
for
logar-
ranged
with :~olvents
meth-
investigation.
solvents
RESULTS
ducted
organic
acetone
fluids
constant
four
especial'y
to
30
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<
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c
10
.!:
UJ
~
Sivapullaiah,
ratio.
eSL. have
been
used
in the
analysis
Sitharam
and
Su~barao
of the
results.
2.
Relationship
between
SLv%
.REFERENCES
Barshad,
I.
1952.
expansion
with
of
16:
octanol-water
00
between
chemicals
and their
~
"'
ii
T.
lth
swelling
water-DMSO
of
systems.
28 : 369-372.
Fredlee,
1983.
Proc.
ConI.
Intracrystalline
in
Miner.
W. J.,
cofficients.
Fungicide
1980.
Clay
Paltt,
Soc.
relationship
partition
G. W.
Green,
.
Soil
simple
montmorillonite
Clays
montmorillonite
Proc.
of organic
InsecticiJe
Brindley,
interlayer
176-182.
adsorption
Brit.
the
and
substances,
G. G. 1973.
soil
affecting
vermiculite
organic
Am.
Briggs,
Factors
G.,
Anne
Environ.
Jones,
Sci.
R.
Technol.
and
17 :
278-282.
~
..,
;..
,1:
Leo,
H. C.
cients
E
~
"c
and
and
their
A.
and
Sridharan,
E
~
"'i
strees
theory
geotech.
-'
..
..
Theng,
Elkins,
J.
B. K. G.
Organic
D.
1971,
uses.
Chemical
G. V.
Rao.
of shrinkage
(No.4)
1974.
Partition
8:
Rev. 71 : 525.
1971.
Effective
phenomenon.
Canad.
503-512.
The
Reactions,
coeffi-
Chemistry
Adam
Hilger,
of
ClayLondon.
343 pp.
Yong,
Fig.
Relationship
between
eSL
R. N.
ction
to
451 pp.
32
and
V~arkentin,
Soil Behavior,
B. P.
1966.
Macmillan,
IntroduNew York..