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CIQl

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

near the surface,

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

During shrinkage water moves from inside the


soil to outside surfaces, from where it evapora.tes.
Evaporation increases the curvature of the water
menisci in pores at the soil surfaces
causing
suction and in turn the hydraulic gradient which is
responsible tor outflow of water .

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

Soil is the environment


into which organic
molecules are put for modifying
soil properties.
Also. with growing industrialization.
fhe land disposal of organic waste is inevitable.
In either
case. it is essential to evaluate the soil properties in different
environments.
Organic additives
to soil may be adsorbed. precipitated or leached.
They may .be changed because of catalytic alterations or biological decomposition.
They may diffuse or volatilize.
The characteristic
range of soil
properties must be understood in order to intelligently predict or interpret soil reactions with organIc molecules and ions.

have been extensively


reviewed
Considerable
work
has
been

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

soil, the dielectric

constant
A

can

tension

constant
is

the total internal


to the
capillary

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

is the pore air pressure

Uw

forces.

void ratio i.e the void


e SL, is dependent
on

contacts.

modified

a function

When

u:

when
equal

between

particle
level

wherein

(1

force due to surface

and

repulsive

phenomenon

offered

the

interparticle

where
is

and

the shrinkage

resistance

and or

water .

using

frictiona.l_properties,

but the resultant


shrinkage
ratio at the shrinkage
limt,

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

the exof 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

0;0 retained on B.S.S.


; sieve No.200

18.80

Specific gravity
solids
Natural
of

water
the

of

content

clay,

~~

MATERIALS

AND

METHODS

study the shrinkage


behaviour with cfay-organic
molecule interaction.
These tests were conducted
according to A.S.T.M. standard 027-61
and care
was taken to see that no air bubbles were present and the evaporation of solvent occured slowly, to avoid the possibility
of cracks developing

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

Table 2 presents the shrinkage


limits on
.../eight basis and volume
basis, and shrinkage
void ratio of. three types of clays in water and in

meth-

investigation.

solvents

RESULTS

ducted

organic

acetone

fluids

constant

four

especial'y

to

30

1/1
c:
Q)
>
-0

U)

c:
Q)
...
Q)

:c

c:
1/1

>
la
u
4>
.c
-

O
1/1
a>
~
la
>

4>
CI
la
~
c:
...
.c
U)

N
~
.c
la
t-

d)
c
o
c:
d)
cc

Q)
EC)
.= Q)
c::-O
"E.x
:Je
--0
>
:I:

aI
"c

o
~
~

.
0

>
"U;
c
Q)
c

~
C)
0

...
G) c
-G)
~E
.-o

()...
.-=

In

-ca
()...
G)
-cQ)

.-0
o()

-0
.5
~
0
0-

-J
U)
/1)

>
-1
U)

-1
(I)
~

-'
"'
0>

..
-l
(/)

-'
1/1
~

-'
C/I
Q)

.
-l
(/)

.J
"'
~

0)

CJ
CJ

,0
0...'

In
a!
>
.D
a!
c

0\
~
M
N

\0
M
~
0

r-0:
M
M

r---

r---

0..
'o:t
~
0

0
V;
-0
M

N
M
-

~
-

N
-.t
~

"'":
"1"

V)
~
00
M

0\
M

M
M

"""
0
-

0
~
oM
-

r"""
("'!

~
00
O
'0

r~
I/")

or--:
M
'-:t"

~
00

N
~
'of"

0:
V)
IV)

'0
00
N

O
-0

r-v

IN

8.

01"\

<"'!
N
00
-

'1")

o
-.r.
..,.

11"1
~
v

~
-0
r-

~
O
-0
Ir)

0:
-0
1-

<"'!
~
..,.
'I")

~
II"\
N
'ot'

0;
O
1-

00
0\

00
00

-0
N

v
0-

oN
0-

O
11"1

~
v

0
~

~
M

0\
0\
~
0

~
0

r-M

N
0'\
r-:
C

""

~
-0

0
~

0\
00
r-:
o

"01"

N
+

M
'C;
N
r")

0
~

Ir\
r"I

N
M

8
o
o
00.
-

"0
I:
tU
.I:
Q)

00
M
-qo
<"'I
-

0
-

O
I

O
r'"I
r-:
M

~
t"";
0'\
r-

r-:
~
-

~
0

O
00
"!
-

00
~
N

\0
~
\0
IrI

00~
0

N
00

O
M

o
r-:
o
~

~
c
~
N
c
~
CD

\i"\
'Q;
N

"'
-

O
I

~
N

~
c:
0
...
~
(J
<
...
0)
IV

~
o

..,.
\Q
~
-

O
c
10
.!:
UJ
~

Sivapullaiah,

ratio.

eSL. have

been

used

in the

analysis

Sitharam

and

Su~barao

of the

results.

From Table 2 it is seen that clays have high


shrinkage void ratios in solvents with large positive log Kow values
(hydrophobic)
and have less
shrinkage void ratios in solvents with large negative log Kow values.
In general, the higher
the
dielectric nonstant of solvent, the lesser was the
shrinkage void ratio or shrinkage limit by volumo.
Shrinkage void ratio, eSL. and shrinkage limit by
volume, SLy are plottcd against log Kow values
for the three clays in
Fig.1
and Fig. 2. Both
eSL and SLy bear a clear relationship with log Ko..'.
This relationship confirms that shrink
behaviour
is related to solvent solubility
in pore water .
F!g.

2.

Relationship

between

SLv%

and log Kow.

.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.

and log Kow.

32

and

V~arkentin,

Soil Behavior,

B. P.

1966.

Macmillan,

IntroduNew York..

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