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Diffuse Double Layer

Diffuse Double Layer

Clay particles are negatively charged due
to isomorphous substitution,
incomplete occupation of the positions
available for metal ions and release of
protons from hydroxides.

As a consequence of the negative charge

at the surface of clay particles,
electrostatic forces exist between the
negative surface and exchangeable
cations.

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The strength of these forces is a function

of:
the charge,
the position of the charge and
the valence of the exchangeable
cations.

Clay Particle in Water

adsorbed water

- - 1nm
- -
- - 50 nm
- -
- -
free water
- -
- -
Diffuse layer

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Diffuse Double Layers

The surface of a clay particle, being
negatively charged, attracts positive
ions.

This region of attracted positive ions in

solution and the negatively charged
surface of the clay is termed the diffuse
double layer.

The diffuse double layer occurs at the

interface between the clay surface and
the soil solution.

It is made up of:
the permanent negative charge of the
clay and
the cations or counter-ions in the soil
solution that balance the negative charge.

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The nature and properties of such layers

are highly dependent on the type of:

mineral and

the chemistry of the pore water.

Adsorbed Water
(Stern Layer)
The innermost layer of doublelayer
water, which is held very strongly by
clay, is known as adsorbed water
(Stern layer).

This water is more viscous than is free

water.

The orientation of water around the

clay particles gives clay soils their
plastic properties.

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Initially, attraction from the negative

colloid causes some of the positive ions
to form a firmly attached layer around
the surface of the colloid;
this layer of counter-ions is
known as the Stern layer.

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The attached counter-ions in the Stern

layer and
the charged atmosphere in
the diffuse layer are
what we refer to as the
double layer.

The thickness of this layer depends upon

the type and
concentration
of ions in solution.

The diffuse layer is called diffuse,

because a net positive
charge of ions extends away from the
surface.

The further from the surface, the less is

the net positive charge of the solution.

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Force of Attraction

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Double Layer Water Free water

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The force of attraction between water

and clay decreases with distance from
the surface of the particles.

All of the water held to clay particles by

force of attraction is known as double-
layer water.

For one cation to leave the double layer

it must be replaced by another from the
soil solution.

The amount of adsorbed water in the

double layer relative to the total volume
of pores varies greatly with mineral type
(van Olphen, 1963).

This variation is clearly illustrated in the

table given by Quigley and Fernandez,
1989.

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The table indicates the volumes of water

adsorbed in 1 nm thick double layers for
saturated clays at a void ratio of 2.5 (Quigley
and Fernandez, 1989).

The figure shows a sodium montmorillonite and

kaolinite crystal with layers of adsorbed water.
The thickness of the adsorbed water is
approximately the same, but because of the size
differences, the montmorillonite will have much
greater activity, higher plasticity, and greater
swelling, shrinkage, and volume change due to
loading.

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The negative surface and the distributed

charge in the adjacent phase are
together termed the diffuse double
layer.

Several theories have been proposed for

the description of diffuse double layer.

The Gouy Chapman Theory of the

diffuse double layer is considered as the
most successful.

Quantitative treatment of the diffuse

double layer presents
an extremely difficult
and, in some respects,
unsolved problem.

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The simplest quantitative treatment is that

due to
Gouy (1910) and Chapman (1913),

which incorporates numerous

assumptions including
the treatment of ions in the double
layer as point charges (van Olphen,1963).

Following from the theory,

the thickness of the diffuse

double layer can be related

to the major pore

fluid properties as follows:

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The Gouy Chapman Theory

Double layer thickness is expressed as:
1/ 2
1 0 DkT

K 2n0 e 2 2
or
1/ 2
1 DkT k= Boltsman constant (1.38x10-16 erg/K)

K 8 n0 2 2 : unit electronic charge
: 4.80x10-10 esu or 16.0x10-20 coulomb.

1/ 2
1 DkT

K 8 n0 2 2
where:
k= Boltsman constant (1.38x10-16 erg/K)
: unit electronic charge 4.80x10-10 esu or
16.0x10-20 coulomb.
n0 : Electrolyte concentration, (ions/cm3)
: Effect of cation valency
T: Temperature
D: Effect of dielectric constant.

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Factors Affecting the Double Layer Thickness

1. Electrolyte concentration, n0 (ions/cm3)
n0 1
K

2. Effect of cation valency ()

1
K
3. Effect of dielectric constant (D)
1
D
K

(The dielectric constant is a measure of the ease

with which molecules can be polarized and
oriented in an electric field)

4. The effect of temperature (T)

1
T K

However as T D so DT same.

TC TK D DT
0 273 88.0 2.4x104
20 293 80.0 2.34x104
25 298 78.5 2.34x104
60 333 60. 2.20x104

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5. Effect of ion size

as size Thickness

6. pH
pH Thickness

The higher the pH, the greater the

tendency for the H+ to go into solution,
and the greater the effective negative
charge of the particle.

pH

pH= log10 H concentration

pH < 7 is acid. High H+ concentration

pH > 7 is basic. Low H+ concentration

Clay particles have hydroxyls (OH)- exposed on

their surfaces and edges. The tendency for
the hydroxyls to dissociate (separate) in
water is strongly influenced by the pH.

SiOH SiO-+H+

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The higher the pH,

the greater the negative charge
of the particle
so the higher the thickness of
the double layer.

H+ pH
0.3 0.53 as H+ pH
0.2 0.69
0.1 1.0

Attractive and Dispersive Forces

The counter-ions (positive ions) are influenced
by two equal but opposing forces:

Attractive Forces
the electrical force attracting the positive ion to
the negative surface, and

Dispersive Forces
the diffusive or thermal forces (responsible for
Brownian motion) which tend to move the
cations away from the surface.

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The binding force on to and between the

clay plates depends on a number of
factors including:

the charge of the cations

the size of the cations, including their

hydration shell

the thickness of the double layer outside

the surface of the clay particles.

Strength of Attraction of Exchangeable Cations

The cations adsorbed on to the surface of
the clay particles can greatly affect how
the clay behaves.

The cations act as a link between the clay

particles.

Similarly, dispersive organic matter (with

negatively charged edges) can be linked
strongly by positively charged cations.

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The strength of the bond depends on the

cations present

Sodium
ions have a single positive charge, so their
clay-binding ability is poor.

Calcium ions have a double positive charge,

so their clay-binding ability is good.

Magnesium
is intermediate because,
although it has a double positive charge
like calcium, when hydrated it is larger
than a hydrated calcium ion.

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Strengths of attraction of common soil cations.

In a dispersive soil with a large exchangeable

sodium percentage and small concentrations
of water-soluble salts, the weak bonding of
the clay particles by sodium ions can be
broken.

As water enters between the clay particles it

hydrates the sodium ions. This in turn forces
the plates away from the ions and lowers the
attractive force between the particles and the
ions.

The plates may move far enough apart for

attraction forces to be overcome.
The result is dispersion.

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Rate of Cation Exchange

The rate of cation exchange varies with:

clay type,
solution concentration,
temperature, etc.

In general, however, exchange reactions in

the kaolin minerals are almost
instantaneous.

In illite, a few hours may be needed for

completion,
because a small part of the
exchange sites may be between unit
layers.

A longer time is required in smectite

because the major part of the exchange
capacity is located in the inter-layer
regions (Mitchell, 1993a).

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Exchangeable Sodium Percentage (ESP)

Exchangeable sodium percentage (ESP)
is a measure of the
number of sodium ions
adsorbed onto the surface of the clay
particles,
compared with other
positive ions.

Soils with low ESP generally have better

aggregate stability in water than soils
with high ESP.

Since the doubly charged calcium ions

are more strongly attracted to the clay
surface than sodium,
the thickness of the double
layer is less and the tendency to swell
is correspondingly less.

Much more importantly, the particular

organisation of the clay particles where
they overlap restricts the swelling, due
to diffuse double layers.

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Individual particles are linked to each other by:

Cementation:
calcite, silica and oxides. These cements are
more or less stable at ambient pressure,
temperature and/or pore fluid chemistry
encountered in regular geotechnical
engineering.

Interlocking of particles, which occurs in

metamorphosed or otherwise compressed
clayey soils.

Electrostatic forces:
These forces depend strongly on the pore fluid
chemistry and the charge at the particle
surfaces.

The thickness of DDLs around clay particles is

governed by the concentration of salt and type
of cation(s) in the soil water.

It also depends on the degree of expansion of

the DDLs, which is controlled by soilwater
content;

the DDLs expand fully only in the abundance of

water.

In dry soils, the thickness of the DDLs is very

small since the DDLs cannot expand fully, and
most clay particles remain isolated resulting in
discontinuous pathways for the flow of
electrical current .

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Electrostatic Double Layer

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