The DLVO theory

Electro-Osmotic

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The Stern Layer

Ions are firmly attached (immobilized) to colloid surface The potential drops from the surface potential almost linearly through the Stern layer

The Stern layer

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The Diffuse Double Layer

The Diffuse layer

Surface Potential

The Stern layer

Stern Layer Zeta Potential Diffuse Layer Zeta Potential (Low Concentration)

The Diffuse Double Layer

Potential

Distance from Colloid

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The Repulsive Energy

(x)

()=0

d Distance between Stern layers

Bentonite Erosion and Colloid Transport Mats Jansson

The Repulsive Energy

(x)

()=0

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The Repulsive Energy

(x)

()=0

d/2
Bentonite Erosion and Colloid Transport Mats Jansson

The Repulsive Energy

(x)

d/2
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The Repulsive Energy

Excess of total ion concentration at d/2 => Osmotic pressure p = pd/2 - p = RT [c+d/2 + c-d/2 - 2c] Together with the Bolzmann equation
ziF x RT

ci, x = ci, e

(F = Faradays constant)

(x)

The osmotic pressure becomes p = RT 2c (cosh (z d/2) 1)

(d/2 = F d/2 / (RT)

d/2

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The Repulsive Energy

Cut the system in two at x=d/2. Look at the point x=d/2 As the electrical field strength is zero, the electrical force exerted on either half of the system is zero The remaining force is due to the osmotic pressure difference (described by the equation below)
The repulsive force is electro-osmotic in nature, not electrostatic in the proper sense!

(x)

p = RT 2c (cosh (z d/2) 1)
(d/2 = F d/2 / (RT)

d/2

Bentonite Erosion and Colloid Transport

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The Repulsive Energy

p = RT 2c (cosh (z d/2) 1) The repulsive force can be calculated if d/2 is known Evaluating d/2 is very difficult Approximation d/2 1 is useful (fulfilled when d is suff. large)

d/2 can be obtained from superposition the potentials of the isolated plates and approximate d/2 = (8/z) 0 e-d/2 0 = surface charge density
=
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F 2 z i2ci , RT
Mats Jansson

= Debye length
10

The Repulsive Energy

p = RT 2c (cosh (z d/2) 1)

d/2 = (8/z) 0 e-d/2

Since d/2 1 cosh (x) = 1 + x2/2

p = 64 RT c 02 e-d
The electro-osmotic energy per surface area is then

el = - p dx

el = 64 RT c 02 (1/) e-d
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The Attractive Energy

The most important interaction energy besides the electro-osmotic is the van der Waals energy (dispersion energy) For our system the van der Waals energy per surface area is vdW = - A / (12 d2) A is the Hamaker constant (typically about 10-20 J) A is very difficult to determine experimentally

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DLVO theory
Derjaguin-Landau-Verwey-Oberbeek
= el + vdW

= 64 RT c 02 (1/) e-d A / (12 d2)

Repulsion (electro-osmotic)

Attraction (van der Waal)

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DLVO theory
= 64 RT c 02 (1/) e-d A / (12 d2)

= 64 RT c

2 0

RT e 2 2 F z c

F 2 z 2c d RT

A 12 d 2

Increase c => Repulsion decreases

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Repulsion c varied
1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6 8 10
2 = 64 RT c 0

RT e 2 2 F z c

F 2 z 2c d RT

A 12 d 2

y=

c e c

c d

c=1 c=0.1 c=0.01

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Secondary minimum
If the surface area of the particle is large Energy in secondary minimum > kT => Causes a stabilization (reversible coagulation)

Secondary minimum

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DLVO summary

Electro-osmotic repulsion van der Waal attraction (difficult to obtain a correct Hamaker constant) At long and short distances vdW > Electro-osmotic Electro-osmotic barrier When surface are is large reversible coagulation may occur at secondary minimum

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Extended DLVO theory

When the DLVO theory fails to explain experimental results, an extra term is often added, such as Hydration forces Hydrophobic forces Oscillatory forces Membrane fluctuations Water structure forces

The theory is then called the Extended DLVO theory

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DLVO extended with hydration

DLVO theory fails to describe systems with very hydrophobic or very hydrophilic particles or in other words DLVO theory is only applicable for lyophobic colloids with advancing contact angle a between 15 and 64 (a for Na-montmorillonite = 17)

Small

Large

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DLVO extended with hydration

The DLVO expression can be extended with a hydration component: = el + vdW + H H = a/2 (C1 e-d/D1 + C2 e-d/D2)
C1, C2 constants, D1, D2 decay lengths

Small

Large

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Extended DLVO vs DLVO

Silica particles (r = 6 nm) in 0.01M NaCl

Shukun Chen Thesis 2007

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DLVO theory: Drawbacks

The DLVO theory does not account for Lifschitz theory of attractive forces Ion fluctuation forces Charge regulations in the double layer Specific ion effects

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DLVO theory: Drawbacks

The DLVO theory has a number of (adjustable) parameters Proper description of vdW force Surface charge density Surface potentials Debye length, etc. Even so, an extended term is often needed to explain the behaviour of a system
Forces can vary in magnitude by a factor of 50 or more by simply changing the counter-ion from e.g. bromide to acetate
Bostrm et al Phys Rev Lett 87, (16) 8103 (2001) (click here to read) Pashley et al J Phys Chem 90 1637 (1986)
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Concluding remarks
The DLVO theory has been established since 1945 It can often describe trends and tendencies, but In many articles I found the DLVO theory fails to quantitatively explain/(predict) experimental results (without parameter fitting or extended theories)

"... DLVO-theory is completely inadequate (to put it gently) in almost every system so far investigated".
Christiansen J Dispersion Sci Technol. 9: 171 (1988)

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