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    Dlvo Theory - KTH

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    The document discusses the DLVO (Derjaguin-Landau-Verwey-Overbeek) theory for predicting colloid stability. It describes the key components of the theory, including electrostatic repulsion in the Stern layer and diffuse double layer, and van der Waals attraction forces. The theory calculates the net energy between colloid surfaces based on these forces. However, the document notes that the DLVO theory has limitations and often fails to quantitatively predict behavior, requiring extensions to account for other forces like hydration forces. It concludes that while useful for trends, the DLVO theory has uncertainties and adjustable parameters that limit its predictive power in many systems.

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    Dlvo Theory - KTH

    Uploaded by

    learningbox
    321 views24 pages
    The document discusses the DLVO (Derjaguin-Landau-Verwey-Overbeek) theory for predicting colloid stability. It describes the key components of the theory, including electrostatic repulsion in the Stern layer and diffuse double layer, and van der Waals attraction forces. The theory calculates the net energy between colloid surfaces based on these forces. However, the document notes that the DLVO theory has limitations and often fails to quantitatively predict behavior, requiring extensions to account for other forces like hydration forces. It concludes that while useful for trends, the DLVO theory has uncertainties and adjustable parameters that limit its predictive power in many systems.

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    colloid theory

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    Dlvo Theory - Kth

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    The document discusses the DLVO (Derjaguin-Landau-Verwey-Overbeek) theory for predicting colloid stability. It describes the key components of the theory, including electrostatic repulsion in the Stern layer and diffuse double layer, and van der Waals attraction forces. The theory calculates the net energy between colloid surfaces based on these forces. However, the document notes that the DLVO theory has limitations and often fails to quantitatively predict behavior, requiring extensions to account for other forces like hydration forces. It concludes that while useful for trends, the DLVO theory has uncertainties and adjustable parameters that limit its predictive power in many systems.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    321 views24 pages

    Dlvo Theory - KTH

    Uploaded by

    learningbox
    The document discusses the DLVO (Derjaguin-Landau-Verwey-Overbeek) theory for predicting colloid stability. It describes the key components of the theory, including electrostatic repulsion in the Stern layer and diffuse double layer, and van der Waals attraction forces. The theory calculates the net energy between colloid surfaces based on these forces. However, the document notes that the DLVO theory has limitations and often fails to quantitatively predict behavior, requiring extensions to account for other forces like hydration forces. It concludes that while useful for trends, the DLVO theory has uncertainties and adjustable parameters that limit its predictive power in many systems.

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    The DLVO theory

    Electro-Osmotic

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    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


    Bentonite Erosion and Colloid Transport Mats Jansson 3

    The Repulsive Energy

    (x)

    ()=0

    d Distance between Stern layers


    Bentonite Erosion and Colloid Transport Mats Jansson

    The Repulsive Energy

    (x)

    ()=0

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    The Repulsive Energy

    (x)

    ()=0

    d/2
    Bentonite Erosion and Colloid Transport Mats Jansson

    The Repulsive Energy

    (x)

    d/2
    Bentonite Erosion and Colloid Transport Mats Jansson 7

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    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

    Mats Jansson

    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
    =
    Bentonite Erosion and Colloid Transport

    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
    Bentonite Erosion and Colloid Transport Mats Jansson 11

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    12

    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)

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    13

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    14

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    15

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

    Secondary minimum

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    16

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    17

    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


    Bentonite Erosion and Colloid Transport Mats Jansson 18

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    19

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    20

    Extended DLVO vs DLVO


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

    Shukun Chen Thesis 2007

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    21

    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

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    22

    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)
    Mats Jansson

    Bentonite Erosion and Colloid Transport

    23

    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)

    Bentonite Erosion and Colloid Transport

    Mats Jansson

    24

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