Section 1

DLVO Theory

Part 1b
DLVO Basics
What is DLVO Theory?
Theory developed to explain colloid stability through the
combination of effects from van der Waals and EDL forces

Boris Derjaguin Lev Landau Evert Verwey Theodoor Overbeek

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What are common surface interactions?
Van der Waals attraction
Spontaneous polarization
Electric Double Layer (EDL) DLVO forces
Ion shell charge interactions

Born repulsion
Electron shell overlap
Acid-Base Interactions
Non-DLVO forces
Polar interactions due primarily to
hydrophobic and hydrophilic
properties
Recall:
Surface Interaction
Force Length-Scales

Van der Waals

<200nm

Electric Double Layer

<50nm

Acid-Base
<5nm

Born
<1nm
Straining vs. Adsorption

http://www.elaguapotable.com/WT%20-%20R2.jpg

Straining Size prevents particles from moving through pores

(eventually leads to clogging)
Adsorption Attachment caused by interfacial surface attraction.
Gravity and drag deliver colloids to surfaces and surface
interactions determines what happens when they get there
How do these forces depend on colloid
size (radius)?
Gravity R3 (volume)

Drag Force R (sphere) or R2 (other)

*General formula is Cross-sectional area times drag
coefficient (function of shape and Reynolds number)

Surface Interactions R (distance)

As particle size decreases, gravity becomes less significant

and surface interactions begin to dominate at short separation
distances.
Significance of Interaction Geometry
Surface-surface interactions dependent on geometry of
macroscopic bodies
Sphere-Sphere Sphere-Plate Plate-Plate

Aggregation Deposition Classic Experiments

Note: Sphere-Plate is generally used for deposition since the curvature of the
collector surface is generally insignificant when compared to the colloid curvature
Electric Double Layer (EDL)
Ions are more ordered near charged surfaces creating the double layer
The EDL is dependent on the quantity of ions present in solution
(measured by IS and pH)
Higher concentrations of ions compresses the double layer

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EDL parameters
Surface Potential,
Potential at particle surface

Zeta potential,
Potential at the slipping plane
Dependent on pH
Debye Length, -1
Distance where the potential
decreases by an exponential
factor
Roughly the thickness of
diffuse layer
http://members.home.nl/lboonen/edl.jpg
EDL Interaction Energy for Sphere-Plate

Lin & Weisner (2012)

absolute permittivity of water

Inverse Debye Length
kB Boltzmann Constant
Similar expressions
T Temperature
exist for Plate-Plate
z Ion valence and Sphere-Sphere
e Charge of an electron geometries
ap Radius of colloid
H Separation distance
Example EDL Curve

Repulsive
pc<0 (Oppositely charged)

Attractive
Example EDL Curve

Repulsive

pc>0 (Similarly charged) Attractive

This scenario is more common in environmental contexts where both surfaces

are negatively charged (i.e., soil surfaces and bacteria surfaces)
Van der Waals
Spontaneous polarizations

Attraction due to induced

polarization

Hamaker Constant
Primary parameter
representing the degree of
polarization that takes place
based on the material
properties of the two bodies
and the medium separating https://universe-review.ca/I12-14-vanderwaals2.gif
them
Retardation
Fleeting electromagnetic dipole interactions travel at the
finite speed of light

By the time the dipole in atom 1 induces a dipole in atom 2,

the dipole in atom 1 has changed causing decreased
attraction.

More retardation at further distances

Significant for distances above ~10 nm

vdW Interaction Energy for Sphere-Plate

Gregory (1981)
A132 Hamaker constant for materials
1 and 2 interacting through media 3 Retardation factor
(ex., bacteria and quarts sand in
water)

ap Radius of colloid
Similar expressions
H Separation distance exist for Plate-Plate
and Sphere-Sphere
geometries
Characteristic wavelength of
interaction (~100 nm)
Example DLVO Curve
Energy Barrier

Repulsive

Secondary Minimum
Attractive
Infinite Primary Minimum
Born Repulsion
Strong repulsive forces due to electron orbitals overlapping
Only applies at very short distances

Born Energy for Sphere-Plate

Gregory (1981)

A132 Hamaker constant for materials 1 and 2 interacting through media 3

ap Radius of colloid
H Separation distance
Similar expressions exist for Plate-
c Born Collision Diameter (~0.5 nm)
Plate and Sphere-Sphere geometries
Lewis Acid-base Effects
Polar interactions due primarily to hydrophobic and hydrophilic properties

Can be attractive or repulsive

Attraction Hydrophobic Interactions
Repulsion Hydrophilic Interactions

Significant in systems with strong hydrogen-bonding or other polar

interactions present (common in biological and environmental systems)

Acid-Base energy at minimum separation shown below are the

surface energy components of each material (p-particle, c-collector, w-
water/fluid)
Lewis Acid-Base Interaction Energy for
Sphere-Plate

Wood & Rehmann (2014)

ap Radius of colloid
H Separation distance Similar expressions
exist for Plate-Plate
AB Acid-base decay length (0.2-1 nm) and Sphere-Sphere
h0 Minimum separation distance geometries
(~0.158 nm)
Gh0AB Energy at minimum separation
(i.e., energy at contact)
Complete Energy Curve
Energy Barrier
Repulsive

Secondary Minimum
Attractive
Finite Primary Minimum
Energy Curve and Colloid Association
Strong association involves access to the primary minimum whereas weak
association involves a strong energy barrier preventing access to the primary
minimum but allowing association with a secondary minimum.
Energy Curve and Diffusion
The intrinsic energy of a colloid is 1.5 kT (0.5 kT per dimension)

Can allow colloids to overcome Can allows colloids to escape

barriers (<0.5 kT) to get from secondary minima (>-0.5 kT) to
secondary minimum to primary bulk solution (weak association
minimum (weak association to to no association)
strong association)
Other Forces: Steric Stabilization
Repulsion due to overlapping polymer domains. Keep
colloids at separation where van der Waals is relatively
weak.

Elimelech (1995)
Other Forces: Polymer Bridging
Typically leads to increased attraction but can lead to
repulsion when too many polymers adsorb to surface

Elimelech (1995) Elimelech (1995)

 Section 1
DLVO Theory

Part 2a
Measuring DLVO parameters
Hamaker Constant

Wood & Rehmann (2014)

Can be calculated based on the optical properties of the materials

involved (1-particle, 2-collector, 3-water/fluid)
Dielectric constant,
Refractive index, n
Electronic adsorption frequency, e
Planck Constant, h
 Zeta Potential
Calculated by measuring
mobility of particles as they
are placed in an electric field

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Measuring%20electrophoretic%20mobility.jpg

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Surface Energy

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Section 1
DLVO Theory

Part 2b
DLVO Activity
DLVO Activity (~1 hr):
1. Consider a mobile S. aureus bacteria in a sand quartz aquifer with the base case conditions below.
a. What are the depths and separation distances of the energy minima?
b. Would diffusion allow the colloid to enter the primary minimum?
c. Would diffusion allow the colloid to escape the energy minimum to bulk solution?
d. Will S. aureus have strong or weak association with the quartz sand? Why?
Radius, ap = 5.0E-7 m
Ionic strength, IS = 25 mM
pH = 7
Hamaker constant (bacteria-water-quartz), A132 = 7.17 E-21 J
p = -30 mV (S. aureus at pH 7)
http://www.cdc.gov/media/subtopi
c = -50 mV (Quartz at pH 7) c/library/DiseaseAgents/img37.jpg
T = 20.0C
Acid-base energy at minimum separation, Gh0AB = -2.81E-2 J/m2

2. Suppose the quartz sand becomes coated with hematite (c = +30 mV at pH 7).
a. What are the depths and separation distances of the energy minima?
b. Would diffusion allow the colloid to enter the primary minimum?
c. Would diffusion allow the colloid to escape the energy minimum to bulk solution?
d. Will S. aureus have strong or weak association with the hematite? Why?
e. How does the depth of the primary minimum compare to the base case?
3. In addition to S. aureus, populations of viruses (ap = 10 nm, p = -5 mV at pH 7) were found in the aquifer. What
would be the nature of the virus association, if any, with the quartz sand? Why?
4. A heavy rain occurs that drives low ionic strength water (2 mM) to the system (p = -35 mV, c = -55 mV at pH 7).
What would be the nature of S. aureus association, if any, with the quartz sand? Why?
Solution - #1
Solutions - #1
a. Primary minimum (H = 0.21 nm, G = -2100 kT), Secondary minimum (H =
14.5 nm, G = -2.9 kT)
b. No, the energy barrier (H = 1.0 nm, G = 690 kT) is significantly greater than
the 0.5 kT intrinsic energy provided by diffusion.
c. No, the 0.5 kT intrinsic energy provided by diffusion would not allow the bacteria
to escape the -2.9 kT secondary minimum
d. Weak association, as the bacteria cannot overcome the barrier nor escape
back to bulk solution
Solution - #2
Solutions - #2
a. Primary minimum (H = 0.21 nm, G = -4300 kT)
b. Yes, there is no energy barrier preventing the bacteria from the primary minimum.
c. No, the 0.5 kT intrinsic energy provided by diffusion would not allow the bacteria to escape the -
4300 kT minimum
d. Strong association, as the bacteria has no energy barrier to overcome to reach the primary
minimum and diffusion does not provide enough energy for escape to bulk solution
e. The primary minimum is about two times deeper than that of the base (unfavorable) case.
Solution - #3
Solutions - #3
a. Primary minimum (H = 0.21 nm, G = -63 kT), Secondary minimum (H = 8.0
nm, G = -0.12 kT)
b. The energy barrier (H = 1.9 nm, G = 0.34 kT) is less than the 0.5 kT intrinsic
energy provided by diffusion.
c. The 0.5 kT intrinsic energy provided by diffusion would allow the virus to escape
the -0.12 kT secondary minimum
d. Strong association, as the intrinsic energy of the virus allows mobility past the
energy barrier but not out of the primary minimum
Solution - #4
Solutions - #4
a. Primary minimum (H = 0.21 nm, G = -1600 kT), Secondary minimum (H = 73 nm,
G = -0.18 kT)
b. The energy barrier (H = 1.2 nm, G = 1400 kT) is significantly greater than the 0.5
kT intrinsic energy provided by diffusion.
c. The 0.5 kT intrinsic energy provided by diffusion would allow the bacteria to escape
the -0.18 kT secondary minimum to bulk solution
d. No association, as the intrinsic energy of the bacteria does not allow mobility past
the energy barrier but does allow mobility out of the secondary minimum to bulk
solution