Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
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
http://gse.ua/images/ARTICLES/2-origins/1- https://media1.britannica.com/eb-
media/38/21038-004-89BEEE01.jpg https://profs.library.uu.nl/applicati
teachers/1-great-scientist/3-deriagin/deriagin.jpg http://resources.huygens.knaw.nl/bwn1880-
on/portraits/UMU_01595_U.jpg
2000/lemmata/bwn3/images/VERWEIJEJW.jpg
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
Acid-Base
<5nm
Born
<1nm
Straining vs. Adsorption
http://www.elaguapotable.com/WT%20-%20R2.jpg
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
http://spie.org/Images/Graphics/Newsroom/Imported-2012/004559/004559_10_fig2.jpg
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
Repulsive
pc<0 (Oppositely charged)
Attractive
Example EDL Curve
Repulsive
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
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
Gregory (1981)
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)
Elimelech (1995)
Other Forces: Polymer Bridging
Typically leads to increased attraction but can lead to
repulsion when too many polymers adsorb to surface
Part 2a
Measuring DLVO parameters
Hamaker Constant
http://departments.agri.huji.ac.il/zabam/myimages/ZS- https://www.youtube.com/watch?v=QrBehihiSB4
Measuring%20electrophoretic%20mobility.jpg
https://image.slidesharecdn.com/introzetapotentialdeterminationwebinarv1-110811102559-
phpapp01/95/introduction-to-zeta-potential-technology-in-the-sz100-15-728.jpg?cb=1313058480
Surface Energy
http://www.ramehart.com/images/ca2.jpg
http://www.ramehart.com/newsletters/youngs_equation.jpg
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