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MES 712

Interfacial Phenomena
Colloidal Stability Supplement
As was discussed during class, nearly all surfaces in water are charged. Therefore, as
many aspects of industrial science utilize particles in water, the interaction of these
particles is of great importance. Colloidal stability is the term used to describe the
ability/inability of small particles, one linear dimension between 1 nm and 1000 nm, to
aggregate in solution and then to precipitate out of solution. To determine whether
particles aggregate in solution, the interaction of the particle double layers must be
considered, along with various other non-electrostatic forces. The first derivation of this
situation was done separately around the time of World War 2, by Derjaguin and Landau
in the Soviet Union and Verwey and Overbeek in the Netherlands. Because these were
done nearly simultaneously and separately, the theory developed is usually called DLVO
theory. In addition to DLVO forces, non-DLVO forces are also now recognized but will
not be considered in this class. The forces can be divided into attractive and repulsive
forces. The sum of the attractive and repulsive forces is the total force between two
particles. To begin, we will examine the repulsive forces, then the attractive forces.
Repulsive forces
Repulsive forces develop between particles primarily due to the
overlap of the diffuse double layers around the particles. First, we will consider the case
of two parallel plates of identical material some distance, H, apart, as shown in Figure 1.
When H is a very large distance as compared to the Debye length (1/), the osmotic
pressure between the plates is given by P1 2nk boltz T ; where n is the total bulk
concentration of ions. As the plates are brought together from H=, to some distance
H=2l apart, the osmotic pressure changes to P2 k boltz T (n n ) , where n+ is the
concentration of positive ions and n- is the concentration of negative ions, both given by
zi e
)] . Substituting in the individual nion
the Boltzmann equation > nion n[exp(
kboltzT
z i e
z e )]
) exp( i
terms into the P2 equation, P2 2nk boltz T [exp(
, where n is
k boltz T
k boltz T
the bulk ion concentration, zi is the absolute value of the valence, e is the electronic
charge constant, and l is the overlapped double layer potential at the midpoint of
separation, l. The potential difference between H=2l and H= is then P2-P1 and is called
the effective pressure, Peff. P2 can be simplified to P2=2nkboltzT coshU; where coshU is the
hyperbolic cosine of U

z i e
k boltz T

. Thus, Peff 2nk boltz T (cosh U 1) .

However, Peff is also the negative of the differential of the repulsive for between surfaces,

dV
Vr, so that Peff r and Vr 2 Peff dx . The 2 comes from there being 2
dx
surfaces going from infinite separation to 2l separation.

Therefore, Vr 2 2nk boltz T (cosh U 1) dx . To integrate this, the value of U must

be remembered to be a function of x based on the l term in U. The value of l/( at any


value of separation x=H for H between and 2l can be found from Gouy-Chapman

H
Double layer potential
No overlap
P1=2nkboltzT
H = 2l
l
l

Overlapped double layer


Figure 1. Double layer repulsion between parallel plates.
theory. Another way to write the GC equation is
( x) (

2k boltz T
1 exp(x)
z (mV )
) ln[
] where tanh( i 0
)
zi e
1 exp(x)
103

tanh is the hyperbolic tangent and 0(mV) is the surface potential in milliVolts. With this
64 nk boltz T 2
exp( H 0 ) , for two
equation for (x), the integration Vr gives Vr

identical surfaces at any separation H0. If the surfaces are not identical, 2 1 2 , where
1, and 2, are the s of the two different interacting surfaces. This equation gives Vr in
units of interaction energy per unit surface area, so that the surface area of the particles
must be included to get the total repulsive interaction energy.
That was two plates, what about 2 spheres, or a sphere and a plate. For two spheres, of
arbitrary radii a1 and a2, the starting point is the same as two plates except that the
interaction area is now defined by the shape of the spheres, rather than the total face area.
In general, the Derjaguin approximation is used (see Figure 2), which results in the
2a1 a 2
interaction area being A
. Vr for the sphere-sphere case then becomes
a1 a 2
128a1 a 2 nk boltz T
Vr
[
] 1 2 exp(H 0 ) . Two important cases with respect to the
a1 a 2
2
nk T
1 2 exp(H 0 ) , and 2. when a1>>a2
radii are 1. a1=a2=a for which Vr (64a ) boltz
2

nk T
1 2 exp(H 0 ) . Case 2 is the
for which a1a2/(a1+a2) a2 and Vr (128a 2 ) boltz
2
case in which a sphere-interacts with a small plate.

Sphere radius a2

Sphere radius a1

Sum interactions between surface points is


2a1a2/(a1+a2)
Figure 2. Derjaguin approximation.
The equations given above are valid only under a small set of conditions. For instance,
the plate-plate Vr is only strictly correct for small surface potentials and symmetrical
electrolytes. The sphere-sphere Vr is correct when the separation is much less than either
particle radius (H0<<ai), ai > 5 and symmetrical electrolytes. Many other equations for

Vr have been derived for various other conditions and these are shown in the tables at the
end of this supplement. These derivations and much other important surface chemistry
material can be found in the references given at the end of this supplement. One final
derivation of Vr I will include is that by Hogg, Healey and Fuerstenau (HHF). This
inclusion is primarily because Fuerstenau is a graduate of SDSM&T. HHF assumed
small surface potentials for two spheres and ai >> 1, and found that

Vr

ln(1 exp(H 0 )
2a1 a 2 nk boltz T
2
[
]( 12 22 ){[ 2 1 22 ][
] ln(1 exp(2H 0 ))}
2
a1 a 2

1 2 ln(1 exp(H 0 )

z i ei
and i is 1 or 2 respectively. This is the end of the repulsive
k boltz T
force section, now onto attractive forces.

, where 1 and 2

Attractive forces
Attractive forces primarily arise from what are termed London-van
der Waals or sometimes just van der Waals forces. London-van der Waals (vdW) forces
arise from the interaction of like materials. Three main types of vdW forces are generally
recognized: 1. Debye which is the name for interactions between permanent and
induced dipoles; 2. Keesom between 2 permanent dipoles; and 3. London between 2
induced dipoles. Va will be negative (and Vr positive) by convention. Two approaches
have been developed to evaluate these forces. Hamaker developed a microscopic
approach based upon pairwise summation of all intermolecular interactions, while
Lifshitz has developed a macroscopic approach using the electromagnetic properties of
the media. Usually, the Hamaker formulation is used due to convenience and retardation
effects are included when necessary. Figure 3 shows the Va equations for a variety of
geometries. One important factor in the equations in Figure 3 is the constant A, called the
Hamaker constant. In Hamakers work Va is calculated by summing the interactions of
all molecules in one particle, with all the molecules in the other particle. Hamaker used a
double integration procedure rather than the summation to derive the first expression in
a
Figure 3, for the case when H0 << ai. This equation is only good to about H 0 i , but
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often Va is zero at this distance so the equation works well quite frequently. Another
important point about the Hamaker constant A is that subscripts denoting the materials
involved and the surrounding medium are necessary to ensure correct calculation of A.
Thus, A11 represents the Hamaker constant between material 1 and itself in a vacuum. A12
is the Hamaker constant between materials 1 and 2 in a vacuum, and A12=(A11A22)0.5. A132
is the Hamaker constant between materials 1 and 2 in medium 3. A132=A12+A33-A13-A23
(A12 0.5 -A330.5)(A220.5 A330.5), so that A131, the Hamaker constant between material 1 and
itself in medium 3, = (A11 0.5 -A330.5)2. Hamaker constants of the types A11 and A12 can be
calculated if the characteristic frequencies and the dielectric constants for the media are
known. Typical Hamaker constant values (A131) lie between about 0.5 and 15 x10-20
Joules when medium 3 is water. Mineral particles are towards the high end, while
biological materials are at the low end of this range.

Non-DLVO forces
Five main types of non-DLV forces have been identified. These
are Born repulsion due to overlap of electron clouds which is very large at very short (< 1
nm) separations, hydration effects as surface ions hydrate which acts over at most about
1.5 nm, hydrophobic interactions between non-polar molecules, which are often long
range > 60 nm, but relatively weak, steric interactions between material with adsorbed
polymers in which the polymer chain extend into solution and can not be penetrated by
other chains. Steric interactions generally stabilize the colloid. Polymer bridging, in
which polymers adsorb to more than one particle causing aggregation, is the final nonDLVO force. Both steric interactions and polymer bridging take place at about the radius
of gyration of the polymer. These forces can be taken into account as part of the total
interaction energy, but only Born repulsion has a well-defined equation governing it.

Va = -Aa1a2/(6H0(a1+a2))
Two spheres of radii a1, a2
separated by distance H0

One sphere of radius a1,


and a flat plate
separated by distance H0

Va = -Aa1/(6H0)

Va = -A/()
Two infinite flat plates
separated by distance H0

Two cylinders of radii a1, a2


And both length L
separated by distance H0

Per unit area

Va = -[AL/(12(2)0.5H0)](a1a2/(a1+a2))0.5

Va = -A(a1a2)0.5/6H0
Two crossed cylinders
of radii a1, a2
separated by distance H0
Va = -[A/(48)][1/d2 + 1/(d+)2 2/(d+/2)2
Two non-infinite flat plates
Per unit area
of thickness
separated by distance 2d=H0
Figure 3. Attractive van der Waals forces for various geometries.

DLVO Theory
In DLVO theory the main objective is to calculate the total
interaction energy of the system. This is done by adding Vr and Va (Vt=Vr+Va) addition
can be done because the repulsive (Vr) and attractive (Va) energies were defined with
opposite signs. Figure 4 shows the three types of interaction energy curves that can be
obtained. Figure 4a has the case in which the interaction energy starts out initially
attractive. A secondary minimum at about 14 nm occurs when the repulsive energy
begins to increase in magnitude more strongly than the attractive energy magnitude. This
causes a cross-over to repulsion as the distance between surfaces decreases. Eventually,
the energy barrier is reached in which the maximum repulsive total interaction energy
occurs. The interaction energy then drops as the attractive forces begin to steeply
increase, but at no time does the total energy become attractive. This type of interaction
is the most stable type. Particles will stay apart by the distance at which the secondary
minimum occurs. Providing energy to the system, by stirring for instance, will never
result in aggregation, because the total energy never becomes attractive. In Figure 4b, a
meta-stable total interaction energy curve is shown. This curve is similar to that in 4a,
except that the total energy between contact and the energy barrier does become attractive
so that a primary minimum occurs. In this case, particles will behave as in 4a except, that
if more energy than the energy barrier is provided, the interparticle distance will shrink to
the primary minimum distance and the dispersed particles will become aggregated. If the
energy barrier is less than 5kboltzT (~2x10-20 J at 298 K), Brownian motion of the particles
will cause aggregation of the particles (this is often called fast flocculation), and is
equivalent to Figure 4c. In 4c, the total interaction energy does not become repulsive
until distances less than the primary minimum, thus the particles will go to the primary
minimum distance upon interaction.
4E-18

Va
Vr
Vt

3E-18

Energy Barrier
Secondary Minimum

Interaction Energy (J)

2E-18

1E-18

-1E-18

-2E-18

-3E-18

-4E-18
0

10

Distance (nm)

(a)

12

14

16

18

20

2E-18

1E-18

Energy Barrier

Interaction Energy (J)

Secondary Minimum
0

-1E-18

-2E-18

Primary Minimum
Va
Vr
Vt

-3E-18

-4E-18
0

10

Distance (nm)

(b)
1E-18
5E-19

Interaction Energy (J)

0
-5E-19
-1E-18
-1.5E-18
-2E-18

Va
Vr
Vt

-2.5E-18

Primary Minimum

-3E-18
-3.5E-18
-4E-18
0

Distance (nm)

(c)
Figure 4. Three stability curve types.

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As the total interaction energy is the sum of the repulsive and attractive energies, the
stability of the colloidal solution can be altered by changing the conditions. In general,
the attractive energy is difficult to change other than by changing the temperature. As the
repulsive energy is due to the double layer interactions, changing the double layer can
change the Vt value. The primary controllers of Vr are the surface potential of the
colloidal particle and the salt concentration in the solution. The magnitude of Vr
decreases as the surface potential decreases or the solution ionic strength increases.
Flocculation can be initiated by sufficiently decreasing Vr. Usually, this is done by
increasing the ionic strength. This is called salting out. Also, the valence of the salt
added is important. The Schulze-Hardy rule indicates that the salting out ability of an ion
increases as z6. This comes from the critical coagulation concentration (CCC), the
concentration at which no barrier exists to coagulation/flocculation/aggregation. K
z i e
tanh 4 (
)
k boltz T . At large , the hyperbolic tangent term goes to one, so that
CCC
2
A131
z i6
CCCz-6. For lower magniutude , CCC z-2 is a closer approximation to reality.