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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

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.

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

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

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

10

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

and a flat plate

separated by distance H0

Va = -Aa1/(6H0)

Va = -A/()

Two infinite flat plates

separated by distance H0

And both length L

separated by distance H0

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

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

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

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.

10

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.

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