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Colloids
A colloidal system is a mixture of two or more components in which one is dispersed within the
other. Examples include emulsions, particle suspensions, soap (surfactant) solutions, smoke and
foams. The particles are usually around 10-9-10-6m in size and as a result of this small size these
solutions will seem homogenous, there will also be a high interfacial area of contact which is the key
factor in considering the properties of a colloidal system.
1
E= z N W
2 b A AA
Where zb is the number of nearest neighbours each molecule has and N A is the number of molecules
in the system.
At the Surface
There are less interactions for molecules on the surface of the
solution than those in the bulk. In this case;
1
E= z N W
2 s A AA
In order to break a bulk liquid into smaller particles, the surface area must increase as several new
interfaces are formed, cohesion is the work required to pull a part a volume of unit cross-sectional
area.
The surface free energy change per unit area when creating a surface is given the term γ, the surface
tension.
W = γ∆A
δG
γ=
δA T,P,n
For example, at 293K, γ for water equals 72.8 milliNewtons per metre (mN m -1) whereas for ethanol
γ is 22.1mN m-1.
Surface tension can be measured using the maximum bubble pressure, which can be determined
with a Willhelmy plate or Du Nouy ring or by blowing a bubble through a capillary tube until it
detaches itself (the point at which favourable surface area is achieved, the surface tension being
equal to βF/4πR where β is a correction factor).The maximum bubble pressure is calculated using
the Young-Laplace equation;
1 1
∆P = γ +
Rx Ry
And since R x and R y are equal for spherical bubbles;
2Y
∆P =
R
Surface tension also applies at solid/liquid interfaces, the contact angle will dictate how large a value
surface tension takes.
∆G=γ∆A
vapour Liquid
droplet dG=γsldA+γlvdAcosθ-γsvdA
As the droplet spreads there will be an increase in A and γlv
θ solid
taking into account the change in contact angle. dA will be
negative for γsv as the contact decreases.
The liquid can be tailored to get the desired contact angle (i.e. Teflon maximises the angle, giving it
it’s waterproof characteristics, soap minimises the angle to ensure water will spread more readily
across the surface).
They can form complex structures in solution known as ‘aggregate structures’ or micelles, 60-100
molecules typically they will form chains associated together to maintain a separation between the
hydrophobic groups and water.
i.e.
At low concentrations (1/1000 molar) the surfactant will float as a separate layer, with very few
molecules immersed in the solution entirely. As the concentration increases more will enter
solution, but most will remain adsorbed at the interface. Once the interface is saturated and there is
no more room to adsorb at the surface it becomes favourable to aggregate as micelles. This is an
abrupt process and the monomers form micelles at a very specific concentration dependant on the
system, this is known as the critical micelle concentration (CMC).
The term surface excess (measured in mol m-2) is given the symbol Γ. Γ is the concentration of
surfactant at the interface, above that which is present in the bulk solution. The Gibbs dividing
surface is that point at which solvent excess is equal to 0.
The Gibbs adsorption isotherm is derived from the chemical potentials within the system;
This defines the chance in internal energy as the
dU
μi = number of moles is changed at constant entropy,
dn S,V,n j≠i
volume and moles of everything else present.
dG
μi =
dn T,P,n j≠i
G = μa na + μb nb … i. e. Σμi ni
dG = Σμi dni
The relationship between chemical potential in a solution and the potential of the purely static solution
and activity is given by;
μ = μo + RTlnα
ni dG dG
Γ= γ= μ= and so;
A dA dn
dγ = −Γdμ
The change in surface energy or tension γ is dependant on the adsorbed amount per unit area and the
change in chemical potential. This is for one component.
For several components;
dγ = −Σi Γi dμi = −Γsolvent dμsolvent + −Γsurfactant dμsurfactant
However Γ for the solvent is deemed 0 at the dividing surface, and so;
dγ = −Γsurfactant dμsurfactant
μ = μo + RTlnα ∴ dμ = RTdlnα, and this substituted into the above gives;
dγ = Γsurfactant RTdlnα
This can be rearranged as;
dγ −1 dγ
Γ= = .
RTdlnα RT dlnα
At low activities concentration can be taken for α, and to account for the number of species n is
placed before RT to give the final equation;
−1 dγ
Γ= .
nRT dlnc
n is the number of species present at the interface, for example an ionic surfactant will have an n=2
as both ions and counterions are present.
Micelle⇋Monomeric Surfactant
The chemical potential at equilibrium between these two states will be equal and so the following
can be derived;
X Sn
k=
X S1 n
n Sn
X Sn =
n Sn + n S1 + n H2 O
n S1
And X S1 =
n Sn + n S1 + n H2 O
X Sn
∆G = −RTln
X S1 n
∆G = −RTln X Sn + nRTln X S1
Divide by ′n′ to remove the dependance on size of micelle
∆G −RT
= ln X Sn + RTln X S1
n n
∆G
= RTln X S1
n
∆Gmic = RTln(X S1 since ∆Gmic represents n = 1
n S1
X S1 =
n(S1 ) + n Sn + n(H2 O)
however n H2 O is a massive value compared to micelle concentration and so;
n S1
X S1 = which is the CMC expressed as a mole fraction, therefore;
n H2 O
∆G = RTln(CMC)
Potential
Energy
Creaming Coalescence
o +E o
w w
Coagulation
Time
To maintain an emulsion the energy barrier involved in creaming or coagulation must be increased
to create a thermal well in which the process becomes forced to remain in the emulsified state due
to thermodynamic barriers.
This is the role of the surfactant. The interfacial area in an emulsion is much larger than in a layered
mixture, this leads to an increase in the Gibbs energy change (due to the relationship dG=γ dA) and
so the surfactant is used to decrease the interfacial tension, γ, and counteract the increase in A.
There is also an associated change in chemical potential as the interfacial area increases, dG=μ dn,
and the surfactant, by lowering this potential again lowers the Gibbs energy change, this is called the
dilution effect.
∆Hdisp will be a very small value since no bonds are breaking or forming, there is only physical
movement, as such the term can be ignored to leave;
T∆Sdisp will be a very large positive value since two bulk phases are becoming droplet sized
dispersions, ∆A will also be a large number and so it is necessary to reduce γ as much as possible in
order to make ∆G as low as possible. A positive ∆G will mean an emulsion is formed, by making ∆G
negative a micro-emulsion will form.
Interaction
energy
Repulsive
Acts as
Total
activation Distance
Attractive
barrier
The larger the droplets the larger the attractive forces,
once an emulsion begins to coalesce it accelerates
since Vaα r/6. Smaller droplets are therefore more
stable and form more stable emulsions.
Types of Micro-emulsion
The 5 systems can be named using the Winsor scale as displayed. Types I and II can be useful for
extractions as the amount of oil in the oil/water phase (or water in water/oil phase) can be fine
tuned with temperature.
Particle Dispersions
Consider solid particles in water, over time (assuming the particles have a density larger than that of
water) the particles will settle in the container.
There are several forces stabilising and destabilising this system, there is a gravitational effect
destabilising the system by pulling the particles downwards, dependent on size and in part
counteracted by a viscous drag force (as the particle moves through the liquid the liquid molecules
must move out of the way) which stabilises the dispersion. There is also the kinetic energy of the
particles stabilising the dispersion as they move randomly as a result of Brownian motion.
As the particle size is reduced, the stability of the dispersion increases.
A particle dispersion can settle in two different manners, flocculated or aggregated.
A flocculated system can be easily re-dispersed without needing to input much energy however an
aggregated system is much less easily dispersed. To control how a system aggregates, again
surfactants can be used.
This provides the same energy diagram as above, with an artificial activation energy barrier
preventing the aggregation of the solid particles, for as long as the barrier is larger than the kinetic
energy of the particles available at the given temperature. This artificial activation energy barrier can
be achieved using ionic surfactants which will leave the surface of the particles like charged,
increasing the repulsive force between them. In some cases a second energy minimum can form,
creating a thermal well in which the dispersion will sit, unable to overcome the repulsive nor the
attractive forces occurring between particles, this is in essence flocculation, the particles may be
easily re-dispersed.
To increase the stability of a system the charge can be increased using a charged polymer or
surfactant, or the particle-particle interaction can be decreased with the addition of an uncharged
polymer.