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CH2204 – Colloidal Systems

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.

The Energy in Pure Liquids


The Bulk
The energy, E, is proportional to a pair wise interaction energy, or EαW AA therefore;

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

Where zs is the number of nearest neighbours at the surface,


zb will always be larger than zs and so to transfer a molecule from the bulk to the surface will require
an energy input to break intermolecular bonds.
The energy required will depend on the intermolecular forces involved, for example hydrogen bonds
require more energy to break than van der Waals forces, this energy can be given the term cohesion.

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.

Free energy per unit area= ½ work of cohesion

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).

Amphiphilic Molecules (otherwise known as surfactants, or surface active agents)


These are molecules which contain both a hydrophilic and hydrophobic moiety, they will adsorb at
surfaces and behave dependant on temperature and concentration.
An example of a surfactant is sodium dodecyl sulphate, Na+ -SO4(CH2)11CH3.

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).

Gibbs Adsorption Isotherm


The interface between a solution and air is considerably difficult to define, vapours from the solution
make it difficult to truly define a boundary separating the two and so a standard definition is used,
that determined by Gibbs.

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.

The Thermodynamics of Micellisation


Phase Separation Model
A micelle can, in thermodynamic terms, be considered as a phase, with monomeric surfactant
forming a second. There exists an equilibrium between these two phases;

Micelle⇋Monomeric Surfactant

The chemical potential at equilibrium between these two states will be equal and so the following
can be derived;

μmonomer = μomonomer + RTlnα


μmicelle = μomicelle
There is no RTlnα term as the micelle is the standard state
At equilibrium μmonomer = μmicelle
μomicelle = μomonomer + RTlnα
∆Gmicellisation = μfinal − μinitial
o
∆Gmic = μomicelle − μomonomer
o
∆Gmic = μomonomer + RTlnα − μomonomer
o
∆Gmic = RTlnα
The activity of the monomeric surfactant in the solution is equal to the Critical Micelle Concentration
(as there must be saturation to form the aggregate micelle structures) and so this equation can be
written as;
o
∆Gmic = RTlnCMC

Closed Association (Mass Action Model)


The equilibrium between monomeric surfactant and micelle can be considered for each individual
monomer added to the aggregate structure, i.e. S1+S1⇋S2, S2+S1⇋S3 and so forth. This can be
summarised as nS1⇋Sn.

For this equilibrium ∆G=-RTlnk where;

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)

Emulsions and Micro-emulsions


An emulsion is a mixture of two or more immiscible liquids (for example, oil and water) in which one
is dispersed within the other. Emulsions are made up of a dispersed and continuous phase and the
boundary between these phases is called the interface. In a system of oil and water only the oil will
sit on top, the interfacial area will be equal to the cross section of the vessel. If a surfactant is added
to the system it will sit on the interface, the hydrophilic and hydrophobic parts sitting in the water
and oil respectively.
Upon shaking the system will become visually isotropic; however it is not a solution. There will be
discrete droplets of one liquid within the other, dispersed with one phase stabilised by the adsorbed
surfactant layer. Emulsions consist of large droplets (a few microns in size), and so are often opaque
(due to light being scattered by the many phase interfaces, they are usually white in colour but
dilute emulsions will become blue due to the Tyndall effect). The size of the droplets means there is
a high interfacial tension and this is why energy input is required to form them, the process is
thermodynamically unstable.
A micro-emulsion can be formed with the addition of more surfactant - in an emulsion there is a high
disperse phase content of 50/50, there is less surfactant, in a micro-emulsion there is a lower
disperse phase content, 90/10. A micro-emulsion contains much smaller droplets (a few nanometres
in size) and so forms a clear mixture with low interfacial tension, these are thermodynamically
stable.

Interaction The energy required to form an emulsion is necessary


energy to break the AA and BB interactions to form AB (less
favourable) interfacial interactions and is usually
Distance
achieved by performing high shear mixing or
ultrasonic dispersion. Over time the emulsion will
Van Der Waals reform the original two phases as van der Waals
acts as an interactions bring the dispersed molecules together
attractive
interaction Coalescence leads to
the reformation of 2
phases
leading to coalescence.
There are several stages involved in the coalescence of an emulsion and these can be typified using
an energy diagram.

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.

The energy involved in dispersion can be equated to;

∆Gdisp = ∆Hdisp − T∆Sdisp + γ∆A

∆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;

∆Gdisp = γ∆A − T∆Sdisp

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

Oil Water Water


Oil
Bicontinuous

Oil in Not discrete droplets,


Water in
water no defined droplet oil
Water structure Oil
Oil
Winsor; I IV III IV II

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.

Flocs Tighter aggregated particles


(loosely aggregated AGGREGATED SYSTEM
particles)
FLOCCULATED SYSTEM

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.