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CH2204 - Colloidal Systems

CH2204 - Colloidal Systems

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10/11/2013

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CH2204
 –
Colloidal Systems
ColloidsA colloidal system is a mixture of two or more components in which one is dispersed within theother. Examples include emulsions, particle suspensions, soap (surfactant) solutions, smoke andfoams. The particles are usually around 10
-9
-10
-6
m in size and as a result of this small size thesesolutions will seem homogenous, there will also be a high interfacial area of contact which is the keyfactor in considering the properties of a colloidal system.The Energy in Pure LiquidsThe Bulk
The energy, E, is proportional to a pair wise interaction energy, or EαW
AA
therefore;
E=12z
b
N
A
W
AA
 Where z
b
is the number of nearest neighbours each molecule has and N
A
is the number of moleculesin the system.At the SurfaceThere are less interactions for molecules on the surface of thesolution than those in the bulk. In this case;
E=12z
s
N
A
W
AA
 Where z
s
is the number of nearest neighbours at the surface,z
b
will always be larger than z
s
and so to transfer a molecule from the bulk to the surface will requirean energy input to break intermolecular bonds.The energy required will depend on the intermolecular forces involved, for example hydrogen bondsrequire 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 newinterfaces are formed, cohesion is the work required to pull a part a volume of unit cross-sectionalarea.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
 γ
=
δ
G
δ
A
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 determinedwith a Willhelmy plate or Du Nouy ring or by blowing a bubble through a capillary tube until itdetaches itself (the point at which favourable surface area is achieved, the surface tension being
 
equal to
β
F/4
π
R where
β
is a correction factor).The maximum bubble pressure is calculated usingthe Young-Laplace equation;
P=
 γ
1R
x
+1R
y
 And since R
x
and R
y
are equal for spherical bubbles;
P=2YR
 Surface tension also applies at solid/liquid interfaces, the contact angle will dictate how large a valuesurface tension takes.
G=
γ∆
AdG=
γ
sl
dA+
γ
lv
dAcos
θ
-
γ
sv
dAAs the droplet spreads there will be an increase in A and
γ
lv
 taking into account the change in contact angle. dA will benegative for
γ
sv
as the contact decreases.The liquid can be tailored to get the desired contact angle (i.e. Teflon maximises the angle, giving itit
s waterproof characteristics, soap minimises the angle to ensure water will spread more readilyacross 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 atsurfaces and behave dependant on temperature and concentration.An example of a surfactant is sodium dodecyl sulphate, Na
+ -
SO
4
(CH
2
)
11
CH
3
.
They can form complex structures in solution known as ‘aggregate structures’ or micelles, 60
-100molecules typically they will form chains associated together to maintain a separation between thehydrophobic groups and water.i.e.At low concentrations (1/1000 molar) the surfactant will float as a separate layer, with very fewmolecules immersed in the solution entirely. As the concentration increases more will entersolution, but most will remain adsorbed at the interface. Once the interface is saturated and there isno more room to adsorb at the surface it becomes favourable to aggregate as micelles. This is an
solidvapour Liquiddroplet
θ
 
 
abrupt process and the monomers form micelles at a very specific concentration dependant on thesystem, this is known as the
critical micelle concentration
(CMC).Gibbs Adsorption IsothermThe interface between a solution and air is considerably difficult to define, vapours from the solutionmake 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 dividingsurface is that point at which solvent excess is equal to 0.The Gibbs adsorption isotherm is derived from the chemical potentials within the system;
μ
i
=
dUdn
S,V,n
j
i
 
μ
i
=
dGdn
T,P,n
j
i
 G=
μ
a
n
a
+
μ
b
n
b
i.e.
Σμ
i
n
i
 dG=
Σμ
i
dn
i
 The relationship between chemical potential in a solution and the potential of the purely static solutionand activity is given by;
μ
=
μ
o
+RTln
α
 
Γ
=n
i
A 
 γ
=dGdA 
μ
=dGdnand so;d
 γ
=
−Γ
d
μ
 The change in surface energy or tension
 γ
is dependant on the adsorbed amount per unit area and thechange in chemical potential.This is for one component.For several components;d
 γ
=
−Σ
i
Γ
i
d
μ
i=
−Γ
solvent 
d
μ
solvent 
+
−Γ
surfactant 
d
μ
surfactant 
 However
Γ
for the solvent is deemed 0 at the dividing surface,and so;d
 γ
=
−Γ
surfactant 
d
μ
surfactant 
 
μ
=
μ
o
+RTln
α
 
d
μ
=RTdln
α
,and this substituted into the above gives;d
 γ
=
Γ
surfactant 
RTdln
α
 
 
This defines the chance in internal energy as thenumber of moles is changed at constant entropy,volume and moles of everything else present.

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