Você está na página 1de 25

CHEM1612 - Pharmacy

Week 13: Colloid Chemistry


Dr. Siegbert Schmid
School of Chemistry, Rm 223
Phone: 9351 4196
E-mail: siegbert.schmid@sydney.edu.au

Unless otherwise stated, all images in this file have been reproduced from:
Blackman, Bottle, Schmid, Mocerino and Wille,
Chemistry, John Wiley & Sons Australia, Ltd. 2008
ISBN: 9 78047081 0866

Colloids and Surface Chemistry

Tyndall effect light scattering by colloid particles


n
n
n
n
n

Particle size
Classification of colloids
Stability of colloids
Steric interactions
Blackman, Bottle, Schmid, Mocerino & Wille: Ch. 7, 22
Lecture 36 - 3

What is a Colloid?
Solution
homogeneous
mixture, e.g.
sugar in water,
single molecules

Suspension
heterogeneous
mixture, e.g
sand in water,
particles visible,
settle out
Colloid
size 1-1000 nm
particles invisible,
remain suspended
Lecture 36 - 4

What is a Colloid?
n
n

No simple definition
Intermediate between a suspension and a solution

Consists of a continuous phase and a dispersed phase.


q Dispersed Phase
(discontinuous phase)
q Dispersion Medium
(continuous phase)

Classified in terms of dispersed substance (s, l, g) in dispersing


medium (s, l, g)

Dispersed phase
q At least one dimension is >1 nm and <1 micron

Thermodynamically unstable
Huge total surface area

Lecture 36 - 5

Surface Effect

The surface area has increased by 1 million times but the volume is the same.
This means most of the substance is now on the surface.

Lecture 36 - 6

Nano Scale

M. Dresselhaus, MIT
Lecture 36 - 7

Figure taken from Basic Principles of Colloid


Science D.H. Everett, RSC paperbacks

Colloidal Dimensions

(a) kaolinite
(b) Plaster of Paris, cement, asbestos
(c) polymer lattices
(d) network structures, e.g. porous glass, gels
Lecture 36 - 8

Classification of Colloids
Dispersed
Phase
Liquid

Dispersing
Medium
Gas

Name of
Colloidal System
Liquid Aerosol

Common Examples

Solid

Gas

Aerosol

Gas

Liquid

Foam

Liquid

Liquid

Emulsion

Solid

Liquid

Sol

Gas

Solid

Solid Foam

Liquid

Solid

Solid Emulsion

Solid

Solid

Solid Sol

Lecture 36 - 9

Examples
Identify the following types of colloids:
Example

Class

Mist
Milk
Blood
Bone
Asphalt
Mayonnaise
Toothpaste
Smoke
Opal
Paint
Foams
Cement
Soap
Silica gel

liquid aerosol
emulsion
bio-colloid (sol)
bio-colloid (solid sol)
emulsion (asphaltene dispersed phase and maltene contin.)
emulsion
slurry/paste (solid in liquid)
liquid and solid aerosol
solid suspension or dispersion (solid sol)
sol or colloidal suspension
gas dispersed in liquid
sol
liquid emulsion
gel

Lecture 36 - 10

Natural Instability of Colloids


n

The interaction between molecules of one substance with another


is almost always more high in energy (unfavourable) than the
interaction of one substance with itself (like dissolves like).

One big lump of clay in a bucket of water is thermodynamically


much more stable than clay particles dispersed throughout the
water.

A system will move in such a way as to eliminate unfavourable


interactions, i.e, to eliminate surfaces. This is achieved when the
particles stick together, rapidly growing in size, resulting in
flocculation, coagulation, and sedimentation.

Much of colloid science is devoted to controlling the stability of


colloidal dispersions.
Lecture 36 - 11

Flocculation
We can break the colloid stability problem into a series of steps.
particles

dimers

flocs gravity-effected
separation

Lecture 36 - 12

Colloid Stability
n

All atoms experience a short range attraction that arises from


dipole/dipole interactions of electron clouds - van der Waals
attraction. These forces are between dipoles, between a
permanent dipole and an induced dipole, and between two
instantaneous dipoles (dispersion forces).

Time = t

Time = t + t

However we know that some colloids are stable, e.g rivers are muddy,
so the clay/s and particles must be stabilised by some force.
n Therefore a repulsive force is required to obtain stable colloids.
n This repulsion can be of different nature:
q
q

electrostatic
steric
Lecture 36 - 13

Charged Surfaces
n

In water most surfaces are electrically charged, due a number of


different mechanisms:

1.

Adsorption of an ionic surfactant from solution

Surface ionisation, due to surface acid-base reactions,e.g. silica in a


pH range
SiOH SiO - + H+
At neutral pH most oxides have negatively charged surfaces.
2.

3.

Differential solubility of cation and anion in an insoluble salt


Lecture 36 - 14

Electrostatic Repulsion
n

This charge induces an electrical double layer in the vicinity of the


solid, i.e. a first layer of charges of opposite sign next to the solid,
where:
[counter ions] > [free ions of same charge as colloid]

Repulsion between atmospheres of charged particles around


charged colloids stabilises the colloid

Electrical
Double
layer

+ -+- -+ +
+ -+- -+ +
--+
++
+ +
++
+ ++- +
- + ++-+
-+
+ + +
+ + +
+
+
Lecture 36 - 15

Electrostatic Interactions
n

Two like-charged surfaces repel each other within a range given by


the Debye length D-1 . For a 1:1 electrolyte, a simplified expression
for the Debye length is:
1

D =
n

0.304
[salt]

For a 1:1 electrolyte, the Debye length is KD-1= 1 nm for 0.1 M NaCl.

Lecture 36 - 16

Debye Length
The Debye Length is a measure of the
thickness of the diffuse layer.
This table shows that the diffuse layer
extends into solution by several
nanometers.

[NaCl] /M

-1 /nm

1.0 x 10-4
1.0 x 10-3
1.0 x 10-2
1.0 x 10-1
1.0

Increasing concentration of counter ions reduces the thickness of


the electrical double layer.
Adding salt to a colloidal solution therefore destabilises it,
because the particles then can approach each other and
coagulate.

Lecture 36 - 17

Atomic Force Microscopy (AFM)


AFM probe: a microscopic tip is mounted at the end of a
microscopic cantilever. The cantilever deflects as a consequence
of forces between it and the sample.
n The cantilever deflection is detected via the optical lever
system, measured by the photodiode and input to the controller
electronics.
n AFM can be used to image surfaces with high resolution, and to
measure forces with high precision.
n

The force F acting upon


the tip is related to the
cantilever deflection x by
Hooke's law:

Laser
Split Photodiode

Cantilever spring

F = -kx
where k is cantilever
spring constant.

AFM Tip and Cantilever

Sample
Piezoelectric
element

Atomic resolution image


of a mica crystal
Lecture 36 - 18

Example: River + Ocean


Figure from Silberberg, Chemistry,

The higher concentration of positive ions in


the sea water allows the negatively charged
clay particles to approach more closely
before they experience a repulsive force.

Positive ions from the sea water bind to the


surface of the clay particles, reducing the
negative charge on them and hence the
interparticle repulsion.

The action of the waves subjects the clay


particles to increased shear forces,
increasing the frequency of collisions.

McGraw Hill, 2006.

The Nile Delta

Lecture 36 - 19

Hardy-Schulze Rule
n

Flocculation is controlled by the valency of the counter-ion (added


electrolyte with charge opposite that of the particle surface)
Fewer 3+ ions than 2+ than 1+ ions are needed to cancel out colloid
charge on negatively charged colloid more compact counter-ion
cloud (the critical coagulation concentration is lower for 3+ than 2+)

+ +
+
+
+- +
+
- +
+ +
+
- - - +
+ +
+
+

-2+ - - 2+
2+
-2+
- 2+
2+- - 2+
2+

3+3+-

- -

3+-

3+
- 3+

Lecture 36 - 20

Steric Interactions

If a colloid surface is coated with an adsorbed hairy layer of


polymer, often short-range repulsive interactions are observed.

A diffuse adsorbed layer is formed at the interface, typically of the


size of a polymer coil, and prevents two polymer-coated particles
from coming into contact and adhering. The polymer layer must be
thick enough so that van der Waals collisions are not adhesive.

The repulsion varies strongly with distance, often with dependence


on 1/r8.
Lecture 36 - 21

Reason for Steric Stabilisation


n
n
n

Polymer chains on particle surface


Bringing chains together is entropically unfavourable
Increasing concentration of chains between particles induces
osmotic repulsion

Solvent flowing in
Lecture 36 - 22

Steric Stabilisation

The volume occupied by polymer chains is changed by varying


q Solvent
q Temperature

Variation: Polyelectrolytes (charged polymers) impart


stabilization by a combination of electrostatics and steric effects
electrosteric stabilization.
q pH: charged polymers least extended at point of zero charge

Lecture 36 - 23

Destruction of Colloids
Coagulation and flocculation are the destabilisation of a colloid to form
macroscopic lumps.
Factors that induce coagulation and flocculation are:
q Heating: increases the velocities of the colloidal particles, causing
them to collide with enough energy that the energetic barriers are
penetrated and the particles can aggregate. The particles grows
to a point where they settle out.
q Stirring: also increases velocities.
q Changing pH: can flatten/desorb electrosteric stabilisers
q Adding an electrolyte: neutralises the surface of the particle
allowing coagulation and settlement

Lecture 36 - 24

You should now be able to


n
n

n
n

Identify the characteristics of a colloid


Classify a colloid according to the nature of the continuous and
dispersed phases
Explain the electrostatic and steric stabilisation of a colloid
Explain the main mechanism of coagulation of colloids, including the
role of electrolytes

Lecture 36 - 25

Você também pode gostar