Colloids and Surface Chemistry
• Simplest: tiny particles dispersed in water
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What is a colloid?
• Finely-divided dispersion of one phase in another
• Size of dispersed (“solute-like”) entity >> ordinary molecules
• Example: blood cell in water.
Solution Suspension
homogeneous heterogeneous
particles are particles settle
molecules out
Colloid
size 1–1000 nm
particles remain
suspended
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Examples
• Continuous phase is often water.
• Wide range of sizes:
– bovine serum albumin: 3 nm
– cells: tens of microns
• Classify colloids as hydrophobic (e.g., carbon black) or hydrophilic (e.g.,
red blood cell).
• Stability of colloid: essential part of its function
– whether or not it will coagulate
• E.g. blood cells:
– normally colloidally stable, but
– colloidally unstable when they clot
• Milk (oil in water emulsion) is on the edge of colloidal stability: it creams
(some coalescence).
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Characteristics of colloids
• Continuous phase and dispersed phase
• Thermodynamically unstable but kinetically stable (i.e. they are stable
indefinitely)
• Classified in terms of dispersed substance (solid, liquid, gas) in
dispersing medium (solid, liquid, gas)
• Dispersed phase 10–1000 nm particles:
– Large surface area to volume ratio
– Size appropriate for scattering light
– May have charged surfaces
• The name: Greek kolla = glue, eidos= like
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More examples
continuous phase dispersed phase type example
gas liquid aerosol fog
gas solid aerosol smoke
liquid gas foam whipped cream
liquid liquid emulsion milk
liquid solid sol paint, blood, ink
solid gas solid foam meringue
solid liquid solid emulsion butter
solid solid solid sol opal
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Surfactants
• Important in colloid and surface chemistry and biology
• Surface-active agent: molecule with
hydrophobic (= lipophilic) and
hydrophilic (= lipophobic) portions.
• e.g: (a) sodium dodecyl sulfate
CH3(CH2)11–OSO3– Na+
(b)salts of bile acids – sodium deoxycholate
OH CO2Š Na+
OH
• Can also be cationic, e.g. C14H29NH3+ Br – (a common disinfectant)
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Ionic surfactants
• Ionic surfactants: e.g. sodium dodecyl sulfate
• Adsorbs onto a (hydrophobic) colloid: hydrophobic part in/on (organic)
colloid, hydrophilic part in water: thermodynamically advantageous.
• Colloidal stability through electrostatic repulsion
Negative charge from adsorbed surfactant attracts opposite charge:
double layer
Repulsion between double layers keeps particles apart (colloidal stability)
– + +
+ – – –– +
– – + – –
–
– + +–
+– – – +
– – + – +
+ – + – –
– – – +
–– – + – double layer
– –
+ + + – – +
+ +
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Micelles
• Fatty acids: C12 = dodecyl, C18 = stearic
• Ions have long nonpolar tail and polar head
•Soap solution:
individual fatty acid anions
dispersed in water
can group: micelles
hydrophilic part in water,
hydrophobic tails with
other hydrophobic tails:
thermodynamically
advantageous
Figure 22.3 Blackman
Micelles form above Critical Micelle Concentration (CMC)
• Soap-water mixture: suspension of micelles in water.
• Relatively large micelles scatter light (colloidal) so soapy water looks cloudy
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Surfactants
• “Dirt” is non-polar. Grease = long chain hydrocarbons
• However water is very polar and will not dissolve ‘greasy dirt’
• Soaps, detergents (e.g. sodium dodecyl sulfate): emulsifying agent
– Suspend normally incompatible grease in water
charges on outside from dirt particle
surfactant solubilise
(organic)
particle in water
• Hence called wetting agent or surfactant (= surface-active agent)
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Surfactants at the interface
• Surfactants have hydrophobic and hydrophilic parts
• Hence both parts “happy” in micelles
(“happy” = low free energy)
• Hydrophobic part also makes them accumulate at air-water
interface
(hydrophobic part is at least out of the water)
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Ions and colloidal stability
• Another effect of ions: they cause perturbation of double layer which
gives electrostatically-stabilised colloids their stability
+ +
+ - -
+- - + - - -+ - - -
+ - +
+ - salt + -
+ - + - -+
- -- -
+ - + -+
- - - -+ +- -
- - -
+ + + + +
+
• Reduces electrostatic barrier
• Can cause coagulation
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Stabilisation of colloids
¾A stable colloidal system is one in which
the particles resist flocculation or
aggregation and exhibits a long shelf-life.
¾Depends upon the balance of the
repulsive and attractive forces that exist
between particles as they approach one
another.
¾If all the particles have a mutual
repulsion then the dispersion will remain
stable.
¾If the particles have little or no repulsive
force then some instability mechanism will
eventually take place e.g. flocculation,
aggregation etc.
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Polymeric surfactants (stabilisers)
• Polymer with hydrophobic & hydrophilic parts
C9H19 OCH2CH2 OH
n
n is typically 10 – 40
Surrounds particle as “hairy layer”
A steric (or polymeric) stabiliser:
the other type of stabiliser
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Polymeric surfactants
• Polymer with hydrophobic & hydrophilic parts
C9H19 OCH2CH2 OH
n
colloidal stability because it is
thermodynamically unfavourable to
force particles together by
compressing chains
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Electrosteric stabilisation
• Some species can function as both electrostatic and steric stabilisers:
–
polymer which can have charge in water phase.
• Commonest: proteins – –
– long polymers. –
– both basic and acidic regions
• Examples:
– mayonnaise stabilised by egg yolk
– casein: polypeptide with many amino acids, phosphate,
polysaccharide (κ-casein):
stabilises the fat emulsion droplets in milk
– cells: these colloids are electrosterically stabilized (discussed later)
– paints
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Coagulation
• Destabilisation of a colloid to form macroscopic lumps...
• Can be by:
– Heating: forces particles together and/or changes nature of stabiliser
– Stirring: forces particles together
– Adding salt (electrolyte): shrinks double layer and/or neutralises
inherent charge (e.g. on clay)
– Changing pH: can flatten/desorb electrosteric stabilisers
– Adding flocculant (Flocculants, or flocculating agents, are chemicals
that promote flocculation by causing colloids and other suspended
particles in liquids to aggregate, forming a floc).
• blood clotting is of this type, although it is a complex process
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