air

surface

oleic acid

L/L water
interface L/G
interface interface
water
Molecular forces at interfaces

bulk phase: isotropic field

interface: anisotropic field
Liquid/Liquid (L/L) interfaces
Liquid droplets are spherical in shape
 “W” m2 ,
mJ/m 2
unit area, and its units are mJ/m2.

mJ/m2:

mJ/m2 x m2 = mJ
mJ/m2
Examples of colloidal systems
from daily life

Detergents

Cosmetics
Colloid science is interdisciplinary
1. partly physical chemistry
- it is not the chemical composition which is important
- the state is independent of the composition
2 partly physics
- the physical properties are of great importance
- basic law of physics can be applied
3 partly biology
- biological materials are colloids
- the mechanisms of living systems are related to colloid- and interfacial chemistry
 The colloidal domain
size range of discontinuity:

1 nm to 500 nm (1000 nm)

1 nm = 10 Å = 10-7 cm = 10-9 m

- small particle size and small pore size imply

large interfacial area and the
interfacial properties are therefore important !
 Colloidal discontinuities

density (x)
density (x)

distance x distance x

colloidal dispersions porous materials; gels

(incoherent systems) (coherent systems)

A. Buzágh: colloids systems with submicroscopic discontinuities (1-500 nm)

W. Ostwald: the colloidal state is independent of the chemical composition
 Classification of colloids
on the basis of structure
colloids

incoherent systems coherent systems (gels)

colloidal macromolecular association porodin reticular spongoid

dispersions solutions colloids

corpuscular fibrillar lamellar

liophobic liophilic liophilic
 Incoherent systems:
(colloidal) dispersions
TEM
cryo
opt TEM
micr
198 ± 17% nm SiO2 particles

22 ± 20% nm O / W SEM
microemulsion particles
3.2 ± 41% µm O / W
emulsion particles

TEM
TEM
HRTEM
TEM
4 ± 31% nm
Pd particles 224 ± 21% nm 4 ± 25 % nm cubooctahedral Pd particles
LDH particles
Surface matters
lamella

fibrilla

corpuscula
Change of surface free energy
with particle size

when the particle size decreases:

the specific surface area increases
the degree of dispersion increases
Size-dependent pecific surface area: S/V
(surface to volume ratio)

S/V
Specific surface area: S/V
(surface to volume ratio)

colloid
Stability of liophilic and liophobic colloids

colloidal dispersions: liophobic colloids

- thermodynamically not stable; kinetically may be stable

macromolecular solutions: liophilic colloids

surfactant solutions: liophilic colloids
- both thermodynamically and kinetically stable

- liophilic (solvent loving)

- liophobic (solvent hating)
- hydrophilic
- hydrophobic
- lipophilic
- lipophobic
Non-particulate incoherent systems:
macromolecular solutions

some possible comformations of structure of a polypeptide molecule

proteins in water in aqueous solution
Non-particulate incoherent systems:
association colloids (surfactants)

chemical structure of a single surfactant molecule: sodium dodecyl sulfate

 Surfactant micelles
surfactant molecule spherical micelle

hydrophobic self-assembling 30-100 molecules

alkyl chain d 3-5 nm
(association)
hydrophilic
head group
hydrophilic shell
hydrophobic core

cationic surfactant
anionic surfactant
nonionic surfactant

orientation energy minimum

Hardy-Harkins principle
Shapes of surfactant aggregates
Surfactants as biocolloids
 Surfactants as biocolloids

plasma membranes are primarily lipid bilayers with associated proteins and
glycolipids
(cholesterol is also a major component of plasma membranes)
Surfactants as biocolloids
 Coherent systems: gels
Gel: it is a solid or semisolid system of at least two constituents,
consisting of a condensed mass and interpenetrated by a fluid (liquid or gas)
(liogel; aerogel). Network without distinct boundaries. No sedimentation.

1) Floccules of small particles bound by strong van der Waals forces:

2) Macromolecules bound by strong van der Waals forces or cross-linked

by chemical bonds:
Formation of liogels

/
/ surfactant molecules + liquid

/
/ ”SOAP” GEL
 Coherent systems: xerogels
(porous MCM-type materials)
 Xerogels:
porous materials
 Coherent systems: liogels
(hydrogels and organogels)

coherent system: gelatin (hydrogel)

 Liogels
Liogels show a variety of flow (rheological) behaviours:
 Liogels

Hydrogels may show distinct temperature and pH dependent behaviour:

T= 15 0C T= 20 0C T= 25 0C T= 30 0C T= 35 0C T= 400C T= 450C
Classification of disperse
systems by size
Classification of dispersed systems
dispersed systems

amicroscopic submicroscopic systems coarse systems

“true” solution colloids micro heterogeneous

1 nm 500 nm
(1000 nm)

homogeneous colloids heterogeneous

homogenous or heterogeneous?
Classification of disperse systems
by size
• true solutions (“molecular dispersions”)
• (molecules, ions) in gas, liquid (solutions)
• < 1 nm, diffuse easily, pass through paper filters
• fine dispersions (colloidal dispersions )
• sols (”lyophobic colloidal solutions”);
• microemulsions, micelles, polymers
(”lyophilic colloidal solutions”);
• smoke, films & foams
• 1 to 1000 nm, diffuse slowly, separated by ultrafiltration
• coarse dispersions
• most pharmaceutical suspensions and emulsions, dust,
powder, cells, sands
• >1µm, do not diffuse, separated by filtration
Solutions Suspensios
Have very large particles
Have small particles
(ions or molecules) Settle out

Are transparent Can be filtered

Do not separate Must stir to stay suspended

Cannot be filtered

Do not scatter light

Have medium size particles

Cannot be filtered
Colloids Separated with semipermeable membranes

Scatter light (Tyndall effect)

Classification of disperse systems
by size
systems Colloid systems

fog

micelles
Classification of colloidal dispersions
by shape

1. prolate(a>b) 2. oblate (a<b) 3 rod 4. plate 5. coil

Classification of colloidal dispersions
in terms of the physical states of the
internal and external phases
 Classification of colloidal dispersions
in terms of the physical states of the
internal and external phases
L/G: fog, mist, spray G/L: sparkling water, foam, G/S: polysterene foam,
(liquid aerosols) whipped cream silica gel
(liquid gas dispersions) (aerogels, xerogels)
S/G: smoke, loose
soot (powders) L/L: milk; mayonnaize; crude oil L/S: opal, pearl
(solid aerosols) ((micro)emulsions) (solid emulsions)

S/L: paint, ink, toothpaste S/S: pigmented plastics

(sols/suspensions) (solid suspensions)
Stability of colloidal dispersions
Some tidbits from the
history of colloids

motion.
Brownian motion
Dynamics of colloidal particles
Brownian motion
 The Faraday-Tyndall effect.
Dark-field microscopy: the ultramicroscope.

Zsigmondy, 1903
Ultramicroscopic images

blood red cells

Ag nanoparticles
The Faraday-Tyndall effect
The Faraday-Tyndall effect
Dialysis
Kidney and dialysis
 Artificial
kidney
Water and small solute particles
pass through a semipermeable
membrane, large particles are
Retained inside.
Hemodialysis is used medically
(artificial kidney) to remove
waste particles such as
urea from blood.
A dialysis unit
Principle of
dialysis