Principles of Colloid

and Surface Chemistry

(Third Edition)
BY: Paul C. Hiemenz
and Raj Rajagopalan

Lecturer: Prof. TQ Liu

1
2
 Contents
Chapter 1: Colloid and Surface Chemistry—
Scope and Variables
Chapter 2: Sedimentation and Diffusion and
Their Equilibrium
Chapter 3: Solution Thermodynamics: Osmo
tic and Donnan Equilibia
Chapter 4: The Rheology of Dispersions

3
Chapter 5: Static and Dynamic Light
Scattering and Other Radiation Scattering
Chapter 6: Surface Tension and Contact
Angle: Application to Pure Substances
Chapter 7: Adsorption from Solution and Mo
nolayer Formation
Chapter 8: Colloidal Structures in Surfactant
Solutions: Association Colloids

4
Chapter 9: Adsorption at Gas-Solid Interfaces

Chapter 10: Van der Walls Forces

Chapter 11: The Electrical Double Layer and
Double-Layer Interaction
Chapter 12: Electrophoresis and Other Electr
okinetic Phenomena
Chapter 13: Electrostatic and Polymer-Induced
Colloid Stability
5
Chapter 1: Colloid and Surface Chemistry
—Scope and Variables

§1.1 Introduction
1. Definition of Colloid
Any particle that has some linear
dimension between 10-9-10-6m is considered
a colloid.

6
 The linear dimension is size range, rather
than particle weight or the number of atoms in
a particle.
The properties of colloid system and
surface phenomena of colloid system depend
mainly on the specific surface area of colloid
particle, little or lightly on the colloid structure
and density of a particle.
10-6 m < 10-9-10-6m < 10-9m
large colloid solution
dispersion
7
2. Surface and Interface
A surface has area but not thickness (or
thickness limits to zero).
The word surface is used in the chemical
sense of a phase boundary rather than in a
strictly geometrical sense.
A interface has area and thickness.
There is a interface between two phase,
the thickness usually about molecular
dimensions
8
 But surface and interface normally alter
each other, as a same term(especially in
China).
3. Other Concepts and Classification of Colloid
Macromolecular colloid
Multiphase dispersion
Stability
Aggregate
Size and shape of colloidal particle

9
 Micelle: A monophasic, fluide, transparent
, isotropic and thermodynamically stable system
composed by surfactant and water, the particle h
as some linear dimension between 10-9-10-6m.

O/W micelle
10
Solvent
layer

Diffusion
interface
doublelayer
O/W micelle structure
11
 Emulsion: A multiphasic, no-transparent
and thermodynamically unstable system comp
osed by surfactant, cosurfactant, oil and water
.
Microemulsion: A monophasic, fluide, t
ransparent, isotropic and thermodynamically s
table system composed by surfactant, cosur-fa
ctant, oil and water.

12
 For microemulsion, the three-componen
t system of surfactant, cosurfactant and water
usually presents some similar properties to the
four-component system of surfactant, cosurfa
ctant, oil and water.
Thus the three-component system is often
used as the basic system of microemulsion to s
tudy the properties of microemulsions.

13
 O/W structure

Microemulsion
W/O structure

Bicontinuous structure
14
 Lamellar liquid
crystal
Lyotropic
liquid Hexagonal liquid crystal
crystal (Cublic liquid crystal)

Reverse hexagonal liquid crystal

15
The exchange of main structures of aggregation

16
4. Impact of Colloid and Surface Chemistry in
Science,Engineering and Technology
Analytical chemistry
Physical chemistry
Biochemistry and molecular biology
Chemical manufacturing
Environmental science
Material science
Petroleum science, geology, soil science
Household and consumer products
Imaging technology
17
Biological and life science:
Biological membranes and cells

Fig. 1.2
18
 §1.2 The Importance of the Surface
for Small Particles

1. Increase in surface area and energy with d

ecrease in size
A = 4R2
V = (4/3)R3

19
 Any array of a sphere (1cm) after n “cut”,
Supposing, the density of any sphere is
same after n “cut”. But, in fact, the density
depends not only on the mass and volume of
the molecules, but also on their packing in a
bulk sample.
See Table 1.2 (in page 7)
Therefore, increase in surface area and
energy with decrease in size.

20
2. Specific Surface Area
Asp = Atol /mtol
= (n 4R2)/[n(4/3)R3]
= 3/R
For a fixed amount of material, the
specific surface area is inversely proportional
to the radius for uniform, spherical particles.

21
 The actual system consists of non-
uniform spheres, an average value of the
radius may be evaluated.
If the particles are nonspherical (or ir
regularly shaped particles), a quantity know
n as the radius of an equivalent sphere may
be extracted from experimental Asp values.

22
For cylindrical particle:
The sum of the area of both ends and
the cylindrical surface:
A = 2(R2) + 2RL
Asp = Atol /mtol
= n(2R2+2RL)/[nR2L]
= (2/)(1/R+1/L)

23
3. Specific Surface Gibbs Energy
(Surface Tension)
 = (G/A)T,P = (U/A)S,V
= (H/A)S,P = (F/A)T,V
= Force/Length
Unite: J·m-2
Total Surface Energy:
G   dG   dA

24
§1.3 Classification of Colloids Based
on Affinity to Carrier Fluid

1. Continuous Phase and Dispersed Phase

Continuous phase refers to the medium.
Dispersed phase refers to the particles
in the colloid range.

25
2. Lyophilic Colloids
Lyophilic means “solvent loving”
Lyophilic colloid refers to soluble macro-
molecular materials in which the individual pa
rticles (to be of colloid dimensions).
Macromolecular colloids are true solutions
and stable system in the thermodynamic sense.
There is no clearly interface between the
continuous phase and the dispersed phase
(individual particles).
26
 The words continuous phase and
dispersed phase refer to the medium and to
particles.
3. Lyophobic Colloids
There are clearly interfaces between the
continuous phase and the dispersed phase
(colloid particles), i.e the presence of two-
phase.
The common feature of all the system
we consider is that some characteristic linear
dimension of the dispersed particles falls in
the range defined (10-7-10-9 m).
27
 Table 1.4 Summary of some of the
descriptive names used to designate
two-phase colloidal system
Continuous phase Dispersed phase Descriptive name
Gas Liquid Fog, mist, aerosol
Gas Solid Smoke, aerosol
Liquid Gas Foam
Liquid liquid Emulsion
Sol,colloidal sol.,
Liquid solid gel,suspension
Solid Gas Solid foam
Solid Liquid Gel, solid emulsion
Solid Solid Alloy 28
 Lyophobic means “liquid repelling’
Lyophobic Colloids are unstable in the
rmodynamically, but stable kinetically.

Figure 1.3 29
 Critical micelle concentration (CMC or c
mc): the concentration of the micellization occ
urs just or just makes micelle formation very li
ke a phase separation.

or

Micellization schematic diagram

30
31
§1.4 Concept of stability of colloidal system

The stability is relative, the instability is

absolute.
1. Kinetic stability
diffusion
Kinetic stability diffusion equilibrium
brownian motion
Because chemical reactions do not
usually occur in colloidal system, colloids are
stable system in kinetic.
32
 The coarsening process of a thermo-
dynamically unstable dispersion is called
coalescence or aggregation.
coalescence
coarsening process
aggregation
Coalescence: the process that many small
particles take together to form a new big
particle, total surface area of the dispersion
system decreases.

33
 Aggregation: the process by which small
particles clump together like a bunch of
grapes (an aggregate), but do not fuse into a
new particle, total surface area of the
dispersion system do not decrease as well .
When aggregation, the small primary
particles retain their origin identity, only their
kinetic independence is lost. Aggregate
moves as a single unit.

34
 Kinetically Unstable Kinetically stable
Fig. 1.5 Schematic illustration of kinetic
stability of colloids
35
Fig. 1.6 Schematic diagram of colloidal

processing of ceramic specimens

36
2. Thermodynamic stability
Thermodynamic stability: The Gibbs
energy of the micellization of surfactants
molecule is less than zero.
So, the processing of the micellization
of surfactants molecule is spontaneous.
Note: The stability of a colloidal system re
lates with many facts, i.e surfactant concen-tr
ation, surfactant properties, temperature, pH,
electrolyte, medium, co-surfactant, etc.
37
 §1.5 Some Physical Characteristics
of colloids

1. Particle Size and Shape

(1) Monodisperse and polydisperse system
Monodisperse system: Particle Size and
Shape are unique. It is characterized by a sin
gle parameter.

38
Electron micrograph of monodisperse system
(Fig. 1.8)

39
 Many solid particles of this system are
actually spherical, and are characterized by a
high degree of symmetry like a sphere and are
often approximated as spheres.

Electron micrograph of carbon black particles

40
Electron micrograph of carbon black particles
(Fig. 1.9) 41
 Polydisperse system: Particle Size and S
hape are various, remarkably different in sha
pe and size.
2. Martin Diameter
The length of a line that bisects the
projected area of a particle is a parameter
know as Martin diameter.

Fig. 1.10a
42
 The direction along which the Martin
diameter is measured is arbitrary, but it is
should be used consistently to avoid subjective
bias.

43
3. Graticule Diameter
For irregular particles, graticule diameter
is a diameter of the circle that by an assortment
of circles of different sizes etched on a trans-pa
rent slide in to the eyepiece of a microscope an
d deciding which circle most closely approxi-m
ates the projected area of the particles.

Fig. 1.10b
44
4. Ellipsoid of revolution
For the particles with a low degree of
symmetry, An ellipsoid of revolution is the
three-dimensional body that results from the
complete rotation of an ellipse around on of
its axes.
We define a as the radius of the ellipsoid
measured along the axis of rotation, and b as
the radius measured in the equatorial plane.

45
Ellipsoid of revolution (Fig. 1.11)

46
If a>b,the particle
is called a prolate
ellipsoid.

If a<b,the particle
is called a oblate
ellipsoid.

47
 a/b is called the axial ratio of the
ellipsoid.
If a/b<<1, the oblate ellipsoid approache
s the shape of a disk.
If a/b>>1, the prolate ellipsoid approaches
a cylinder or rod-shaped particle.

48
5. “Model particles” of various shapes and sizes
To control the shapes and sizes of the
particles to produce “model” particles that
can be used to study properties old colloids
and to develop new uses for colloid.
“model colloids” are illustrated by the fol
lowing partial list (Page 23 line 3 to bottom, t
o page 25).

49
Fig 1.13 Spherical and cubic particles with
crystalline or amorphous microstructure
50
Fig. 1.14 Model particles of different shapes with
the same or different chemical compositions
51
6. Particle Aggregation
In many situations, the dispersed phase is
present as aggregates, not as primary particles
. In such cases, it is the size, shape, and con-c
entration of the aggregates that determine the
properties of the dispersion itself.
The size and the shape of the aggregates
are obtained normally by transmission electron
microscopy (TEM) or scanning electron
microscopy (SEM).
52
Fig. 1.15 TEM of aggregates of gold particles

53
Fig. 1.16 Aggregates obtained through
computer simulations
54
7. Statistical analysis of polydispersed colloid
A brief theoretical distribution functions of s
tatistical analysis is given in Appendix C for p
olydispersed colloid.
A experiment distribution functions of
statistical analysis is given in Fig. 1.18

55
Fig. 1.18
56
(1) Average diameters and standard deviation
Table 1.6 Some of the more widely encounter size
“average”
name symbol definition Quantity
average
Number average  n idi diameter
or mean d n or d  in
Second moment 2 n d Square of
2

About origin d i

n i
i

diameter
Surface average ds  
d 2
1/ 2 Square of
diameter
Volume average dv  
d 3
1/ 3 Cube of
diameter
Third moment 3 n d
i
3
iCube of
about origin d n i diameter

   Square of
2
1/ 2 mr
Radius of gyration Rg 2
i i

radius
m i
57
Note: the relative magnitudes of the number, s
urface and volume average diameters are give
n by the sequence for a polydisperse:
dn < ds < d v
Only for a monodisperses system woul
d all three parameters have identical values.

58
(2) Molecular weight averages
name symbol definition Methods
Osmotic pres
Number average n M  f M
i i s, other colli
molecular weight Mn n i
i i gative proper
ties
Number average w M  f Light scatteri
i i
Mi ng, sedimenti
molecular weight Mw w i
w ,i
on velocity
viscosity average 1/ 
  n i M1i   Intrinsic
molecular weight M vis 
 n M 
 i i 

viscosity

M w / M n 1 for a polydispersed system.

59
§1.6 Some Classical and Emerging Expe
rimental Tools

For measurement of sizes and for surface

force measurements, to present a few examples
of instruments available for visual observation
and imaging of colloid and surfaces.

60
1. Optical microscopy
(1) contrast
For a particle to be visible optically,
there must be an acceptable different its
refractive index and that its surroundings.
This is known as contrast.
The contrast between a particle and its
surrounding arises depends on the radiation
and probing technique used.

61
(2) Optical principle of an optical microscope
A beam of light is always diffracted at
the edges of an object to produce a set of
images of the edge known as a diffraction
pattern.
We know from physic, positive
reinforcement through diffraction occurs
whenever such an extra distance equals
some integral number of wavelengths of
light.
62
Fig. 1.19
63
 For first-order diffraction, it must be
obeyed by Bragg equation:
d sin   '
d sin    / n
To be intercepted by the lens and
thereby become part of the image, rays from
different parts of the source must travel
paths that differ by 2dsin.

64
 The resolving power d is defined to be
the magnitude of the separation between
objects that is required to produce discernibly
different images.
d   /(2n sin )
  / 2( NA)
NA is called the numerical aperture of the
lens. The signification of above equation: any
points closer together than the distance d will
produce a first-order diffraction image with
light having a wavelength equal to /n at
some angle greater than . 65
 d   /(2n sin )
Above equation shows that the resolving
power is decreased by increasing  or by
decreasing /n.
But, the subtended angle 2 is increased
by increasing the diameter of the lens and by
decreasing the distance between the object and
the lens, the design of the lens limits the range
of theses parameters. The ratio /n may be
decreased by decreasing  or by increasing n.

66
 d   /(2n sin )
As a example, if =500nm, n = 1.5
(immersion oil), and 2 = 140o, the resolving
power d = 142nm. This result represents the
power limit of resolved particle size under
completely idea circumstances.
Under closer too average
circumstances, a figure twice this value (d =
142nm) may be more typical.

67
 These results reveal that direct micro-sc
opic observation is feasible only for particles a
t the upper end of the colloidal size range and t
hen only if the particle contrasts sufficiently in
refractive index with its surroundings.
This is the reason for exploring the use of
other radiations such as X-ray and neutron and
other techniques to “visualize” submicroscopic
particles and features of interest in colloid
science.

68
(3) Dark-field microscopy
By dark-field microscopy, particles as
small as 5nm may be detected under optimum
conditions, with about 20nm as the lower
limit under average condition.
In dark-field microscopy, the sample is
illuminated from the side rather than from
below as in an ordinary microscopy.

69
 If no particles are present, no light wou
ld be deviated from the horizontal into the micr
oscope, and the field would appear totally dark
. However, the present of small dispersed parti
cles leads to the scattering of some light from t
he horizontal into the microscope objective (so
metimes called the Tydall effect).
In dark-field microscopy, some rough
indication of the symmetry of the particles is
afforded by the twinkling that accompanies
the rotation of asymmetrical particles ,but this
is a highly subjective observation.
70
 In dark-field, as in direct observation
microscopy, the refractive index difference
between the particles and the medium is one
of the crucial factors that influences the
feasibility of the method.
Very good resolving power is obtained
with metallic particles, which offer maximum
contrast refractive index. The technique played
an important historic role in colloid science,
particularly in the study of metallic colloids.
R. Zsigmondy (Nobel Prize, 1925) made
extensive use of this technique in his study of c
olloidal gold. 71
2. Electron microscopy
(1) Transmission Electron Microscopy (TE
M)
d   /( 2n sin )
It is clear that the best prospect for
extending the range of microscopy lies in the
extension by orders of magnitude of the
wavelength used to produce the image.

72
 According to the de Broglie equation:
 = h/m
The wavelength of a particle is inversely
proportional to its momentum.
In an electro microscopy, a beam of
electrons replaces light in producing an
image.An electron beam is produced by a hot
filament, accelerated by an electron gun, and
focused by electric or magnetic fields that
function as lenses.
73
Basic principle of
electro microscopy
If the electron
beam is the trans-
mitted electron bea
m, the method is c
alled transmis-sion
electron microscop
y (TEM).

74
 Schematic comparison of light
and electron microscopy

light electron microscopy

microscopy 75
Note: The intensity of the electron beam that
is transmitted through the specimen in an
electron microscopy depends on the thickness
of the sample and the concentration of atoms
in the sample. And the contrast difference of
image depends also on the characteristics
between the particles of the sample and the
support on which they rest (i.e. medium).
The low-contrast situation leads to a
poor-quality image, which looks as a (white)
needle on a white page.
76
(2) Shadow casting
The most common way of overcoming
the low-contrast situation is by the method of
a technique known as SHADOW CASTING.

Fig. 1.21 Shadow casting

77
 Therefore, with shadow casting, the image
shows much more detail. The particle size and
shape and some behaviors or properties can be
obtained if the particle is observed from more
anger sides.
The length of the shadow cast by a
spherical reference particle may be used as a
standard to calculate the thickness of particles.

78
Comparison of application of light and
electron microscope:
The light microscope is limited in
range, but the electron microscope clearly has
access to the entire colloidal size range.
A very real disadvantage persists even
with the conventional electron microscope: TE
M and SEM require that the sample be placed i
n an evacuated enclosure for examina-tion by t
he electro beam. The result bears about as muc
h resemblance to the original dispersion.
79
(3) Scanning electron microscopy (SEM)
The technique is most used to surface
analysis, combined with spectroscopic
methods.
In contrast to the TEM, the SEM works
somewhat like a TV cathode-ray tube. An
electron gun is used to scan a surface with the
help of deflection coils and focusing “lenses”
in a raster pattern, and the “reflected”electron
single is used synchronously to generate an
image of very high magnification on a screen.
80
(4) Scanning tunneling microscopy (STM)
When a probe , usually a metal tip
down to the size of an atom, is brought to
within a nanometer from the surface of a
conductor or a semiconductor, electrons can
be made to jump from the surface to the tip
by applying what is bias potential, called the
tunneling effect. The resulting current is
known as the tunneling current (P55).

81
 By keeping the tunneling current
constant as one moves the probe along a
surface, one can follow the surface contour
with atomic-scale precision.
In the constant current mode of ope
ration, the vertical displacement of the prob
e can be mapped with angstrom- level precis
ion using the deflections of the piezo-electri
c ceramic piece on which the metal tip is mo
unted. The data can be converted to images t
o allow one to see the surface.
82
Fig. 1.22 One type of operation of STM
83
 (5) Scanning probe microscopy (SPM)
The atomic force microscopy (AFM), o
ne type of scanning probe microscopy , can b
e used to measure forces such as Van der Wa
als forces, ion-ion interaction, hydration force
s on polymer-coated surfaces, biologi-cally re
levant bilayers, and so on (P55).
In the force-measuring mode, an SPM is
often referred to as a surface force microscope
(SFM), but the label APM signifies the more
general capability of these devices (P54-55).
84
3. Size and molecular weight measurement
(1) Particle size measurement
Main methods: Optical microscopy,
Electron microscopy (TEM, SEM, SPM,
AFM, STM), static light scattering,
dynamic light scattering, chromatographic
technique, field-flow fractionation method,
NMR, SMR, and so on.

85
(2) Molecular weight
Main methods: static light scattering,
dynamic light scattering, chromatographic
techniques, field-flow fractionation method,
NMR, SMR, viscosity, and so on.
(3) Force measurement
A. Indirect methods: adhesion, peeling, UV,
contact angle, adsorption, optical techniques,
NMR (nuclear magnetic resonance), light
scattering, X-ray scattering, neutron
scattering, and so on.
86
Fig. 1.26 (a-e) Indirect
methods 87
B. Direct methods: optical techniques,
Electron microscopy (TEM, SEM, SPM,
AFM, STM), NMR (nuclear magnetic
resonance), light scattering, X-ray
scattering, neutron scattering, surface
tension, interface tension, viscosity, and so
on.

88
Fig. 1.26 (g-h) Indirect methods

89
Fig. 1.27 SFM measurement
90