Colloid Chem 2024 - Revised

Colloid chemistry
Introduction
Chemistry of heterogeneous, highly dispersed systems
Heterogeneous system ≠ solutions

(highly) Dispersed systems ≠ solutions ??
Chemistry of (homogeneous) solutions ??
Heterogeneous dispersed systems ≠ solutions ??

Colloid chemistry
Characteristics of colloid systems

Heterogeneous system ≠
Heterogeneous (highly) dispersed systems ??
(Area & properties of) interfaces in heterogeneous systems –

specific areas, shapes, sizes of dispersed species (phases)
Thermodynamic stability of (colloid) systems
Spontaneous processes inside colloid systems

= direction, limitation, nature & observations
Colloid chemistry
Classification of colloid systems

Criterion – selective properties of ??
The interfacial area inside systems

→ the sizes of dispersed species
~ 10-6 – 10-7 – (10-9) m
Nature of dispersed phases &

dispersion media
Colloid chemistry
Properties of colloid systems
Kinetic properties
Optical properties
Electric properties
Thermodynamic vs. kinetic (in-)stability
Colloid chemistry
Dynamic properties of colloid systems
Do colloidal particles perform / show / exhibit random

(thermal) motion – Brownian motion in their
dispersion media or not ?
Reasons & consequences !
Colloid chemistry
Brownian motion
In 1826, Brown observed the constant random motion of

suspended pollen grains in water, which is now referred to
as Brownian motion.
Colloid chemistry
Brownian motion
Do colloidal particles perform / show / exhibit random
(thermal) motion – Brownian motion in their
dispersion media ?
In essence, Brownian motion is the result of random collisions

between suspended particles and the molecules of dispersion
medium
Colloid chemistry
Diffusion
Driving force: ΔC, ( Δμ , Δμφ ) ≠ 0
dci
dni   Di  S   dt
dx
2
dci d ci
 Di  2
dt dx
R T k T
D  
6   r  N 6   r
Spherical shape
with radius r
Colloid chemistry
Sedimentation
Observation: Colloid particles settle down towards

the vessel bottom or floating up onto
the top of dispersion medium
Driving force: gradient of specific weights and

gravitation or other forces
Limits: Stationary sedimentation

Sedimetation equilibrium
Colloid chemistry
Sedimentation in the gravitational field


gravitational force
F  V par .  (d par .  d solv. )  g  B  u

Gravitaional force friction (force)
Colloid chemistry
gravitational force
F  Vpar.  (d par.  d solv. )  g  B  u
4
Spherical particle V par.    r 3
Friction coefficient B  6    r
Colloid chemistry
Stationary state
F  Vpar.  (d par.  d solv. )  g  B  u  0
2r2
u   d par  d solv.  g
par
Stationary (constatnt)
sedimentation rate 9 
9  u
r 
2 d par .  d solv.  g
Particle radius
Colloid chemistry
Stationary state
2r 2
u   d par .  d solv.  g
9 
The stationary (constatnt) sedimentation rate is
Proportional to the gradient of specific weights of phases
Proportional to the cross section of particles
Proportional to the rciprocol of viscosity of dispersion
medium
Colloid chemistry
equilibrium state
Conditions to be fulfilled:
Longer sedimentation path compared to the stationary
sedimentation
Colloid particles perform diffusion opposing
sedimentation
Colloid chemistry
equilibrium state
 d par.  d solv.  g   D 
2
2r dc
c u  c
9 dx
 d par.  d solv.  g  dx
2
dc 2r
  
c 9  D
Colloid chemistry
equilibrium state
ch
 
h 2
dc 2r
c c   0 9  D  d par.  d solv  g  dx
o
 d par.  d solv.  g  h
2
ch 2r
ln  
co 9  D
Colloid chemistry
equilibrium state
 2 r 2  d par .  d solv.  g  h 
ch  co  exp  
 9   D 
 
 V par .  d par .  d solv.  g  h 
ch  co  exp  
 k T 
Colloid chemistry
Sedimentation in the centrifugal field


centrifulgal force
F  V par.  (d par.  d solv. )   x


2
 B u
centrifugal acceleration
Colloid chemistry
Stationary sedimentation (constant sedimentation rate)
dx
F  V par.  (d par.  d solv. )   x  B

2
 0
dt
2r 2
u   d par .  d solv   x

2
Spherical 9 
9  u
particles
rpar . 
2 d par .  d solv.   x
2
Colloid chemistry
Sedimentation equilibrium (sedimentation rate = 0)
Particles distribution along the sedimentation path
 V par  d par.  d solv.    x

2 2

c par., x  c par, x max  exp  
 2kT 
 
ln
c2

V par.  d par.  d solv    2
 x2  x1 
2 2
c1 2kT
Colloid chemistry
Optical properties of colloid systems
Light absorption vs. light scattering
Tyndall
effect
I0 I I0
solution Colloid system

Light absorption Light scattering
Colloid chemistry
Light absorption vs. light scattering
    C
I  I0  e Tyndall
effect
I0 I I0
24   Cd 
2
 n n 
3 2 2 2
I scat,total  I 0    
particle 1 0
2 

4
 n  2 n0 
2
1
Colloid chemistry
Light scattering
Remember !
Lights = electromagnetic waves ( λ = 200 nm – 800 nm )
Electromagnetic waves + dipoles induced oscillations
Induced oscillating dipoles = sources to emit

electromagnetic waves (lights) of the same wavelength in
all directions.
Colloid chemistry
Light scattering
Conditions
1. The medium (of lights transmission) must be optically

heterogeneous, i.e. the particles’ size must be higher
enough compared to those of the solvent.
2. Any light reflex is impossible, i.e. the particles’ sizes

must be smaller than the incident light wavelength.
Colloid chemistry
Scattered lights
Colloid chemistry
Scattered lights
1. Emitted in all direction around the sources, i.e. could be

measured in all angles relating the incident light beam.
2. Same wavelength as the incident light, but polarized.

3. Intensity depending on the “scattered” angle θ and the
distance r to the detector, e.g. Rayleigh equation
2
i  r 9  n n 
 
2 2 2 2
R    2   C N  par   
par . solv . 2 2
1 cos
I incident 2 4  n 2n 2  .
 par . solv . 
Colloid chemistry
Raylegh theory of light scattering
1. Colloid particles considered as POINT scattering source

(relating to the incident wavelength, i.e. < λ/20)
2. No interactions among colloid particles, intensity of

scattered lights = sum of intensities of all particles, i.e.
the colloid particles concentration is very low
3. Colloid particles isotropic, nonabsorbing, isulating

Colloid chemistry
Raylegh equation of light scattering
2
i  r 9  n n 
 
2 2 2 2
R    2   C N  par   
par . solv . 2 2
1 cos
I incident 2 4  n 2n 2  .
Rayleigh ratio Rθ
represents the ability of the
dispersion system (sample)
to scatter light at distance r
from the scattering source
and observation angle θ
relating to the incident beam
Colloid chemistry
2
i  r 9  n n 
 
2 2 2 2
R    2   C N  par   
par . solv . 2 2
1 cos
I incident 2 4  n 2n 2  .
• iθ = intensity of scattered light produced by unit volume of
scattering source, as measured at distance r and angle θ
• I = intensity of the incident beam
• n1 = refractive index of the colloid particle
• n0 = refractive index of the solvent
• CN = number concentration of colloid particles per unit
volume of dispersion (sample in question)
Colloid chemistry
2
i  r 9  n n 
 
2 2 2 2
R    2   C N  par   
par . solv . 2 2
1 cos
I incident 2 4  n 2n 2  .
2
i  r 9  n n  Cm
 
2 2 2 2
R    2    par .  1  cos 2 
par . solv .
I incident 2 4  n 2n 2  
Remember ! By assuming the sample is monodisperse, colloid
particles are spheres with radius a, the particle volume
4
 par .   a 3
3
Colloid chemistry
Characteristics of light scattering
2
i  r 9  n n  Cm
 
2 2 2 2
R    2    par .  1  cos 2 
par . solv .
I incident 2 4  n 2n 2  
1. Scattering intensity inversely proportional to λ4 so

blue light (λ ¬ 450 nm) is scattered much more than red light
(λ ¬ 650 nm)
That’s why the Tyndall cone is blue viewing from the side (esp. at
right angle to the incident beam, and red viewing from the end on)
Colloid chemistry
2
i  r 9  n n  Cm
 
2 2 2 2
R    2    par .  1  cos 2 
par . solv .
I incident 2 4  n 2n 2  
2. The greater the gradient in refractive indexes of dispersed

phase and dispersion medium, the more intensive light scattering
(higher Rayleigh ratios) and vice versa.
so
Solid colloid particles exhibit more intensive light scattering
compared to the macromolecules
Colloid chemistry
2
i  r 9  n n  Cm
 
2 2 2 2
R    2    par .  1  cos 2 
par . solv .
I incident 2 4  n 2n 2  
3. Scattering intensity proportional to the mass concentration Cm
and volume of (spherical, monodispersed) particles
So
More “concentrated” colloid systems exhibit more intensive light
scattering (higher Rayleigh ratios) and vice versa.
Bigger colloid particles exhibit more intensive light scattering
compared to the small one
Colloid chemistry
Application of light scattering
2
i  r 9  n n  Cm
 
2 2 2 2
R    2    par .  1  cos 2 
par . solv .
I incident 2 4  n 2n 2  
To characterize the “concentration” and radius of
(by assumption) monodispersed spherical colloid particles
in the samples investigated
To characterize the concentration and averaged molecular

weights of macromolecules in the samples investigated
Colloid chemistry
Electrical properties of colloid systems
Electrokinetic phenomena
electric fields colloid

systems
 (relative) movements
Electrophoresis Electroosmosis
particles move solvents move
Sedimentation potential Streaming potential

particles settle in solvents flow through
gravitational or centrifugal (stationary) capillaries
fields or porous plugs
colloid systems ( 
relative) movements
electric potentials
Colloid chemistry
Remember: Only charged particles forced to move
by applying electric fields
electric fields colloid
systems
 (relative) movements
Electrophoresis Electroosmosis
particles move solvents move
Colloid surface and surrounding solvent layers

are (electrically) charged
Colloid chemistry
Colloid surface and surrounding solvent layers
are (electrically) charged
How? Where from?
1. From colloids (dispersed phase)

(by) nature
(by) interactions with the surrounding liquids
2. From surrounding liquids (dispersion medium)

(by) interactions with the colloid surfaces
3. BOTH
Colloid chemistry
Charging colloid surfaces
(& the surrounding solvent layers)
1. From colloids (dispersed phase)

isomorphous replacement within the lattice
dissociation of functional groups on surfaces
2. From surrounding liquids (dispersion medium)

adsorption of ions onto colloid surfaces
(specific) adsorption of molecules & dissociation
3. BOTH
Colloid chemistry
Electrokinetic phenomena
Electric double layers
between colloid surfaces Movements caused by electricity
& their surrounding Electrophoresis Electroosmosis
dispersion medium particles move solvents move
Sedimentation potential Streaming potential

particles settle in solvents flow through
gravitational or (stationary) capillaries
centrifugal fields or porous plugs
Electricity caused by movements

Colloid chemistry
Electric double layer
One (charges) layer on colloid surface – caused by the potential
creating ions on colloid surface
One (charges) layer in surrounding dispersion medium – caused by the

neutralizing excess of counter-ions over coions
1. Parallel-plate capacitor model – Helmholtz model
2. Diffuse double layer model – Gouy-Chapman model
3. (Combined) Stern model

Colloid chemistry
Colloid surfaces considered planes, constituting one plate of a
parallel-plate capacitor.
Surface charge (potential creating ions on colloid surfaces)

uniformly distributed.
Counter ions gathered at (very short) distance from colloid

surfaces, also uniformly distributed at this distance from colloid
surfaces, constituting the 2nd parallel plate of capacitor.
Electric potential linearly decreases from one capacitor plate to
another (from colloid surfaces)
Colloid chemistry
qualitative interpreting electro-kinetic phenomena – colloid
surfaces (colloids themselves) & dispersion medium as capacitor
plates could move in opposite directions by an outer electric field.
Rather simple relation between the surface charge density σ0 , -

electric potential ψ0, and the capacitor thickness δ
  0
0 

ε – the dielectric constant (of the dispersion medium)
Colloid chemistry
Potential Counter
creating ions
ions
1 8   c0
 z0  F 
   R T
Colloid chemistry
The shearing planes (distance between plates) in electrokinetic
phenomena would be too close to the colloid surfaces
No distinction between the electrokinetic potential ζ

(experimentally measurable) and surface electric potential ψ0
(experimentally non-measurable)
Colloid chemistry
2. Diffuse double model – Gouy-Chapman model
Colloid surfaces considered planes, surface charge (potential
creating ions on colloid surfaces) uniformly distributed.
Counter ions assumed to be point charges, not parallel arranged
at a very short distance, but diffusely distributed over
substantially longer distances from colloid surfaces, forming a
diffuse double layer at equilibrium – the Boltzmann distribution
The dielectric constant of dispersion medium assumed constant
Only 1 electrolyte in dispersion medium, assumed symmetrical of
charge number z
Colloid chemistry
Applying the Boltzmann
distribution to express the
number concentration of
co-ions and counter-ions
in a distance x from
particle surface, with a
corresponding potential ψ
ze

n  n0  e kT
ze
n  n0  e kT
Colloid chemistry
(In a distance x from
particle surface, with a
corresponding potential ψ)
then the net volume charge
density (“charge conc.”)
  z  e  (n  n )
ze
   z  e  2n0  sinh
kT
Colloid chemistry
Hyperbolic functions sinh, cosh
Hyperbolic sine
e x  e x e2 x  1 1  e 2 x
sinh x   
2 2e x
2 e x
Hyperbolic cosine
e x  e x e2 x  1 1  e 2 x
cosh x   
2 2e x
2 e x
Colloid chemistry
Applying the Poisson’s
equation to express the

relation between the net
volume charge density, the
electric potential and the
dielectric constant

  
2

  2
 2
 
2
   2  2  2 
2
 x y z 
Colloid chemistry
Considering only one
dimension x, small surface

potential (<< 25.7 mV)
and temperature 298K
   0  e   x
2 e 2  n0  z 2 2 e 2  N A  C(2z )
  
  k T   k T
Colloid chemistry
3. Combined (Stern) model
A thin (1-2 ions) rigid
(Stern) layer, the potential

decreases linearly
 0  
A diffuse layer with
manageable thickness, the
potential decreases
exponentially
 x     e   x  0
Colloid chemistry
Zeta potential ζ
Electric potential gradient

 at the surface of shear
(somewhere in the diffuse
layer)
Colloid chemistry
Zeta potential ζ
4     volumetric
 
 I electroosmosis
4   dis tan ce
  
 E electrophoresis
4      Estreamin g
  Streaming potential
 P
3    Esedimentation
 
  r  d  d 0  g  c particles
3 Sedimentation potential
Colloid chemistry
Factors affecting values of Zeta potential ζ
Presence / addition of (strong) electrolytes: Nature &

conc. of the applied electrolytes should be “tailor-made”.

Viscosity & dielectric constant of dispersion medium
Characteristics (nature, size & shape) & density -

“concentration” of colloid particles
Temperature
Colloid chemistry
Model of the electric

double layer
Something else
present around
colloids except
for the co- &
counter ions ?
Colloid chemistry
The solvation / hydratation layer
Solvent / water molecules neighbouring to the colloid

surfaces.

More or less bound to colloid surfaces (their thermal

motion limited due to interaction with colloid surfaces.
(Relatively) weaker compared to the electric double

layer.
(strongly) dependent on the interfacial tension.

Colloid chemistry
Factors affecting the solvation / hydratation layer
Presence / addition of (strong) electrolytes due to the

competitive hydratation layers of ions.

Presence / addition of surface active agents by lowering
the interfacial tension.
Viscosity of dispersion medium
Characteristics (nature, size & shape) & density -
“concentration” of colloid particles
Temperature
Colloid chemistry
(In-) Stability of colloid systems
Thermodynamically instable due to very high

interfacial energy  spontaneous process to lower this
property by lowering the (total) interfacial area = step-by-
step phase separation = coagulation.

Dynamically (in-)”stable” due to the actual coagulation

rates
Colloid chemistry
(In-) Stability of colloid systems
Factors affecting the dynamic (in-)”stability”
of colloid systems
Presence / addition of (strong) electrolytes due to their
effects on the electric double layer as well as the solvation

/ hydratation layer  CCC = Critical Coagulation Conc.
Presence / addition of surface active agents due to their

effects on the solvation / hydratation layer
Colloid chemistry
Coagulation thermodynamics
DLVO ( Derjaguin – Landau – Verwey – Overbeek)

theory of colloid stability
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Colloid chemistry

Heterogeneous system ≠ solutions

Chemistry of (homogeneous) solutions ??

Heterogeneous dispersed systems ≠ solutions ??

Characteristics of colloid systems

(Area & properties of) interfaces in heterogeneous systems –

Thermodynamic stability of (colloid) systems

Spontaneous processes inside colloid systems

Classification of colloid systems

The interfacial area inside systems

Nature of dispersed phases &

Properties of colloid systems

Do colloidal particles perform / show / exhibit random

In 1826, Brown observed the constant random motion of

In essence, Brownian motion is the result of random collisions

Observation: Colloid particles settle down towards

Driving force: gradient of specific weights and

Limits: Stationary sedimentation

Observation: Colloid particles settle down towards

Driving force: gradient of specific weights and

F  V par .  (d par .  d solv. )  g  B  u

Observation: Colloid particles settle down towards

Driving force: gradient of specific weights and

F  V par.  (d par.  d solv. )   x

u   d par .  d solv   x

 V par  d par.  d solv.    x

solution Colloid system

Induced oscillating dipoles = sources to emit

1. The medium (of lights transmission) must be optically

2. Any light reflex is impossible, i.e. the particles’ sizes

1. Emitted in all direction around the sources, i.e. could be

2. Same wavelength as the incident light, but polarized.

1. Colloid particles considered as POINT scattering source

2. No interactions among colloid particles, intensity of

3. Colloid particles isotropic, nonabsorbing, isulating

1. Scattering intensity inversely proportional to λ4 so

2. The greater the gradient in refractive indexes of dispersed

To characterize the concentration and averaged molecular

electric fields colloid

Sedimentation potential Streaming potential

Colloid surface and surrounding solvent layers

1. From colloids (dispersed phase)

2. From surrounding liquids (dispersion medium)

1. From colloids (dispersed phase)

2. From surrounding liquids (dispersion medium)

Sedimentation potential Streaming potential

Electricity caused by movements

One (charges) layer in surrounding dispersion medium – caused by the

1. Parallel-plate capacitor model – Helmholtz model

2. Diffuse double layer model – Gouy-Chapman model

3. (Combined) Stern model

Surface charge (potential creating ions on colloid surfaces)

Counter ions gathered at (very short) distance from colloid

Rather simple relation between the surface charge density σ0 , -

No distinction between the electrokinetic potential ζ

Hyperbolic functions sinh, cosh

Electric potential gradient

Presence / addition of (strong) electrolytes: Nature &

Viscosity & dielectric constant of dispersion medium

Characteristics (nature, size & shape) & density -

Model of the electric

Solvent / water molecules neighbouring to the colloid

More or less bound to colloid surfaces (their thermal