Theories of the stability of colloidal disperse systems

(1 nm – 10 µm)
 Instability of liophobic colloids

aggregation:

coalescence:
Colloid stability requires repulsive forces between
colliding particles
Main types of (de)stabilization of colloidal dispersions

electrostatic potential steric potential

Coulombic repulsion entropy hindrance

electrostatic stabilization steric stabilization
 van der Waals attractive interactions;
attraction potential : VA

x r

attraction potential attraction potential

between spherical between plate-like
particles: particles:

Ar A
VA (x) VA (x) 2
12 x 2 S
0
x 12 x
A: Hamaker constant
(attraction parameter) A: Hamaker constant
(attraction parameter)
TABLE 10.1 Partial List of Interactions Between Pairs of Isolated Ions and/or Molecules, with a Listing of Functions That Describe
the Potential Energy Versus Separation, Along with Appropriate Proportionality Constants

Attributed Value of n in
Description Definitions and restrictions* to (9ax-"

Ion 1-ion 2 z = valence, e = electron charge under Coulomb 1

vacuum - otherwise er in denominator (sign
depends on the z value)
Ion 1-permanent dipole 2 p = dipole moment, 8 = angle between line Coulomb 2
of centers and axis of dipole; length of
dipole small compared to x (sign depends
on z and orientation)
Permanent dipole 1- Numerical constant (including sign) depends Coulomb 3
permanent dipole 2 47rd on orientation: const. = JZ for average
overall orientations; const. = + 2 for
parallel and - 2 for antiparallel alignment
Permanent dipole 1- a0 = polarizability (always negative) Debye 6
induced dipole 2
Permanent dipole 1- Free rotation of dipoles (always negative) Keesom 6
permanent dipole 2
Induced dipole 1-induced U = characteristic vibrational frequency of London 6
dipole 2 electrons (always negative)
Induced dipole 1-induced h = Planck's constant, c = speed of light; Casimir and 7
- 723h c - QO,lQO,2
dipole 2 (retarded) 87r (47r&0)~x' applies if x > c/u (always negative) Po lder
Repulsion
+-XI24 Exponent in range 9 to 15; 12 mathematically
convenient (always positive)
12

*The signs indicated are for the sign of (9.

Hamaker constants of various materials
 Combination of Hamaker constants

A132: particle(1)-particle(2)
A132 A131 A232 interaction through medium (3)

A12: particle(1)-particle(2)
A12 A11 A 22 interaction in vacuum

2
A131 A 313 A11 A 33 2 A13 A11 A 33

A132 A11 A 33 A 22 A 33
van der Waals attractions in colloidal disperse systems

The stability of a colloidal disperse system

is strongly dependent on the attractive pair
potential, VA, between the dispersed particles.
VA is determined by the geometric arrangement,
G, of the particles (e.g. lamella-lamella;
sphere-sphere; sphere-lamella; etc. interactions,
independently of the chemical composition),
and the Hamaker constant, A, of the overall system
(which depends on the chemical composition of the
constituting species, but is independent of the
geometrc arrangement). Formally:

VA = A × G

The Hamaker constant A of the overall system

originates from a combination of the individual
Hamaker constants, Ai, of the dispersion medium
and that of the dispersed particles. It can be derived
from the summation of the der Waals dispersion
forces between the constituting species (dispersion
medium; dispersed particles).
 Dependence of the van der Waals pair potential VA between two
colliding particles on the overall Hamaker constant ”A” of the system

VA, van der Waals interaction energy (kT)

two spherical
particles, R=4µm

surface separation, x (nm), of two interacting particles

 Electrostatic forces &
the electrical double layer

Sources of interfacial charge

Electrostatic theory: the electrical double layer
Electrokinetic phenomena
Electrostatic forces (DLVO theory; colloid stability)
 Sources of interfacial charge
at the solid/aqueous solution interface

I - Ag+ I-
(1) Differential ion solubility; I-
Some ionic crystals have a slight I-
Ag+

imbalance in number of lattice I-

Ag+

I-
cations or anions on surface,
I- I-
Ag +
Ag+

eg. AgI, BaSO4, CaF2, NaCl, KCl Ag+

(2) Substitution of surface ions HO O O O OH

eg. lattice substitution in kaolin Si Al Si Si
HO O O O OH
 Sources of interfacial charge
at the solid/aqueous solution interface

OH
(3) Specific ion adsorption
M
+ + + O O O

• OH- and H+ ions

• multivalent ions: Ca+2, Mg+2, La+3, SO42-,
• ionic surfactants, polyelectrolytes
+
+

+ +
+
+ + + +
+
+2 + +
+

+
- - - -
-
 Surface charge formation
at the solid/aqueous solution interface

(4) Direct Ionization of surface groups

H H H
O O O
H OH-
M M M + H2O
O O O O O O O O O
 4) Ionization of surface groups, cont.

Strong acid sites (indep. of pH) Mixed acid and basic sites;
Weak acid sites (dep. on pH) (dependent on pH)

Note: (1)-(3) result in the formation of permanent surface charges;

(4) implies the formation of variable surface charges
 Surface charge formation
at the solid/aqueous solution interface

(5) Ion exchange adsorption (non-equivalent ion adsorption)

• Resins:
– Organic or inorganic polymers used to exchange cations or anions from a solution phase
Organic resins: polymer backbone not involved in bonding
functional group for complexing anion or cation
– Inorganic resins: aluminosilicates (e.g.) zeolite, montmorillonite: cation exchangers
layered double hydroxides (LDHs): anion exchangers
• Properties
– Capacity: amount of exchangeable ions per unit quantity of material
ion exchange capacity (CEC; AEC)
– Selectivity: cation or anion exchange (positive or negative ions)
some selectivities within group
Exchange proceeds on an equivalent base
Charge of the exchange ion must be neutralized
 Ion exchangers

SO3 H CH2 N(CH3 )3 OH

organic cation exchanger organic anion exchanger linkage group

OH OPO(OH)2 OH OPO(OH)2
inorganic
Zr O Zr O Zr O Zr anion exchanger

OPO(OH)2 OPO(OH)2 OPO(OH)2 OPO(OH)2

Deionization of water
Deionization of water
Large-scale ion-exchange columns
 Concentration dependence of the surface charge density ( ),
the surface potential ( o) and the electrokinetic (zeta) potential ( )
on the electrolyte concentration (c)

Plateau: maximum amount adsorbed ( max) surface potential o

at c* implies maximum surface charge Stern potential St
density ( max) which, in turn implies zeta-potential
maximum surface potential ( omax)
o

surface charge density (amount surface potential o distance x from the zeta potential
of surface charge determining plotted against the solid surface plotted against the
ions adsorbed, ) plotted against electrolyte concentration towards the bulk solution electrolyte concentration
ion concentration c c in the bulk solution c in the bulk solution
zi e i
 Electrical double layer

- -
- potential + +
+ + -
+ -- determining + - - -
+ - ions + - -
-
+ + - - +
- -
+ + - +
-
+ counter ions + counter ions +
+ - + - - -
+ - - + - co-ions
- -
+ - +
+ + - - -
- + -
+ + - +
- -
+ + - -
+ - + +
- - - +
+ - + -
+ - + -
+ + - -
- - -
+ - - +
+
+ -
+ -
-
+

Helmholtz model (1879) Gouy-Chapman model (1914)

 THE GUOY-CHAPMAN DOUBLE LAYER
potential
determining +
counter ions
+ - 0
ions + -
Assumptions: + - -
+ - - +
+ -
+ +
1. The surface charge is smeared
+
- - C-(x) -
co-ions
2. Ions are point charges +
+ - -
3. No specific ion adsorption + + -
4. Dielectric constant is constant + -
+
+ - -
+
zie + - C+(x) (x)
c i (x) c exp 0 exp x +
kT + - - - =0
+ -
Boltzmann equation + - +

x
The thickness ( 1/ ) of the diffuse electric double layer

counter ions (x) Potential profile:

+
+
0
- -
+ - - - 0
(x) x
+
+ - oe
+ -
- -
+ (x = 0 ; = 0
co-ions
+
+ - x ; = 0)
+ - - -
+
+ - -
-
C (x)
0 /e
+ -
+
+ - (x)
+
+
- C (x) -
+ -
+ - x -
1/ x

1 kT 1
const (Debye length) I ci z 2
I 2 i
i
 THE GUOY-CHAPMAN DOUBLE LAYER

(x) x
oe

surface potential, 0

0/e potential decay, (x)

distance, x
1/

1 kT
const
I
Ion concentration profiles

For water, 25˚C:

1 0.30
nm
z C(M)
“double layer thickness”
1
0 1000 nm
(counter ions)
typically,
1
0 100 nm
(co-ions)
 Effect of valency number on Debye-length 1/
100
90 1-1 electrolyte
2-2 electrolyte
80 3-3 electrolyte

(nm)
70

-1,
60

Debye-length
50
40
30
20
10
0
10-5 10-4 10-3 10-2 10-1 100 101
electrolyte concentration (M)

Charge screening increases with the valency number of the acting ion;
double layer thickness decreases
 Effect of salt concentration on Debye-length 1/

potetial, (x) 0 c1 < c2 < c3

c3 c2 c1
o/e

1/ 3 1/ 2 1/ 1
distance, x

Charge screening increases with the concentration of the acting ion;

double layer thickness decreases
 STERN MODEL (1924)

+ - -
+
+
-
Surface potential 0
+ - - Stern layer
+ -
+ - - -
+
+
-
+ - x-xSt)
Stern potential
+ - - ( x) St e
St
+ -
+
+
-
+ - - -
+ -
+ - - (x)
+
+
- -
- xSt

Stern layer thickness

For strong specific adsorption in the Stern layer…

St

St

…even surface charge reversal may occur!

 General rules for the adsorption of ions on crystal lattices

On poorly soluble crystalline solids, such anions and cations are preferentially adsorbed which
are the same as, or very similar to, the anion or the cation constituting the crystal lattice.
Example. Solid: AgCl in contact with an aqueous solution of KCl, AgNO3, KBr or CuSO4.

In acidic solution H+, in alkaline solution OH- tend to be specifically adsorbed on the solid.

Schulze-Hardy rule: trivalent ions (Al3+; PO43-) adsorb more strongly than
bivalent ions (Ba2+; SO42-), and bivalent ions adsorb more strongly than
univalent ions (Na+; Cl-).

More hydrated ions adsorb less strongly, less hydrated ions adsorb more strongly on the solid.
(e.g. the hydration of alkali metal ions decreases in the sequence of Li+>Na+>K+>Rb+>Cs+;
their adsorption increases in the same sequence.

Surfaces in contact with water are fare more often negatively chraged than positively charged
because cations are usually more hydrated than anions..
 Preferential ion adsorption on crystal lattices

- + -
- + + +
- - -
- - + + -
+
- - + -
- + KCl + AgNO3
+ - + +
- - - + +
+

AgCl
+
AgCl

- + - + -
- - +
- - + -
+ - + +
-
- + + -
- - +
+ + -
- - +
- - +
- + +
- - - + -
- +
+ + +
- +
-
An ion which is the same kind as, or similar to, one of the ions in the crystal lattice.
Example: solid: AgCl in aquesous soltions of KCl, AgNO3, KBr, CuSO4.
 DLVO theory:
Electrostatic stability
Derjagin Landau Verwey Overbeek
van der Waals attraction

electrostatic repulsion

Aggregation is hindered by electrostatic repulsion

DLVO theory: the theory of electrostatic stabilization
(Derjagin-Landau and Verwey-Overbeek)

The electrostatic repulsion depends on the...

1. …Stern potential St
2. …thickness of the electric double layer, -1
 Electric double layer interaction energies;
repulsion energies VR

A
VA
12 x 2
between two sheets (lamellae):
64 n kT x
VR e

Ar
VA
12 x
between two spheres: 2
ze
8 k 2T 2 r x e zkT
1
VR e ze
e2 z 2
e zkT
1
 DLVO theory: the resultant (total) potential is:
VT = VA + VR

attraction potential repulsion potential

(van der Waals forces) (Coulombic repulsion;
DLVO theory aqueous medium, large )
VA Derjagin
VR
kT Landau
kT
Verwey
0 x
Overbeek 0 x
VT
kT
total
potential 0 x
(VT/kT) 10:
VT = VA + VR “colloid stabiliy”
DLVO theory: conditions for colloid stability
Stability Coagulation

repulsive forces attractive forces

overwhelm overwhelm
attractive forces repulsive forces
DLVO theory: conditions for colloid stability
Colloid stability/flocculation/coagulation/ are controlled by the relative
magnitudes of the van der Waals and the Coulombic forces

repulsion
potential

total aqueous Al2O3 suspension

0 at different pHs

attraction

particle-particle distance
(surface separation)

aqueous As2S3 sol with increasing

background electrolyte concentraion
(1:1 electrolyte, mM)
Colloid stability/flocculation/coagulation/ are controlled by the relative
magnitudes of the van der Waals and the Coulombic forces

stable emulsion stable suspension

unstable unstable

(coagulation; creaming and (coagulation / flocculation;

coalescence) sedimentation)
 For VT = 0, VR = -VA. In this case, the DLVO theory predicts
the ccc ratio for 1:2:3 valence of charge of ions to be 1000:16:1.3.

1 1 1 1
Schulze-Hardy rule: ccc : 6: 6
z6 6
1 2 3

electrolyte ccc (M) (As2S3 dispersion) Schulze-Hardy-rule

NaCl 5,1 10-2 1000

KCl 5,0 10-2 1000 (980)

MgCl2 7,2 10-4 16 (14)

CaCl2 6,5 10-4 16 (13)

AlCl3 9,3 10-5 1,3 (1,8)

 ccc
c increases
interaction energy / 10-19 J

c = 1 mM

23 mM
4 mM

90 mM

ccc = 65 mM As2S3 sol in 1:1 electrolyte

360 mM
1500 mM

r = 0.1 m; T=298K; A212=10-19J;

St=50mV; z = 1;
 ccc

stable Fe(OH)3 sol The sol undergoes coagulation upon

the addition of Al2(SO4)3 solution
 Mechanisms of coagulation

perikinetic differential orthokinetic

settling

perikinetic: collisions by Brownian motion

differential settling (polydisperse suspensions)
orthokinetic: induced collisions through stirring; shear
 The kinetics of coagulation

x r

Fast coagulation (Smoluchowski): each collision leads to aggregation

(high electrolyte concentration, Vmin 0, rate constant: kf)
no
n
1 4 (2 r x ) D n o t

Slow coagulation (Fuchs): only part of the collisions leads to aggregation

(low/intermediate electrolyte concentration, Vmin ~ kT, rate constant: ks)
no kf t s,1 / 2
n where W
1 W 4 (2 r x ) D n o t ks t f,1 / 2

( t12: half life time )

Colloid stability: thermodynamic and kinetic aspects

W 1: stability ratio (Fuchs)

V( x ) d x 1 Vmax kf t s,1 / 2
W 2 r exp 2
exp W
2r
kT x 2 r kT ks t f,1 / 2

turbidity measurements
log W

2:2

1:1
e lec

ele
tro
lyt W

ctro
e

ly
te
fast coagulation
region

log c
logW a b log c
Summary of main types of particle-particle interactions

(x > )

(x < 2 ), e.g.:

interactions.
Colloid stability requires repulsive forces between
colliding particles
Main types of (de)stabilization of colloidal dispersions

electrostatic potential steric potential

Coulombic repulsion entropy hindrance

electrostatic stabilization steric stabilization
Conformations of adsorbed polymer chains
 Conformations of adsorbed polymer chains

(a) polymer in solution; (b) chemisorbed (end-grafted) copolymer; (c) physisorbed homopolymer;
(d) adsorption at low surface coverage with no neares neighbour overlap (‘mushrooms’);
(e) adsorption at high coverage (‘brush’); (f) bridging
 Typical Polymer Adsorption Isotherms
the effect of molecular weight

1.4 c
(mg/m2)
Langmuir isotherm: max
K c
1.2
MW33
MW
1
MW22
MW
Amount adsorbed,

0.8
0.6 MW1
MW1

0.4
0.2 MW3 >> MW
MW3 MW2> MW1
2 > MW 1

0
0 100 200 300 400 500 600
c (mg/L)
Typical thickness of the adsorption layer in case of
electrostatic stabilization and steric stabilization

1:1 electrolyte 1/ polymer ho

c [mmol.dm-3] [nm] M [g.mol-1] [nm]
0.01 100 1,000,000 60
0.1 30 100,000 20
1 10 10,000 6
10 3 1,000 2
100 1 - -
(thickness (end-to-end
of the electric distance polymer
double layer) layer thickness)
Polymers at interfaces

C
 Conditions for efficient steric stabilization
(1) large (point C in the Figure)
(2) large (layer thickness)
(3) large s (adsorption energy)
(4) < 0.5 (good solvent for the polymer chain)
(5) low c (free polymer concentration)
cpolymer note: (3) may conflict with (4) for homopolymers;
this conflict is absent for graft- and block copolymers

bridging aggregation for small values of

(below point B in the Figure)
flocculation
Steric interaction

r x/2

x=2

x
Typical potential function of steric stabilization

VT

VS
steric
repulsion

~ coil x
diameter, rg
VA
van der Waals
attraction
 Brownian movement/
agitation

electrolytes polymers