ELECTRICAL DOUBLE LAYER ELECTRICAL DOUBLE LAYER ELECTRICAL DOUBLE LAYER ELECTRICAL DOUBLE LAYER

AND AND AND AND
ZETA POTENTIAL ZETA POTENTIAL
Outline Outline
1) Charge Development at Solid Interfaces
2) Electrical Double Layers
3) Zeta Potential 3) Zeta Potential
Origin of Surface Charge Origin of Surface Charge
Immersion of some materials in an electrolyte solution. Two
mechanisms can operate.
(1) Dissociation of surface sites.
O
M
H H
O
M
H
O
M
H
OH
+ H O
M
M M
O
O
O
O
O O
O
O O
H
(2) Ad i f i f l i
+ H
2
O
OH
(2) Adsorption of ions from solution.
M
O
O O
+ + +
(3) Some ionic crystals have a slight imbalance in number of
Origin of Surface Charge Origin of Surface Charge
(3) Some ionic crystals have a slight imbalance in number of
lattice cations or anions on surface, eg. AgI, BaSO
4
,
CaF
2
,NaCl, KCl CaF
2
,NaCl, KCl
(4) Surface charge due to crystal lattice defects, eg. lattice
substitution in kaolin substitution in kaolin
HO O O O OH HO
Si
HO
O
O
Al
O
O
Si
O
O
Si
OH
OH
Other Surfaces with Charge Other Surfaces with Charge
The bacteria membrane is The bacteria membrane is
made of a self organizing
lipid bi-layer. Most of the
lipids head-groups are lipids head groups are
negative charged.







Oil droplets develop









Bubbles develop negative









O p p
negative charge.






charge since cationic species
are more mobile, than anionic
species and accumulate to the
i t f

interface.
Electrical Double Layer Electrical Double Layer
÷
-
Water molecules
x
Distance from Surface
+
+
÷
-
-
-
+
+
÷
-
-
Surface
P t ti l
Counter-Ions
+
+
÷
OHP
-
-
Ψ
0
Potential
Co-Ions
OHP
÷
• Helmholtz (100+ years ago) proposed that surface charge ( y g ) p p g
is balanced by a layer of oppositely charged ions
Gouy Gouy- -Chapman Model 1910 Chapman Model 1910--1913 1913
+
+
x
-
-
Distance from Surface
+
+
÷
÷
-
-
+
+
+
-
-
-
÷
÷
Diffusion plane
-
-
Ψ
0
• Assumed Poisson-Boltzmann distribution of ions from surface
Diffusion plane
• ions are point charges
• ions do not interact with each other
• Assumed that diffuse layer begins at some distance from the surface • Assumed that diffuse layer begins at some distance from the surface
Stern (1924) / Grahame (1947) Model Stern (1924) / Grahame (1947) Model
Distance from Surface
Diffusion layer
-
-
x
÷
Distance from Surface
+
+
+
-
-
÷
Ψ
ζ
+
+
÷
+
÷
-
-
-
+
÷
÷
-
-
-
Shear Plane Gouy Plane
Bulk Solution
Stern Plane
-
-
÷
Ψ
0
Gouy/Chapman diffuse double layer and layer of adsorbed
-
charge
Salt Addition Salt Addition
Distance from Surface
Diffusion layer
-
-
x
Ψ
ζ
÷
Distance from Surface
Original Curve
+
+
+
-
-
÷
+
+
÷
+
÷
-
-
-
÷
+
÷
÷
-
-
-
+
÷
Shear Plane
Bulk Solution
Stern Plane
-
-
÷
Ψ
0
+
Gouy Plane
-
Salt will not effect the value of Ψ
0
, but will effect the value of Ψ
ζ 0
,
ζ
Distance from Surface
Salt Addition Salt Addition
+
Diffusion layer
-
-
x
Ψ
ζ
=0
÷
Distance from Surface
Original Curve
+
+
+
+
÷
-
-
-
÷
÷
+
+
+
÷
+
÷
-
-
-
÷
+
+ +
÷
-
-
÷
÷
+
Shear Plane
Bulk Solution
-
-
÷
Ψ
0
Gouy Plane
÷
÷
Stern Plane
Further salt addition can collapse the EDL Further salt addition can collapse the EDL.
Debye Length: EDL Thickness Debye Length: EDL Thickness
Debye-Hückel parameter (κ) describes the decay length
2 / 1
2
| |
2 / 1
1
2
0
2
|
|
.
|

\
|
=
¿
=
n
i
i i
r
Z C
kT
e
c c
k
Z
i
= electrolyte valence
e = elementary charge (C)
C
i
= ion concentration (#/m
3
)
n = number of ions
ε = dielectric constant of medium ε
r
dielectric constant of medium
ε
0
= permittivity of a vacuum (F/m)
k = Boltzmann constant (J/K)
T t t (K) T = temperature (K)
κ
-1
(Debye length) has units of length ( y g ) f g
Zeta Potential – Effect of pH
OH
-
H
+
+
+
Shear
Plane
+
-
+
-
+
-
+
-
+
ζ
Plane
-
+
-
+
ζ
-
+
-
+
ζ
-
+
-
+
ζ
-
+
-
+
-
+
-
+
-
+
-
+
Shear
Plane
Shear
Plane
-
+
-
+
Low pH: Not
enough OH
-
so
High pH: Not
enough H
+
so there
There is a point that
there is enough OH
-
enough OH so
there is a excess
positive charge.
enough H so there
is a excess negative
charge.
there is enough OH
and H
+
to completely
balance out the
f h surface charge
Zeta Potential – Effect of pH
+
-
+
-
+
-
+
ζ
+
Isoelectric Point (IEP):
pH at which ζ = 0
-
+
-
+
-
+
ζ
m
V
)
pH at which ζ = 0
+
-
+
-
pH
ζ
(
m
ζ
+
-
+
-
+
-
+
+
-
+
-
+
-
+
ζ
+
-
+
-
+
-
+
-
+
-
Zeta Potential – Effect of pH
Question: What will happen to a mixed suspension of Alumina and
Si N particles in water at pH 4 7 and 9? Si
3
N
4
particles in water at pH 4, 7 and 9?
Zeta Potential Zeta Potential
Effect of Ionic Strength Effect of Ionic Strength
Increasing
I S
40
50
-- -- Effect of Ionic Strength Effect of Ionic Strength -- --
I.S.
Z
e
t
a

P
o 20
30
40
o
t
e
n
t
i
a
l

(
m
0
10
m
V
)
30
-20
-10
-50
-40
-30
Alumina
pH
1 2 3 4 5 6 7 8 9 10 11
• Free energy decrease upon adsorption greater than predicted
Specific Adsorption Specific Adsorption
• Free energy decrease upon adsorption greater than predicted
by electrostatics
• Have the ability to shift the isoelectric point y p
• Can reverse zeta potential
• Types of Specific Adsorption Ions
• Multivalent ions: Ca
+2
, Mg
+2
, La
+3
, hexametaphosphate,
sodium silicate
• Self assembling organic molecules: surfactants • Self-assembling organic molecules: surfactants
• Polyelectrolytes
+
+
+
+
+
+
+
+
+2
+
+
+
+
+
+
+
+
+
- - - - -
+
Specific Adsorption Specific Adsorption
PO
4
3-
Ca
2+
4
Multivalent cations shift IEP to right (calcite supernatant)
pH
Multivalent cations shift IEP to right (calcite supernatant)
Multivalent anions shift IEP to left (apatite supernatant)
Amankonah and Somasundaran, Colloids and Surfaces, 15, 335 (1985).
Electrokinetic Phenomena Electrokinetic Phenomena
l h i • Electrophoresis
Movement of particle in a stationary fluid by an applied
l t i fi ld electric field.
• Electroosmosis • Electroosmosis
Movement of liquid past a surface by an applied electric field
• Streaming Potential
Creation of an electric field as a liquid moves past a stationary Creation of an electric field as a liquid moves past a stationary
charged surface
• Sedimentation Potential
Creation of an electric field when a charged particle moves
relative to stationary fluid
Zeta Potential Measurements Zeta Potential Measurements
• Electrophoresis
, determined by the rate of diffusion (electrophroretic , y ( p
mobility) of a charged particle in a applied DC electric field.
• PCS
, determined by diffusion of particles as measured by photon
correlation spectroscopy (PCS) in applied field
• Acoustophoresis
, determined by the potential created by a
particle vibrating in its double layer due to an acoustic wave
• Streaming Potential
, determined by measuring the potential created as a fluid
moves past macroscopic surfaces or a porous plug
Zeta Potential Measurements Zeta Potential Measurements
Electrophoresis Electrophoresis Electrophoresis Electrophoresis
Smoluchowski Folmula (1921) Smoluchowski Folmula (1921)
assumed κa >> 1 κ = Debye length
a = particle radius
l i l d bl l hi k h ll h i l electrical double layer thickness much smaller than particle
v = velocityy
ε
r
= media dielectric constant
ε
0
= permittivity of free space
ζ = zeta potential
E
q
, c c
=
0 r
v
ζ = zeta potential
η = medium viscosity
E = electric field
l h i bili
q
, c c
= µ
q
E
0 r
μ
E
= electrophoretic mobility
q
Zeta Potential Measurements Zeta Potential Measurements
Electrophoresis Electrophoresis Electrophoresis Electrophoresis
Henry Formula (1931)
expanded for arbitrary κ a p y
assumed E field does not alter surface charge density (σ
o
)
- low σ
0
v = velocity v = velocity
εr = media dielectric constant
ε0 = permittivity of free space
) a ( f
3
2
v
1
0 r
E k
q
, c c
=
ζ = zeta potential
η = medium viscosity
E = electric field
) a ( f
3
2
3
1
0 r
k
q
, c c
= µ
q
E
μE = electrophoretic mobility
q
Hunter, Foundations of Colloid Science, p. 560
Zeta Potential Measurements Zeta Potential Measurements
Streaming Potential Streaming Potential Streaming Potential Streaming Potential
k = Debye parameter
) kT 2 / Ze exp( ,
a = particle radius
, = zeta potential
1
a
) kT 2 / Ze exp(
<<
k
,
p
K
E
0 r
A
, c c
= A
AE = Potential over capillary (V)
K
E
q
p y ( )
c
r
= media dielectric constant
c
0
= permittivity of free space (F/m)
q = medium viscosity (Pa·s)
K
E
= solution conductivity (S/m)
A d ill (P ) Ap = pressure drop across capillary (Pa)
Equipment for Measuring Zeta Potential Equipment for Measuring Zeta Potential
Electrophoresis - Zeta Mark 21 particles ~ .10 microns- 300 μm
Equipment for Measuring Zeta Potential Equipment for Measuring Zeta Potential
Electroacoustic - Colloidal Dynamics Acoustosizer
powders/slurries < 10nm - up to 50 weight% p p g
Equipment for Measuring Zeta Potential Equipment for Measuring Zeta Potential
Photocorrelation Spectroscopy Brookhaven Zeta Plus dilute Photocorrelation Spectroscopy - Brookhaven Zeta Plus dilute
msuspensions <5microns light scattering technique
Equipment for Measuring Zeta Potential Equipment for Measuring Zeta Potential
S i P i l P Ph i EKA l Streaming Potential – Paar Physica EKA granular
particles, surfaces

Outline

1) Charge Development at Solid Interfaces 2) Electrical Double Layers 3) Zeta Potential

Origin of Surface Charge Immersion of some materials in an electrolyte solution. (1) Dissociation of surface sites. Two mechanisms can operate. f l i OH + + + M O O O . H O M O O O H H O M O O O H OH O M O O O + H2O (2) Ad Adsorption of i i f ions from solution.

Origin of Surface Charge (3) Some ionic crystals have a slight imbalance in number of lattice cations or anions on surface. eg. lattice substitution in kaolin O O O OH Si Si Si Al O O O OH HO HO . BaSO4. AgI.NaCl. CaF2. eg. KCl (4) Surface charge due to crystal lattice defects.

Other Surfaces with Charge The bacteria membrane is made of a self organizing lipid bi-layer. than anionic species and accumulate to the − − interface. Bubbles develop negative charge since cationic species − − − − are more mobile. − −− − −− − − − − − − −− − − − − − − − − − − − O Oil droplets develop p p negative charge. Most of the lipids head groups are head-groups negative charged. i t f − .

Electrical Double Layer Distance from Surface Surface Potential P t ti l Ψ0 Water molecules x  + + + Counter-Ions OHP      Co-Ions  • Helmholtz (100+ y ( years ago) p p g ) proposed that surface charge g is balanced by a layer of oppositely charged ions .

GouyGouy-Chapman Model 1910-1913 1910Distance from Surface Ψ0 + +   + +  Diffusion plane • • Assumed Poisson-Boltzmann distribution of ions from surface • ions are point charges • ions do not interact with each other Assumed that diffuse layer begins at some distance from the surface    x .

Stern (1924) / Grahame (1947) Model Distance from Surface Ψζ Ψ0 Diffusion layer x     + +  + + Stern Plane Shear Plane +    Gouy Plane Bulk Solution  Gouy/Chapman diffuse double layer and layer of adsorbed charge .

Salt Addition Distance from Surface Ψζ Ψ0 Diffusion layer Original Curve x      + + + +  +  +     + Stern Plane Shear Plane Gouy Plane Bulk Solution Salt will not effect the value of Ψ0. but will effect the value of Ψζ .

EDL .Salt Addition Ψζ=0 Ψ0 Distance from Surface + + + + + + + + Shear Plane Stern Plane Gouy Plane Diffusion layer Original Curve x        +  +  +     Bulk Solution   Further salt addition can collapse the EDL.

Debye Length: EDL Thickness Debye-Hückel parameter (κ) describes the decay length  e      kT  r 0 2   Ci Z   i 1  n 2 i 1/ 2 Zi e Ci n εr ε0 k T = electrolyte valence = elementary charge (C) = ion concentration (#/m3) = number of ions = dielectric constant of medium = permittivity of a vacuum (F/m) = Boltzmann constant (J/K) =t temperature (K) t κ-1 (Debye length) has units of length ( y g ) f g .

.Zeta Potential – Effect of pH + + + + + + + + + + + + + + H+ OH- ζ ζ Shear Plane Low pH: Not enough OH. ζ Shear Plane + + + + + + + Shear Plane There is a point that there is enough OHand H+ to completely balance out the surface charge f h High pH: Not enough H+ so there is a excess negative charge.so there is a excess positive charge.

Zeta Potential – Effect of pH ζ ζ (m mV) + + + + + + + Isoelectric Point (IEP): pH at which ζ = 0 pH + + + + + + + + + + + + + + + ζ - ζ .

7 and 9? 4 .Zeta Potential – Effect of pH Question: What will happen to a mixed suspension of Alumina and Si3N4 particles in water at pH 4.

Effect of Ionic Strength -50 40 30 20 10 0 -10 -20 30 -30 -40 -50 1 Increasing I.Zeta Potential -. IS Zeta Po otential (m mV) Alumina 2 3 4 5 6 7 pH 8 9 10 11 .S.

La+3. sodium silicate • Self assembling organic molecules: surfactants Self-assembling • Polyelectrolytes + + + + + + + + +2 + + + + + + + + . Mg+2.Specific Adsorption • Free energy decrease upon adsorption greater than predicted by electrostatics • Have the ability to shift the isoelectric point y p • Can reverse zeta potential • Types of Specific Adsorption Ions • Multivalent ions: Ca+2. hexametaphosphate.

335 (1985). 15. pH .Specific Adsorption Ca2+ PO43- Multivalent cations shift IEP to right (calcite supernatant) Multivalent anions shift IEP to left (apatite supernatant) Amankonah and Somasundaran. Colloids and Surfaces.

Electrokinetic Phenomena • Electrophoresis l h i Movement of particle in a stationary fluid by an applied electric field. l t i fi ld • Electroosmosis Movement of liquid past a surface by an applied electric field • Streaming Potential Creation of an electric field as a liquid moves past a stationary charged surface • Sedimentation Potential Creation of an electric field when a charged particle moves relative to stationary fluid .

• PCS  determined by diffusion of particles as measured by photon correlation spectroscopy (PCS) in applied field • Acoustophoresis  determined by the potential created by a particle vibrating in its double layer due to an acoustic wave • Streaming Potential  determined by measuring the potential created as a fluid moves past macroscopic surfaces or a porous plug .Zeta Potential Measurements • Electrophoresis  determined by the rate of diffusion ( y (electrophroretic p mobility) of a charged particle in a applied DC electric field.

Zeta Potential Measurements Electrophoresis Smoluchowski Folmula (1921) assumed κa >> 1 κ = Debye length a = particle radius electrical double layer thickness much smaller than particle l i l d bl l hi k h ll h i l  r 0 v    r 0    v = velocity y εr = media dielectric constant ε0 = permittivity of free space ζ = zeta potential η = medium viscosity E = electric field μE = electrophoretic mobility l h i bili .

Foundations of Colloid Science. 560 .low σ 0 v = velocity εr = media dielectric constant 2 r  0  f1 ( a )  v ε0 = permittivity of free space 3 ζ = zeta potential 2 r  0  η = medium viscosity f1 ( a )   3 E = electric field μE = electrophoretic mobility Hunter. p.Zeta Potential Measurements Electrophoresis Henry Formula (1931) expanded for arbitrary κ a p y assumed E field does not alter surface charge density (σo) .

Zeta Potential Measurements Streaming Potential  = Debye parameter exp( Ze / 2 kT )  1 a = particle radius a  = zeta potential  r 0 E  p K E  = Potential over capillary (V) p y( ) r = media dielectric constant 0 = permittivity of free space (F/m)  = medium viscosity (Pa·s) KE= solution conductivity (S/m) p  = pressure d drop across capillary (Pa) ill (P ) .

300 μm .Equipment for Measuring Zeta Potential Electrophoresis .Zeta Mark 21 particles ~ .10 microns.

Colloidal Dynamics Acoustosizer p powders/slurries < 10nm .up to 50 weight% p g .Equipment for Measuring Zeta Potential Electroacoustic .

Brookhaven Zeta Plus dilute msuspensions <5microns light scattering technique .Equipment for Measuring Zeta Potential Photocorrelation Spectroscopy .

surfaces .Equipment for Measuring Zeta Potential Streaming P S i Potential – P i l Paar Physica EKA granular Ph i l particles.

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