CHEE2940: Particle Processing

Lecture 17: Electrical Double Layers

This Lecture Covers

Origin of surface charge and structure of EDL

Structure of EDL, conc. & potential distributions
EDL interparticle force & energy
Measuring surface potentials

Chee 2940: electrical double layers

17.1 THE ELECTRICAL DOUBLE LAYER

• The electrical double layer or EDL occurs at

the interface between a solid surface and its
liquid medium.

• How does this happen? Does it happen just

between solid particles and water?

• Understanding this is crucial to addressing the

stability and aggregation of particles in liquid.

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 Particle-solution interface

Solid
particle
Solution

The electrical double layer (EDL)

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17.2 ORIGIN OF SURFACE CHARGE

• Most particles in an aqueous colloidal

dispersion carry an electric charge.
• There are many origins of this surface charge
depending upon the nature of the particle and
it's surrounding medium.
• Three important mechanisms include:
o Ionisation of surface groups
o Differential loss of ions
o Adsorption of charged species.
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• Ionisation of Surface Groups

Dissociation of any acidic groups on a particle

surface will give a negatively charged surface.

Dissociation of any basic groups on a particle

surface will give a positively charged surface.

The magnitude of the surface charge depends

on the acidic or basic strengths of the surface
groups and on the pH of the solution

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 In vacuum In solution Examples:
Oxides (SiO2)

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• Differential loss of ions from the crystal lattice

If a crystal of Agl is placed in water, it starts to

dissolve.
+ -
If equal amounts of Ag and l ions were to
dissolve, the surface would be uncharged.
+
In fact, Ag ions dissolve preferentially leaving a
negatively charged surface.

Further examples: carbonates & phosphates.

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• Adsorption of charged species (ions and ionic
surfactants)

Surfactant ions may be specifically adsorbed

onto the surface of a particle.

Cationic surfactants would lead to a positively

charged surface.

Anionic surfactants would lead to a negatively

charged surface

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17.3 STRUCTURE OF EDL

The double layer consists of two parts:

• An inner region (Stern layer) where the

counter-ions are strongly bound to the
surface, and

• An outer (diffuse) region where the counter-

and co-ions are less firmly associated with
the surface.

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 Particle-solution interface
Stern plane

Solid
particle
Solution

Diffuse layer
Stern layer

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Diffuse layer of EDL

Distribution of ions in the diffuse layer is determined

by the balance between the electrostatic (Coulomb)
force and the Brownian force of thermal diffusion
(First described by Boltzmann).

The Boltzmann distributions (Balance between

electric potential energy and thermal energy)

 zi eψ ( x ) 
ni ( x ) = ni∞ exp − 
 k BT 
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where x … distance from the solid surface
ψ ( x ) … electric potential
ni ( x ) … number concentration of ions i
ni∞ … ni ( x ) in solution (at x = ∞ )
zi … valency of ions i
-23
k B … Boltzmann constant (= 1.381×10 J/K)
T … absolute temperature.

Examples: For a solution containing CaCl2

 2eψ   eψ 
nCa ( x ) = nCa∞ exp − , nCl ( x ) = nCl∞ exp + 
 k BT   k BT 
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 n∞

Variation of co-ions and counter-ions at a

charged surface
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17.4 POTENTIAL DISTRIBUTION

The potential distribution, ψ ( x ), at the surface is

required for quantifying the diffuse layer & EDL.

It can be predicted using the Poisson equation

(PE) from electrostatics.

The PE states that the total electric flux through

a closed surface is proportional to the total
electric charge enclosed within the surface.

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Mathematical description for the PE:

dψ
2
εε 0 2 = − ρ ( x )
dx

ε0… permittivity of vacuum (8.854×10 C J m ) -12 -1 -1

ε … dielectric constant of solution (=80 for water)

ρ … charge density (of all ions) determined as

ρ ( x ) = ∑ ni ( x ) zi e (= Sum of all ionic charges)

i
-19
e… electronic charge (1.602×10 C)
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Inserting Boltzmann’s distribution for the ion
concentration gives

dψ 2
 zi eψ 
εε 0 2 = −∑ zi eni∞ exp − 
dx i  k BT 

POISSON-BOLTZMANN EQUATION

Example for NaCl salt

dψ
2
 eψ   −eψ 
εε 0 2 = en∞ exp   − en∞ exp  
dx  k BT   k BT 
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 Debye-Hückel linearisation (DHL)

For small potential, exponential functions in the

±x
PE can be linearised (e = 1 ± x + ⋅⋅⋅) to give (by
Debye and Hückel)

d ψ  zi e ni∞ 
2 2 2
= ψ = κ ψ (DHL)
2

 εε 0 k BT 
2
dx
1/ 2
 e 2 ∑ zi ni∞ 
2

κ =  = Debye constant
 εε 0 k BT 
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Practical note:
Salt concentration is given in molar concentration, ci [mol/L].
3
Relationship between ci and ni [molecules/m ]:
ni = ci N A1000; NA …Avogadro #
Practical equations for κ:
1/ 2
1000 N Ae ∑ zi ci∞  2 2 1/ 2
 2000 N Ae 
2
κ =  =  I
 εε 0 k BT   εε 0 k BT 
I = ∑ zi ci∞ / 2 = ionic strength [mol/L]
2

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Useful expressions
o
At 20 C: κ [1/ m] = 3.283 × 10 I [mol/L] or
9

κ [1/ nm] = 3.283 I [mol/L]

o
At 25 C: κ [1/ m] = 3.255 × 10 I [mol/L] or
9

κ [1/ nm] = 3.255 I [mol/L]

Example calculation for 0.01 mol/L solution of
o
CaCl2 at 20 C

cCa∞ = 0.01 mol/L , cCl∞ = 0.02 mol/L

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 mol mol
( +2 ) × 0.01 + ( −1) × 0.02
2 2

L L mol
I= = 0.03
2 L

κ = 3.283 0.03 = 0.569 nm -1

1/ κ = 1.759 nm

1
is the measure of the diffuse layer thickness
κ
“The higher the ion concentration, the thinner the
diffuse (EDL) layer”
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Solution of the DHL for single planar surfaces

ψ ( x ) = ψ 0 exp ( −κ x )

where ψ0 is the potential at x = 0 (at the

‘surface’)

Electric potential at the surface decays

exponentially with the distance x.

Electric potential is zero far from the

surface (in the bulk).
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 Particle-solution interface
Shear plane

Solid
particle Potential Solution

ζ = zeta potential
= Potential at the shear plane

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δ 1/κ Distance 23
17.5 INTERACTION BETWEEN EDL’s

• The double layer force occurs due to the

interaction between two electrical double layers
• The EDL force is due two contributions:
The overlap of the electric potential
distributions at the two surfaces (the Maxwell
stress).
The overlap of the ion concentration
distributions at the two surfaces (the osmotic
pressure).
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 ψ0

Potential profile between

surfaces
ψm

Potential profile at single

surfaces before interaction

Potential profiles at interacting EDL’s

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• The EDL force can be attractive and/or
repulsive
• The EDL force depends on the charging
mechanims (boundary conditions) occurring at
the surfaces during the EDL interaction:
- The constant surface potential (long
contact time), or
- The constant surface charge density (short
contact time).
• In this course: The EDL interaction between
identical particles (the simplest case).
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 EDL repulsion between identical surfaces

In this case, the EDL pressure, Π, only depends on

the overlap of concentration (relative to the bulk)
 
Π = k BT  ∑ ni ( D / 2 ) − ni∞ 
 i 
Boltzmann Eq. gives
 zi eψ 
ni ( x ) = ni∞ exp − 
 k BT 
  zi eψ m  
Π = k BT ∑ ni∞ exp −  − 1
i   k BT  
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 ψm … potential at the middle plane

For low potentials, the series expansion gives

 z eψ 1  z eψ 
2

Π = k BT ∑ ni∞ 1 − i m +  i m  + ⋅⋅⋅ − 1
i  k BT 2  k BT  
( eψ m )
2

Π = −eψ m ∑ ni∞ zi + ∑ 2
ni∞ zi + ⋅⋅⋅
i 2k BT i
( eψ m )
2

Due to electroneutrality: Π =
2k BT i
∑ ni∞ zi
2

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We have κ = 2 e 2
∑zi
2
ni∞
and the superposition
εε 0 k BT
solution for planar surfaces at low potentials
gives (see p. 22): ψ m = 2ψ 0 exp ( −κ D / 2 )

Π ( D ) = 2εε 0κ ψ 0 exp ( −κ D )
2 2

EDL interaction energy per unit area of planar

surfaces (Lecture 15, p. 19)
∞
E ( D ) = ∫ Π ( h ) dh = 2εε 0κψ 0 exp ( −κ D )
2

D
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For the EDL interparticle force, the Derjaguin
approximation (Lecture 15, p. 18) gives

F ( D ) = π RE ( D ) ; R … radius of the particles

F ( D ) = 2πεε 0κ Rψ 0 exp ( −κ D )
2

The EDL interparticle energy, V ( D ) , is calculated as

∞
V ( D ) = ∫ FdD
D
V ( D ) = 2πεε 0 Rψ 0 exp ( −κ D )
2

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17.6 MEASURING SURFACE POTENTIAL
The surface potential is required for determining the
EDL interparticle force and energy.
It can be measured by applying a voltage over the
particles and move them relative to the liquid.
Balancing the applied electric force and the drag
force on a particle gives
E field Q = 6πµ RU
Efield … applied electric field, Q … particle charge,
µ … liquid viscosity, U… particle velocity
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Electrophoretic mobility (measurable) is defined as
U
m=
E field
Charge on the particle surface is calculated as

Q = 4πζεε 0 R

ζ … zeta (surface) potential (at the shear plane)

3mµ
ζ = (Hückel equation)
2εε 0
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Measuring the particle velocity allows the calculation
of the zeta potential. Measuring techniques include:

1) Microscope for measuring distance and time

travelled by a particle
2) Laser light scattering – Doppler shift
3) Electro acoustic method, etc.

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Example data for the zeta potential versus pH

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Isoelectric Point – IEP

• IEP is the pH at which the zeta potential is zero

(The surface is net neutral).
• It depends on the material through the surface
charging mechanisms.

Point of Zero Charge – PZC

• Is usually the same as the IEP except when
polyvalent specifically adsorbed ions are on
the surface.

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Zeta potential of alumina vs pH and KNO3 concentration

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Zeta potential of alumina vs pH and LiNO3 concentration

IEP changes due to the specific adsorption of Li.

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