The Electric Double Layer

• Development of a nett charge at the particle surface affects the distribution of ions in the surrounding interfacial region,
resulting in an increased concentration of counter ions (ions of opposite charge to that of the particle) close to the surface
• Thus an electrical double layer exists round each particle

• An electrical double layer exists around each particle.

• The liquid layer surrounding the particle exists as two parts; an
inner region (Stern layer) where the ions are strongly bound and
an outer (diffuse) region where they are less firmly associated
• Within this diffuse layer is a notional boundary known as the
slipping plane, within which the particle acts as a single entity

The potential at this boundary is known as the Zeta Potential

Zeta Potential

The zeta potential is the overall charge a particle acquires in a

specific medium.

• The magnitude of the zeta potential gives an indication of the

potential stability of the colloidal system
• If all the particles have a large negative or positive zeta
potential they will repel each other and there is dispersion
stability
• If the particles have low zeta potential values then there is no
force to prevent the particles coming together and there is
dispersion instability
• A dividing line between stable and unstable aqueous
dispersions is generally taken at either +30 or -30mV
• Particles with zeta potentials more positive than +30mV are
normally considered stable
• Particles with zeta potentials more negative than -30mV are
normally considered stable
The Influence of Zeta Potential

Zeta Potential and pH

• The most important factor that affects zeta potential is pH

• A zeta potential value quoted without a definition of it's environment (pH, ionic strength, concentration of any additives) is a
meaningless number

Imagine a particle in suspension with a negative zeta potential

• If more alkali is added to this suspension then the particles tend to acquire more negative charge
• If acid is added to this suspension then a point will be reached where the charge will be neutralized
• Further addition of acid will cause a build up of positive charge
• In general, a zeta potential versus pH curve will be positive at low pH and lower or negative at high pH
• There may be a point where the curve passes through zero zeta potential
• This point is called the isoelectric point and is very important from a practical consideration
• It is normally the point where the colloidal system is least stable

In the above example it can be seen that if the dispersion pH is below 4 or above 8 there is sufficient charge to confer stability.
However if the pH of the system is between 4 and 8 the dispersion may be unstable. This is most likely to be the case at around pH
6 (the isoelectric point)

Electrophoresis

• When an electric field is applied across an electrolyte, charged particles suspended in the electrolyte are attracted towards
the electrode of opposite charge
• The particles move with a characteristic velocity which is dependent on the strength of the electric field (measured by the
instrument), the dielectric constant and the viscosity of the medium (known from literature) and the zeta potential
• The velocity of a particle in a unit electric field is referred to as its electrophoretic mobility
• Zeta potential is related to the electrophoretic mobility by the Henry Equation
Henry's Function F(ka)

Zeta potential is related to the electrophoretic mobility by the HENRY EQUATION

UE = 2 ε z f(k a)
3η

UE = electrophoretic mobility
z = zeta potential
ε = dielectric constant
η = viscosity

f(k a) = Henrys function

• The units of k are reciprocal length and 1/k="thickness"

of the electrical double layer (the Debye length)
• a = the particle radius
• ka = the ratio of particle radius to double layer thickness
• For particles in polar media the maximum value of F(ka)
is 1.5 (Smoluchowski approximation)
• For particles in non-polar media the minimum value of
F(ka) is 1 (Hückel approximation)

Electroosmosis

• The walls of the capillary cell carry a surface charge so

the application of the electric field causes the liquid to
flow along the cell walls. This is called electroosmosis
• Colloidal particles will be subject to this flow
superimposed on their electrophoretic mobility and this
needs to be taken into account
• However, in a closed system the flow along the walls
must be compensated for by a reverse flow down the
center of the capillary in a parabolic profile. The position
of the stationary layer is dependent on the geometry of
the cell and can be determined for any capillary cell
• There is a point in the cell at which the electroosmotic
flow is zero and the measured particle velocity is the true
electrophoretic mobility
• This point is called the stationary layer and is where the
measurement is performed
Measuring Electrophoretic Mobility

• An electrophoresis system consists of a capillary cell with electrodes at either end to which a potential is applied

Early methods involved directly observing individual particles using a microscope and timing their transit across a graticule

Current technology uses the technique of laser Doppler velocimetry

Laser Doppler Velocimetry

• Laser beams are aligned at the stationary layer in the cell

• At the crossing point of the beams, Young's interference fringes of known spacing are formed
• Particles moving through the fringes under the influence of the applied electric field scatter light whose intensity fluctuates
with a frequency that is related to the particles velocity
• Photons detected are input to a digital correlator
• A frequency spectrum is produced from which the mobility and hence zeta potential are calculated
What about particles with no charge?

• Particles with no charge will not move in an applied electric field

• They will not be able to be detected
• This problem is overcome by making the interference fringes move
• This is done by using a device called a modulator

What happens if the fringes move but the particles do not?

What happens if the fringes and the particles are moving?