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Zeta potential

Research · May 2015

DOI: 10.13140/RG.2.1.4554.3844

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Kamyar Khoshnevisan Mohammad Barkhi

Shahid Beheshti University of Medical Sciences Geological Survey of Iran
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 Information about Zeta Potential
K. Khoshnevisan1, M. Barkhi1
1
Institute of Agricultural Biotechnology, Nano Department, Karaj, Tehran, Iran

1 
 
Zeta potential is a measure of the magnitude of the repulsion or attraction between particles. Its
measurement brings detailed insight into the dispersion mechanism and is the key to electrostatic
dispersion control. The measurement of zeta potential is an extremely important parameter
across a wide range of industries including brewing, ceramics, pharmaceuticals, medicine,
mineral processing and water treatment.

Introduction to Colloids

• Three states of matter - gas, liquid and solid

• If one of these states is finely dispersed in another then we have a COLLOIDAL SYSTEM
• These systems have special properties which are of great practical importance
• They consist of a dispersed phase distributed uniformly in a finely divided state in a dispersion
medium

Colloidal Stability

• Particles in a dispersion may adhere together and form aggregates of increasing size which may
settle out due to gravity
• An initially formed aggregate is called a FLOC and its formation FLOCCULATION - this process
is reversible (DEFLOCCULATION)
• If the aggregate changes to a much denser form it is said to undergo COAGULATION - this
process is irreversible
• In the 1940s Derjaguin, Verway, Landau and Overbeek developed a theory which dealt with
colloidal stability (DVLO)

2 
 
Maintaining Colloidal Stability

• For colloidal stability, the repulsive forces between particles must be dominant
• There are two fundamental mechanisms that affect colloidal stability:

STERIC REPULSION  

ELECTROSTATIC (CHARGE)

REPULSION

Mechanisms Affecting Dispersion Stability

Steric Stabilization - this involves polymers added to the system adsorbing onto the particle surface and
causing repulsion

• It is a simple process requiring just the addition of a suitable polymer

• However it can be difficult to subsequently flocculate the system if required
• The polymer can be expensive and in some cases undesirable (e.g. when a ceramic slip is cast
the polymer has to be burnt out causing shrinkage and possible defects)

3 
 
Mechanisms Affecting Dispersion Stability

Electrostatic or Charge Stabilization - this is the effect on particle interaction due to the distribution
of charged species in the system

Stabilization or flocculation of a system may be modified simply by altering the concentration of

ions in a system

It is a reversible process

It is potentially inexpensive

Zeta Potential is a very good index of the magnitude of the interaction between colloidal particles
and Zeta Potential measurements are used to assess the stability of colloidal systems

Origins 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
• Consider the more important mechanisms

• Ionization of surface groups

• Differential loss of ions

• Adsorption of charged species

4 
 
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

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

5 
 
Ionization 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

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

6 
 
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

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

7 
 
 In this 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 thedispersion
may be unstable. This is most
likely to be the case at around pH
6 (the isoelectricpoint)

Electrokinetic Effects

• An important consequence of the existence of electrical charges on surfaces is that particles will
be affected by an applied electric field
• These are collectively defined as electrokinetic effects

There are distinct effects depending on the way in which the motion is induced

• Electrophoresis: the movement of a charged particle relative to the liquid it it suspended in under
the influence of an applied electric field
• Electroosmosis: the movement of a liquid relative to a stationary charged surface under the
influence of an electric field

8 
 
 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

References:
Derjaguin, B.V. and Landau, L. (1941) Acta Physiochim. URSS, 14, 633.
Verway, E.J.W. and Overbeek, J. Th. G. (1948) Theory of the Stability of Lyophobic Colloids, Elsevier,Amsterdam.
Hunter, R.J. (1988) Zeta Potential In Colloid Science: Principles And Applications, Academic Press, UK.
Simplifying the Measurement of Zeta Potential Using M3-PALS, Technical Note available from www.malvern.co.uk

9 
 

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