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The Electric Double Layer

Development of a net 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 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 is an abbreviation for electrokinetic potential in

colloidal systems. In the colloidal chemistry literature, it is usually denoted using the Greek letter zeta, hence -potential. From a theoretical viewpoint, zeta potential is electric potential in the interfacial double layer (DL) at the location of the slipping plane versus a point in the bulk fluid away from the interface. In other words, zeta potential is the potential difference between the dispersion medium and the stationary layer of fluid attached to the dispersed particle.
Zeta potential should not be confused with electrode potential or

electrochemical potential (because electrochemical reactions are generally not involved in the development of zeta potential).

Zeta Potential
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 value of 25 mV (positive or negative) can be taken as the arbitrary value that separates low-charged surfaces from highly-charged surfaces.

Zeta Potential [mV] Stability behavior of the colloid: from 0 to 5, Rapid coagulation or flocculation from 10 to 30 Incipient instability from 30 to 40 Moderate stability from 40 to 60 Good stability more than 61 Excellent stability

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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)
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Methods for experimental determination of zeta

potential Zeta potential is not measurable directly but it can be calculated using theoretical models and an experimentally-determined electrophoretic mobility or dynamic electrophoretic mobility.

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Electrophoretic

velocity is proportional to electrophoretic mobility, which is the measurable parameter. There are several theories that link electrophoretic mobility with zeta potential. They are briefly described in the article on electrophoresis and in details in many books on Colloid and Interface Science.

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Electrophoresis: The movement of a charged particle

relative to the liquid it suspended in under the influence of an applied electric field This technique finds application in the measurements of zeta potentials of model systems (like polystyrene latex dispersion) to test colloidal stability theory To asses the stability of coarse dispersion In identification of charge groups

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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

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Zeta Potential (Smoluchowskis Formula)

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Protective colloid The addition of large amount of the hydrophile, to a

hydrophobic colloid stabilize the system, the hydrophile possibly being adsorbed as a monomolecular layer on the hydrophobic particles. This phenomenon is known as protection. The added hydrophile is known as protective colloid
Gold number: Is the minimum wt in mg of the protective

colloid required to prevent a colour change from red to violet in 10 ml of gold sol on the addition of 1ml of a 10% NaCl solution

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