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Colloid chemistry

Lecture 8: electrokinetic phenomena

Characteristics of Surface Charge: Definitions


Particle surface Stern Layer: Rigid layer of ions tightly bound to particle; ions travel with the particle Plane of hydrodynamic shear: Also called slipping plane: Boundary of the Stern layer: ions beyond the shear plane do not travel with the particle. Zeta () potential: the electrical potential that exists at the slipping plane Diffuse Layer: Also called Electrical Double Layer: Ionic concentration not the same as in the bulk solution; there is a gradient in concentration of ions outward from the particle until it matches the bulk

Characteristics of Surface Charge: Definitions

o St

diffuse double layer

Characteristics of Surface Charge: Definitions

Characteristics of Surface Charge

Electrokinetic phenomena result from the differential movement of two phases where the interface is an electrical double layer. The region containing the double layere is sheared at some distance from the solid surface creating a thin film associated with the solid. The electrical potential at the shearing plane is the zeta potential.

Electrokinetic phenomena

St

x
shear plane

Positive particle with negative ion atmosphere

Elektrokinetic phenomena; the electrokinetic (zeta, ) potential


Plateau: maximum amount adsorbed (max) at c* implies maximum surface charge density (max) which, in turn implies maximum surface potential (omax) surface potential o Stern potential St zeta-potential

% o

*
distance x from the surface charge density (amount surface potential o solid surface of surface charge determining plotted against the ions adsorbed ) plotted against electrolyte concentration towards the bulk solution ion concentration c c in the bulk solution zeta potential plotted against the electrolyte concentration c in the bulk solution

Electrokinetic phenomena
A solid surface in contact with a solution of an electrolyte usually carries an electric charge, o. This gives rise to an electric potential, o, at the surface, and a decreasing potential, , as we move through the bulk solution away from the surface, and in turn this effect the distribution of ions in the liquid. Two regions are of primary importance: the Stern layer immediately adjacent to the surface where ion size is important; and outside this region there is a diffuse layer. Because of difference in charge between the diffuse layer and the solid suface, movement of one relative to the other will cause charge separation and hence generate a potential difference, or alternatively, application of an electrical potential will cause movement of one relative to the other. The relative movement of the solid surface and the liquid occurs at a surface of shear. The potential at the shear plane is known as the zeta () potential and its value can be determined by measurement of electrokinetic phenomena. Zeta potential is almost identical with the Stern potential thus gives a measure of the potential at the beginning of the diffuse layer.

Electrokinetic Phenomena

Shear plane

Isoelectric point

Zeta Potential Effect of pH


+ + + + + + + + + + + + + +

H+ OH-

Shear Plane Low pH: not enough OH- so there is an excess positive charge.

Shear Plane

+ + + + + + +

Shear Plane

There is a point at which there are enough OH- and H+ ions to completely balance out the surface charge

High pH: not enough H+ so there is an excess negative charge.

Zeta Potential Effect of pH


+ + + + + + +

(mV)

Isoelectric Point (IEP): pH at which = 0 pH


+ + + + + + + + + + + + + +

Zeta Potential Effect of pH and ion concentration

(mV)

pH

Isoelectric point of several common proteins

Electrokinetic phenomena
Electrophoresis a suspended, charged particle moves as a result of an applied electrical field Sedimentation potential an electrical potential created by the movement of charged particles through a liquid by gravity Electrosmosis a liquid flows along a charged surface when an electric field is applied parallel to the surface Streaming potential an electric potential created when a liquid is forced to move along a charged surface

Elektrokinetic phenomena
Electrophoresis - Movement of particle in a stationary
fluid by an applied electric field. 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

Elektrokinetic phenomena
Electrophoresis - Movement of particle in a stationary fluid by an applied electric field. Electroosmosis - Movement of liquid past a surface by an applied electric field Streaming potential - Creation of an electric field as a liquid moves along a stationary charged surface Sedimentation potential - Creation of an electric field when a charged particle moves relative to stationary fluid

Electrophoresis
the movement of a charged particle through a liquid under the influence of an applied potential difference (electric current) Voltage source

Moving boundary electrophoresis

charged colloidal particles

Paper electrophoresis, continuous separation


sample buffer solution

Zone electrophoresis (from1950)


(Horizontal electrophoresis)

support media: filter paper; cellulose acetate; gel media: starch gels; polyacrylamide gels; agarose gels; polyacrylamide-agarose gels

Schematic of capillary electrophoresis

Detector

Measurement of potential by microelectrophoresis

uelf =

velf Ex

[ =]

( m/s) (V/cm)

electrophoretic mobility

Smoluchowski equation

Hckel equation

velf =

dx [ =] m/s dt

electric drift velocity electric field strength

= uelf r

= uelf

3 2

U E x = [ =] V/cm l

(big particle thin double layer)

(small particle thick double layer)

Electroosmosis
The movement of a liquid relative to an immobile charged surface of a capillary tube under the influence of an electric field

Electroosmosis
Movement of liquid past a surface by an applied electric field

Streaming potential
creation of an electric field as a liquid moves along a stationary charged surface
pressure
glass glass capillary capillary
i

steady state conditions: E = streaming potential i = flow current

Sedimentation potential (Dorn-effect)


creation of an electric field when a charged particle moves relative to stationary fluid

E = sedimentation potential

Equipment for Measuring Zeta Potential

Electrophoresis - Zeta Mark 21; particles ~ 0.10 - 300 m

Equipment for Measuring Zeta Potential

Electroacoustic - Colloidal Dynamics Acoustosizer; powders/slurries < 10nm - up to 50 weight%

Equipment for Measuring Zeta Potential

Photocorrelation Spectroscopy - Brookhaven Zeta Plus; dilute suspensions; < 5 m; light scattering technique

Equipment for Measuring Zeta Potential

Streaming Potential Paar Physica EKA; granular particles, surfaces

Diagnostic applications of electrophoresis


Proteins are essential for metabolism identified by electrophoresis based on size, shape, and charge of particles. Applications: clinical diagnosis.

Normal protein patterns

Abnormal protein patterns

Abnormal protein patterns

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