N.

Vamsi Krishna

Introduction:
Colloidal system are the ones in which one of three states (solid, liquid and gas) is finely dispersed in another. Colloids were named first in the early 19th century by the Father of Physical Chemistry, Thomas Graham (1805-1869). In 1920's and 1930's, the importance of colloids to industrial processes and biochemistry changed everything making it a hot field. A colloidal system consists of an internal phase (dispersion phase), which is the material of colloidal dimensions, and an external phase (dispersion medium) .Similar to the terms solute and solvent used for simple solutions. As the particles of a colloid system become smaller and smaller, we go over imperceptibly from a two-phase colloid to a single-phase solution, and there is no definite boundary i.e. true solution.

Table 1: Characteristics of Suspension, Colloid and Solution

Properties
1. 2.

Suspension
>100nm possible possible Settles under gravity opaque Not possible shows shows

Colloid
1-100nm not possible possible Settles on Centrifugation Generally clear Diffuses slowly shows shows

Solution
<1nm not possible not possible Does not settle clear Diffuses rapidly Not observable Not observable

Particle size Separation 1)ordinary filtration 2) ultra filtration Settling Appearance Diffusion Brownian motion Tyndall effect

3. 4. 5. 6. 7.

 Total interfacial area (NAp) per 1cm3 of colloid is given by, NAp = N4 R2 = 4 R2 /(4/3 R3 ) = 3 /R Where R = radius, = volume fraction Number of particles per 1cm3 of colloid N = /Vp = / (4/3 R3 ) The large area emphasizes surface effects relative to volume effects, giving colloids different properties than those of bulk matter. Because of their various properties, colloidal systems have many applications in various industries like food industry (diary products, chocolate etc), pharmaceutical and cosmetic industry (gels and emulsions), Photographic industry (films, carbon paper, ink etc), Electrical and electronic industry (liquid crystals, isolating materials etc), paint industry and agrochemical industry.

Classification of colloids:
Colloids can be classified mainly by 3 ways; Classification Based on the State of the Dispersed Phase and Dispersion Medium Classification of Colloids Based on Type of Particles of the Dispersed Phase Classification Based on the Nature of Interaction Between Dispersed Phase and Dispersion Medium

Classification Based on the State of the Dispersed Phase and Dispersion Medium

Table 2: Types of colloids

Dispersion Medium Dispersed phase Type of colloid
Gas Gas Liquid Liquid Liquid Solid Solid Solid Liquid Solid Gas Liquid Solid Gas Liquid Solid Aerosol Aerosol Foam Emulsion Sol Foam Gel Solid Sol

Example
Fog, clouds Smoke Whipped cream, soda water Milk, hair cream Paints, cell fluids Pumice, plastic foams Jelly, cheese Ruby glass

Classification of Colloids Based on Type of Particles of the Dispersed Phase a) Multimolecular colloids usually have lyophobic character. Ex: gold and sulphur sols b) Macromolecular colloids resemble true solutions Ex: proteins, cellulose, starch and polymers such as polyethylene, nylon and polystyrene c) Associated colloids type of micelle it forms depends on the nature of solvent (hydrophilic or hydrophobic) Kraft Temperature (Tk ) Critical micelle concentration (CMC) Ex: soaps and synthetic detergents

Surfactant

Micelle

Classification Based on the Nature of Interaction Between Dispersed Phase and Dispersion Medium

Table 3: Distingustion between lyophilic and lyophobic colloids

Property Surface tension Viscosity Reversibility Stability Visibility Lyophilic sols (suspensoid)
Lower than that of the medium Much higher than that of the medium Reversible More stable Particles cant be detected even under ultra microscope Particles may migrate in either direction or do not migrate in an electric field because do not carry any charge. Addition of smaller quantity of electrolyte has little effect Extensive hydration takes place Gum, gelatin, starch, proteins, rubber etc.

Lyophobic sols (Emulsoid)

Same as that of the medium Same as that of the medium Irreversible Less stable Particles can be detected under ultra microscope. Particles migrate either towards cathode or anode in an electric field because they carry charge. Coagulation takes place No hydration Metals like Ag and Au, hydroxides like Al(OH3), Fe(OH)3 metal sulphides like AS2S3 etc.

Migration

Action of electrolyte Hydration Examples

Preparation of colloids:

1) lyophilic sols 2) lyophobic sols

easy to prepare unstable and irreversible, difficult to prepare

a) Condensation or aggregation method b) Dispersion method

a) Condensation or aggregation method

Chemical methods:
By Reduction: Metal sols are generally prepared by this method. Ex: HAuCl4 (aq)
AgO (aq)

HCHO
H2, 50-60 0C

Au (sol) Ag (sol)

By Oxidation: Sulphur sols are easily obtained by the oxidation.

Ex: 2H2S+SO2 2H2O + 3S (sol)

By double decomposition: Ex: As2O3 (aq) + 3H2S

As2S3 (sol)+ 3H20

By hydrolysis: To obtain sols of oxides or hydroxides of weakly electropositive metals.

Ex: FeCl3 + 3H2O Fe(OH)3 (sol) + 3HCl

Physical methods:
By excessive cooling: used to prepare a colloidal solution of ice. By exchange of solvent:
Ex: S (alc) + H2O S (sol)

By change of physical state: Sols of substances like mercury and sulphur are prepared

b) Dispersion method Mechanical disintegration: Colloidal solutions of black ink, paints, varnishes, dyes etc. and food products like concentrated milk, food additives etc.

Figure1: Pictorial view of colloidal mill

 Peptization: The process of dispersing a precipitate in to a colloidal solution by adding small quantity of electrolyte is called peptization. Ex: Fe(OH)3 + FeCl3 [ Fe(OH)3Fe3+] (sol) + 3Cl

 Bredigs arc method: used to prepare sols of platinum, silver, copper or gold. Traces of KOH are required to stabilize the colloidal solution.

Figure 2: Bredigs arc method

Generally used methods to prepare other colloidal systems are; Aerosol is formed by passing gas jet to a liquid spray. Emulsions are usually prepared by vigorously shaking the two constituents together, often with the addition of an emulsifying agent . The phase in which emulsifier is more soluble forms the outer layer. lyophobic colloids . Gels are often formed by cooling lyophilic sols that contain large linear molecules and have a much greater viscosity than the solvent. Elastic and Rigid gels. Foams are formed when gas and liquid are mixed together in a container and shaken along with a foaming agent.

Purification of colloidal solutions:

Colloidal solutions prepared by the above methods contain some soluble impurities and excess of electrolytes; these have to be removed to obtain pure sols. Generally a) Dialysis, b) ultra filtration and c) ultra centrifugation are the techniques used. Ultra filtration: colloidal sols are filtered through ultra-filtrers. pore size of filter paper is decreased such that it will restrict the passage of colloidal particles. Ultra-centrifugation: Centrifugation is carried out at very high speeds such that the colloidal particles settle down at the bottom of the tube and the impurities remain in the solution . It is important to note that above methods to purify colloidal solution do not produce 100% solution.

Figure 3: Electro-dialysis

used for purification of blood in case of kidney failure.

Properties of colloids:
a) Optical properties

Figure 4: Size dependent change of colour in Au sol

Figure 6: Schematic drawing of ultra microscope

Opalescence in colloids is due to scattering of light by particles. This effect was studied by Tyndall and is generally known as tyndall effect. Tyndall observed that scattered beam to be polarized and intensity of the same to be dependent on position of observer, nature of system and wavelength of light used.

b) Colligative Properties
The magnitudes of these properties for colloidal solutions are much smaller than those obtained for true solutions. They exhibit measurable osmotic pressures. This property is used for the determination of the average molecular masses of the colloids.

c) Kinetic properties
liquid undergoes continuous chaotic and random motions. This motion of the particles is called Brownian motion. This Brownian motion is found to decrease by increase in particle size or by increase in viscosity of medium. r = (3b / 4 nd) where, b = number of grams of substance per dm3 n = number of particles observed in view = volume dm3 d = density of dry substance

c) Electrical properties
Lyophobic sols carry charge, because of which they get repelled on approaching another particle avoiding their coagulation. i) Due to presence of electrolytes Ex: positive charge on ferric hydroxide sol prepared by hydrolysis of ferric chloride is due to adsorption of Fe3+ ions on surface. ii) dissociation of molecular electrolytes adsorbed on the surface of particles. Ex: H2S molecules get adsorbed on sulphides during precipitation. H2S undergoes dissociation and the hydrogen ions are lost. The particles become negatively charged due to (S2-) which are left on the colloidal particles. iii) by dissociation of surface molecules Ex: soaps, proteins

Figure 7: Electrical double layer

The influence of net charge decreases with distance and so the number of oppositely charged ions, equaling the number of ions of both charges prevailing electro neutrality.

The difference in potential between the surface of shear plane and electro neutral region of solution is called Zeta potential ( ), which is given by Helmholtz- Smoluchowski equation. = 4 u/ r where = viscosity of dispersion medium r = relative permittivity of dispersion medium u = mobility of colloidal particle

 In case of lyophobic colloids; (i) Coagulation is brought about by ions having opposite charge to that of the sol. (ii) The efficiency of an ion to cause coagulation depends upon the square of its valency. Thus efficacy of cations Al3+>Mg2+> Na+ and PO43->SO42->Cl-. (iii)The minimum concentration of an electrolyte required to cause coagulation of a sol is called its flocculation value. The other methods to coagulate sol are by mutual mixing of oppositely charged sols, persistent dialysis and by mechanical means. In case of lyophilic sols, i) water of solvation (cage of water surrounding) prevents particles from coagulation. ii) Their coagulation is due to removal of salvation water a s electrolytes binds them. Thus efficacy of cations Al3+>Mg2+> Ca2+> Ba2+>Na+>K+ and efficacy of anions PO43>SO42->Cl->NO3-> ClO3->I- for coagulation of lyophilic sols and this is known as lyotropic series or Hofmeister series. iii) Zsigmondy quantified stabilizing action of protective colloids by gold number, which is defined as largest number of milligrams of a protective colloid when added to 10 ml of standard gold sol, just fails to prevent the colour change from red to blue upon addition of 1 ml of 10% sodium chloride solution

Properties of colloids: Purification of water by alum (coagulation)

In rubber platting In tanning Artificial rains Formation of deltas (coagulation) Blood clot formation Colloidal medicine: Argyrol and protargyrol are colloidal solution of silver and are used as eye lotions .Colloidal sulphur is used as disinfectant and colloidal gold, calcium and iron are used as tonics. A wide variety of medicines are emulsions. Coating of Photographic plates Sewage disposal Metallurgy

 Smoke precipitation (Coagulation)

Figure 8: Schematic diagram of Cottrell smoke precipitator